description
stringlengths 2.59k
3.44M
| abstract
stringlengths 89
10.5k
| cpc
int64 0
2
|
|---|---|---|
BACKGROUND OF THE INVENTION
This invention relates to thermal treatments of aluminum base alloys. More particularly, the invention relates to an improved aging process for an aluminum base alloy containing zinc, magnesium and copper as the alloying constituents.
Aluminum base alloys, particularly 7000 series alloys containing zinc, magnesium and copper, are conventionally solution heat treated at a temperature of from 750°-1000° F. The alloy is then quenched by exposure to cool air, hot water or cold water to retain a substantial portion of the dissolved components in a state of solid solution. The rate of quenching is influenced by several factors, including the possible inducement of residual stresses as well as the overall physical dimensions of the article to be quenched. Certain physical properties, particularly the tensile properties are dependent on the rate of quench. More particularly, the slower quench rates which may be necessary to avoid inducement of residual stresses or which may be necessary due to the physical bulk of the article, can significantly lower the tensile properties of the resultant article.
Conventionally, aluminum articles which have been heat treated and quenched are subsequently subjected to an aging process to enhance certain physical properties, including tensile properties. While aging, in its most simplified and traditional form, might simply involve allowing the material to remain at ambient temperature for a significant period of time prior to use, the more common and economically efficient practice today involves artificial aging. In an artificial aging practice, the heat treated and quenched material is maintained at an elevated temperature with respect to room temperature to accelerate the aging. For example, the aging temperature may range from 150°-350° F. The article is maintained at this temperature for a period of time of perhaps 4 to 24 hours and then allowed to cool to room temperature.
Some time ago, employees of the assignee of the present invention determined that significant improvements in certain physical properties, such as resistance to stress corrosion, cracking and tearing, could be improved if subsequent to the solution heat treatment and quenching the aging was carried out in two distinct steps at two different temperatures. Thus, in Sprowls et al, U.S. Pat. No. 3,198,676, assigned to the assignee of this invention, a two-step aging process is disclosed wherein the article is first aged at a temperature of from 175° to 275° F. for a period of from 3 to 30 hours (depending on the amount of zinc) followed by a subsequent aging step within the range of 315° to 380° F. for a period of from 2 to 100 hours. While the patentees disclosed a rather broad temperature range (175° to 275° F.) for the first step, in actual practice the patentees only illustrated aging carried out in the first step at a temperature range of from 225° to 270° F.
While the practice of the process disclosed in the aforementioned patent does result in enhanced properties, the overall tensile properties are still undesirably low for aluminum alloys which have been quenched at a slow rate.
SUMMARY OF THE INVENTION
It is, therefore, an object of the invention to provide an improved process for the aging of aluminum base alloys containing zinc, magnesium and copper.
It is another object of the invention to provide an improved aging process wherein aluminum base alloy articles previously subjected to solution heat treatment and subsequent quenching are artificially aged in a three-step aging process.
It is yet a further object of the invention to provide an improved aging process wherein aluminum base alloy articles are aged in a three-step aging process wherein the temperature at which the article is aged is increased with each subsequent aging step.
These and other objects of the invention will be apparent from the subsequent description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flow sheet illustrating the process of the invention.
FIG. 2 is a graph illustrating the practice of the invention at two different first step temperatures versus prior art two-step processes at various quench rates.
DESCRIPTION OF THE INVENTION
In accordance with the invention, an aluminum base alloy containing alloying amounts of zinc, magnesium and copper is aged in a three-step process subsequent to solution heat treatment and quenching.
The aluminum base alloy, generally known as 7000 series alloy, consists essentially of aluminum, 1.5 to 14 wt.% zinc, 0.8 to 3.8 wt.% magnesium, 0.25 to 2.6 wt.% copper and at least one additional alloying element selected from the group consisting of 0.05 to 0.4 wt.% chromium, 0.1 to 0.75 wt.% manganese, 0.05 to 0.3 wt.% zirconium, 0.05 to 0.3 wt.% vanadium, 0.05 to 0.3 wt.% molybdenum and 0.05 to 0.3 wt.% tungsten, the ratio of magnesium to zinc being 0.2 to 0.5 parts by weight magnesium per part by weight of zinc.
The aluminum base alloy is fabricated into an article of desired shape which may be a forging, extrusion or plate. The aluminum base alloy article is then subjected to a solution heat treatment which involves heating to a temperatures within the range of 750° to 1000° F., but below the range of incipient fusion and then holding the article at that range for a length of time sufficient to obtain substantially complete solution of the zinc, magnesium and copper components. Generally, this can be accomplished with a period of from 3 or 4 minutes up to 10 hours, depending on the thickness of the article and whether the surface of the article is directly exposed to the heating medium. Thus, an article having a thickness of 1/2 inch can be treated in a shorter time in an air atmosphere than one which has a thickness of 2 inches.
At the conclusion of the heat treatment, the article is rapidly cooled to substantially room temperature by quenching. The quenching may comprise contacting the article with cold water, hot water or with air, depending upon the desired rate of quench. It should be noted here that while rapid quenching is desirable to achieve certain physical properties, the mass of the article may prevent the use of very rapid quenching because of the inducement of residual stresses thereby.
The heat treated and quenched article is then subjected to aging in accordance with the invention. The first stage of aging consists of heating the aluminum base alloy article to a temperature of from 190° to 230° F., preferably 195° to 205° F. Upon reaching this temperature, the article is maintained at this temperature for from 4 to 30 hours, preferably at least 8 hours. The temperature is then raised for the second aging step to a temperature of from over 230° to 260° F., preferably 245° to 255° F. The article is then maintained at this temperature for an additional 4 to 30 hours, preferably 8 hours. Finally, the temperature is raised from 315° to 380° F., preferably 335° to 350° F., for the third aging step. The article is held at this temperature for from 2 to 100 hours, preferably 8 hours, but longer if needed, to achieve T7 temper conditions.
To further illustrate the invention, a number of samples were prepared using a 7075 alloy. The samples were solution heat treated for 30 minutes in a circulating air furnace at 880° F. The samples were then quenched at varying rates in water or air according to the following table.
TABLE 1______________________________________ Quench RateSample Quench Media °C./sec (°F./sec)______________________________________I Water at 21° C. (70° F.) 1089 (1960)II Water at 77° C. (170° F.) 370 (666)III Water at 99° C. (210° F.) 39.1 (70.3)IV Air Blast 8.22 (14.8)V Still Air 1.9 (3.42)______________________________________
The quenched samples were then aged using, respectively, two-step aging in accordance with the prior art and three-step aging in accordance with the invention. For each quench rate, four samples were aged. Samples A(I-V) were aged for 8 hours at 200° F. followed by a second aging step for 8 hours at 340° C. Samples B(I-V) were aged for 8 hours at 200° F. in a first step; 8 hours at 250° F. in a second step; and 8 hours at 340° F. in a third step. Samples C(I-V) were aged at 225° F. for 8 hours in a first step and 8 hours at 340° F. in a second step. Samples D(I-V) were aged for 8 hours at 225° F. in a first step; 8 hours at 250° F. in a second step; and 8 hours at 340° F. in a third aging step. The three-step aging process to which each of the B and D series samples were treated is representative of the novel process of the invention while the two step process used for the A and C series samples is representative of the prior art as taught by the aforementioned Sprowls et al patent.
Turning to FIG. 2, the resulting yield strengths (KSI) are plotted for the various samples. In each instance, the samples subjected to the three-step aging process of the invention resulted in a higher yield strength although the results are more marked at the lower quench rates. In addition, it is noted that at the lower quench rates (Samples IVB, IVD, VB and VD), the samples quenched using a lower first step temperature (200° F. instead of 225° F.) resulted in a higher yield strength than when the higher temperature was used in the first step.
Thus, it can be seen that the invention, although useful at all quench rates, is particularly effective at lower quench rates and, thus, will find its greatest usefulness in the aging of larger and more massive forgings, extrusions or plate which cannot be subjected to rapid quenching.
While the inventors do not wish to be bound by any theory of operation for the aging process of the invention, it has been proposed that the success of the invention is related to the favorable effect of the process on the precipitates distribution in the material quenched at low rates. It appears that the temperature at which GP zones (first precipitates formed after quenching) dissolve upon reheating decreases with decreasing quenching rate. Thus, the amount of dissolution of the GP zones upon subsequent heating to a given first step aging temperature will be dependent upon the quench rate to which the aged sample was subjected.
Furthermore, the use of a low temperature first aging temperature appears to foster the growth of the GP zones which, in turn, raises the critical reversion temperature at which the precipitates may redissolve. This critical reversion temperature apparently is very high in rapidly quenched articles and, therefore, is not exceeded in subsequent aging. However, if it is exceeded by the aging temperature in more slowly quenched products, the GP zones formed during natural aging would revert, and some or all of the remaining solute would precipitate directly in a form to which the GP zones are gradually transformed during growth, thereby resulting in a coarser distribution resulting in additional losses of maximum attainable strength.
In any event, however, by the practice of the invention, the deleterious effects of slower quench rates, regardless of their possible cause and effect on nucleation and precipitation, can be effectively reduced. | Aluminum base 7000 series alloys can have improved tensile properties when, after heat treatment and subsequent quenching, they are subjected to a three-step aging process comprising a first aging step at 190°-230° F., a second aging step at over 230° F. and a third aging step at 315°-380° F. The improved process is particularly effective in improving the tensile properties of slowly quenched materials such as large extrusions or forgings. | 2 |
RELATED U.S. APPLICATION DATA
[0001] This application claims priority from U.S. Provisional Patent Application No. 60/422,330 filed Oct. 30, 2002, incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to surgical tools and procedures generally and relates more particularly to the use of electrosurgical ablation to treat atrial fibrillation.
[0003] In patients with chronic atrial fibrillation or having atrial tachycardia that is resistant to medical treatment, the Maze III procedure has been employed. This procedure controls propagation of the depolarization wavefronts in the right and left atria by means of surgical incisions through the walls of the right and left atria. The incisions create blind or dead end conduction pathways, which prevent re-entrant atrial tachycardias from occurring. While the Maze procedure is successful in treating atrial fibrillation, the procedure is quite complex and is currently practiced by only a few very skilled cardiac physicians in conjunction with other open-heart procedures. The procedure also is quite traumatic to the heart, as in essence the right and left atria are cut into pieces and sewed back together, to define lines of lesion across which the depolarization wavefronts will not propagate.
[0004] It has been suggested that procedures similar to the Maze procedure could be instead performed by means of electrosurgical ablation, for example, by applying radiofrequency (RF) energy to internal or external surfaces of the atria to create lesions across which the depolarization wavefronts will not propagate. Such procedures are disclosed in U.S. Pat. No. 5,895,417, issued to Pomeranz, et al., U.S. Pat. No. 5,575,766, issued to Swartz, et al., U.S. Pat. No. 6,032,077, issued to Pomeranz, U.S. Pat. No. 6,142,944, issued to Swanson, et al., U.S. Pat. No. 5,871,523, issued to Fleischman, et al. and U.S. Pat. No. 6,502,575, issued to Jacobs et al., all incorporated herein by reference in their entireties. Hemostat type, electrosurgical or cryo-ablation devices for use in performing such procedures are described in U.S. Pat. No. 5,733,280 issued to Avitall, U.S. Pat. No. 6,237,605 issued to Vaska, et al, U.S. Pat. No. 6,161,543, issued to Cox, et al., PCT published Application No. WO99/59486, by Wang and in pending U.S. patent application Ser. No. 09/747,609 filed Dec. 22, 2000 by Hooven, et al., all incorporated herein by reference in their entireties. In order for such procedures to be effective it is desirable that the electrosurgically created lesions are continuous along their length and extend completely through the tissue of the heart (i.e. transmural lesions). These goals may be difficult to accomplish employing dry ablation electrodes or electrodes applied only to the interior or exterior surfaces of the heart tissue. Electrosurgical hemostats configured to allow fluid—assisted tissue ablation are generally described in U.S. Pat. No. 6,096,037, issued to Mulier, also incorporated by reference in its entirety.
SUMMARY OF THE INVENTION
[0005] The present invention provides an ablation hemostat, particularly useful in performing a maze type procedure by applying ablation energy (e.g. RF energy) across the walls of the left and right atria by means of delivery means located on either side of the atrial walls. In a preferred embodiment of the invention, the hemostat is provided with elongated RF electrodes malleable to assume various straight and curved configurations to produce lesions that approximate the incisions that would occur during the Maze III procedure as described in the book ‘ Cardiac Surgery Operative Technique’ by Donald B. Doty, M. D. at pages 410-419, incorporated herein by reference in its entirety, or to allow creation of lines of lesion corresponding to the incisions that would be provided by other forms of the Maze procedure. The hemostat may be useful in conjunction with other procedures as well.
[0006] The hemostat of the present invention is provided with a number of useful features, particularly adapted to ease its use in conjunction with creating elongated lines of lesion. While the disclosed and most preferred embodiments of the invention employ all of the improved features, each of the improved features discussed below is believed valuable in and of itself to improve the performance and ease of use of prior art electrosurgical hemostats.
[0007] In order to allow the hemostat to produce straight and curved elongated lesions, the jaws of the hemostat are malleable to allow the physician to set the specific jaw configuration. The jaws are fabricated of a flexible plastic sheath enclosing elongated bendable or malleable backbones and electrodes to achieve this result. The backbones and electrodes may be shaped by the physicians' fingers into a desired curvature and serve to retain the curvature imparted to them until reshaped for creation of a subsequent lesion. The backbones take the form of elongated plates having thicknesses substantially less than their widths to encourage bending of the jaws within a single plane so that the opposed electrodes can more readily be maintained in alignment along their lengths. The backbones are also preferably tapered along their length such that the width of the backbones diminishes as they approach the tips of the jaws, in turn making it easier to provide the jaws with the curvature extending over the entire length of the jaws.
[0008] The hemostat includes an elongated handle portion or handle and a jaw assembly mounted at the distal end of the handle. The jaw assembly preferably includes two elongated jaws carrying RF electrodes or other ablation elements, extending along the lengths of the jaws and arranged so that they are located on opposite sides of tissue compressed between the jaws. In preferred embodiments, the electrodes take the form of fluid irrigated RF electrodes, however, other ablation mechanisms such as cyroablation, direct current ablation, microwave ablation, and the like may be substituted for RF ablation electrodes.
[0009] The jaw assembly preferably includes a swiveling head assembly adapted to allow the jaws to be rotated relative to the axis of the handle (roll) and allowing the jaws to pivot around an axis perpendicular to the axis of the handle (pitch). Adjustment of the jaws relative to the handle (pitch and roll) is made manually by the physician, and the jaws are retained in their desired orientation relative to the handle by means of detent mechanisms.
[0010] The jaws are mounted to one another at a pivot point and are opened and closed by means of a trigger, mounted to the handle, which applies tensile force to a cable or other tension member extending along the handle. The cable, when pulled, pulls the jaws toward one another to compress tissue between them. In the particular embodiments disclosed, the cable is anchored offset from the pivot point to a first one of the jaws. The first jaw is fixed, i.e. retains its location during jaw closure regardless of the pitch and roll adjustment made to the jaw assembly. The second, pivoting jaw, is mounted to the fixed jaw at a pivot point and the cable passes around an internal boss within the pivoting jaw, also offset from the pivot point. Application of tension to the tension member pulls the internal boss in the pivoting jaw toward the cable mounting point in the fixed jaw and thereby causes movement of the jaws toward one another. Tissue placed between the jaws can thus be engaged by the jaws and compressed between the jaws as the jaws close.
[0011] The cable enters the jaw assembly along its rotational (roll) axis, so that rotation of the jaw assembly about the roll axis does not alter the operation of the cable. The cable extends around a shoulder internal to the fixed jaw, which shoulder remains essentially in the same location regardless of the pitch adjustment of the jaw assembly, so that pitch adjustment of the jaw assembly does not significantly effect operation of the cable to close the jaws.
[0012] In preferred embodiments, the trigger mechanism is provided with a locking detent mechanism which may be engaged or disengaged and which, when engaged, retains the trigger in its position, in turn maintaining compression of the jaws against tissue located there between. The detent mechanism in a preferred embodiment is activated or deactivated by means of a sliding button, mounted to the handle.
[0013] In preferred embodiments, irrigation fluid is provided to the electrodes by means of plastic tubing that is provided with in-line flow limiters, controlling the delivery rate of irrigation fluid to the electrodes. This feature allows the use of a simplified fluid pumping mechanism and also provides balanced, even fluid flow to the electrodes. In its preferred embodiment, the trigger, when released, also serves to block fluid flow to the electrodes, preventing irrigation while the hemostat is not in use.
[0014] In one embodiment, the RF electrode assembly can take the form of an elongated porous material coupled to the fluid delivery lines and carrying elongated electrode wires on their inner, facing services. The electrode wires may be coupled to the porous material by means of a series of spikes extending from the electrode wires into the porous material. Other alternative electrode designs may of course be substituted, including electrodes comprised of elongated coil electrodes or perforated tubular electrodes with porous material located either inside of or surrounding the electrodes. For example, a perforated tubular electrode can be seated inside a porous polymeric support such the electrode is entirely within the support. In this embodiment, conductive fluid flows through the interior of the electrode, out of perforations in the electrode and through the porous support to facilitate ablation such that the polymeric support, not the electrode, is on the facing surfaces of the jaws to contact the tissue to be ablated.
[0015] The hemostat may optionally also include a thermocouple, located along the jaws allowing for temperature controlled feedback of power provided to the RF electrodes and may also preferably includes an indicator LED mounted to the handle, activated to indicate that delivery of RF energy is underway. The hemostat is usable useable with conventional RF generators. Alternatively, the hemostat may be used in conjunction with an RF generator system, which incorporates a transmurality measurement and automatic shut off of ablation energy.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a plan view of an assembled hemostat according to one embodiment of the present invention.
[0017] [0017]FIG. 2 is an exploded view of the jaw assembly of the hemostat of FIG. 1.
[0018] [0018]FIG. 3A is a cross-section view through the jaw assembly of the hemostat of FIG. 1.
[0019] [0019]FIG. 3B is a cross-section view through lines 3 B- 3 B of FIG. 3A.
[0020] [0020]FIG. 4 is an end view in partial cross-section of the proximal end of the knuckle portion of the jaw assembly of the hemostat of FIG. 1.
[0021] [0021]FIG. 5A is a plan view of an elongated tubular electrode used in the hemostat of FIG. 1.
[0022] [0022]FIG. 5B is an enlarged cross-section view taken along lines 5 B- 5 B of the electrode illustrated in FIG. 5A.
[0023] [0023]FIG. 6A is an end view of an electrode support as used in the jaw assembly of the hemostat of FIG. 1.
[0024] [0024]FIG. 6B is a cross-section view taken along lines 6 A- 6 A of FIG. 6A illustrating the electrode support.
[0025] [0025]FIG. 7A is an end view of an electrode sheath as included in the jaw assembly of the hemostat of FIG. 1.
[0026] [0026]FIG. 7B is a cross-section view taken along lines 7 B- 7 B of FIG. 7A illustrating the electrode sheath.
[0027] [0027]FIG. 8A is a plan view of the right half of the handle employed in the hemostat of FIG. 1.
[0028] [0028]FIG. 8B is an enlarged plan view of the distal portion of the right handle half illustrated in FIG. 8A.
[0029] [0029]FIG. 8C is a cross-section view taken along lines 8 C- 8 C through the right handle half of the hemostat of FIG. 1.
[0030] [0030]FIG. 9A is a plan view of the left half of the handle employed in the hemostat of FIG. 1.
[0031] [0031]FIG. 9B is an enlarged plan view of the distal portion of the left handle half illustrated in FIG. 9A.
[0032] [0032]FIG. 9C is a cross-section view taken along lines 9 C- 9 C through the left handle half of the hemostat of FIG. 1.
[0033] [0033]FIG. 10 is an enlarged view of the trigger portion of a hemostat as in FIG. 1 with the left handle half removed.
[0034] [0034]FIG. 11A is a perspective view of a trigger lock as employed in the trigger assembly of the hemostat as in FIG. 1.
[0035] [0035]FIG. 11B is a plan view of the trigger lock of FIG. 11A.
[0036] [0036]FIG. 12A is a top plan view of a link arm as employed in the trigger assembly of an assembled hemostat as in FIG. 1.
[0037] [0037]FIG. 12B is a side plan view of the link arm of FIG. 12A.
[0038] [0038]FIG. 13A is a side plan view from the distal end of the trigger employed in the trigger assembly of the hemostat of FIG. 1.
[0039] [0039]FIG. 13B is a cross-section view taken along lines 13 B- 13 B through the trigger of FIG. 13A.
[0040] [0040]FIG. 14 is a cut-away view of the proximal portion of the hemostat of FIG. 1 with the left handle half removed.
[0041] [0041]FIG. 15A is a sectional view through an alternative embodiment of an upper and lower jaw for use with a hemostat otherwise as in FIG. 1.
[0042] [0042]FIG. 15B is a cross-sectional view taken along lines 15 B- 15 B of FIG. 15A.
[0043] [0043]FIG. 16A is a plan view of an electrode extension employed in the alternative embodiment of the upper and lower jaw depicted in FIGS. 15A and 15B.
[0044] [0044]FIG. 16B is an expanded view of a barb of the electrode extension depicted in FIG. 16A.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0045] In reference to FIG. 1, a preferred embodiment of the hemostat of the present invention generally comprises an elongated handle assembly or handle 10 having a jaw assembly 90 mounted at handle distal end 15 , a trigger 20 intermediate the handle proximal and distal ends 95 and 15 , and a strain relief 60 located at handle proximal end 95 . An elongated cable is coupled to the strain relief 60 and comprises a fluid conduit 70 extending to a proximal fluid fitting 75 adapted to be coupled to a source of conductive fluid and a multi-conductor electrical cable 80 extending to a proximal electrical connector 85 adapted to be coupled to an electrosurgical unit. The trigger 20 is employed to move the jaws of the first or lower jaw assembly 40 with respect to the second or upper jaw assembly 30 of the jaw assembly 90 together to compress tissue therebetween to allow for creation of a linear RF ablation by electrically conductive fluid emitted from electrodes and contacting tissue or direct contact of the electrodes located along the upper and lower jaws 35 and 45 .
[0046] The jaw assembly 90 includes the upper jaw assembly 30 , the lower jaw assembly 40 , and a swivel assembly 50 , discussed in more detail below. The upper jaw and lower jaw assemblies 30 and 40 have opposed upper and lower jaws 35 and 45 , respectively, each comprising a fluid assisted elongated electrode assembly. The upper and lower jaw assemblies 30 and 40 support elongated electrodes, discussed in more detail below, each coupled to one of the insulated conductors within conduit 70 extending proximately through the strain relief 60 to electrical connector 85 . Each of the jaws 35 and 40 of respective upper and lower jaw assemblies 30 and 40 are also coupled to fluid conduit 80 enabling delivery of saline or other conductive fluid from a source coupled to fitting 75 along the lengths of the opposed jaws 35 and 45 .
[0047] The swivel assembly 50 , provides the physician with the opportunity to position the jaw assembly 90 in a variety of orientations relative to the handle 10 , to facilitate placing the 35 and 45 jaws against tissue to form desired lines of lesions, e.g., the heart wall in performance of the above-described Maze procedure. The physician can manually grasp and rotate the swivel assembly 50 and the jaw assembly 90 to provide a roll adjustment R, preferably through an arc of at least 300 degrees, relative to the axis of the distal end 15 of the handle 10 through interaction of components of the handle and swivel assembly described further below. In addition, the physician can grasp the jaw assembly 90 and adjust it in pitch P relative to the swivel assembly 50 through the interaction of components of the jaw assembly 90 and the swivel assembly 50 described further below. Preferably, the available arc of pitch P adjustment extends over at least 90 degrees. Moreover, the upper and lower jaws 35 and 45 are malleable as described further below. The combination of these features and the S-shape handle 10 make the hemostat highly versatile in use.
[0048] The trigger 20 is employed to open (separate apart) and close (draw together) the jaws 35 and 45 and to compress tissue between the jaws 35 and 45 prior to application of RF energy to create an elongated lesion. A thumb slide 25 is provided in conjunction with an internal trigger lock, allowing the position of the trigger 20 and the jaws 35 , 45 to be locked. After the trigger 20 is drawn toward the handle 10 to close the jaws 35 and 45 , the thumb slide 25 is moved distally relative to the handle 10 to cause an internal trigger lock to engage one of a series of ratcheting-lock points that define a set of locking locations for the jaws 35 , 45 , as described further below. Movement of the thumb slide 25 proximally relative to the handle 10 releases the trigger 20 and the jaw assembly 90 , allowing the jaws 35 , 45 to return to a fully open position. The interaction of the trigger 20 , thumb slide 25 and the associated trigger lock mechanism frees the physician from the need to maintain pressure on the trigger 20 to compress tissue between the jaws 35 , 45 during the ablation, simplifying operation of the hemostat.
[0049] Referring to FIG. 2, the upper jaw assembly 30 includes a pivotable, relatively rigid, upper jaw mount 300 , an elongated backbone 310 , an elongated insulated electrode sheath 320 , an elongated conductive electrode 330 , and an elongated electrode support 340 . Upper jaw mount 300 may be fabricated of plastic or other insulated material, and in preferred embodiments may be fabricated of Teflon filled polycarbonate plastic. Backbone 310 is preferably fabricated of malleable stainless steel or other malleable metal and is attached at a proximal end to upper jaw mount 300 . An insulated electrode sheath 320 is fitted over spine 310 with its proximal end located adjacent upper jaw mount 300 . The elongated conductive electrode 330 comprises a length of malleable conductive metal tubing as shown in FIGS. 5A and 5B is fitted into a lumen of the elongated electrode support 340 . The insulated electrode sheath 320 is formed with a channel that receives the sub-assembly of the elongated conductive electrode 330 and electrode support 340 disposed along the jaw 35 . Electrode sheath 320 may be fabricated of a flexible, electrically insulating, material, for example, silicone rubber. Elongated electrode support 340 is preferably fabricated of a porous material, such as Porex™ plastic, allowing for conductive fluid infiltration through its sidewall along its length and correspondingly delivery of conductive fluid along the length of jaw 35 . The jaw 35 can therefore be bent laterally with respect to the upper jaw mount 300 to form a curve along the length thereof.
[0050] The lower jaw assembly 40 also includes a relatively rigid, lower jaw mount 400 , an elongated backbone 410 , an elongated insulated electrode sheath 420 , an elongated conductive electrode 430 , and an elongated electrode support 440 that are all formed of the same materials as the corresponding elements of the upper jaw assembly 30 . The assembly of the elongated backbone 410 , elongated insulated electrode sheath 420 , elongated conductive electrode 430 , and elongated electrode support 440 is also shown in FIG. 3B.
[0051] The jaw 45 can therefore also be bent laterally with respect to the lower jaw mount 400 to form a curve along the length thereof. In use, the physician manually forms a lateral curve in both the upper and lower jaws 35 and 45 to fit the contour of the tissue, e.g., the heart wall.
[0052] The lower jaw mount 400 is formed with a pair of spaced apart, parallel, plates or flanges 401 and 403 each bearing a series of notches 402 and 404 , respectively, along the edges thereof. When assembled, a proximal portion of the upper jaw mount 300 is fitted between the flanges 401 and 403 . A pin 480 extends through aligned holes through the proximal portion of upper jaw mount 300 and the flanges 401 and 403 . The ends of pin 480 are fixed to the flanges 401 and 403 allowing the proximal portion of the upper jaw mount 300 to be rotated about the pin 480 , thereby allowing jaws 35 and 45 to open and close. The upper and lower jaws 35 and 45 are separated apart a predetermined distance in the fully closed positions although the electrically insulated distal ends of the insulated electrode sheaths 320 and 420 may contact one another. A spring 450 urges the upper and lower jaws 35 and 45 apart from one another, facilitating opening of the jaws 35 and 45 upon release of the trigger 20 after application of RF energy.
[0053] As shown in FIGS. 2 and 3A, the swivel assembly 50 includes a swivel 500 that may also be fabricated of Teflon filled polycarbonate plastic to have a tubular proximal swivel portion 506 , a pair of parallel plates or flanges 502 and 504 extending distally from swivel proximal portion 506 and a extending detent 501 extending laterally between flanges 502 and 504 . The jaw assembly 90 is mounted to the swivel assembly 50 by outwardly and laterally extending bosses 405 on the outer surfaces of flanges 401 and 403 that are fitted into bores 503 through swivel flanges 502 and 504 . The upper jaw mount 300 is mounted to the lower jaw mount 400 by pin 480 as described above, and the lower jaw mount is 400 pivotably mounted relative to the swivel 500 . Therefore, the upper and lower jaw assemblies 30 and 40 may be pivoted together relative to the swivel 500 , allowing for movement of the jaws 35 and 45 together through the range of pitch P adjustment. The selected pitch P adjustment is maintained by the engagement of the detent 501 into an opposed pair of notches 402 and 404 , stabilizing the upper and lower jaws 35 and 45 in a desired orientation relative to the swivel assembly 50 . In use, the physician adjusts the relative positions of the jaws 35 and 45 relative to the swivel assembly 50 by simply manually moving the jaw assemblies 30 and 40 in the pitch P direction around the pivot axis defined by bosses 405 within the corresponding bores 505 in swivel flanges 502 and 504 . The detent 501 simply rides over the ridges separating adjacent notches 402 and 404 .
[0054] As noted above, the swivel assembly 50 and the upper and lower jaw assemblies 30 and 40 can be rotated around the axis of the distal end 15 of the handle 10 to a desired roll adjustment R to facilitate positioning the jaws 35 and 45 for creation of elongated lesions. The proximal portion 506 of swivel 500 is rotatably mounted within a collar 550 that is mounted fixedly to the distal end 15 of the handle 10 as shown in FIG. 3A. The collar 550 has a wavy or sinusoidal distally facing surface 551 of collar 550 . A washer-shaped insert 510 having a wavy or sinusoidal proximally facing surface 511 is fitted over the elongated proximal portion 506 of swivel 500 and attached to the swivel 500 through notches 514 , engaging corresponding bosses 557 and 567 (shown in FIG. 4) formed on swivel 500 . A C-clip 524 mounted in a circumferential groove formed in the proximal portion 506 of swivel 500 maintains the proximal portion 506 within the lumen of collar 550 . A spring washer 522 and a flat washer 520 are interposed between the C-clip 524 and the proximal end of collar 550 . Spring washer 522 urges the wavy or sinusoidal surfaces of collar 550 and insert 510 against one another, whereby a plurality of detent locations are defined that maintain a selected roll R adjustment relative to the distal end 15 of the handle 10 . In use, the physician adjusts the roll R of the jaw assembly 90 by simply turning the swivel assembly 50 relative to the handle 10 . The detent mechanism maintains the swivel assembly 50 in the selected desired roll R adjustment prior to and during closure of the jaws 35 , 45 to compress tissue during application of RF energy.
[0055] A cable 390 is also shown in FIGS. 3A and 4 that extends from the trigger 20 and that is employed to open and close the jaws 35 and 45 . Cable 390 passes through the internal lumen of proximal swivel portion 502 , through cable bore 565 , around shoulder 404 of lower jaw mount 400 , around boss 303 in upper jaw mount 300 and then upward into bore 408 in lower jaw mount 400 . The distal end of the cable 390 is maintained within bore 408 by ball 350 . When the cable 390 is pulled proximally by squeezing trigger 25 , boss 303 of upper jaw 300 is pulled toward bore 408 in lower jaw 400 , thereby pulling upper jaw 35 toward lower jaw 45 , allowing for compression of tissue there between. It should be noted that during this operation, the lower jaw mount 400 remains fixed relative to the swivel assembly 50 and only upper jaw mount 300 moves relative to the swivel assembly 50 or the handle 10 . Proximal movement of cable 380 does not affect the position of the lower jaw 45 relative to the handle 10 , nor does it affect the selected roll R adjustment of swivel 500 . Rotation of the jaw assembly 90 and swivel 500 about the roll axis does not affect the operation of the cable 390 because the cable 390 passes through the swivel 500 and enters the jaw assembly 90 along the roll axis. Pitch P adjustment of the jaw assembly 90 does not significantly effect operation of the cable 390 in opening or closing the jaws 35 , 45 because shoulder 404 is at the center of rotation of lower jaw mount 400 relative to swivel 500 and remains essentially in the same location regardless of the pitch P adjustment.
[0056] [0056]FIGS. 3A and 4 also internal electrical wiring and fluid delivery conduits of this embodiment of the invention including, insulated conductors 360 and 460 and fluid conduits 370 and 470 that both terminate at connections with the proximal ends of the upper and lower electrodes 330 and 430 , respectively. The fluid conduits 370 and 470 deliver conductive fluid into the lumens of the tubular upper and lower electrodes 330 and 430 , respectively. As shown in FIG. 4, the upper insulated conductor 360 and the upper fluid conduit 370 are routed to one side of the cable 390 , and the lower insulated conductor 460 and the lower fluid conduit 470 are routed to the other side of the cable 390 while passing through the lumen 534 .
[0057] The elongated tubular electrodes 330 and 430 are illustrated in FIGS. 5A and 5B. The tubular electrodes 330 and 430 are preferably formed of thin-walled, malleable stainless steel tubing extending between a proximal open end 331 , 431 and a distal closed end 333 , 433 . A series of fluid ports 335 , 435 are formed, e.g., by laser drilling, through the sidewall of the tubing from the lumen 339 , 439 and extending in a single line, although the fluid ports could be formed in any selected array extending around the circumference of the sidewall of the tubing. The proximal ends 331 , 431 are notched in alignment with the series of fluid ports 335 , 435 to assist in assembly so that the fluid ports 335 , 435 are directed in a particular alignment with the porous electrode support 340 , 440 .
[0058] The porous electrode support 340 , 440 , depicted in FIGS. 6A and 6B, comprises a length of non-conductive, porous, malleable tubing having a channeled side 343 , 443 adapted to fit within an elongated channel 323 , 423 of the insulated electrode sheath 320 , 420 , depicted in FIGS. 7A and 7B. The porous electrode support 340 , 440 is conically shaped at the support distal end 347 , 447 to fit within a conically shaped terminus 327 , 427 of the elongated channel 323 , 423 of the insulated electrode sheath 320 , 420 . During assembly, the elongated tubular electrode 330 , 430 is inserted into the elongated lumen 341 , 441 of the porous electrode support 340 , 440 . Preferably, the series of fluid ports 335 , 435 are oriented toward the channeled side 343 , 443 so that the conductive fluid emitted from the lumen through the series of fluid ports 335 , 435 then migrates laterally through the pores of the porous electrode support 340 , 440 and around its circumference to thoroughly and uniformly wet the porous electrode support 340 , 440 along the upper and lower jaws 35 and 45 .
[0059] The sub-assembly so formed is fitted into the shaped terminus 327 , 427 and the elongated channel 323 , 423 of the insulated electrode sheath 320 , 420 as also shown in FIGS. 3A and 3B. Adhesive is applied to the contacting surfaces 323 , 343 and 423 , 443 to maintain the sub-assembly of the elongated tubular electrode 330 , 430 inserted into the elongated lumen 341 , 441 of the porous electrode support 340 , 440 affixed to the insulated electrode sheath 320 , 420 . The adhesive does not block migration of conductive fluid around the porous electrode support 340 , 440 . Electrode sheathe 320 , 420 is also formed having an elongated tapered internal recess 421 441 that receives the malleable backbone 310 , 410 as shown in FIGS. 2 and 3. Again, adhesive may be applied to the contacting surfaces of the backbone 310 , 410 and the elongated tapered internal recess 421 441 .
[0060] The handle 10 is formed of a right handle half 600 depicted in FIGS. 8 A- 8 C and a left handle half 700 depicted in FIGS. 9 A- 9 C. Trigger sections 620 and 720 of the respective right and left handle halves 600 and 700 include downwardly opening recesses 621 and 721 in which trigger 20 is mounted (as shown in FIGS. 1 and 10) to pivot inward to apply tension on cable 390 or outward to release tension on cable 390 . Upward openings 627 and 727 in respective right and left handle halves 600 and 700 receive the thumb slide 25 . Inwardly extending projections 630 and 730 are also formed in respective right and left handle halves 600 and 700 that function to constrict the fluid conduits 370 and 470 to prevent conductive fluid flow therethrough when the trigger 20 is released as described further below.
[0061] A set of circular matching, laterally opposed, sockets 623 and 723 are formed in the interior surfaces of the respective right and left handle halves 600 and 700 . The set of sockets 623 , 723 , receive a pair of pivot bosses 206 , 206 ′ of trigger 20 (shown in FIG. 13A) about which the trigger 20 pivots as described further below. A set of matching, laterally opposed, and slightly elongated or oblong, sockets 624 and 724 are formed in the interior surfaces of the respective right and left handle halves 600 and 700 . The set of sockets 624 , 724 receive and guide a trigger lock 27 (shown in FIGS. 11A and 11B) that interacts with trigger 20 as described further below. The oblong shape of the set of sockets 624 , 724 assists in allowing the trigger 20 to ratchet along the trigger lock 27 when trigger is drawn inward to tension the cable 390 during closing of the jaws 35 , 45 as described further below.
[0062] A further set of matching, laterally opposed, elongated sockets 625 and 725 are also formed in the interior surfaces of the respective right and left handle halves 600 and 700 . The set of sockets 625 , 725 receive and guide a link arm 26 (shown in FIGS. 12A and 12B) that interacts with trigger 20 as described further below.
[0063] As shown in FIGS. 8B and 9B, the distal portions of right and left handle halves 600 and 700 are formed with internal cylindrical recesses or sockets 612 and 712 that receive the laterally extending bosses 552 of collar 550 (FIG. 2). Internal grooves 611 and 711 are also formed within the distal portions of right and left handle halves 600 and 700 in which the c-clip 524 , flat washer 520 and spring washer 522 (FIGS. 2 and 3A) are fitted.
[0064] As shown in FIGS. 8C and 9C, the right and left handle halves 600 and 700 are also provided with a series of laterally extending, perpendicular internal walls 628 and 728 that include slots and recesses for routing the fluid conduits or tubes 370 and 470 , the cable 390 and the insulated wire conductors 360 and 460 that extend through the length of handle 10 .
[0065] The trigger 20 , thumb slide 25 , and the associated link arm 26 and trigger lock 27 are shown assembled to the right handle half 600 in FIG. 10 with the trigger 20 in the released position and the thumb slide 25 in the unlocked distal or retracted position. The trigger lock 27 is shown in greater detail in FIGS. 11 A- 11 B, the link arm 26 is shown in greater detail in FIGS. 12 A- 12 B, and the trigger 20 is shown in isolation in FIGS. 13 A- 13 B.
[0066] Trigger 20 is provided with laterally extending cylindrical pivot bosses 206 , 206 ′ that are mounted into sockets 723 and 623 , respectively. When released, trigger 20 extends outward through downwardly opening recesses 621 and 721 . When pulled, trigger 20 is pivoted inwardly into the handle recesses 621 and 721 about pivot bosses 206 , 206 ′ to apply tension to the cable 390 that draws the upper and lower jaws 35 and 45 together. Cable 390 is mounted within a lubricious tube 391 , extending from the proximal wall 628 to the distal end 15 of the handle 10 , to allow the cable 390 to move freely within the handle 10 when trigger 20 is pulled or released.
[0067] Trigger 20 is coupled to the proximal end of cable 390 through link arm 26 , illustrated in isolation in FIGS. 12A and 12B. Link arm 26 is provided at a distal end with two laterally extending bosses 262 and 262 ′ that are received in circular sockets 204 (one of which is shown in FIG. 13B) formed on the interior walls of the internal chamber 202 of trigger 20 to thereby pivotally mount the distal end of the link arm 26 to the trigger 20 . Link arm 26 is formed with a longitudinally extending slot 266 , allowing compression of the distal end of the link arm 26 to facilitate positioning of cylindrical bosses 262 and 262 ′ within the corresponding sockets 204 within the trigger 20 . As also shown in FIG. 13B, longitudinal slots 215 are provided in the interior 202 to assist insertion of the bosses 262 , 262 ′ on link arm 26 into sockets 204 in trigger 20 during assembly. Link arm 26 is provided at its proximal end with two laterally extending, circular bosses 264 and 264 ′ that are received within the elongated slots 625 and 725 , respectively, in the respective right and left handle halves 600 and 700 . When trigger 20 is released, the circular bosses 264 and 264 ′ are disposed at the distal ends of the opposed elongated slots 625 and 725 , respectively. When trigger 20 is pulled inward, the proximal end of the link arm 26 is moved proximally within the opposed slots 625 and 725 , applying tension to cable 390 .
[0068] Cable 390 is coupled to the link arm 26 by means of a swaged retainer 24 , mounted within a coil spring 28 . Coil spring 28 is fitted within a generally cylindrical chamber 266 formed extending at 90 degrees to the proximal end of link arm 26 . Cable 390 passes through an upwardly facing slot 270 in link arm 26 and through the interior of spring 28 to retainer 24 . Spring 28 is normally extended within chamber 266 but is compressed to provide protection against over tensioning of the cable 390 , if the upper and lower jaws 35 and 45 encounter significant resistance to further movement toward one another. The configuration of the trigger 20 , link arm 26 and slots 625 and 725 provide a mechanism whereby, the cable 390 is pulled proximally relatively quickly during initial upward movement of the trigger 20 to facilitate initial rapid closing of the jaws 35 and 45 . The cable 390 is pulled relatively more slowly during further upward movement of the trigger 20 to provide increased control to the physician during final compression of the jaws 35 and 45 against the tissue to be ablated.
[0069] Trigger 20 is also provided with a distally extending projection 208 terminating with a laterally extending, generally cylindrical, boss 210 shown best in FIG. 13B. As illustrated in FIG. 10, when the trigger 20 is released and in its most downward position (corresponding to the point of maximum jaw opening), the fluid conduits or tubes 370 and 470 are disposed side by side and compressed between cylindrical boss 210 and the inwardly extending projections 630 and 730 . This compression of the fluid conduits or tubes 370 and 470 prevents flow of conductive fluid from the fluid source and out of the electrodes 330 and 430 and the electrode mounts 340 and 440 when the hemostat is not in use.
[0070] The trigger 20 is also formed with a laterally extending slot 212 having an array of teeth 214 formed along one side of the slot 212 . A trigger lock mechanism is provided involving the interaction of the thumb slide 25 with the trigger 20 through a trigger lock 27 that is coupled at one end with the thumb slide 25 and selectively engages the teeth 214 to retain the upper and lower jaws 35 and 45 at a fixed position adjacent tissue to be ablated without requiring the physician to continually apply pressure to trigger 20 . Distal or forward movement of the thumb slide 25 causes the trigger lock 27 to engage the teeth 214 , and proximal or rearward movement of the thumb slide 25 releases the engagement. The trigger 20 can be operated freely by the physician to open or close the upper and lower jaws 35 and 45 when the thumb slide 25 is in the rearward position. With the thumb slide 25 in the forward position, the trigger 20 can be moved inward ratcheting over the teeth 214 to close the upper and lower jaws 35 and 45 , but the trigger 20 will not move outward upon release by the physician.
[0071] The trigger lock 27 depicted in isolation in FIGS. 11A and 11B comprises an elongated link arm 275 having rods 272 and 278 laterally extending parallel to one another from opposed ends of the link arm 275 . As shown in FIG. 10, the rod 272 is inserted through the slot 202 so that the link arm 275 extends alongside the trigger 20 within the recess 721 . The rod 278 extends into a generally centrally located notch 252 of a resilient beam section 250 of the thumb slide 25 . Cylindrical pivot bosses 276 and 276 ′ extend laterally on either side of the link arm 275 in alignment with rod 272 and are inserted into sockets 724 and 624 , respectively.
[0072] The rod 272 inserted through the slot 212 extending through the trigger 20 is formed with a laterally extending ramped tooth 274 that is selectively engagable with one of the ramped teeth 214 formed along the proximal edge of slot 212 , when the trigger lock 27 is pivoted forward from the position illustrated in FIG. 10 by distal or forward movement of the thumb slide 25 by the physician. Movement of the trigger 20 inwardly into the handle recess with the trigger lock 27 advanced forward from the position illustrated in FIG. 10 causes the interaction of the tooth 274 on the trigger lock 27 with the teeth 214 to retain the trigger 20 in position when pressure is released. The oblong configuration of sockets 624 and 724 that receive bosses 276 ′ and 276 of the trigger lock 27 allow the trigger lock 27 to move slightly forward during inward movement of the trigger 20 so that the tooth 276 on trigger lock 27 may ratchet along the ramped teeth 214 of trigger 20 . Interaction of the teeth 214 with the ramped tooth 274 on the trigger lock 27 prevents outward movement of the trigger 20 as long as the thumb slide 25 remains in the forward position in the slot formed by openings 627 and 727 .
[0073] Release of the trigger 20 is accomplished by proximal or rearward movement of thumb slide 25 , pivoting the ramped tooth 274 out of engagement with a tooth of the teeth 214 along slot 212 which allows the upper and lower jaws 35 and 45 to open unless the physician holds the trigger 20 in position. The trigger 20 is urged outwardly out of the recess in handle 10 by spring 23 upon release of the trigger 20 and rearward movement of the thumb slide 25 . When the trigger 20 reaches its full outward position, flow of conductive fluid through fluid conduits 370 and 470 is terminated as the tubing is compressed between the laterally extending boss 210 and the inwardly extending projections 630 and 730 , as discussed above.
[0074] The thumb slide 25 is provided with a resilient beam section 250 , having a generally centrally located notch 252 which engages the laterally extending rod 278 on trigger lock 27 , coupling the thumb slide 25 to the trigger lock 27 . The thumb slide 25 is preferentially retained at either the proximal, rearward or distal, forward point of its travel, without the necessity of the physician manually maintaining pressure on the thumb slide 25 due to the resilience of the beam 250 and the arcuate path of travel of the rod 278 .
[0075] [0075]FIG. 14 illustrates a proximal portion of the assembled hemostat of FIG. 1 with the left handle half 700 removed to show the multi-conductor cable 80 and fluid conduit 70 extending through the strain relief 60 and their joinder to the wire conductors 360 , 460 and the fluid conduits 370 , 470 .
[0076] The distal end of the fluid conduit 80 is coupled through a fitting 802 to proximal end of flexible tubing 804 . The distal end of flexible tubing 804 is coupled to the trunk of a Y-connector 806 , and the distal legs of the Y connector 806 are coupled to arms of a D-connector 810 . The D connector 810 is formed of a flexible plastic, e.g., silicone rubber, providing spaced apart fluid channels that are coupled to the proximal ends of the fluid conduits 370 and 470 .
[0077] The fitting 804 supports a proximal flow controller or regulator 820 that has a precisely sized orifice that limits conductive fluid flow into the Y-connector 806 . The flow regulator 820 establishes a fixed flow rate and pressure within the Y-connector 806 regardless of the pressure of the fluid source that is available in the surgical theatre. The flow rate is established depending upon the upper and lower electrode area and design.
[0078] The D connector 810 supports a pair of downstream flow regulators 822 and 824 that have equal, precisely sized orifices that further reduce the fluid flow rate and pressure of the conductive fluid entering the fluid conduits 370 and 470 . The downstream flow regulators 822 and 824 ensure that an even flow of conductive fluid is provided from within the Y connector 806 into the fluid conduits 370 and 470 . By this mechanism, the hemostat may be operated without the necessity of an associated pressurized fluid source and still provide controlled and even fluid flow to the upper and lower jaws 35 and 45 that contact the tissue to be ablated.
[0079] An optional light emitter, e.g., an LED 830 , is depicted in FIG. 14 located within the strain relief 60 and coupled through an electrical junction 832 with the insulated wire conductors 360 and 460 . The wire conductors 360 and 460 can take the form of a twisted wire cable that extends distally from the electrical junction 832 through the length of the handle to the swivel assembly 50 where they are separated as shown in FIGS. 3A and 4. Separate wire conductors within a cable 834 extend from the electrical junction 832 to the LED 830 . In use, the LED 830 is illuminated in response to activation of an associated RF electrosurgical generator, and the LED illumination illuminates the strain relief 60 , which is preferably fabricated of a translucent flexible material, such as silicone rubber or the like. The physician will typically hold the handle 10 in orientations that make the strain relief 60 visible, and illumination of the LED 830 indicates to the physician that RF energy is being applied to the electrodes
[0080] The proximal portion of the handle 10 may also optionally carry other electronic components including circuitry containing calibration information, for example calibrating a thermocouple if provided to sense electrode or tissue temperature. Circuitry containing identification information or providing re-use prevention may also be included, however such features are not believed to be essential to or a part of the present invention.
[0081] [0081]FIGS. 15A and 15B illustrate an alternative embodiment of the electrode described above that can be employed in modified upper and lower jaw assemblies 30 A and 40 A corresponding generally to upper and lower jaw assemblies 30 and 40 . The upper and lower jaw assemblies 30 A, 40 A have a malleable backbone 310 , 410 and a sheath 320 , 420 as described above that are attached to the respective upper and lower jaw mounts 300 and 400 as shown in FIGS. 2 and 3. However, electrode 330 A, 430 A incorporates an exposed elongated electrode extension 350 A, 450 A extending to the outer surface of porous electrode support 340 A, 440 A and along the jaw 35 , 45 that is intended to directly contact the tissue to be ablated. In this embodiment, conductive fluid is delivered as described above into the lumen of the internal tubular electrode 330 A, 430 A, which may be substantially the same as the tubular electrodes 330 , 430 . An elongated electrode surface 352 A, 452 A of the electrode extension 350 A, 450 A and the contacted tissue are irrigated by conductive fluid emitted through the fluid ports of the internal tubular electrode 330 A, 430 A and conducted through the pores of the electrode support 340 A, 440 A.
[0082] The electrode extension 350 A, 450 A is depicted prior to assembly with the electrode support 340 A, 440 A and the elongated tubular electrode 330 A, 430 A in FIGS. 16A and 16B. As formed, the electrode extension 350 A, 450 A includes an elongated straight portion 352 A, 452 A that is mounted against the exposed to the exterior of the electrode support 340 A, 440 A. A distally extending portion 360 A, 460 A is adapted to be inserted into the lumen of the electrode support 340 A, 440 A to extend alongside the elongated tubular electrode 330 A 430 A as shown in FIG. 15B.
[0083] A series of barbed projections 354 A, 454 A extend laterally away from the elongated straight portion 352 A, 452 A. The electrode extension 350 A, 450 A is adapted to be bent back at junction 356 A, 456 A to enable insertion of the series of barbed projections 358 A, 458 A into the electrode support 340 A, 440 A. The proximal end 362 A, 462 A is electrically connected to the proximal ends of the tubular electrodes 330 A, 430 A and the distal ends of the wire conductors 360 , 460 .
[0084] This alternative exposed electrode embodiment can be formed by modifying the tubular electrode 330 , 430 to have a conductive electrode band extending from the tubular electrode along the surface of the electrode support 340 , 440 . Alternatively, this alternative electrode design can be accomplished without use of the tubular electrode 330 , 430 , whereby conductive fluid is delivered to a lumen of the electrode support 340 , 440 or to a fluid channel between the electrode support 340 , 440 and the sheath 320 , 420 , and the exposed electrode band is supported by the electrode support 340 , 440 .
[0085] The embodiments of the electrosurgical hemostat described above contain a number of valuable features and components, all of which contribute to provide a hemostat, which is convenient to use while providing substantial flexibility in use. However, many of the features of the hemostat could be employed in hemostats of other designs. For example, the trigger mechanism and/or the trigger lock mechanism of the above-described hemostat would certainly be of use in conjunction with cable activated hemostats having jaws of alternative designs to that described above. Similarly, the jaw assembly of the present hemostat might well be employed in conjunction with alternative trigger mechanisms. And/or in conjunction with alternative electrode designs, including electrodes which might not include provision for fluid irrigation and/or in the context of the hemostat having jaws that are rigid and not malleable by the physician to assume desired configurations. Further the specific electrode design employed in the hemostat design described above would be of significant use in conjunction with other hemostat types, including hemostats having jaws which are moved toward one another by alternative mechanisms. Similarly, a strain relief of the type described above including an LED indicator is believed to be of value in conjunction with any number of electrosurgical tools, particularly those in which the strain relief is within the physician's field of view, during normal operation of the hemostat. As such, the above description should be taken as exemplary, rather than limiting, with regard to the claims which follow. | A hemostat-type device for ablative treatment of tissue, particularly for treatment of atrial fibrillation, is constructed with features that provide easy and effective treatment. A swiveling head assembly can allow the jaws to be adjusted in pitch and roll. Malleable jaws can permit curved lesion shapes. A locking detent can secure the jaws in a closed position during the procedure. An illuminated indicator provides confirmation that the device is operating. A fluid delivery system simplifies irrigated ablation procedures. | 0 |
This is a Continuation-In-Part Application of prior application Ser. No. 09/851,932 which was filed on May 10, 2001, now abandoned.
BACKGROUND
1. Field of Invention
This invention relates to folding sawhorses, trestles, and the like, referred herein a sawhorses. The purpose of the invention provides for a sawhorse which self locks resulting in a sawhorse that is easy to use, can be made from standard off-the-shelf materials, is very stable without any specialized locking hardware, and has more functional uses than a standard sawhorse.
2. Description of Prior Art
A number of patents issued on various sawhorses relate, however none disclose the features of the present invention. Several disadvantages exist. One such disadvantage is the inability to self-lock without the addition of special hardware or specific manual procedures as illustrated by U.S. Pat. No. 4,756,385 and U.S. Pat. No. 4,429,765.
The invention uses opposing forces to provide a natural self-locking capability, induced by the opening and closing of the sawhorse. The resulting opposition of the two opposing forces produces a fixed and stable sawhorse when opened, without having to tighten or twist or adjust any specialized bolts, pins, ropes, chains or arms.
The ability to use of simple off-the-shelf hinges and screws in the invention make it easy and cheap to manufacture.
Another disadvantage illustrated by U.S. Pat. No. 4,620,613 is the load-bearing requirements placed upon the hinges, which provide the folding capabilities. This invention places the load upon the main structure and only uses hinges mainly for positional alignment of the main structure resulting in a sawhorse, which can withstand heavy usage and loading without failures or excessive wearing of the hinges.
Many other sawhorses illustrate various designs for being foldable or collapsible. These designs require spring loaded bolts or hinges to induce the forces necessary to have the sawhorses close as illustrated in U.S. Pat. Nos. 4,429,765 and 4,620,613. This invention is collapsible without requiring springs and closes automatically upon the release of the opposing forces and lifted from the ground.
Another disadvantage illustrated by U.S. Pat. Nos. 4,756,385, 2,825,606 and 4,620,613 is the ease of use. The present invention can be deployed using one hand and unemployed the same. This makes it easier to use and more convenient. There are no complicated actions or procedures needed to open and lock the invention as well as unlock and collapse the invention. In the unlocked state, the invention tends toward a folded position when carried.
A disadvantage illustrated by U.S. Pat. No. 4,113,056 is the inability to provide a stable work surface free from falling due to drifts in load or work forces. The clamping action of the invention holds or grips materials placed in the jaws. A tabletop with two screws protruding at each end can easily be held by this invention, resulting in a sturdy worktable. The locking jaws make a functional holder. There are many uses for the holding capabilities such as holding a saw for sharpening. The invention can hold guides to ensure materials won't slip or move. The locking feature makes this invention resistant to the affects of unleveled work surfaces and the rigidity doesn't allow creeping.
A disadvantage illustrated by U.S. Pat. Nos 6,021,866, 4,756,385, 4,620,613, 4,429,765, 4,319,663 and 2,825,606 is the restriction to using hand clamps for holding material. The designs of these prior an examples don't provide usable surface shapes for easily using hand clamps to hold work. This invention when in the locked position, maintains a rigid flat top allowing the easy use of commercially available clamps,
SUMMARY
In accordance with the present inventions a sawhorse comprising a trestle structure using two opposing forces to create a locking action made using standard off-the-shelf components where the invention acts like a fixed structured sawhorse while locked and a foldable sawhorse when not locked maximizing it's ease and diversity of use.
OBJECTS AND ADVANTAGES
Accordingly, several objects and advantages of my invention are:
(a) to provide a stable sawhorse that resist moving, closing, creeping or collapsing due to strain while in use;
(b) to provide a folding sawhorse which can be deployed with a single hand and single action and collapsed as easily for compact storage;
(c) to provide a sawhorse that gives excellent function without the need for nothing more also simple hinges with no spring loaded bolts or hinges, no ropes, chains or adjustment arms;
(d) to provide a sawhorse easily manufactured from standard off-the-shelf components and require a minimum amount of material;
(e) to provide a load bearing sawhorse, capable of handling heavy loading without deforming, loosing stability, shifting or causing excessive wear on components;
(f) to provide a sawhorse capable of retaining functionality when used on unleveled work surfaces;
(g) to provide a sawhorse where most load bearing forces are maintained by the main structural members and not the hinges used to allow folding;
(h) to provide a sawhorse based upon, opposing forces to make it a rigid sawhorse without wobble when in use and still be collapsible when not in use;
(i) to provide a sawhorse that is very light weight and easy to carry and move;
(j) to provide a sawhorse with alternative uses by incorporating a set of locking jaws capable of folding many different items or materials;
(k) to provide a sawhorse which can be used to provide a quick and easy assembly of a work surface which can combine with two sawhorses and provide a stable and locked surface that won't wobble of shift with use;
(l) to provide a sawhorse where changes in dimensions won't change the self locking character of the invention when differing sizes are desired;
(m) to provide a sawhorse which can lock into runners to provide resistance and stability to wind and can be used as a barricade or warning device,
(n) to provide easy use of guides to hold and maintain material being worked which are easy to position, change and remove.
(p) to provide a sawhorses which can be made of differing materials such as wood, molded plastic or metal and still operate with the same locking forces.
(p) to provide a sawhorse where clamps can be easily used to hold the work.
Further objects and advantages of my invention will become apparent from a consideration of the drawings and ensuing description.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, closely related figures have the same number but different alphabetic suffices.
FIG. 1 a shows a perspective view of the sawhorse.
FIG. 1 b shows the top member of the sawhorse and the locking jaws.
FIG. 1 c shows the locking hinged lever used to create all opposing force to the top member.
FIG. 1 d shows a detail of the hinged lever.
FIG. 2 shows a side view of the sawhorse, which represents both sides since each side is identical.
FIG. 3 a shows an end view of the sawhorse in the unlocked state.
FIG. 3 b shows an end view of the sawhorse in the locked state.
FIG. 3 c shows a detail view of the sawhorse hinge members joined to the longitudinal side member.
FIG. 3 d shows a side view of the union of the sawhorse and a leg.
FIG. 4 shows a top view of the sawhorse.
FIG. 5 shows a bottom view of the sawhorse.
FIG. 6 a shows a perspective view of the union of the sawhorse and a base.
FIG. 6 b shows a side view of the union of the sawhorse and a base.
FIG. 6 c shows a side view of the union of the sawhorse and a base.
FIG. 6 d shows the base and a protruding holding pin.
FIG. 7 a shows an example of a rigid work surface used with two sawhorses to make a rigid and locked worktable.
FIG. 7 b shows how a rigid surface is held by the top jaws of the sawhorse.
FIG. 8 shows an example using the sawhorse for holding a handsaw.
FIG. 9 a shows an example of using guides for holding materials.
FIG. 9 b shows the use of a hand clamp.
FIG. 10A is an end view of the spit beam in a locked position.
FIG. 10B is an end view of the hinged locking lever in an unlocked position.
FIG. 11A is an end view of the device with a safety line secured thereto in accordance with the present invention.
FIG. 11B is a side view of the safety lines shown in FIG. 11 A.
FIG. 12 is an end view of a locking lever with a handle secured thereto in accordance with the present invention.
FIG. 13A is a perspective view of an alternative design for a leg member in accordance with the present invention.
FIG. 13B is a side view of the leg member of FIG. 13 A.
FIG. 14A is a perspective view of an alternative design of a locking foldable sawhorse in accordance with the present invention.
FIG. 14B are two end views of two pivotally joined leg connectors shown in loaded and unloaded positions in accordance with the resent invention.
FIG. 14C is a perspective view of the leg connector of FIG. 14 B.
FIG. 14D is a perspective view of a single leg connector of FIG. 14 C.
FIG. 14E is an end view of a locking lever included in the device of FIG. 14 A.
FIG. 14F is a perspective view of the left portion of the locking lever of FIG. 14 E.
FIG. 14G is a perspective view of a mating connector which ties the locking lever to a horizontal brace.
FIG. 14H is a different perspective view of the mating connector of FIG. 14 G.
FIG. 14I is a perspective view of a leg bottom connector.
SOME REFERENCE NUMERALS
20 Elongated split beam
21 Grove
22 Vertical member leg
23 Beveled edge
24 Horizontal member brace
25 Beveled edge
26 Hinged locking lever
28 Hinge
30 Small hinge
32 Screw
34 Base
36 Hole
37 Holding pin
40 Holder attached to base
42 Rigid table surface
44 Long screw
46 Hand saw
48 Flat elongated plate
50 Clamp
DESCRIPTION—FIGS. 1 , 1 A, 1 B, 1 D, 2 , 3 A, 3 B, 3 C and 3 D—PREFERRED EMBODIMENT
A preferred embodiment of the sawhorse of the present invention is illustrated in FIG. 1A (Perspective View), FIG. 1B (Perspective of top member 20 ) and FIG. 1C (locking lever 26 ). The sawhorse has two symmetrical sides connected by attachment by the top member 20 as illustrated by FIG. 1B and a locking lever 26 illustrated by FIG. 1 C. The top member 20 illustrated in FIG. 1B provides one of the opposing forces while the locking lever 26 shown by FIG. 1C provides a second opposing force necessary to create a rigid locked condition as illustrated by FIG. 1 D. The top member 20 acid locking lever 26 each have beveled edges to eliminate pinching while still providing a mating surface necessary for creating the opposing forces.
The top member 20 has two symmetrical parts connected and held by two pivot hinges 28 . The opening and closing of the top member 20 allows the folding and unfolding of the two sides and limits the pivotal movement of the aides in the open position. The pivoting action of the locking lever 26 is provided by three hinges as illustrated by FIG. 1 C and FIG. 1 D.
The locking ever 26 abuts a horizontal member 24 illustrated by FIG. 3 C. FIG. 3A illustrates the unlocked position of the sawhorse and FIG. 3B shows the locked position. FIG. 3A illustrates the unlocked position of the locking lever 26 and the opened position of the top member 20 whereby the sawhorse pivots to a closed position upon being lifted from a surface. FIG. 3B shows the locked position of member 26 and the closed position of the top member 20 which creates the counter balance of the two opposing forces exerted by the top member 20 and the locking member 26 .
The side of the sawhorse is comprised of two vertical members 22 and one horizontal brace 24 and the two vertical members are attached to the hinged top members 20 as illustrate in FIG. 2 and attached to the looking lever 26 at the midpoint of the horizontal brace 24 as illustrated by FIG. 3 C.
The side vertical members 22 abut the top member in the groove 21 on the underside of the top member 20 illustrated by FIG. 3 D. The horizontal brace 24 is attached to each of the two side vertical members 22 at each end illustrated in FIG. 2 . The horizontal brace 24 and the vertical side member 22 can be the same thickness and width as illustrated in FIG. 2 . The locking lever 26 can be the same thickness and width as illustrated in FIG. 1 A.
FIGS. 3 A, 3 B, 3 C and 3 D—ADDITIONAL EMBODIMENTS
Another embodiment is shown the FIGS. 3C and 3D. The loading of the present invention by placing a load on the top member 20 is maintained by the vertical side members 23 instead of the pivot points. As seen in FIGS. 3A and 3B, the hinges 28 and 30 at the pivot points of this invention-serve to maintain position of the members and not to bear the loads placed upon the top member 20 . The load bearing characteristics (if the invention is maximized since the loading is supported directly by the vertical members 22 .
In the open and locked position as illustrated by FIG. 3 b , the invention remains rigid and inflexible due to the compression force of the top member 20 opposing the expansion force of the locking lever 26 . The sawhorse remains fixed and rigid while in use exhibiting the same steadiness seen in a non-foldable sawhorse.
The present invention is easy to deploy by the simple looking of the locking lever while remaining light and easy to carry and store as illustrated by FIG. 3 A and FIG. 3 B.
BRIEF DESCRIPTION OF THE INVENTION
Folding sawhorses are used as warning or barricade devices. The present invention can be used as a barricade or warning device and with the addition of a base as illustrated in FIG. 6 a . The base provides additional stability. The same locking feature used to deploy the sawhorse will also attach it to a base 34 , 40 while the base and sawhorse remain easy to transport and store. The mating of the sawhorse vertical member 22 and the base are shown by FIG. 6 b where a pin 38 protruding from the base fits into a hole 36 placed near the bottom of the sawhorse's vertical members 22 . FIG. 6 c shows the bottom of the vertical member 22 with hole 36 for accepting the pin 38 from the base. FIG. 6 d shows the base member with the pin 36 used to ensure the vertical members of the sawhorse remain mated to the bases.
Also, this embodiment using the sawhorse with a base member overcomes the problems encounter when working on ground surfaces which are too wet or unleveled.
Another alternative embodiment is illustrated in FIG. 7 a showing the use of two sawhorses and a rigid top surface 42 to assemble a table. The table surface attaches to the sawhorses using four countersunk screws 44 as depicted FIG. 7 b . Since the sawhorse's top member 20 compresses, the screws are held securely and two locked sawhorses and the top 42 become a fixed and rigid worktable.
This invention's locking jaws in the top member 20 provides compression and holding capability when the sawhorse is in the locked position. The jaws of the top member 20 act as a clamp and hold items placed between the jaws. FIG. 8 illustrates the use of the sawhorse as a holder for working on materials placed in the jaws. FIG. 8 shows the use of the sawhorse to hold a hand saw 46 for sharpening.
Many of the sawhorses made that are foldable don't provide a top member where guides or clamps can't be easily employed. In the locked position this invention's top member 20 provides a shape making it easy to employ a guide or clamp as illustrated in FIG. 9 a for employing guides and FIG. 9 b for employing a clamp.
FIG. 9 a shows how the locking jaws can accept thin plates as guides 48 , which keep materials from slipping. The guides 48 can be adjusted by unlocking the sawhorses locking lever 26 and repositioning.
Advantages
From the description above, a number of advantages of my foldable locking sawhorse become evident;
(a) A sawhorse that is easy to build with a minimum of components, but still provides a foldable sawhorse, which is convenient to use and store. Under load the sawhorse design places most the load upon the members and not the connecting mechanisms such as the hinges and screws.
(b) The sawhorse remains rigid while in use as if it were a fixed structure providing a steady sawhorse due to the use of two opposing forces to induce a counterbalance of locking forces.
(c) The lightweight design makes to sawhorse easily transportable or carried and the construction material can vary from wood, plastic, metal or a combination of the three without losing the benefit of the interlocking forces.
(d) The sawhorse's design gives it easy adaptation to other uses such as a traffic-warning device or to support a work surface.
(e) The holding capabilities of the sawhorse allow many more uses for holding work.
(f) Once locked into position, the sawhorse will remain fixed and rigid not allowing loading changes to cause shifting or wobbling.
OPERATIONS—FIGS. 3 A, 3 B, 6 A, 7 A, 8 , 10 A and 10 B
The manner of using the sawhorse is identical to using a sawhorse constructed with fixed rigid members that is not foldable. Namely, the sawhorse is opened upon being carried to a location by gently squeezing the top member 20 and dropping the sawhorse into place (FIG. 3 A). The sawhorse is made rigid by pressing down on the locking lever 26 until horizontal (FIG. 3 B). When in the horizontal position, the locking lever 26 remains looked due to the opposing force on it exerted by the top member 20 .
While in the locked position, the sawhorse can be used or moved as if moving a rigid non-foldable sawhorse.
To remove the sawhorse from a work location, one first pushes up on the locking lever 26 to unlock the rigid locked state and picks the sawhorse from the ground by the top member 20 which causes the sawhorse to automatically go to a folded position.
The sawhorse used as warning or barricade device by the addition of a base 34 to the vertical members 22 shown in FIG. 6A is accomplished by opening the sawhorse while on two bases. The pins 38 of the bases fit into the holes of the vertical members 22 and the bases are then connected to the sawhorse. When the sawhorse locks, the bases remain attached until the sawhorse in unlocked. The pins 38 ensure the mating of the sawhorse and bases remain attached when the sawhorse is moved while in the locked position.
In FIG. 7A, the drawing shows how two sawhorses can hold a rigid surface to create a worktable. The rigid table 42 is placed on two unlock sawhorses with the screws 44 protruding from the tabletop fitting between the jaws of the sawhorses top members 20 . The locking levers 26 of the sawhorses are pushed down and the two sawhorses lock onto the screws 44 holding the tabletop 42 . The three lock together and provide a stable worktable.
The sawhorse becomes a valuable tool for holding work or work tools when needed. FIG. 8 shows an example of a handsaw 46 being held by the sawhorse. The sawhorse can hold other items as it does the handsaw 46 .
DETAILED DESCRIPTION OF THE INVENTION
Accordingly, the locking feature of this invention can easily transform a foldable sawhorse in a rigid sawhorse simply and efficiently by using the application of two opposing forces. In addition, one can see that this invention remains rigid and won't wobble while in the open lacked position, yet allows one to employ the sawhorse with little procedure or difficulty. Furthermore, the locking foldable sawhorse has the additional advantages in that
it permits it's user to easily carry and deploy using a single hand without the need for excessive procedures for set up and use,
it maintains a fixed rigid form while in use just like a non-foldable unit, yet remains lightweight, strong and foldable,
it allows heavy loading of the structure without deforming due to the design's use of the main structural member abutments for load bearing instead of the folding devices,
it permits the use of the sawhorse for use as a barricade or warning device with or without the addition of it base member. The open locked position of the sawhorse makes it resistant to wind or position changes,
it permits the use of the sawhorse and base to overcome the problems associated with working on wet or unleveled ground,
it permits the use of the sawhorse as a platform for creating a rigid worktable using the locking ability of the top member for attaching to a tabletop,
it allows the user to employ the sawhorse as a clamp for holding materials or tools.
It permits the use of guides and hand clamps to hold materials by insertion into the jaws or by applying clamps directly to the top of the sawhorse.
In operation, a locking foldable sawhorse device 10 is carried in a folded position by an individual to a job site whereupon opposing legs 22 of the device 10 are separated until opposing jaw members 12 of the top member 20 or elongated split beam engage thereby originating the device 10 in an “opened” position. The device 10 is stabilized and “locked” by forcibly positioning a locking lever 26 such that opposing side walls 14 of the locking lever 26 engage as illustrated in FIG. 11 ). In the locked position, the lever 26 is prevented from “folding” downward to form a “V” configuration due to the lower hinge 30 holding the two side walls 14 of the two portions of the lever 26 together thereby using the abutting side walls 14 to limit downward movement and allow only upward movement of the lever 26 from the locked position. Thus, the present device 10 is differentiated from the prior art devices that utilize bracing members that collapse either upward or downward and are at best limited in a downward direction by adjacent members of the prior art device such as the step or rung of a ladder placed proximate to and beneath a bi-directional, movable brace.
When relatively “light” loads are set upon an elongated split beam 20 , the legs 22 may be joined to opposing planar side walls 15 of the beam 20 via screws or similar attaching means. The side walls 15 forming a right angle with corresponding planar bottom walls 16 of the beam. Alternatively, the side walls 15 may be inclined such that an acute angle is formed with the bottom walls 16 thereby configuring the legs 22 so that bottom end portions 8 that engage the ground are separated a greater distance than top end portions 19 to provide a stable base for the device 10 . When the device 10 is used to support relatively “heavy” loads, the stability of the device 10 is increased by including a groove 21 in each side wall 15 of the beam 20 . The groove 21 provides a support wall 17 and a connection wall 18 that form an obtuse angle. The walls 17 and 18 cooperatively engage top end portions 19 of the legs 22 as illustrated in FIGS. 1A and 3D, whereby the legs 22 are angled with respect to the upper surface of the beam 20 , and the legs 22 support the beam 20 via an end wall 13 that engages the support wall 17 , and a side wall 11 that engages and is joined to the connection wall 18 .
A table may be fabricated from two locking foldable sawhorse devices 10 and a rigid surface 42 such a plywood. The surface 42 is secured to the devices 10 by countersinking screws 44 through the surface 42 ; the screws 44 ultimately being secured between opposing jaw members 12 of the device 10 . When a relatively “light” load is placed upon the surface 42 , the screws 44 need only be “pinched” between the jaw members 12 . The inherent flexibility of the materials (wood, fiberglass, plastics and some metals) used to fabricate the device, allow the locking lever 26 to be positioned such that the side walls 14 of the locking lever 26 engage thereby locking the position of the device 10 , while allowing the jaws members 12 of the beam 20 to remain separated a distance corresponding to the diameter of the screws 44 . Although the top portion of the beam 20 supporting the surface 42 will form an inverted “V” when taking a side elevation view of the device 10 , sufficient stability will be provided due to the locked lever 26 and a relatively small distance separating the jaw members 12 due to the screws 44 having a small diameter. Should a relatively “heavy” load be placed upon the surface 42 , threaded recesses 45 would be provided that would removably receive the screws 44 therein to allow the jaw members 12 of the beam 20 to engage thereby providing a beam 20 with a planar top portion to support the surface 42 , and providing a device 10 having increased stability to withstand the heavier load.
The inherent flexibility of the device 10 and the pinching feature of the jaw members 12 of the beam 20 may be utilized to hold relatively “thin” objects therebetween. For example, a hand saw 46 requiring sharpening could be positioned between the jaw members 12 , then locked in position by the locking lever 26 with sufficient stability to allow sharpening tools to be forcibly applied to the hand saw 46 . Further, flat plates 48 may be locked between the jaws 12 to maintain the position of a workpiece 52 , such as a board or pipe, upon the beam 20 . Also, a clamp 50 may be included to further stabilize the workpiece 52 upon the beam 20 as illustrated in FIG. 9 B. When utilizing the clamp 50 , the beam 20 should have a planar top surface which correspondingly requires the jaw members 12 to be positioned together.
Referring now to FIGS. 11A and 11B, the device 10 is alternatively designed to include a safety line 54 attached to the horizontal member brace 24 via the small hinges 30 that join the hinged locking lever 26 to the member brace 24 . The safety line 54 may be fabricated from a myriad of materials including but not limited to nylon, polyester strapping, steel cable or nylon cord—the preferred material. The line 54 ensures that the legs 22 will not spread beyond a predetermined limit the thereby protecting the locking lever 26 from being over extended and forcibly removing the hinges 30 from the brace 24 . The safety line 54 protects the locking lever 26 without interfering with the operation of the lever 26 due to the hinges 30 collapsing the lever 26 away from the safety line 54 .
Referring to FIG. 12, the locking lever 26 of the device 10 is depicted with a handle 55 attached to one side of the lever 26 to allow an user to lock and unlock the lever 26 without the risk of the user's fingers being “pinched” between the cooperatively engaged side walls 14 of the lever 26 as the legs 22 of the device 10 are spread apart or brought together during normal operation.
Referring now to FIGS. 13A and 13B, the elongated split beam 20 of the device 10 is depicted with an alternatively designed leg 22 . Instead of a groove 21 in the beam 20 forming support and connection walls 17 and 18 which join to form an obtuse angle that cooperatively receives a top end 19 of the leg 22 , a recess 56 is provided in the top end 19 of the leg 22 . The recess 56 includes a connection wall 56 a and a support wall 56 b which are configured to form an obtuse angle. The connection wall 56 a engages the side wall 15 of the beam 20 while the support wall 56 b engages the bottom wall 16 of the beam 20 . The top end 19 of the leg 22 is secured to the beam 20 via screws 32 inserted through the top end 19 and continuing perpendicularly through the connection wall 56 a while engaged with the side wall 15 , and extending into the beam 20 a distance sufficient to provide stability to the assembled device 10 when a load is set thereupon.
Referring to FIGS. 14A-14I, an alternative sawhorse 58 is depicted that includes one or more removable beams 57 set upon a beam support structure 57 a . The beams 57 and support structure 57 a may be fabricated from a myriad of materials including but not limited to wood, metal, fiberglass and plastic. The preferred material of fabrication for the beams 57 is wood. The preferred material of fabrication for the support structure 57 a is fiberglass channel joined together with metal. The support structure 57 a includes two sets of two pivotally joined leg top connectors 69 that are attached to four corresponding top ends of four leg members 71 via rivets 61 forcibly inserted through orifices 62 . The support structure 57 a further includes metal, horizontal braces 63 joined to mid-portions of adjacently positioned fiberglass legs 71 on each side of the structure 57 a , and metal leg bottom connectors 65 attached to bottom ends of the four leg members 71 via rivets 61 forcibly inserted through orifices 62 . The support structure is attached to the beams 57 via screws 32 through orifices 59 in connectors 69 .
The leg top connectors 69 are relatively “Y” configured when taking an end view of the device 58 , have first arm members 64 shorter longitudinally then second arm members 66 , and are pivotally joined via relatively long rivets 68 inserted through aligned, alternately positioned, hinge loops 68 a joined to the end of the first arm members 64 . The connectors 69 form a rectangular configuration when taking an end view of the device 58 in a stable, load bearing position. The respective lengths of the first and second arm members 64 and 66 are dependant upon the quantity and size of the beams 57 to be snugly inserted between the arm members 64 and 66 .
The metal locking levers 63 are pivotally coupled together and are secured to an inside wall of the horizontal brace 67 via a mating connector 73 by utilizing rivets 61 and orifices 62 . The locking levers 63 function in the same manor as described above for the hinged locking lever 26 when stabilizing the sawhorse device 10 . The bottom connectors 65 include a rubber pad 81 joined to an inclined bottom portion that positions the pad 81 in congruent engagement with the surface supporting the device 58 when the legs 71 of the device 58 are spread and locked in a load bearing or open position. The safety line 54 described above for the sawhorse device 10 may also be included for the alternative device 58 . The alternative device 58 would have the safety line 54 joined to the mating connectors 73 such that the locking levers 63 would be above and parallel to a taught line 54 when the device 58 was in an open position. The levers 63 would angle away from the line 54 when the legs 71 of the device 58 are brought together.
The aforementioned locking levers 26 and 63 are not limited to sawhorse devices 10 and 58 , respectively, but may be utilized with any collapsible support device such as ladders, signs, scaffolding, pipe stands and the like that include pivotally joined leg or “V” configured support members. Generally, the locking levers 26 or 63 form a “triangle” that includes the pivot point and portions of the leg members joined thereto whereby the collapsible support device is stabilized and locked in an open position until the support device is relocated to another job site or placed in storage.
The foregoing description is for purposes of illustration only and is not intended to limit the scope of protection accorded this invention. The scope of protection is to be measured by following claims, which should be interpreted as broadly as the inventive contribution permits. | A folding and self-locking sawhorse comprised of two frames connected by the tops ( 20 ) and the middle horizontal brace ( 24 ) to create a combination of two opposing forces which product a rigid sawhorse in the open position, but remains collapsible and folds for storage when the two forces are not in opposition. The sawhorse has a clamping top ( 20 ) top which can hold items with a compression force created by the expansion force induced by a folding hinged lever ( 26 ) against the two side frames. The clamping top ( 20 ) accepts tabletops ( 42 ) and other items ( 46 ) and the locking divergence of the legs ( 22 ) can be used to mate the sawhorse with a base ( 34 ) for better stability. An alternative embodiment of the locking foldable sawhorse ( 58 ) includes one or more beams ( 57 ) set upon a beam support structure ( 57 a ). The beam support structure ( 57 a ) includes two sets of two pivotally joined leg top connectors ( 69 ) that are attached to four corresponding top ends of four leg members ( 71 ) via rivets ( 61 ) forcibly inserted through orifices ( 62 ). The support structure ( 57 a ) further includes braces ( 63 ) joined to fiberglass legs ( 71 ) on each side of the structure ( 57 a ); and leg bottom connectors ( 65 ) attached to bottom ends of the leg members ( 71 ). | 1 |
DISCUSSION OF PRIOR ART AND BACKGROUND OF THE INVENTION
The subject invention relates to the general area of amusement park rides that are self-driven. In particular, the subject invention pertains to an improved adaptation of the ferris wheel, which is a conventional amusement park ride, and is an adaptation thereof.
This invention is adapted to provide an additional dimension or dimension of movement over and above the conventional movement of a vertical ferris wheel used as an amusement ride. Specificaly, as is well known, the conventional ferris wheel amusement ride, or rides similar to the ferris wheel, is adapted to rotate while in a vertically upright plane, about a horizontally-fixed rotor. As is well known and which can be readily observed, the conventional ferris wheel apparatus is thus structured to rotate in a fixed vertical plane about a centrally disposed horizontal axle, which axle is disposed in a horizontal plane. As a result of this structural arrangement, the movement of the ferris wheel, as thus commonly known, is limited in its dimensional movement for rotation about a fixed axis in a fixed vertical plane. This latter aspect is well known in the pertinent art.
While a ferris wheel is indeed a thrill-inducing amusement ride for most people, there is always a constant quest to produce even more thrill-producing rides, with different and varying movements. In this latter respect, there is no amusement ride, of the nature of the basic overall ferris wheel movement, that has the added features of multiple dimensional movement which are in addition to the singular dimensional rotational movement described above. While many rides do produce certain multiple movement variations of a moving wheel, none are known by which a vertical wheel moves about a horizontal axis and simultaneously rolls along a horizontal path. Moreover, there is no known amusement ride known by which the wheel also moves in a circular, horizontal plane over and above the foregoing described two movements.
This invention is adapted and conceived as an improved variation of a ferris wheel that will permit a ferris wheel, as known, to move in two or even three spatial dimensional movements. The following objects of the subject invention are directed accordingly.
OBJECTS
It is an object of the subject invention to provide an improved amusement park ride;
A further object of the subject invention is to provide a novel ferris wheel ride, with features of additional rotational movements over and above the usual rotational movement in a vertical plane;
Yet another object of the subject invention is to provide a multi-dimensional movement amusement ride;
A further object of the subject invention is to provide an improved amusement ride;
Still another object of the subject invention is to provide an amusement ride that has three modes of simultaneous movement;
A further object of the subject invention is to provide a novel amusement ride.
Yet another object of the subject invention is to provide an improved amusement apparatus based on multiple planar movement.
Other and further objects of the subject invention will become apparent from a reading of the following description taken in conjunction with the claims.
DRAWINGS
FIG. 1 is a side elevational view of the apparatus incorporating the subject invention;
FIG. 2 is an end elevational view of the apparatus incorporating the subject invention;
FIG. 3 is a top elevational view of the apparatus incorporating the subject invention;
DESCRIPTION OF GENERAL EMBODIMENT
The subject invention is an improved amusement park ride apparatus which is an adaptation of an upright vertical ferris wheel ride of the type that is rotated about a fixed axis, such invention being an upright wheel structure having chairs thereon to hold riders as the wheel rotates in a vertical plane. The axle of rotation of the wheel is adapted to move horizontally along a horizontally disposed track, essentially back and forth between positions along such horizontally disposed track. In a further embodiment of the subject invention, the horizontal track upon which the ferris wheel can move may be optionally mounted on a rotatable platform to yield a horizontal circular movement of the entire apparatus in addition to the foregoing reciprocal linear movement.
DESCRIPTION OF PREFERRED EMBODIMENT
In describing the preferred embodiment, it is to be stressed that the following description is of only one embodiment within the overall scope of the subject invention and that the subject invention may encompass other embodiments, as seen in the claims annexed hereto. Therefore, the following description shall not be considered as limiting the scope of the invention herein, as more fully set forth in the claims annexed hereto.
Referring now to the drawings in which a preferred embodiment of the subject invention is shown. A ride apparatus 10 is shown as being the apparatus incorporating the features of the subject invention, such ride apparatus 10 being basically comprised of an upright rotatable wheel 30 of vertically upright disposition and a generally horizontal support and guide ramp 60. The rotatable wheel 30 is generally constructed along the mechanical principles of a conventional ferris wheel which is rotatable in a vertical plane about a fixed horizontal axis, but with the additional features of this invention as more fully discussed below. For this latter purpose, the rotatable wheel 30 is mounted on a centrally disposed axle 80 having a first end 200 and a second end 210, such axle being generally and preferably mounted in a horizontal position relative to the ground surface 100, as seen in FIGS. 1 and 2. In the usual construction of a ferris wheel member, the axle 80 is mounted some distance above the ground, usually at least by a vertical distance that is usually marginally greater than the radius of the wheel 30 itself.
As can be observed from the drawings, and particularly FIG. 1, the rotatable wheel is provided with a plurality of radially extending support spokes disposed radially on each side of the axle. Radial spokes 120A, 120B, 120C and 120D are integrally affixed directly or indirectly to end 200 of central axle 80, while the opposing mating spokes are not shown. These latter described support spokes are longitudinally extending, rigid members affixed directly or indirectly on their inner ends to respective ends 200 and 210 of the axle 80, and each such spoke projects radially outwardly, as seen, with all such spokes being preferably of an equal length from such central axle 80, as shown. The number of such radial spokes may vary in number depending on the size and the characteristics of the wheel and the representation of the embodiment shown in the drawings with eight such spokes being exemplary only. In the larger type of ferris wheel, there are correspondingly more support spokes. Thus, in the usual embodiment, although this is not critical, each set of radial spokes parallel the other mating radial spokes.
As can be seen from the drawings, the preferred embodiment of the subject invention, affixed to the outer extremity of the radial spokes 120A, 120B, 120C and 120D is a circumferentially extending outer rim member 140A. This circumferentially extending outer rim 140A is preferably, although not critical, a continuous member that defines the outer extremity of the wheel 30. In similar fashion, circumferential rim 140B is integrally and circumferentially disposed on the radially outer extreme portions of the radial spoke members integrally affixed to the second end 210 of the axle 80. The two circumferential rim members 140A and 140B together form the outer circumferential extremity of the wheel 30, and both such rim members 140A and 140B are preferably of a similar diameter and also are preferably situated relative to one another in parallel planes, with a spatial area between such rims. Such spatial area between the rims 140A and 140B is the area in which seating members are affixed, as more fully discussed below.
As can be seen from the drawings, in the preferred embodiment of the subject invention, joining mating portions of the interior surface of the respective rim members 140A and 140B are a series of horizontal bar members 250A, 250B, 250C and 250D. These horizontal bar members 250A, 250B, 250C and 250D are usually and preferably cylindrically-shaped members joined at those portions of the circumferential rim members 140A and 140B where the radial spokes join to the rim. The function of such horizintal bar members is multifaced, one being to join the rim members together to maintain the integrity of the wheel, and secondly, the horizontal bars function to hold rotatably mounted seat members 280A, 280B, 280C and 280D. The seat members 280A, 280B, 280C and 280D may vary in number, shape and other aspects depending on the overall size of the wheel. The seat members 280A, 280B, 280C and 280D are affixed to the respectively connected joinder bar in a limited rotational manner, so that the seat may move back and forth a limited degree as the wheel 30 rotates about the axle. One of the main functions of this limited rotational ability is to keep the seat member substantially aligned up and down in a vertical plane, with the help of gravity, as the wheel rotates about the axle 30.
The wheel member 30 as thusly described above is conventional in construction as a basic ferris wheel structure as known in the art and no novelty is claimed in the constructional arrangement of the wheel 30 itself, or the concept of such wheel rotating with riders thereon about a fixed axle, as described above. The additional and improved features to this wheel are as described below.
As can be seen from FIGS. 1 and 2, means are integrally affixed to either one or both ends of the wheel axle to permit the wheel 30 to roll in a rolling manner, in addition to its rotational movement, so that the wheel 30 can be rolled along in a linear line. More specifically, mounted integrally and concentrically, on the ends 200 and 210 of the axle 80 are flanged wheel members 310A and 310B respectively. These flanged wheel members 310A and 310B are integrally and concentrically mounted to the ends 200 and 210 of the axle 80. Motive means, such as a motor, not shown, can be geared or connected to the axle 80 to cause said axle to be moved in a linear path along a given linear track or similar mechanism.
As seen in the drawings, a support platform 550 is provided to support the wheel 30 and can be elevated above the ground level 100. Preferably, the support platform 550 is of such a height that it can support the wheel 30 above the ground level so that the wheel 30 can be rotated from ground level or above.
In the embodiment shown in the drawings, the support platform is shown as being a rectangular structure, although this configuration is not critical. The platform 550 has an upper frame member 570 and a lower base frame member 560, as well as side frame members 550 and 560. Disposed inside said frame, in a longitudinally extending disposition are parallel track members 300A and 300B, such parallel track members being integrally supported to the side frame members 555 and 560 of support frame 550. Flanged wheel members 310A and 310B of the ride wheel 30 are placed on and adapted to ride along rails 300A and 300B in a rolling movement along the extent of the rails 300A and 300B. As can be seen from the drawings, the track members 300A and 300B extend the length of the support frame, and are blocked by the respective ends of the support frame so that the wheels 310A and 310B cannot tranverse beyond such limits.
Thus, as can be seen, the wheel 30 can roll from one end of the support platform 550 to the other. Thus, the wheel 30 will rotate in a vertical plane about axle 80, and will also roll along the rails 300a and 300B, as an added movement aspect.
The support ramp 550 is preferably positioned above ground level 100 or positioned at some distance above the ground, as shown, however, other variations are envisioned whereby the wheel 30 can rotate and roll along a path simultaneously. In this respect, a linear pit can be used as an alternative with the wheel moving partly underground level at any time. Other variations on this aspect are available.
As can be seen from the drawings, in another embodiment of the invention the support platform is rotatably affixed on 510 cylindrical support affixed upright to the ground 100. The support platform by this embodiment can rotate on rollers 600A and 600B around a circular track 700. By this embodiment, yet another movement dimension is introduced for the ride which incorporates the inventive features herein.
In summary, the subject invention is an amusement ride, based on an improvement of a ferris wheel assembly comprising a rotatable wheel member with a base platform member, such base platform assembly being affixed to the ground and wherein such platform has track members, and wherein such wheel member is rotatably mounted on such tracks on such platform member.
Alternately stated, the subject invention is an amusement ride, based on an improvement of a ferris wheel assembly, comprising a base platform assembly, such base platform being affixed to the ground and wherein such platform is elevated above the ground, and wherein such platform member has linear track members thereon, with a rotatable wheel adapted to ride on such track members.
Also summarized in another manner, the subject invention is a novel ferris wheel apparatus for emplacement on the ground comprising a platform member, such platform member having an imaginary longitudinal central axis extending along the longest extent of such platform member, such platform member having longitudinally extending track members thereon with a vertically disposed rotatable member having an axle of rotation about which such rotatable member is adapted to rotate about and rotatably mounted on such track member. | The subject invention is an improved amusement park ride apparatus which is an adaptation of an upright vertical ferris wheel ride of the type that is rotated about a fixed axis, such invention being an upright wheel structure having chairs thereon to hold riders as the wheel rotates in a vertical plane. The axle of rotation of the wheel is adapted to move horizontally along a horizontally disposed track, essentially back and forth between positions along such horizontally disposed track. In a further embodiment of the subject invention, the horizontal track upon which the ferris wheel can move may be optionally mounted on a rotatable platform to yield a horizontal circular movement of the entire apparatus in addition to the foregoing reciprocal linear movement. | 0 |
This application is a continuation-in-part of application Ser. No. 07/607,865 filed Nov. 1, 1990 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is directed toward an educational game apparatus which requires the players to match key words or symbols to one or more subwords or subsymbols. Correct matches by a player translate into moves for the player's pieces around a gameboard and result in the eventual achievement of the gameboard objectives.
2. Prior Art Statement
Game apparatus utilizing gameboards or card decks make common subject matter for patent applications. While the prior art teaches game boards and card decks designed to stimulate the mental faculties of the players, it does not teach the combination of both, whereby the cards exercise and expand the player's knowledge of a particular subject area and the movement of playing pieces on the gameboard, (moves being awarded for correct answers to the stimulus on the cards), requires strategic logic on the part of the player to have the playing pieces land on their final resting spaces.
Various configurations of gameboards have been patented for their designs. U.S. Pat. No. 41,844 to Cooke describes a gameboard with spokes radiating from a center circle, where the spokes intersect two additional rings of circles of larger diameter concentric to the center circle, and whereby spaces are located at these intersections. U.S. Pat. No. Des. 223,846 to Richard D. Smith, similarly describes the design of a game board comprising a plurality of line-connected circles which outline a hexagon. A design laid out in rectangular areas, so connected as to depict a pathway for movable game pieces, is described in U.S. Pat. No. 57,982 to Loring.
Some game apparatus teach the manipulation of playing pieces on a gameboard of concentric design for the sole effort of capturing an opponent's playing pieces. U.S. Pat. No. 1,196,748 to R.B. Smith describes a game where spaces on the gameboard are located at the intersection of spokes radially extending to intersect concentric circles of varying diameters and the play is governed by rules outlining the specific directions in which playing pieces may move. U.S. Pat. No. 1,295,993 to Kleissl also permits circular and radial movement of playing pieces but stands apart from the prior art because the players begin with different numbers of playing pieces and because of the variety of ways in which one player may be declared the champion.
U.S. Pat. No. 3,935,651 to Mankoff demonstrates a card game where a standard deck of playing cards bears a vocabulary word with a plurality of definition words to choose from on the front face of the card. Proper identification of the definition corresponds to a value on each card, so that once the correct definitions of vocabulary words have been chosen and the cards receive a value, the deck is then adaptable to traditional card games.
Another card game which may be played by one or more players is taught in U.S. Pat. No. 3,143,348 to Carsen, et. al. and describes cards bearing a question and a choice of answers on a front face and indicia on the back face which, when the player marks his answer by directing placement of the card in a certain group, identifies whether the player's response is correct.
U.S. Pat. No. 3,678,602 to Alam teaches the use of combining cards marked with word parts such as roots, prefixes and suffixes to create words and expand the user's vocabulary.
U.S Pat. No. 4,306,725 to Sawyer describes a deck of cards with words and their dictionary definitions printed thereon which players may use to test themselves or each other and where play progression is advanced by the spinning of a dial, the face of the dial bearing certain indicia identifying the next card to be selected.
U.S. Pat. No. 1,201,100 to Rice-Wray describes a board game designed to simulate a golf course, which uses a shuffle board method to determine the number of moves a player may advance, the object of the game being for each player to reach each `hole` and then to select a synonym from strips bearing words for the word located at that hole.
U.S. Pat. No. 3,594,003 to Elder is directed toward an educational word association board game wherein groups of two-sided play pieces, each side bearing information related to the other side and to other play pieces in a group, are laid out on a gameboard having plural arrays of unique playing positions and wherein players must guess the associated word/symbol on the back of the play piece to attain the opportunity to score.
Most similar to the invention at hand is the game described in U.S. Pat. No. 4,171,816, to Hunt which teaches a language game apparatus comprising a field made up of rows and columns for each player, with grammatical or language categories at the top of each column, one of the categories being selected by a player by chance, that player then having to select from a store of two-sided strips, a word that matches the category heading.
United Kingdom Pat. No. GB 2,187,393 to Hann shows a word related board game that has six apex spaces. Each space has a letter thereupon that spells out the name of the game "MASTER". Hann further comprises a deck of playing cards, wherein each card has a key word and a plurality of related subwords printed thereon.
U. S. Pat. No. 4,124,214 to Pavis shows a board game utilizing a plurality of decks of playing cards, each deck being distinguishable and corresponding to various levels of difficulty in play.
U S. Pat. No. 4,854,594 to Eaton shows a timing device to limit a player's response during play on a board game and the use of a penalty/reward deck separate from other card decks.
U. S. Pat. No. 1,518,306 to Clegg shows colored playing pieces that correspond to colored spaces on a game board, the game board having color neutral spaces positioned thereon for safe passage of game pieces that land on such spaces.
U. S. Pat. 4,932,667 to Gorski shows a game board with a plurality of apex spaces and a reciprocating game board pattern.
Finally, the unpatented game "What's the Word" discloses a word definition board game having a playing path and cards having key words and corresponding definitions, the cards being divided into differently colored decks with varying degrees of difficulty.
While only a few of the prior art inventions show more than one element of the currently claimed invention, the combination of all the prior art elements creates a substantial field of materials. Even when combined, the present invention differs in two respects: by allowing players to select the level of difficulty at each turn, and by asking players to make decisions regarding the parts of speech at each turn, thus allowing players of all competence levels to play simultaneously. Knowing that correct answers in different levels lead to different point awards which correspond to the number of moves a player may use to achieve an objective on the gameboard, a player may exercise his ability to logically manipulate the playing pieces to achieve such objectives, as well as increase his knowledge in the subject matter of the particular category at hand at the same time.
In view of this prior art, no prior invention or combination of inventions teaches, suggests or renders obvious all the elements of the now claimed invention. No prior art shows the use of the color organization, layout and substance of the game board, double sided playing pieces and cards. The unique combination of the game elements, as described below, describe an educational game that increases a player's vocabulary and provides entertainment in a manner previously not shown by prior art.
SUMMARY OF THE INVENTION
The present invention is directed toward a method of playing an educational game which tests the player's ability to match a key word or key symbol to one or more subwords or subsymbols. The key and list of possible answers are provided on cards, where the correct answer to the match is noted on the card back. Correct answers by a player translate into moves for the player's pieces around the continuous playing path of a gameboard. To win the game, a player must land each of his game pieces on individually lettered spaces of the playing path to spell out the name of the game (i.e., T-H-E-S-A-S-R-U-S). Players have the opportunity during the game to increase the number of moves awarded them by gambling on the correctness of their answers. Special rules for game play arise when a player lands on a space already occupied by an opponent.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be more fully understood by referring to the following detailed specifications, the above specification and the claims set forth herein, when taken in connection with the drawings appended hereto, wherein:
FIG. 1 shows one preferred embodiment for the game board of the present invention, with all the playing elements being present on the board.
FIG. 2 shows a front view of one preferred embodiment for the playing cards of the present invention.
FIG. 3 shows a reverse view of the embodiment shown in FIG. 2.
FIG. 4 shows a perspective view of one embodiment for the holding tray of the present invention in combination with card decks and the means of recording responses.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed toward educational game apparatus. In the preferred embodiment, the present invention is predicated on the vocabulary of the English language. The game includes a plurality of playing cards. On one side of the card is a key word with a list of subwords. Included in the list of subwords are either synonyms, antonyms, or both. On the reverse side of the card is a code telling the player which words properly correspond to the key word. Correct answers translate directly into the number of moves that an individual's game pieces may travel around the gameboard. Different levels of difficulty in word knowledge are established by the use of at least two different decks, identifiable by certain indicia, during the play of the game. Optionally, the game may be played with more than two such decks. For example, in one embodiment three decks are used. Correct answers for card problems from decks with higher degrees of difficulty result in an increased number of moves a player may take. Winning the game entails landing each of a players' pieces on designated home spaces on the gameboard.
Referring to FIG. 1, the equipment for the claimed game apparatus can best be described. The primary element of the game is the game board 15. The gameboard 15 is constructed of a durable material and has a continuous path of spaces imprinted thereon. The path on the game board 15 consists of at least five differing types of spaces, each type of space being identifiable by color or another identifying indicia. All the spaces are configured concentrically on radiating spires 17, creating a continuous reciprocating path. The apex space of one of the spires 17 is designated as the starting position 23. The other spaces located at the apex of each spire 17 are designated home spaces 32, 33, 34, 35, 36, 37, 38, 39, 40. In the preferred embodiment shown in FIG. 1, home spaces 32, 33, 34, 35, 36, 37, 38, 39, 40 are identified by individual letters marked on each home space which, when read clockwise, spell out the name of the game, "T-H-E-S-A-U-R-U-S". Between each home space 32, 33, 34, 35, 36, 37, 38, 39, 40 is a pathway of spaces. Each space between any two home spaces is a different color. In the shown embodiment the spaces follow a pattern of a green space 60, red space 61, gray space 63, brown space 62, orange space 65, blue space 64, yellow space 66 and purple space 67. This color pattern is repeated continuously between each home space 32, 33, 34, 35, 36, 37, 38, 39, 40. The color pattern is also present between the starting space 23 and the first home position 40. Located between the starting space 23 and the last home position 32 are a path of spaces 27 that have either no color, or some indicia differing from all other spaces, preferably a colored dot placed in the middle of each space 27. It should be understood that although an eight space path is shown between all home spaces 32, 33, 34, 35, 36,a 37, 38, 39, 40, any number of spaces can be used as long as the color of each varies. Similarly, the neutral space 27 between starting space 23 and the last home position 32 would complete the continuous geometric pattern created by the rest of the spaces.
Game pieces are moved around the game board 15. The game pieces come in a plurality of matched sets. There is one set of game pieces for each varied colored space between any two home spaces 32, 33, 34, 35, 36, 37, 38, 39, 40. Thus, in the present embodiment there would be eight sets of playing pieces, in compliance with the eight differing colored spaces 60, 61, 62, 63, 64, 65, 66, 67 present on the game board 15. The game pieces have two sides. On one side, the color of one set of game pieces will match the color one space 60, 61, 62, 63, 64, 65, 66, 67. As an illustration, brown game piece 58 and the purple game piece 57 represent sets of game pieces that correspond in color to brown game spaces 62 and purple game spaces 67. On the reverse side of all turned game pieces 56 is an identifying indicia, preferably the letter "R", which would stand for "ROGET", in memory of the famous man.
FIG. 1 also shows the other equipment needed to play the game. Shown are an electronic timer with alarm 55, an eight-sided die 70 and a plurality of decks of game cards 51, 52, 53, 54. Each deck of game cards 51, 52, 53, 54 has a blank top card 73, 75, 72, 71 that covers the information printed on the cards below. The shown embodiment has three decks, 51, 52, 54. Each deck is color coded and contains information that corresponds to a varying level of play. For example, the first deck 51 may contain easy questions, the second deck 52 intermediate questions, and the third deck 54 difficult questions. The fourth deck 53 shown, is a penalty/reward deck comprised of cards from the other decks 51, 52, 54.
Referring to FIGS. 2 and 3, the details of the cards 1 held within the plurality of decks 51, 52, 53, 54 can be explained. The card 1 has two sides. FIG. 2 shows the front face 3, and FIG. 3 shows the reverse side 9. As is illustrated on the front face 3, there appears a keyword 5. In the present illustrated embodiment, the keyword is "AGGRESSIVE". Beside the keyword 5 is a subscript letter 7, the subscript being an "A", "N" or "V", representing the words "Adjective", "Noun" or "Verb". Below the keyword 5 and the subscript letter 7 there is a list of six subwords 4, 6, 8, 10, 12, 14 numbered 1 through 6, respectively. Within the subwords 4, 6, 8, 10, 12, 14 are either synonyms of the keywords, antonyms of the keywords, or both. On the reverse side 9, in the present embodiment of the card 1, there is printed the keyword and an answer code 13, 11, one side 13 of the code showing which numbered subword 4, 6, 8, 10, 12, 14 was a synonym and the other code 11 showing which subwords 4, 6, 8, 10, 12, 14 were antonyms. For example, in FIG. 2 the keyword 5 is "Aggressive", the subwords 4, 6, 8, 10, 12, 14 numbered 1 through 6 are potential answers. In FIG. 3 the answer 13, 11 is shown as "2-S/3-A", meaning the subword numbered 2 is a synonym and the subword numbered 3 is an antonym.
The last piece of equipment associated with the game is a carrying tray 41. The tray holds the multiple decks of cards 51, 52, 54 and holds two answer pads, the first being a paper pad 49 with pencil 95 for scorekeeping and the second being a self-cleaning pad 92 with probe 91 used to write and transfer answers.
Referring now to FIGS. 1, 2 and 3 in combination, the interaction of all the game elements can best be explained. Prior to the playing of the game, the decks of cards 51, 52, 54 are organized. The players, in deciding how far he or she wants to advance in one turn, can choose a card from either the easy, intermediate or hard deck of cards 51, 52, 54. The existence of decks of cards 51, 52, 54 have varying ability levels, allowing differently skilled players to play simultaneously. If the players of the game are of varying abilities, then a plurality of decks 51, 52, 54 can be used, each player playing from the deck 51, 52, 54 that matches his or her abilities. The decks 51, 52, 54 are then shuffled, a sampling of cards 1 are taken from each used deck to create the penalty/reward deck 53.
Each player then chooses one set of playing pieces 56, 57, 58 and places one playing piece on the start position 23. To begin play, each player may roll the eight-sided die 70 (pictured in FIG. 1) to determine who will play first. With the order determined, the first player must answer a card 1 chosen by him, or her, depending on how far they would like to advance. The player then reads aloud the keyword 5 and the six subwords 4, 6, 8, 10, 12, 14. If the player correctly matches the keyword 5 with the appropriate subwords 4, 6, 8, 10, 12, 14, then the player may advance his or her game piece. The number of spaces a player may advance is determined at the beginning of the game and is dependent upon the deck of cards 51, 52, 54 being used. For example, a correct answer from the difficult card deck may be worth 6 spaces, the intermediate deck may be worth 4 spaces, and the easy deck may be worth 2 spaces. Since each card 1 has two subwords 4, 6, 8, 10, 12, 14 that match the keyword 5, the space advancement value may be proportioned for correctly guessing both answers, or only choosing one correct answer.
Once a player selects his answers for any given card 1 and before the correct answers are revealed, the player may opt for bonus moves by stating "bonus". The answer shown on the backface 9 of a playing card 1 is then checked and, if correct, player receives an additional number of moves ("bonus moves") equal to twice the maximum number of moves attainable for correct responses. An incorrect answer will result in the loss of all points during that turn for the player, plus a penalty of retreating the number of spaces that the bonus would have been worth.
At the time a player elects to opt for bonus moves, any opponent may challenge the correctness of the responses of the player. If the challenger gives the correct answer(s) he moves his game piece forward the same number of bonus moves that the player, had he answered correctly, would have moved. A wrong answer by a challenger results in the same penalty as that for the player who guesses incorrectly.
Players may introduce as many as nine playing pieces from their playing piece set into play at one time.
Players answering properly during their turn may divide the number of bonus moves awarded them among their game pieces, advancing whatever pieces they choose. Challengers, however, are confined to advancing only one game piece for each successful challenge.
Game pieces landing on a home space 32, 33, 34, 35, 36, 37, 38, 39, 40 (shown in FIG. 1) or a safe space (space with the same color as the player) may not be disturbed by an opponent whose game piece subsequently lands on the same space for a period of a single round. In any other situation where a game piece 31 is overtaken by an opponent, the player overtaken must, on his next turn, select a card 1 from the penalty/reward deck 53. Correct responses must be given within half the pre-arranged time period normally allowed for response time, and are rewarded with the same number of moves given for typical correct responses. The overtaking opponent shall then retreat to the previous space of the same color and lose his or her next turn. If player fails to respond correctly or within the given time period, the penalty incurred in same as above.
In the effect to achieve the goal of the game, a player desiring to remain on a home space 32, 33, 34, 35, 36, 37, 38, 39, 40 permanently indicates same by placing his game piece upside down on the home space. Each playing piece has an "R" printed on its reverse side. Pieces so positioned are not subject to the penalty/reward rules outlined above but are allowed to remain positioned on the home spaces for the remainder of the game. In one embodiment of the present invention the home spaces 32, 33, 34, 35, 36, 37, 38, 39, 40 may be referred to as "ROGET" spaces throughout the game and its instructions. The first player to have a playing piece on each home space 32, 33, 34, 35, 36, 37, 38, 40 wins the game.
If in the course of play, a player is forced to retreat behind the start space 23 as a result of losing in bonus option play, the player locates his playing piece on one of the neutral spaces 27 between the last home space 32 and the start space 23. If the neutral spaces 27 prove insufficient, debit moves may continue counter-clockwise beyond the last home space 32, for as many spaces as are required. However, player may opt to permanently remain on home space 32, 33, 34, 35, 36, 37, 38, 39, 40. The individual player shall be required to use his next turn, or as many turns as may be necessary, to extricate his token from the neutral zone, and may not move any of his other tokens on the board until it is accomplished.
Play continues until a player secures each of his game pieces on a designated home space 32, 33, 34, 35, 36, 37, 38, 39, 40. In attempting to land the final playing piece on a home space, a player needs to achieve a sufficient number of points to land directly on the home space or in a differing embodiment the player needs to achieve enough points to pass the remaining home space.
In the modern world of advancing technology the above described game apparatus may be adapted for use on a personal computer. In that embodiment, keyword 5 and subwords 4, 6, 8, 10, 12, 14 could be generated from a dictionary database and both the selection of game cards and movement about a gameboard may be accomplished by screen graphics.
The game apparatus may also be modified to teach other specific concepts such as geography, spelling or foreign languages. Depending on the subject matter chosen for the game, the educational purpose behind the game may be directed at any classification of persons, including children, the handicapped or, as in the preferred embodiment describing "THESAURUS", adults.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | This invention is directed toward an educational game apparatus which tests the player's ability to match a key word or key symbol to one or more subwords or subsymbols. The key and list of possible answers are provided on cards, where the correct answer to the match is noted on the card back. Correct answers by a player translate into moves for the player's pieces around the continuous playing path of a game board. To win the game, a player must land each of his playing pieces on individually lettered spaces of the playing path to spell out the name of the game (i.e., T, H, E, S, A, U, R, U, S). Players have the opportunity during the game to increase the number of moves awarded them by gambling on the correctness of their answers. Special rules for game play arise when a player lands on a space already occupied by an opponent. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is the U.S. national phase of PCT/EP2008/010136 filed Nov. 28, 2008. PCT/EP2008/010136 claims the benefit under the Convention of German Patent Application No. 10 2008 012 283.1 filed Mar. 3, 2008 and German Patent Application No. 10 2008 049 860.2 filed Oct. 1, 2008.
FIELD OF THE INVENTION
[0002] The invention relates to a method for producing an optical glass part, component or element, in particular a motor vehicle headlight lens or a lens-type shaped body or element for a vehicle headlight, wherein glass is melted, wherein a blank is moulded from the glass, and wherein the optical glass element, in particular the motor vehicle headlight lens or the lens-type shaped element for a motor vehicle headlight, is, in particular on both sides, blank-moulded from the blank.
BACKGROUND INFORMATION
[0003] Methods for manufacturing motor vehicle headlight lenses are disclosed e.g. in WO 2007/095895, DE 103 23 989 B4, DE 196 33 164 C2, DE 10 2004 018 424 A1, DE 102 16 706 B4 and DE 10 2004 048 500 A1.
[0004] DE 103 23 989 B4 discloses a method for producing blank-moulded glass bodies for optical equipment, wherein a liquid (glass) batch is supplied to a levitation pre-mould into which the glass batch is pre-moulded into a blank without contacting the pre-mould, which blank is delivered to a separate pressing mould after a defined period of time has expired, and is pressed therein by means of a press-moulding tool into the final shape, wherein the transfer of the blank to the pressing mould occurs in such a way that the blank falls into the pressing mould from the pre-mould in free fall, wherein, for delivery of the glass batch, the pre-mould is moved over the pressing mould, is stopped in this transfer position and is pivoted away from the glass batch in a downward direction
[0005] DE 101 40 626 B4 discloses a method for producing a press-moulded glass body, in which melted liquid glass mass is poured into a mould, is pressed in the mould by means of a pressing die, and is cooled and subsequently removed from the mould as the press-moulded glass body, wherein the liquid melted glass mass is subjected to plural pressing operations within the mould, wherein cooling occurs between the pressing operations, and wherein, at least once, heating of the outer regions of the glass mass is performed between the pressing operations such that the cooling of the glass mass in the outer region is adapted to the cooling in the core.
[0006] DE 102 34 234 A1 discloses a method for blank-moulding a glass body for optical applications using a pressing mould comprising an upper mould and a lower mould and a ring, which pressing mould serves to receive the glass body heated to a temperature above its deformation temperature, in which method an electric potential is applied between the upper mould and the lower mould and a compression pressure is applied to the glass body at the latest after adapting the temperature of the glass body to the temperature of the pressing mould.
[0007] DE 103 48 947 A1 discloses a press for heat-moulding optical elements from glass with the aid of means for heating a form block comprising an upper mould, a lower mould and a guide ring, which form block receives the glass material, wherein inductive heating is provided as heating means and the form block is arranged on a thermally insulating body during said heating.
[0008] DE 196 33 164 C2 discloses a method and an apparatus for an at least one-sided blank-moulding of optical components serving illumination purposes, wherein, by means of a gripper, at least one mechanically portioned glass element is transferred to at least one annular receptacle adapted to be moved out from at least one furnace, and is moved into the furnace by the receptacle and heated therein on the receptacle, wherein the heated glass element is moved out of the furnace by the receptacle and is transferred back to the gripper which delivers the heated glass element to a press for at least one-sided blank-moulding, and wherein the blank-moulded glass element is then removed from the press, delivered to a cooling path and carried away from the same.
[0009] DE 103 60 259 A1 discloses a method for blank-moulding optical elements from glass, in which method a glass batch arranged in a mould block is heated to a temperature T above its transformation temperature T G , the glass batch is pressed and cooled to a temperature below T G , wherein the cooling is initially performed in a first temperature interval lying above T G at a first cooling rate and subsequently, in a second temperature interval which includes T G at a second cooling rate, and wherein active cooling is performed for adjusting the first and second cooling rates.
[0010] DE 44 22 053 C2 discloses a method for manufacturing glass blanks, in which method melted liquid glass is pressed into a pressing mould defining its outer shape, in a pressing station by means of a pressing die defining the inner shape of the glass blank, wherein the pressing die remains in contact with the glass blank in the pressing mould only as long after the pressing step, and with heat being lead away from the surface of the glass blank, until the glass blank has cooled down in its region close to the surface to such a temperature that it will have obtained sufficient structural stability of its surface for being removed from the pressing mould, and wherein the glass blank is subsequently taken out of the pressing mould and transferred to a cooling station, before it becomes deformed due to partial heating, and the glass blank is cooled in the cooling station until it has completely solidified.
[0011] FIG. 7 shows a principal representation of a typical motor vehicle headlight 61 having a light source 70 for generating light, a reflector 72 for reflecting light being generated by means of the light source 70 , and a shield 74 . The motor vehicle headlight 61 , moreover, comprises a headlight lens 62 for changing the (light) beam direction of light to be generated by the light source 70 , and for imaging an edge 75 of the shield 74 as a light-dark-border 95 .
[0012] The headlight lens 62 comprises a lens body 63 made of glass, which body includes an essentially planar surface 75 facing the light source 70 , and an essentially convex surface 64 facing away from the light source 70 . The headlight lens 62 furthermore comprises a brim 66 by means of which the headlight lens 62 can be attached within the vehicle headlight 61 . Headlight lenses for motor vehicle headlights are subjected to rather narrow design criteria with respect to their optical properties or their recommended light-technical values. This, in particular, applies with respect to the light-dark-borderline 95 as has been represented by way of example in FIG. 10 in a diagram 90 and by way of a photograph 91 . In this respect, important light-technical guideline values are considered to be the gradient G of the light-dark-borderline 95 and the glare value HV of the vehicle headlight into which the headlight lens will be installed. It is a particular challenge to meet these narrow criteria of design with the aim of achieving a cost-efficient mass production of headlight lenses for motor vehicle headlights.
[0013] It is an object of the invention to reduce the costs for manufacturing optical glass elements. It is, in particular, an object of the invention to reduce the costs for manufacturing headlight lenses for motor vehicle headlights. It is a further object of the invention to produce a particularly high-quality headlight lens for a motor vehicle headlight within a restricted budget with, in particular, light-technical requirements having to be met with respect to gradient and glare value.
SUMMARY
[0014] The aforementioned objects are achieved by a method for producing an optical glass element, in particular a motor vehicle headlight lens or a lens-type shaped body for a motor vehicle headlight, wherein glass is melted in a melting aggregate having a capacity of not more than 80 kg/h, wherein the glass comprises
0.2 to 2% by weight Al 2 O 3, 0.1 to 1% by weight Li 2 O , 0.3 (in particular 0.4) to 1.5% by weight Sb 2 O 3, 0.3 to 2% by weight TiO 2 , and/or 0.01 (in particular 0.1) to 1 (in particular 0.3) % by weight Er 2 O 3,
wherein a blank is moulded from the glass, and wherein the optical glass element, in particular the motor vehicle headlight lens or the lens-type shaped element for a motor vehicle headlight is blank-moulded, in particular on both-sides. By “capacity”, the average or mean capacity relating to one day is to be understood.
[0020] In the sense of the invention, an optical glass element serves for a specific, purposeful alignment of light, in particular for illuminating or imaging purposes. In the sense of the invention, an optical glass element serves the specific alignment of light for technical purposes, which optical glass element, in particular, has to be distinguished from purely aesthetical glass elements. In a particularly advantageous manner, an optical glass element, in the sense of the invention, is a motor vehicle headlight lens or a lens-type shaped body for a motor vehicle lens. An optical glass element, in the sense of the invention, specifically consists of (essentially) inorganic glass. In particular, an optical glass element, in the sense of the invention, (essentially) consists of silicate glass. An optical glass element, in the sense of the invention, is, in particular, a lens and/or a prism. An optical glass element, in the sense of the invention, may comprise one or several optical structures for a purposeful alignment of light. An optical glass element, in the sense of the invention, is, in particular, a precision lens. A precision lens, in the sense of the invention, is, in particular, a lens the contour of which differs by no more than 8 μm, in particular by no more than 2 μm, from the desired nominal value, and/or the surface roughness of which amounts to no more than 5 nm. In the sense of the invention, surface roughness is to be defined, in particular, as Ra, specifically according to ISO 4287. A precision lens, in the sense of the invention, is, in particular, a lens the contour of which differs by no more than 1 μm (lens diameter/10 mm) from a desired nominal contour. An optical glass element, in the sense of the invention, may be a concentrator for sunlight as well as an array having several concentrators.
[0021] In an embodiment of the invention the glass comprises
60 to 75% by weight SiO 2, 3 to 12% by weight Na 2 O , 0.3 to 2% by weight BaO , 3 to 12% by weight K 2 O , and/or 3 to 12% by weight CaO.
[0027] In a further embodiment of the invention the glass comprises
0 to 5% by weight MgO , 0 to 2% by weight SrO, and 0 to 3% by weight B 2 O 3 .
[0031] In a further embodiment of the invention the glass comprises 0.5 to 6% by weight ZnO.
[0032] In a further embodiment of the invention the glass comprises
0.3 to 0.8 (in particular to 1.4) % by weight Al 2 O 3, 0.1 to 0.4% by weight Li 2 O , 0.1 (in particular 0.3) to 2% by weight BaO, and/or 0.01 to 0.3% by weight Er 2 O 3 .
[0037] In a further embodiment of the invention the glass comprises
0 (in particular 0.1) to 2 ppm CoO , 0 to 0.1% by weight Cr 2 O 3, 0 (in particular 0.1) to 0.2% by weight Pr 6 O 11, 0 (in particular 0.1) to 1.5% by weight MnO , 0 to 0.1% by weight NiO, and/or
0 (in particular 0.1) to 0.2% by weight Nd 2 O 3 .
[0044] In a further expedient embodiment of the invention the glass is melted in the melting aggregate from a conglomerate or (glass) batch. In a further embodiment of the invention the glass is melted in the melting aggregate at a temperature of no more than 1500° C. In a further expedient embodiment of the invention the glass is melted in the melting aggregate at a temperature of not less than 1000° C. In a further embodiment of the invention a batch carpet having a thickness of between 2 cm and 7 cm is maintained on the glass melted in the melting aggregate.
[0045] In a further embodiment of the invention the temperature gradient of the blank is reversed, wherein the blank is expediently (for reversing the temperature gradient) moved (in particular essentially continuously), lying on a cooled lance, through a tempering device (for cooling and/or heating the blank), or is held in a tempering device. An appropriate, cooled lance has been disclosed in DE 101 00 515 A1. In a further embodiment of the invention, the lance is passed by cooling medium according to the principle of counter-flow. In a further embodiment of the invention the cooling medium is heated additionally and actively, respectively.
[0046] In a further embodiment of the invention the temperature gradient of the blank is adjusted such that the temperature of the core of the blank lies above room temperature by at least 100° C. In a further embodiment of the invention the blank, for reversing its temperature gradient, is, in first place, cooled, in particular by adding heat, and subsequently it is heated, wherein there is in particular provided that the blank is heated such that the temperature of the surface of the blank, after the heating, is higher than the transformation temperature T G of the glass by at least 100° C., in particular by at least 150° C. The transformation temperature T G of the glass is the temperature at which the glass becomes hardened. In the sense of the invention, the transformation temperature T G is to be, in particular, the temperature of the glass at which this has a viscosity log in a region of about 13.2 (corresponding to 10 13.2 Pa·s), in particular between 13 (corresponding to 10 13 Pa·s) and 14.5 (corresponding to 10 14.5 Pa·s).
[0047] In a further embodiment of the invention the blank is cooled at a temperature of between 300° C. and 500° C., in particular of between 350° C. and 450° C. In a further embodiment of the invention the blank is cooled at a temperature of between 20K and 200K, in particular between 70K and 150K, below the transformation temperature T G of the glass of the blank. In a further embodiment of the invention the blank is heated at a temperature of between 1000° C. and 1250° C.
[0048] In a further embodiment of the invention the gradient of the viscosity of the blank before pressing is at least 10 4 Pa·s, in particular at least 10 5 Pa·s. It should be noted that by the term gradient of the viscosity of the blank, in particular the difference between the viscosity of the core of the blank and the viscosity of the surface of the blank is to be understood.
[0049] In a further embodiment of the invention the mass of the blank amounts to (approximately) 50 g to 250 g.
[0050] In the sense of the invention, a motor vehicle is, in particular, a land vehicle to be used individually in road traffic. In the sense of the invention, motor vehicles are, in particular, not restricted to land vehicles having a combustion engine.
[0051] Advantages and details of the invention may be taken from the following description of examples of embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
[0052] FIG. 1 shows a schematic representation of an apparatus for producing a motor vehicle headlight lens or a lens-type shaped element for a motor vehicle headlight;
[0053] FIG. 2 shows an exemplary course of a method for producing a motor vehicle headlight lens or a lens-type shaped element for a motor vehicle headlight;
[0054] FIG. 3 shows an example of embodiment of a melting aggregate represented by way of a schematic view;
[0055] FIG. 4 shows an exemplary blank before entering into a tempering device;
[0056] FIG. 5 shows an exemplary blank having a reversed temperature gradient after leaving a tempering device;
[0057] FIG. 6 shows an apparatus for pressing a headlight lens;
[0058] FIG. 7 shows a schematic representation of a typical motor vehicle headlight lens;
[0059] FIG. 8 shows an example of embodiment of a lens-type shaped element for a motor vehicle headlight;
[0060] FIG. 9 shows a further example of embodiment of a lens-type shaped element for a motor vehicle headlight; and
[0061] FIG. 10 shows the distribution of illumination by a headlight.
DETAILED DESCRIPTION
[0062] FIG. 1 shows an apparatus 1 (shown by way of a principle representation) for performing a process, as represented in FIG. 2 , for producing motor vehicle headlight lenses, such as the motor vehicle headlight lens 62 as represented in FIG. 7 , or of lens-type shaped elements for motor vehicle headlights as, for example, the lens-type shaped elements 250 and 260 for motor vehicle headlights such as represented in FIG. 8 and FIG. 9 . The apparatus 1 comprises a melting aggregate 2 shown in detail in FIG. 3 and having a capacity of no more than 80 kg/h, in which aggregate glass is melted in a procedural step 20 . The glass comprises
60 to 75% by weight SiO 2 , 3 to 12% by weight Na 2 O, 3 to 12% by weight K 2 O, 3 bis 12% by weight CaO, 0.2 to 2% by weight Al 2 O 3 , in particular 0.3 to 1.4% by weight Al 2 O 3 , 0 to 1% by weight Li 2 O, in particular 0 to 0.5% by weight Li 2 O, 0 to 5% by weight MgO, 0 to 2% by weight SrO, 0.5 to 6% by weight ZnO, 0 to 3% by weight B 2 O 3 , in particular 0 to 2% by weight B 2 O 3 , 0 to 2% by weight TiO 2 , in particular 0.3 to 2% by weight TiO 2 , 0.3 to 2% by weight BaO, 0.3 to 1.5% by weight Sb 2 O 3 in particular 0.4 to 1.2% by weight Sb 2 O 3 , 0 to 1% by weight Er 2 O 3 , in particular 0 to 0.3% by weight Er 2 O 3 , particularly 0 to 0.2% by weight Er 2 O 3 0 to 2 ppm CoO, 0 to 0.1% by weight Cr 2 O 3 , 0 to 0.2% by weight Pr 6 O 11 , 0 to 0.2% by weight NiO, 0 to 0.2% by weight Nd 2 O 3 .
[0082] In particular there is provided that the glass comprises no more than 0.3, in particular no more than 0.2% by weight Er 2 O 3 .
[0083] Furthermore, the glass comprises no (i.e. in particular no more than 0.1% by weight) Fe 2 O 3 , ZrO 2 , Nb 2 O 5 , Ta 2 O 5 , and F. Furthermore, the glass preferably comprises no, in particular no more than 0.2% by weight NiO. Furthermore, the glass preferably comprises no, in particular no more than 0.05% by weight Se. Furthermore, the glass preferably comprises no, in particular no more than 2% by weight MnO 2 .
[0084] Table 1 shows a particularly appropriate glass composition:
[0000]
TABLE 1
Component
Target value (% by weight)
SiO 2
68.00
Al 2 O 3
0.70
Fe 2 O 3
0.010
CaO
3.98
MgO
2.80
BaO
1.15
K 2 O
8.68
Na 2 O
8.79
TiO 2
0.95
Sb 2 O 3
0.62
ZnO
3.33
B 2 O 3
1.00
[0085] It has, in particular, been provided that the Fe 2 O 3 content of the glass amounts to below 0.015% by weight and that traces of (<0.01% by weight) Er 2 O 3 and/or other metal oxides of rare earths and/or transition metal oxides are applied for decolouring glass.
[0086] The melting aggregate 2 , which has been represented in detail in FIG. 3 by way of a schematic view, comprises a melting vat 30 having a support structure 31 and a fire-resistant lining 32 . By means of the melting vat 30 , glass 35 is melted from a batch delivered by means of a batch feeder 38 with non-shown electrodes being provided for applying energy. The batch feeder 38 is controlled, adjusted and/or varied such that a batch carpet 36 having a thickness of between 2 cm and 7 cm is formed on the molten glass 35 . The melting aggregate 2 , moreover, comprises an outlet 33 which, for example, can be controlled/varied.
[0087] In a procedural step 21 , liquid glass is passed from the melting aggregate 2 into a pre-moulding apparatus 3 for producing a blank having, in particular, a mass of 50 g up to 250 g, such as, for example, a gob or a blank having a shape which is close to the final shape (a blank with a shape close to the final shape has a contour which is similar to the contour of the motor vehicle headlight lens or the lens-type shaped element for motor vehicle headlights to be pressed). Such pre-moulding apparatus may, for example, include moulds into which a defined amount of glass is poured. The blank is produced by means of the pre-moulding apparatus 3 in a procedural step 22 .
[0088] The procedural step 22 is followed by a procedural step 23 in which the blank is passed, by means of a transfer station 4 , to one of the cooling devices 5 A, 5 B, or 5 C, and is cooled by means of the cooling devices 5 A, 5 B, or 5 C at a temperature of between 300° C. and 500° C. In a subsequent procedural step 24 the blank is heated, by means of one of the heating devices 6 A, 6 B, or 6 C, at a temperature of between 1000° C. and 1250° C., wherein it has in particular been provided that the blank is heated such that the temperature of the surface of the blank is higher than T G , by at least 100° C., in particular at least 150° C. An example for a tempering device for setting the temperature gradient in the sense of the claims is reflected by a combination of the cooling device 5 A and the heating device 6 A, by a combination of the cooling device 5 B and the heating device 6 B, and by a combination of the cooling device 5 C with the heating device 6 C, respectively.
[0089] The procedural steps 23 and 24 are, as will be explained in the following with reference to FIG. 4 and FIG. 5 , made to match each other such that a reversing of the temperature gradient is achieved. In this context, FIG. 4 shows an exemplary blank 40 before entering one of the cooling devices 5 A, 5 B, or 5 C, and FIG. 5 shows the blank 40 having a reversed temperature gradient after leaving one of the heating devices 6 A, 6 B, or 6 C. While the blank is warmer in its interior than on the outside before procedural step 23 (supposing there is a continuous temperature profile), the blank, following procedural step 24 , will be warmer on the outside than in its interior, also in the case of a continuous temperature profile. The wedges designated by reference numerals 41 and 42 symbolize the temperature gradients with the width of each wedge 41 and 42 , respectively, symbolizing the temperature.
[0090] For reversing its temperature gradient, in an embodiment, a blank is moved, lying on a non-shown cooled lance (in a particularly essentially continuous manner) through a tempering device including one of the cooling devices 5 A, 5 B, or 5 C and one of the heating devices 6 A, 6 B, or 6 C, or it is maintained in one of the cooling devices 5 A, 5 B, or 5 C and/or one of the heating devices 6 A, 6 B, or 6 C. An appropriate, cooled lance has been disclosed in DE 101 00 515 A1. Cooling medium flows through the lance, in particular according to the principle of counter-flow. Alternatively or additionally there may be provided that the cooling medium be heated additionally and actively, respectively.
[0091] A procedural step 25 follows, in which the blank 40 is blank-moulded, by means of an apparatus represented in FIG. 6 , which forms a part of the press 8 , between a first mould 50 and a second mould, which comprises a first partial mould 51 and a second partial mould 52 which is of annular shape and surrounds the first partial mould 51 , into a motor vehicle headlight lens 62 or a lens-type shaped element for a motor vehicle headlight having an integrally moulded lens border or brim 66 , wherein, by means of an offset 53 provided between the first partial mould 51 and the second partial mould 52 and depending on the volume of the blank 40 , a step is pressed into the motor vehicle headlight lens 62 or the lens-type shaped element for motor vehicle headlights. Herein, pressing particularly occurs neither in a vacuum nor under significant low pressure. In particular, pressing occurs in atmospheric air pressure. The first partial mould 51 and the second partial mould 52 are coupled with each other non-positively by means of springs 55 and 56 . In this context, the pressing occurs such that the distance between the first partial mould 51 and the first mould 50 is dependent on the volume of the blank 40 or the headlight lens 62 or lens-type shaped element for motor vehicle headlights pressed from the blank, respectively, and that the distance between the second partial mould 52 and the first mould 50 is independent of the volume of the blank 40 and the headlight lens 62 or the lens-type shaped element for motor vehicle headlights pressed from the blank, respectively.
[0092] Subsequently the motor vehicle headlight lens 62 or the lens-type shaped element for motor vehicle headlights is transferred to a cooling path 10 by means of a transfer station 9 . The motor vehicle headlight lens or the lens-type shaped element for motor vehicle headlights is cooled in a procedural step 26 by means of the cooling path 10 . Moreover, the apparatus 10 represented in FIG. 1 comprises a computing device 15 for controlling or varying the apparatus 1 shown in FIG. 1 . The computing device 15 in particular provides a continuous linking of the individual procedural steps.
[0093] The elements shown in FIG. 1 , FIG. 3 , FIG. 4 , FIG. 5 , FIG. 6 , and FIG. 7 have not necessarily been drawn to scale for the reason of consideration of simplicity and clearness. Thus, for example the orders of dimension of some elements have been exaggerated with respect to other elements in order to enhance the comprehension of the examples of embodiment of the present invention.
[0094] The process for producing motor vehicle headlight lenses having been described with reference to FIG. 1 , FIG. 3 , FIG. 4 , FIG. 5 , and FIG. 6 may also well be applied for producing other optical glass elements in an analogous manner. However, it should be noted that the process is, in a very particular way, appropriate for a cost-effective, economic production of high-grade motor vehicle headlight lenses. | The invention relates to a method for producing an optical glass part, particularly of a motor vehicle headlight lens or a lens-like free form for a motor vehicle headlight, wherein glass is melted, wherein a perform is formed from the glass, and wherein from the perform the motor vehicle headlight lens or the lens-like free form for a motor vehicle headlight is bright molded, particularly on both sides, wherein the glass is melted in a melting unit having a capacity of no more than 80 kg/h, wherein the glass comprised 0.2 to 2% weight Al 2 O 3 , 0 to 1% by weight Li 2 O, 0.3 to 1.5% by weight Sb 2 O 3 , 0.3 to 2% weight TiO 2 , and 0 to 1% by weight Er 2 O 3 . | 2 |
FIELD OF THE INVENTION
This invention is related to the tennis racket and the like.
Description of the Prior Art
There are some problems with the tennis racket of prior art.
During a game, determining the position and orientation of the head face of the racket is crucial for a player. A little error of the judgement may cause him/her to lose the point. With the racket of prior art a player has to determine the position and orientation of the racket head by visual adjustment. It is rather inconvenient for a player to look at the tennis ball, the racket, the tennis court, and his opponent at the same time and return the ball properly.
The other problem of the racket of prior art is that the grip is easy to become slippery during a game. The slippery may be caused by the centrifugal force in the longitudinal direction when a player swings the racket to strike the tennis ball, or by the collision force of the ball in the cross-sectional direction when a player strikes the ball eccentrically with the head face of racket. As a result, the player must always grip the racket handle very tightly when swinging the racket and striking the ball. It leads to fatigue of the hand of the player easily, and ultimately to deterioration of the quality of the player. Also, since the player's wrist muscle is always tense during a strike it is detrimental for the player to make good use of the breakout force of the wrist.
In addition, the handle of prior art does not give a full utilization of the hand muscular power of a player. When a player uses the racket of prior art to serve, to have a forehand stroke, or to have a backhand stroke, some parts of the hand of the player do not make contributions, or are not utilized fully.
These problems have been recognized for a long time, and some modifications have been made to improve the performance of the racket. A number of inventions comprise the closer known prior art:
U.S. Pat. No. 3,203,697;
U.S. Pat. No. 3,817,521;
U.S. Pat. No. 3,868,110;
U.S. Pat. No. 3,905,598;
U.S. Pat. No. 4,006,896;
U.S. Pat. No. 4,072,311;
U.S. Pat. No. 4,226,418;
U.S. Pat. No. 4,721,305;
U.S. Pat. No. 4,861,030;
U.S. Pat. No. 4,978,123.
The innovation by Berzatzy (U.S. Pat. No. 3,203,697) provides a tennis racket handle with a cross-section of flat elliptical configuration and a L-shaped bracket. Although this innovation provides the improvement to the problems of slippery in the cross-sectional direction and flying out of hand due to centrifugal force when a player swings the racket and strikes the ball, it does not provide a structure which gives the full use of the hand power. Also, the device of the L-shaped member severely limits the wrist and hand mobility which is very important for the quality of a player in a game.
The innovation by Wright (U.S. Pat. No. 3,817,521) provides an upstanding backhand thumb stop. It intends to transmit thumb pressure force to the tennis racket held in a manner to hit a tennis ball in a backhand drive. However, it does not describe and provide a structure which emphasizes and reinforces the thumb force in forehand stroke although it provides a forehand index finger separator structure.
The innovation by Bertucci (U.S. Pat. No. 4,072,311) describes an index finger positioning device between the index finger and the middle finger when the racket is gasped by a player, which emphasizes and encourages the full use of the index finger. The device does have the index finger apply more power during a strike, but since the index finger is relatively weaker, it does not make a significant contribution to improve the conventional racket.
The innovation by Belfour (U.S. Pat. No. 4,226,418) provides a hand grip for a racket which includes four finger holes and further a plurality of finger engaging slots. Although the device does have some improvements to the problem of tactile indication of the position and orientation of the racket face and the problem of slippery it does not encourage and reinforce the full use of the hand power of a player. Also, the structure may make the player feel uncomfortable, or may hurt the player when the hole rings are inserted between the fingers in a game. It is also noticed that for the hands of different sizes, different models must be provided if the comfortableness of the user is considered.
The innovation by Burt (U.S. Pat. No. 4,861,030) uses the frame extensions from the racket head to form a handle. Two separate grips are arranged on the handle so that a player can hold the racket by both grips, and can simply let go of one grip and swing the racket with the other hand to play forehand shots. However, it is not intended for single hand user, and is not intended to reinforce the hand muscular force of the player by providing a new handle structure.
The innovation by Ashihara (U.S. Pat. No. 4,978,123) provides a racket featuring a rotary cross handle added on the shaft of a conventional racket so that a user can swing the racket while gripping the cross handle as a pivotal axis. The device allows a player to exert centrifugal force instead of muscular strength to hit a coming ball. Nevertheless, it does not provide a structure to encourage and reinforce the hand muscular power of the player.
Some other innovations (U.S. Pat. No. 3,868,110, No. 3,905,598, and No. 4,006,896) provide the modifications of the handle structure with finger grooves to place the fingers and thumb of the hand of a player. Although the finger grooves may increase the engagement with the hand of the player they do not necessarily increase the tactile perception of the angle of the face of the racket, and the hand power of the player can not be used fully with these handle structures.
All of these structures of the prior art, generally speaking, do not necessarily describe a very reasonable structure which can fully use the thumb, fingers and palm muscular force and at the same time do not limit the mobility of the hand of a player in a strike. Nor do they necessarily solve the problem of fatigue of the hand by reducing the slippery in the cross-sectional and longitudinal directions. They cannot necessarily have the player make good use of the breakout force of the wrist. Nor do they necessarily increase the tactile indication of the position and orientation of the head face of racket. Furthermore, almost all of these structures have a common disadvantage, that is, for different hands of different players, correspondence to a particular size of hand grips must be produced. Also, for right hand users and left hand users the models must be doubled. The numerous sizes and configurations of the different hands make the manufacture of these models very inconvenient, if at all possible.
SUMMARY OF THE INVENTION
In this invention, a new racket with a special handle formed by a two-bar grip and two accessary shafts is provided. The grip is formed by head frame extensions of the racket, or to be more general, by two parallel small bars or the like with proper length and width so that a player can grasp and hook the two bars as a grip with the hand. The accessary shafts are formed by the fixing screw, support shaft and fixing nut. The invention is characterized by providing some significant features of improvement to the prior art.
One of the features is to provide a new two-bar grip to reinforce the grasping force of the hand. The two-bar grip is easy for a player to generate a larger cross-sectional resisting torque than the handle of prior art, and is also easy for a player to hook the bars of the grip to have full use of the finger power.
Another feature of improvement is to provide a thumb shaft to reinforce the thumb force to generate an extra resisting force and torque in a forehand stroke.
Another feature is to provide a palm shaft to reinforce the hand palm side force to generate an extra resisting force and torque in a backhand stroke. Said palm shaft will not have the bad influence of limiting the mobility of the hand and wrist of a player when it is being used.
Also, another feature of improvement is to provide a unique combined structure of handle which can easily help a player to judge the position and orientation of the head face of racket by the tactile sensation of the hand.
Still another feature is to provide a new handle which can alleviate the fatigue of the hand of a player by mitigating the slippery in the cross-sectional and longitudinal directions, and moreover, have the player carry forward the breakout force of the wrist during a strike.
The invention with its organization, simplified force diagram analysis, manner of operation, and utilization can be best understood by making reference to the following description of the drawings and the depiction of the invention.
DESCRIPTION OF THE INVENTION
FIG. 1 is a general view of the invention for a fight hand player.
FIGS. 2, 2a and 2b show is a three direction projection view of the invention for a fight hand player.
FIG. 3 is the view of a fight hand player holding the invention in a forehand stroke.
FIGS. 4a, 4b, 4c and 4d show a is the simplified force analysis diagram with the prior art and the invention during a forehand stroke.
FIGS. 5a, 5b, 5c, 5d show a is the simplified force analysis diagram with the prior art and the invention during a backhand stroke.
FIGS. 6a, 6b, and 6c show a is the comparison and analysis of the handle with different cross section held by a user.
FIG. 7 is a general view of the accessary shafts.
FIG. 8 is the assembly view of the accessary shafts.
FIGS. 9, 9a and 9b show a is the front, vertical and cutaway side view of the opened hole clamp.
FIGS. 10, 10a and 10b show a is the front, vertical and cutaway side view of the stopped hole clamp.
With reference to FIG. 1, it is a general view of the invention for a right hand user. Structure 3 is the head of the racket. The two bars of the head extensions 1 converge gradually and are fixed first by the opened hole clamp 2, then the two bars of extension 1 are made symmetrical and parallel and extend a certain length with a proper width, and then are fixed at the end by the stopped hole clamp 6. The two parallel bars of the extension 1 and clamp 6 may all be covered with soft material. The thumb shaft 4 and palm shaft 5 are mounted and fixed on each of the two bars of the extension 1, and the mounting position and orientation can be adjusted by the individual requirement of the player. In the case of a left hand user, the user only needs to adjust the mounting orientation of the accessary shafts to 180 degrees different from that of the right hand user.
From FIG. 2 which shows the three direction projection view of the invention for a right hand player and FIG. 3 which shows the view of a right hand player holding the innovation in a forehand stroke, it is easy to understand that the invention has provided a unique structure to indicate the position and orientation of the racket head face to the player. When the player holds the racket to have a strike, the position and orientation of the racket head face can be easily judged by the tactile sensation of the hand.
FIG. 4 presents a simplified force diagram when a player uses the innovation in comparison with the prior art to have a forehand stroke. Here, the arrows are the simplified forces. When a player uses the racket to hit a coming ball there is a collision force on the racket head face which in turn causes a collision force and torque on the hand of the player. To stand the activities caused by the collision force, the player must generate necessary resisting force and torque. With the handle structure of prior art the thumb muscular force is not fully used. By comparison, with the invention the thumb force is fully used to generate an extra resisting torque to stand the collision activities through the thumb shaft 4. When the thumb force is certain, the longer the distance h, the larger the generated extra resisting torque. Also, the extra thumb force can be used to resist the centrifugal force of the racket in the longitudinal direction caused by swinging the racket during a strike. FIG. 5 indicates the simplified force analysis diagram in a backhand stroke when a player uses the prior art handle structure versus the invention. The arrows in this diagram are the simplified forces. It demonstrates that when the handle structure of the invention is utilized the large force of the low palm side of the hand is fully used to generate an extra resisting torque with the palm shaft. Also, the extra low palm side force is used to resist the centrifugal force in the longitudinal direction caused by swinging the racket.
From FIG. 6, it is clear from general knowledge that when the total length of envelope lines of the cross section is the same the racket handle with the flat elliptical cross section is easy to be used by a player to generate larger cross-sectional resisting torque than the conventional handle with the cylindrical or octagonal cross section. Also, it is clear that the invention is better to be used to generate a cross-sectional resisting torque than the handle with flat elliptical cross section because the fingers of a player can hook the bars of the handle so that the finger power of the hand can be fully utilized.
The delineation of FIG. 4, FIG. 5, and FIG. 6 indicates that since the structure of the invention can easily be used by a player to generate a larger cross-sectional resisting torque than the structure of prior art, and to have an extra force to stand the centrifugal force in the longitudinal direction, the player does not always need to grasp the handle tightly, and the tension of the wrist muscles of the player can be relaxed in a strike before hitting the ball. It leads to alleviating the fatigue of the hand of a player and lets the player take advantage of the breakout force of the wrist.
As can be seen in FIG. 7, it shows the general view of the accessary shafts 4 and 5. The accessary shafts 4 and 5 may be of the same size and shape. FIG. 8 shows the assembly view of the accessary shafts. The accessary shaft is comprised by the fixing screw 7, support shaft 8 and fixing nut 9 which form a adjustable fixing loop. The thumb and palm shafts are mounted and fixed on the two bars of the extensions 1 with their loops to reinforce the thumb and low side palm power.
FIG. 9 displays the opened hole clamp 2. The front, vertical and cutaway side view are demonstrated. Parts 10 and 11 are of the same size and shape. They are fastened by the bolt 13 and nut 12 to fix the bars of the extension 1 with the open holes. FIG. 10 is the stopped hole clamp 6. Here, the front, vertical and cutaway side view are also shown. Parts 14 and 15 are of the same size and shape. They are fastened by the bolt 17 and nut 16 to fix the end of the two bars of the extension 1 with the half stopped holes. The opened hole and stopped hole clamps are used to fix the two-bar grip and increase the rigidity and strength of the handle structure. | A racket for the sports of tennis and the like with a special handle is presented. The handle includes a two-bar grip and two accessary shafts. The two-bar grip is formed by the extensions from the head frame of the racket which are arranged to be symmetrical and parallel, and are fixed with predetermined length and width by a opened hole clamp and a stopped hole clamp. The two accessary shafts are mounted on each of the bars of the two-bar grip with their fixing loops, and the mounting position and orientation can be adjusted. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 13/013,723, filed Jan. 25, 2011, which is a continuation of U.S. patent application Ser. No. 10/901,866, filed July 29, 2004, which issued as U.S. Pat. No. 7,887,823 on Feb. 15, 2011, which is a divisional of U.S. patent application Ser. No. 09/979,396, filed Nov. 6, 2001, which issued as U.S. Pat. No. 6,818,232 on Nov. 16, 2004, which is a §371 national stage entry of International Application No. PCT/EP2000/004046, filed May 5, 2000, which claims priority to European Patent Application No. 99108965.7, filed May 6, 1999, the entire contents of which are incorporated herein by reference.
A simple and efficient method for the production of stable, clear, high-potency oat extracts is disclosed. The method employs the use of differential dissociation constants and ultrafiltration to stabilise extracts, prevent hazing, and prevent the loss of functional activity as an anti-irritant and anti-oxidant. Also claimed are compositions of oat extracts derived from whole oat grains and oatmeal.
Further claims are made to compositions of oat extracts for use in cosmetic, nutraceutical, therapeutic medical and veterinary preparations.
FIELD OF THE INVENTION
The present invention relates to the production and use of solubilised, liquid oat extracts with formulations having utility in the personal care, cosmetics, nutraceutical, and pharmaceutical industries. More specifically the oat extract compositions of the present invention are useful as anti-irritants, anti-oxidants and skin-protection agents applied to the skin or when consumed.
BACKGROUND OF THE INVENTION
Oats ( Avena sativa ), and especially colloidal oatmeal suspensions have been used historically as adjuncts to the treatment of atopic dermatitis. It is desirable to extract the active ingredients from the oat in order to facilitate the use of the grain in medicinal and cosmetic applications.
Oat derivatives such as colloidal oatmeal, hydrolysed oat protein, oat starch, and β glucan have been used in the cosmetics and pharmaceutical industries as a skin protectant which provides a smooth feel after use. Specifically, the carbohydrates and protein in the oat derivatives have been known to function as a protectant to aid in enhancing the skin's barrier properties and thereby soothe the skin. Oat β glucans and lipids have also been known to function as emollients to lubricate and soothe the skin. For example, colloidal oatmeal has been used for bar soaps, bath powders, lotions, and poultices to treat skin that has been damaged, irritated, or distressed by a wide variety of causes. However, some oat derivatives, for example, colloidal oatmeal, are not fully soluble in aqueous solutions and leave undesirable residues on the skin and other surfaces.
U.S. Pat. No. 5,219,340 describes a cloth applicator designed to retain colloidal oatmeal insoluble fractions.
Furthermore, hydrolysed oat protein undergoes processes such as hydrogenation, which may alter or adversely effect their properties. In particular, acid hydrolysed oat protein is known to have a strong odour which may adversely affect some consumer's acceptance of the product.
Liquid oat extracts prepared by extraction with alcohol, glycols, ethers, esters, mixtures, and aqueous mixtures thereof are typically unstable materials, which if not emulsified, readily separate into oil and aqueous phases which may further separate into soluble and insoluble phases. The loss of materials from solution results in hazing and the loss of functional activity. Haze is irreversible and the extract cannot be clarified by heat, dilution, addition of surfactants, or solvents or pH. Attempts to clarify the extracts using filtration resulted in the loss of functional activity. The instability of oat extracts has limited utility in cosmetic and medical applications.
Paton (19951 Cosmetics and Toiletries 110:63 describes the cosmetic use of oat extracts and provides information on cosmetic formulations. The oat extract described, OSTAR ARRIVEEN™, is produced from oats by a pearling process by which oat bran is obtained, which was then extracted with solvent. Charcoal was used in the process to clarify the preparation. The product is typically a dark brown coloured, non-homogeneous, bi-phasic extract. The utility of this product was limited by instability resulting in varying performance. The product could not be sterilised resulting in a high microbial load high due to non-kilned, non-stabilised oat bran.
Collins et al U.S. Pat. No. 5,169,660 describes the preparation of bran from cereal grains using aqueous alcohol extraction (83% w/w) and the recovery of crude by-products from waste through ion-exchange chromatography. The described process does not use pH pre-treatment or membrane filtration and so results in only recovered small quantities of by-product from waste. Utility is not described in cosmetic applications and pharmaceutical claims are not enabled.
Collins in Oats: Chemistry and technology (1986) Ed. Webster AACC St. Paul. Minn. pp 227-286 describes oat phenolic compound structure, occurrence and phytological function. Methods of extraction of these compounds and potential utility in the cosmetic and medical fields of use were not disclosed.
Onitsuka et al US 5J 16.605 describe the use of glycolic extracts of oats for the treatment and care of hair and the scalp. The extraction method described is different to the method of the present invention.
Cioca et al U.S. Pat. No. 5,552,135 describes improved sunscreen compositions including extracts from cereal plants. The primary extraction is made with chloroform or ethanol and further processed further in alcohol following evaporative concentration.
Hammonds et al PCT/US97/10724 describes fibrous sheet materials containing oat extracts to provide a soothing effect to the skin of the user. The oat extracts claimed are made by treating oats with extraction agents by methods known to those skilled in the art. Methods of preparing oat extracts are not disclosed; the described product used specific concentrations of OSTAR ARR1VEEN™ in the preferred mode.
Zimmerman U.S. Pat. No. 5,888,521 describes compositions for topical use consisting of hydroxycarboxylic acid and oat extract, and also relates to methods of enhancing the rate of skin desquamation. Methods of preparing oat extracts are not disclosed; the described product used specific concentrations of OSTAR ARRIVEEN™ in the preferred mode.
Roger et al U.S. Pat. No. 5,026,548 describes a phospholipid surfactant for use as a viscosity reducing agent in chocolate, or an emulsifier, surfactant or foam stabilizer in the food and other industries is produced by extracting oats using an alcohol such as ethanol or propanol, extracting the alcohol extract with methanol and evaporating the methanol.
Targan U.S. Pat. No. 5,468,491 describes a method for producing an aqueous oat syrup involving enzymatic digestion, cooking, filtration through on oat bed, and concentration to produce an extract composed of 80% sugars and 20% water. Utility is expressed as a flavour, colour, sweetener, and or texture enhancer. The composition is different to the present liquid oat extract.
Rouanet et al PCT/FR98/00826 describes a method for making a solid preparation of white colloidal oats, comprising the following steps: using cultivated oat seeds; stabilizing by at least one operation whereby dry vapour is injected followed by sudden cooling, preferably at about room temperature; pinning and drying; breaking and eliminating the bran; dimensional selecting of particles.
Vallet Mas et al EP 0 661 047 describes the combination of topical anti-histamines with solid oat flour to form an emulsion for the treatment of itching, reduction of inflammation and facilitation of spreading over the effected area. No reference is made to the anti-irritant potential of oat extracts.
Kovacs EP 0 282 002 describes the use of combinations of nettle ( Urtica ) and oat extracts as food additives or pharmaceutical preparations. The methods of preparing the oat extracts are described as, “classical methods” and no enabling details are provided.
Lawrence U.S. Pat. No. 5,573,785 describes an oat derived, skin conditioning, cosmetic component produced by dispersing in water a water-soluble fibre composed of about 4 to 6 weight percent beta glucan, about 1 to 5 weight percent fat, about 80 to 94 weight percent carbohydrates and less than 8 weight percent protein. No data relating to anti-irritant and redness reduction is provided. Furthermore, composition is radically different.
The commercial uses of ultra-filtration are known to those skilled in the art. Uses include water purification, milk processing, fruit juice, and wine clarification. However, ultra-filtration cannot be used for processing oat extracts without first stabilising the product by reducing pH. The high oil content of oats compounds this problem.
Reverse osmosis is known to those skilled in the art for the production of water from salt solutions. The use of reverse osmosis for the concentration of alcoholic extracts and solvent recovery as described in the present invention is novel.
DISCLOSURE OF THE INVENTION
1. Primarily, the present invention provides a method for the production of an oat extract that offers several advantages over the known methods of extraction and enhances the properties of the extract.
Histological staining of intact oat kernels indicated that the phenolic compounds were located primarily in the aleurone layer of the oat kernel. This implied that enriched preparations of the functional compounds would best be made from bran obtained by conventional milling or debranning processes. We were surprised to discover that the maximum yield of Avenanthramides came from the whole oat, not a bran fraction. The present invention is based on the discoveries that (a) the extraction of active ingredients from oat may be enhanced in terms of production and efficiency, and furthermore (b) the resulting extracts are stable for extended shelf-life periods and may be concentrated readily. Thus, according to a first aspect of the present invention there is disclosed a method for producing of an oat extract comprising the following steps:
a. Milling whole oats, b. Extracting the resulting oatmeal with a solvent, c. Adjusting the pH of the resulting oat extract to <4.0 (favorably <3.5), d. Membrane filtration (e.g. ultra-filtration) of the oat extract through a membrane <10 4 MWCO
The oat extract produced according to the method of the present invention is quantifiable in terms of activity and certified product quality assurance can be given. In accordance with the invention, aqueous alcoholic extracts of whole oats or groats are refined to provide materials for use in cosmetic and pharmaceutical compositions such as creams, gels, powders, lotions, and the like. The oat extract of the present invention preferably contains Avenanthramide (as defined below) at a concentration of between 1 and 1500 ppm of Avenanthramide, more preferably between 3 and 450 ppm of Avenanthramide, and most preferably between 15 and 150 ppm of Avenanthramide. Other compounds, for example phenolics, benzoic and cinnamic acids, flavones, flavonols, chalcones, flavanones, proanthocyanidins, aminophenolics, tocols, and saponins, are also found in the oat extract. These compounds may have utility as for example, anti-oxidants, sunscreens, and surfactants. The oat extract according to the present invention contains no or very little amounts of β glucan, for example less than about 0.01%, and less than 0.01% protein of molecular weight greater than 10,000 Da. Preferably in step d of the method according to the present invention the membrane filtration is an ultra-filtration. Preferably, reverse osmosis is used to further concentrate and purify the oat extract obtained by step d. In step b the solvent for extracting the oatmeal favorably comprises water and a primary alcohol. The primary alcohol is preferably selected from the group consisting of ethanol, methanol, propanol (n-, iso-), butanol (n-, iso-, tert-), or mixtures thereof. Ethanol:water is preferred. The oat extract may be incorporated into a solvent for ease of handling. For example in a preferred embodiment, the oat extract is incorporated in a 1:1 w/w mixture of 1,3 butylene glycol and water. The oat extract obtained according to the method of the present invention can be easily sterilised by heat, microfiltration, or irradiation (after step c or d).
2. According to a second aspect the present invention relates to therapeutic (pharmaceutical) or cosmetic compositions, in particular for treatment of skin, which may be formulated as solution, gel, lotion, cream, ointment, or other acceptable form.
The composition favorably comprises Avenanthramide in a concentration of between 0.01 and 150 ppm, more preferably between 0.01 and 50 ppm, even more preferably between 0.3 and 15 ppm, and most preferably between 1.5 and 4.5 ppm. Equally favorable is a therapeutic or cosmetic composition comprising between 0.1 and 25 weight percent, preferably 1 and 10 percent, of an oat extract comprising Avenathramide in a concentration of, referring to the oat extract, between 1 and 1500 ppm, preferably 3 and 450 ppm of Avenanthramide. The oat extract comprised in the composition is preferably produced according to the method of the present invention (see 1. above). The composition according to the second aspect of the present invention may also contain various known and conventional therapeutic and/or cosmetic ingredients providing they do not detrimentally affect the desired reduction of skin irritation. For example, cosmetic ingredients such as alcohols, fats and oils, surfactants, fatty acids, silicones, humectants, moisturisers, viscosity modifiers, emulsifiers, stabilisers, colourings agents, and perfumes or fragrances may be included. The composition can be used as a dermatological cosmetic product, in particular for use in the treatment of sensitive skin and/or redness (and/or wrinkles of the skin and/or pigment spots). Typically, therapeutic or cosmetic compositions according to the present invention are topically applied to the skin.
3. A third aspect of the present invention relates to the use of an oat extract which comprises Avenanthramide, preferably an oat extract
(a) prepared according to the present invention and/or (b) comprising Avenathramide in a concentration as stated above,
for the preparation of a topical dermatological therapeutic composition for treating erythema, pruritus, otitis, inflammations, irritations, and/or allergies affecting the skin, for the preparation of a topical dermatological composition with enhanced therapeutic effect for use in the treatment of disorder of skin and/or for the treatment of inflammations, and for the preparation of a topical dermatological composition with enhanced therapeutic effect for use in the treatment of disorder of skin and/or for the treatment of erythema, pruritus, otitis, inflammations, irritations, and/or allergies affecting the skin.
The use of the oat extract for the respective purposes corresponds to methods of imparting the respective therapeutic activity to a substance by adding a therapeutically effective amount of the oat extract.
4. A fourth aspect of the present invention relates to Avenanthramide for use in the therapeutic treatment of disorder of skin and/or inflammations. This aspect corresponds to
(a) a method for therapeutic treatment of disorder of skin and/or inflammations, comprising applying a therapeutically effective amount of Avenanthramide to the skin, preferably in form of an oat extract and/or formulated in a suitable carrier, (b) the substance(s) Avenanthramide for use in the therapeutic treatment of disorder of skin and/or inflammations, and (c) a therapeutic composition, in particular for treatment of disorder of skin and/or inflammations, comprising a therapeutically effective amount of Avenanthramide. Details of therapeutic treatment are given below.
5. A fifth aspect of the present invention relates to an oat extract containing a minimum of 10 ppm of Avenanthramide, wherein the oat extract can be produced by a method comprising steps a-d as above, and the additional step
e. Adjusting the concentration of Avenanthramide in the permeate after membrane filtration to >10 ppm
DETAILED DESCRIPTION OF THE INVENTION
The practise of the present invention will employ, unless otherwise indicated, conventional methods of chemistry, cereal chemistry, cosmetic chemistry, pharmacy, and biochemistry within the skill of the art.
All publications, patents and patent applications cited herein, whether supra or infra, are incorporated by reference in their entirety.
As used in this specification and the appended claims, the singular forms “a”, “an”, and “the” include the plural references unless the content clearly indicates otherwise. Thus the term “an Avenanthramide' can include more than one member of the group of Avenanthramides.
Definitions
In describing the present invention, the following terms are employed, and are intended to be defined as indicated below
By an “Avenanthramide” in singular or plural is meant a member of a group of more than 36 naturally occurring anthranilic acid derivatives found in oats, and are unique to cereal grains. Nomenclature follows the convention described in Oats: Chemistry and technology (1986) Ed-Webster AACC St. Paul. Minn. pp 227-286 with specific Avenanthramide compounds by the prefix ‘AF’ followed by a number, for example AF-1, AF-2 and AF-6.
Avenanthramides AF-1, AF-2 and AF-6 are based on Formula I:
“AF-1” refers to compounds of Formula I, where R 1 ═OH, R 2 ═H, and R 3 ═H.
“AF-2” refers to compounds of Formula I, where R 1 ═OH, R 2 ═H, and R 3 ═OCH 3 .
“AF-1” refers to compounds of Formula I, where R 1 ═OH, R 2 ═H, and R 3 ═OH.
By “Oatmeal” is meant the product of grinding or milling whole naked (hulless) oats or oat groats.
By “Oat bran” is meant the product of grinding oat groats or rolled oats and separating the resulting oatmeal by sieving, bolting and/or other suitable means into fractions such that the oat bran fraction is not more than 50% of the starting material, and has a total β glucan content of at least 5.5% (dry weight basis) and a total dietary fibre content of at least 16.0%.
By “Oat flour” is meant the product of grinding oat groats or rolled oats and separating the resulting oatmeal by sieving, bolting and/or other suitable means into fractions that 100% of the flour passes through a 100 Mesh screen.
By “Ultra-filtration (UF)” is meant the process of tangential filtration whereby solutes are retained by a membrane the parameters of which are based on molecular weight
By “Reverse Osmosis (RO)” is meant the process of tangential filtration whereby water and/or low molecular weight solvent, for example ethanol, passes through a membrane thereby concentrating the Retentate.
By “Membrane filtration” (MF) is meant the process of filtration whereby solutes are retained by a membrane the parameters of which are based on molecular weight. UF and RO are examples of MF.
By “Molecular Weight Cut-Off (MWCO)” is meant that above a specified MWCO, the membrane will retain most species of that molecular weight.
By “Permeate” is meant the fluid containing the solutes that passes through the UF/RO membrane.
By “Retentate” is meant the fluid containing the solutes that are retained by the UF/RO membrane.
By “Flow” is meant the volumetric filtration rate (flow rate) through a given membrane area per unit time. Units are usually litres per square meter per hour (LMH).
By “Diafiltration” is meant the efficient method of recovering solutes (<MWCO) in low concentrations from the solution, by addition of fresh solvent at a rate equal to the UF rate. At constant volume, the permeate solutes are removed from the Retentate. The rate of recovery is a function of the UF rate and is independent of the concentration of the permeate solutes.
By “Membrane fouling” or “concentration polarization” is meant the accumulation of retained or absorbed material on the membrane surface.
By “Concentration” is meant the accumulation of rejected permeate solutes on the membrane
By “Percent recovery” is meant the amount of desired solute as a percentage of the amount present in the feed-stream.
General Methods
In accord with the present invention, an intermediate oat extract can be prepared by milling whole oats, extracting the oatmeal by mixing with a solvent, separating the resulting intermediate extract from the spent grain and adjusting the pH of the intermediate extract to <4.0 (preferably <3.5). The pH adjustment leads to high Avenanthramide yields in the extract.
Once extracted and acidified the intermediate oat extract is stable for several months.
The intermediate extract is subjected to membrane filtration, preferably ultra-filtration, whereby the filtrate of <10,000, more preferably <5,000 molecular weight is collected.
The resulting oat extract may be used for therapeutic or cosmetic purposes directly in alcohol. Alternatively it may be subjected to solvent exchange and the extract made up in a solvent of choice including, but not limited to, for example, butylene glycol, pentylene glycol, propylene glycol, glycerine, mixtures of these solvents, and combinations of these solvents or solvent mixtures with water.
The resulting oat extract is readily formulated as solution, gel, lotion, cream, ointment, or other pharmaceutically acceptable form. Preparations are formulated using methods known to those skilled in the art. For the reduction of erythema, the compositions should contain about 1-3% of the liquid oat extract (provided as a standardised 15 ppm Avenanthramide solution).
EXAMPLE 1
Oat Extract Preparation Process
Two or three replicates for each method were processed and analysed.
METHOD. Oat groats (Variety Hinoat) were ground through a Willey Mill to pass through a 10 Mesh screen. Oatmeal at a mixing ratio of 1:4 (w/v) oatmeal:solvent was added to a stirred solution of 50% (v/v) aqueous ethanol at 40 C. The resulting mixture was stirred for 30 minutes and then cooled to room temperature. The mixture was then centrifuged at 2830 g for seven minutes and the supernatant drawn off. The pellet was re-suspended in fresh solvent and re-centrifuged. The supernatant was drawn off and the pellet re-suspended a third time in fresh solvent. All supernatants were combined and filtered through a course sintered glass filter.
To show the difference between the method (process) for producing an oat extract according to the present invention, which comprises the step of adjusting the pH of the extract to <4.0, and a method which does without pH adjustment, a comparison test series was carried out. Test samples were designated UF-B1, UF-B3, UF-C1, UF-C2, and UF-C3, respectively.
For samples of the I.D. series UF-B1 (comparison samples), in contrast to the method according to the present invention the oat extract was applied directly to the ultrafiltration module.
For samples of the series UF-B3, UF-C1, UF-C2, and UF-C3, in accord with the present invention the pH of the extract was adjusted to 2.5 with hydrochloric acid (IN) and ethanol added (−1%) to clarify the solution. The pale yellow extract was passed through a 0.45 μm filter (Gelman; Supor DCF) before ultrafiltration.
For ultrafiltration a Millipore Corporation MINI-PLATE™ Tangential-Flow Bioconcentrator (10,000 MWCO) was used. The unit contains a low protein binding YM membrane with a surface area of 108 cm2. Pump rate was 1000 ml/min. and the flux (flow) was typically 14 L/m 2 /h (LMH).
Weight profiles were conducted on the sample ID series UF-B by lyophilisation for 72 hours.
ANALYSIS High Performance Liquid Chromatography (HPLC) analysis was performed using a Thermo Separations Products (TSP) Spectra P4000 pump, a Varian column oven, and a Waters 991 Photodiode Array (PDA) detector with accompanying software. The column used was a CSC-Hypersil (5 μm, 120 A, 0.46×25 cm—serial #039775) at 25° C. UV monitoring at 330 nm was used. The flow rate was set at 1.0 ml/min.
All samples and standards were prepared in ethanol/water (1:1).
AF-1 standard (0.1 μg/μl): 5 μl injected Retention time: 23.68 minutes
AF-2 standard (0.1 μg/μl): 5 μl injected Retention time: 26.95 minutes
Avenanthramide fractions were prepared in 50% ethanol/water (5 ml) and 5 μl injected
Table 1 describes the HPLC solvent program for the analysis of Avenanthramides.
TABLE 1
5% Acetic
Time (min.)
MeOH
H 2 O
Acid
0
40
55
5
40
55
40
5
45
85
10
5
50
100
0
0
53
40
55
5
55
40
55
5
RESULTS As provided in Table 2 total Avenanthramides were calculated and expressed as AF-1 equivalents and recovery efficiency expressed as percentage recovery of Avenanthramides from the permeate are based on total Avenanthramides.
TABLE 2 UF Method Conc. Sample I.D. pH Permeate Retentate Clean in place Recovery Diafiltration polarization UF-B1P 7.5 33.8 — — 57% No No UF-B1R 7.5 — 21.8 — 37% No No UF-B3P 2.5 45.5 — — 77% No No UF-B3R 2.5 — 8.1 — 14% No No UF-B3C 2.5 — — 1.1 2% No No UF-C1P 2.5 38.6 — — 75-109% Yes No UF-C2P 2.5 43.3 — — 84-122% Yes Yes UF-C3P 2.5 42.5 — — 82-120% Yes Yes Notes: 1. Values based on AF-1 equivalents 2. Percent Avenanthramide recoveries of the permeate fraction for the C-Series are given as a range from UF-C 1, C2, and C3 values
Qualities of the Oat Extract
1. No haze formation has been observed in any oat permeate extracts produced to date. 2. Efficiency of the Avenanthramide extraction is >75%, more typically 85-100%. 3. The oat extract can be concentrated up to 50-fold without precipitation occurring. 4. The oat extract has low or no bacterial counts due to the permeate feed-stream being sterile before concentrating. 5. The oat permeate extract has a clean, clear yellow colour with a shelf life of more than 12 months. 6. The oat extract has a pleasant oat odour. 7. The permeate fraction was readily soluble at neutral pH in 35-70% ethanol/water.
EXAMPLE 2
Oat Extract Process Scale-Up
METHOD Oat groats (Variety AC Ernie) were ground through a Willey Mill to pass through a 10 Mesh screen seive. Oatmeal (1.5 kg) was added to a stirred solution of 50% (v/v) aqueous ethanol (6000 ml) at 40° C. The resulting mixture was stirred for 30 minutes and then cooled to room temperature. The mixture was then centrifuged at 2830 g for seven minutes and the supernatant drawn off. The pellet was re-suspended in fresh solvent (3000 ml) and re-centrifuged. The supernatant was drawn-off and the pellet re-suspended a third time in fresh solvent (3000 ml). All supernatants were combined and filtered through a coarse sintered glass filter. The pH of the extract was adjusted to pH 3.5 with hydrochloric acid (1 M) and ethanol added (˜1%) to clarify the solution. The pale yellow extract was passed through a 0.45 μm filter (Gel an; Supor DCF) and made up to 12000 ml before ultrafiltration.
The extract was ultrafiltered at ambient temperature through a modified PES (Omega) T-screen membrane (0.09 m 2 ; 5000 MWCO, Pall Filtron) using a Pall Corporation CENTRASETTE™ unit. Flux rates (flow rates) ranged from 20-25 LMH. The pH of the resulting permeate was adjusted back to 6.5 with aqueous potassium hydroxide (5M).
A 200 ml aliquot was evaporated to dryness under reduced pressure and made up to 10 ml in 1:1 (v/v) aqueous ethanol. The solution was applied to a calibrated open column containing 100 mls. of LH-20 chromatographic gel (AP Biotech, Sweden) pre-equilibrated in ethanol:water:acetic acid (40:59:1). The column was washed with 2 Vb of solvent and the resulting fraction discarded. The Avenanthramides were eluted from the column with 2 bed volumes of 80%) aqueous acetone. The sample was evaporated to dryness under reduced pressure and made up in 1:1 aqueous ethanol (5 ml). The sample was filtered through a 0.45 μm filter into a screw-capped vial for HPLC analysis.
ANALYSIS HPLC analysis for total Avenanthramides was conducted using a Thermo Separations Products (TSP) solvent delivery system and Hewlett Packard (HP) data collecting software on a C1 8 CSC HYPERSIL™ column (250×4.6 mm, 120 A, 3 um). An HP photodiode array (PDA) detector monitoring from 190-400 nm, and specifically at 340 nm was used to detect all Avenanthramides. All peaks were integrated using retention times relative to an authentic AF-1 standard (obtained from Agriculture and Agri-Food Canada, ECORC, Ottawa, Canada). The solvent system consisted of acetonitrile, water, and aqueous 5% acetic acid as shown in Table 3.
TABLE 3
5% Acetic
Time (min.)
Acetonitrile
H2O
Acid
0-20
25
70
5
20-25
100
0
0
25-30
25
70
5
30-35
25
70
5
To complete product formulation 3382 ml of permeate feedstream was concentrated to dryness under reduced pressure and made up to 2000 ml (90% aqueous 1,3 butylene glycol) and 0.3% (w/w) phenoxyethanol added. The solution was filtered through a 0.45 μm filter (Whatman) before packaging. The finished oat extract contains 1 Oppm of total Avenanthramides.
EXAMPLE 3
Anti-Erythema Testing in Human Subjects
Skin tests were carried out on healthy male and female volunteers
a. 18 to 60 years of age; b. Fair-skinned with skin types I-III, determined by the following guidelines:
I Always burns easily; never tans (sensitive) II Always burns easily; tans minimally (sensitive) III Bums moderately; tans gradually (normal) IV Bums minimally; always tans well (normal) V Rarely burns; tans profusely (insensitive) VI Never burns; deeply pigmented (insensitive)
The following exclusion criteria were followed:
a. Subjects with a history of abnormal response to sunlight; b. Subjects exhibiting current sunburn, suntan, or even skin tone which might be confused with a reaction from the test material or which might interfere with evaluation of the results of the test; c. Pregnant or lactating females; d. Subjects taking medication which might produce an abnormal response to sunlight or interfere with the results of the test; e. Subjects who regularly use UVA sunbeds; or f. Subjects exhibiting any visible skin disease which could be considered to affect the purpose or integrity of the study.
Nine (9) subjects who met the inclusion criteria were selected for participation.
A xenon arc solar simulator (Solar Light Source, Philadelphia, Pa.) was used as the source of ultra-violet light. A continuous emission spectrum in the UV range (290-400 nanometres) was utilised during the course of this testing procedure. The lamp output was measured with a UV intensity meter (Model PMA 2100) with the appropriate detector attached.
A Minolta CHROMA METER™ CR-300 (Minolta Corporation Ltd., Osaka, Japan) was used to measure erythema levels. The a* value of the L*a*b* colour notation system is indicative of colour changes in the red-green colour axis. The higher the value, the more intensely red the object being evaluated. Therefore, the a* value was used as a measure of redness (erythema) on the skin surface. An increase in a* values is considered indicative of increased erythema.
On day 1 the minimal erythemal dose (MED) of each subject was determined by a progressive sequence of timed UV light exposures, each of which was graduated incrementally by 25% over that of the previous site. An MED is defined as the time interval or dosage of UV light irradiation sufficient to produce a minimal, perceptible erythema on untreated skin.
On day 2 subjects returned to the laboratory approximately 24 hours after irradiation for determination of their MEDs. The sites were evaluated for erythema according to the following visual scoring criteria:
0=negative, no visible reaction 0.5=minimal erythema 1.0=defined erythema 2.0=moderate erythema 3.0=severe erythema
A technician outlined seven 1″×1.5″ test-sites areas on each subject's back, between the scapulae and the belt-line, lateral to the mid-line, with a surgical marking pen. Six test sites were designated for the test materials and one for the untreated irradiated control.
The sites were then exposed to UV light 1.5 times the pre-determined MED values.
On day 3,approximately 24 hours after irradiation, erythema was evaluated and scored visually by a trained technician using the criteria outlined above. Baseline a* value readings were also taken with the Minolta CHROMA METER™. Three consecutive chroma meter readings were taken and averaged.
Approximately 0.2 ml of test product was applied to the appropriate test site. Approximately 4 hours after product application, the test sites were visually scored and Minolta chroma meter reading taken.
On day 4 the subjects returned to the clinic approximately 24 hours after the product application. The 7 sites were again evaluated for erythema using both the visual grading system and the Minolta CHROMA METER™.
The results were subjected to statistical analysis using t-Test (dependent) to determine if any significant differences were observed in the mean chroma meter a* value readings from baseline (24-hours post-irradiation) to 4-hours post-treatment and 24-hours post-treatment, for each test site. Significance was observed if p<0.05.
Product test solutions consisted of oat extract in butylene glycol:water 1:1 w/w adjusted to the required concentration (ppm) of Avenanthramide.
The results of testing oat extract in human volunteers are shown in Table 4.
TABLE 4
Change from
Oat Extract
Average a* Value
Baseline (%)
Avenanthramide
Base-
4
24
4
24
(PPM)
line
Hours
Hours
Hours
Hours
45.0
Site #2
11.47
*10.39
*9.33
−9.4
−18.7
15.0
Site #3
12.47
*11.03
*10.18
−11.5
−18.4
9.0
Site #4
12.65
11.30
*10.19
−10.7
−19.4
1.5
Site #5
12.04
*10.67
*10.35
−11.4
−14.0
0.5
Site #6
12.42
*11.10
11.54
−10.6
−7.1
Untreated
Site #7
13.22
*12.03
12.53
−9.0
−5.2
Irradiated Control
Note:
*denotes statistically significant difference from baseline readings
The tests indicated that the oat extracts were efficient at reducing erythema. The dose response kinetics indicated that between 0.03 and 0.3 ppm the relationship between dose and response was linear. Maximum response was obtained at >0.3 ppm of Avenanthramide.
EXAMPLE 4
Isolation and Purification of an Avenanthramide Fraction
Further to Example 2,the permeate (270 ml) was evaporated under reduced pressure and made-up to 10 mls in 1:1 (v/v) aqueous ethanol. The solution was applied to a LH-20 column (100 ml) pre-equilibrated in ethanol:water:acetic acid (40:59:1). The column was washed with 2 Vb of solvent and the resulting fraction discarded. The Avenanthramides were eluted from the column with two bed volumes of 80% aqueous acetone. The sample was evaporated to dryness under reduced pressure and then redissolved in 100 mls of 90% aqueous butylene glycol. The solution was filtered through a 0.45 μm filter (Whatman Inc.) before packaging. The finished, isolated Avenanthramide fraction contained 15 ppm of total Avenanthramide.
The results of testing the isolated Avenanthramide fraction, oat extract, and untreated control are shown in Table 5.
TABLE 5
Change from
Average a* Value
Baseline (%)
Base-
4
24
4
24
Sample
line
Hours
Hours
Hours
Hours
Isolated
Site #1
12.62
11.95
*10.74
−5.3
−14.9
Avenanthramide
(15.0 ppm
Avenanthramide)
Oat Extract
Site #3
12.47
*11.03
*10.18
−11.5
−18.4
(15.0 ppm
Avenanthramide)
Untreated
Site #7
13.22
*12.03
12.93
−9.0
−5.2
Irradiated Control
Note:
*denotes statistically significant difference from baseline readings
EXAMPLE 5
Rapid Analytical Method for Avenanthramide
High Performance Liquid Chromatography (HPLC) for total Avenanthramides was conducted using a Beckman binary solvent delivery system using 32 KARAT™ analytical software for Microsoft WINDOWS NT™ (Beckman Coulter Inc.). Avenanthramides were separated on a CSC ODS HYPERSIL™ column (250×4.6 mm, 12θ A, 3 μm) using a C 18 guard column (Supelco:Sigma-Aldrich Corporation) at 22 C. A Beckman photodiode array (PDA) detector monitoring from 210-400 nm, and specifically 330 nm was used to detect all Avenanthramides. The peaks of three major Avenanthramides; AF-1, AF-2, and AF-6 were integrated using retention times and spectral data relative to authentic standards synthesized by Dragoco Gerberding & Co. AG.
Extracts were diluted in equal portions with distilled water and stored at 4 C in amber sample vials before analysis. Twenty (20 μl aliquots) were injected in triplicate. The HPLC solvent system consisted of acetonitrile, and 0.01 M aqueous phosphoric acid is shown in Table 6.
TABLE 6
Time (min.)
Acetonitrile (%)
0.01M Phosphoric acid
0
25
75
20
37
63
22
100
0
25
100
0
28
25
75
33
25
75
EXAMPLE 6
Large Scale (Commercial) Production of Oat Extract
Method. Hulless oats, 500 kgs (variety NO141-1) frozen overnight at −18 C. The frozen grain was ground through a FITZ MILL® COMMINUTOR® (The Fitzpatrick Company: Elmhurst, Ill.) equipped with a ⅛ th inch screen to produce a coarse oatmeal (100% passed through a 10 Mesh and <10% passed through a 100 Mesh screen sieve).
The meal was vigorously dispersed in 1500 kg of 50% (w/w) ethanol at 20° C. and mixed for 2-16 hours. The resulting slurry was centrifuged through a decanter centrifuge (Westphalia Separator). The pH of the supernatant was adjusted to pH 2.8±0.5 with hydrochloric acid (17.5% w/w) and stirred for one hour.
The extract was then subjected to ultrafiltration using 5,000 MWCO spiral membrane (21.4 m 2 Synder Filtration, Vacaville, Calif.).
The sterile permeate was next concentrated using reverse osmosis (RO) membrane filtration (15 m 2 FilmTec Corporation, Minneapolis, Minn.). Before RO concentration the pH was adjusted to pH 6±0.5). Following concentration the resulting oat extract had an Avenanthramide concentration of between 200 and 1500 ppm. This extract was found to be stable for more than four months with no loss of activity, clarity or other measurable parameters of product quality.
The high Avenanthramide extract was used as a stock solution for direct use in therapeutic or cosmetic formulations, or alternatively, the ethanol: water was replaced with an alternative solvent for example butylene glycol:water or glycerine:water.
EXAMPLE 7
Formulation of Oat Extract Concentrate into Butylene Glyco Water
A diluent solution was prepared by taking >90% of the required final volume of butylene glycol:water (50% w/w) to which is added the calculated volume of oat extract concentrate. The required volume of concentrate is readily calculated from the values of concentrate Avenanthramide concentration, together with the final desired concentration and volume. Oat extract has been formulated into butylene glycol:water at Avenanthramide concentrations in the range of 15-200 ppm of Avenanthramide.
The product was thoroughly mixed and then heated to 70 C. The product was then passed through an evaporator (Pfaudler, Inc. Wiped Film Evaporator) to remove ethanol. Residual ethanol was tested for using standard gas chromatographic (GC) techniques. Following passage through the evaporator, the butylene glycol:water ratio was checked and adjustments made to account for any loss of water in the evaporator. For cosmetic and therapeutic use the pH of the product was adjusted to pH 6.0-7.5.
Finally, the preservative 2-phenoxyethanol was added (0.3% w/w) to the product. The product was sterilized by membrane filtration. The product Avenanthramide content was then analysed and confirmed to meet the desired product specification.
EXAMPLE 8
Formulation of Oat Extract Concentrate in Glycerine: Water
A diluent solution was prepared by taking >90% of the required final volume of glycerine:water (>30% w/w) to which is added the calculated volume of oat extract concentrate. The required volume of concentrate is readily calculated from the values of concentrate Avenanthramide concentration, together with the final desired concentration and volume. Oat extract has been formulated into glycerine:water at Avenanthramide concentrations in the range of 15-250 ppm of Avenanthramide.
The product was thoroughly mixed and then heated to 70 C. The product was then passed through an evaporator (Pfaudler Wiped Film Evaporator) to remove ethanol. Residual ethanol was tested for using standard gas chromatographic techniques. Following passage through the evaporator, the glycerine:water ratio was checked and adjustments made to account for any loss of water in the evaporator. For cosmetic and therapeutic use the pH of the product was adjusted to pH 6.0-7.5. For functional food/nutraceutical use the pH of the product was adjusted to pH4.0.
Finally, the preservative system consisting potassium sorbate (0.1% w/w) and sodium benzoate (0.1% w/w) was added to the product. The product Avenanthramide content was then analysed and confirmed to meet the desired product specification.
EXAMPLE 9
Hypo-allergenic Shampoo for Veterinary Use
Table 7 presents an example of a therapeutic shampoo formula falling within the scope of the present invention with amounts provided expressed as weight percent.
TABLE 7
Percent
Phase
Material Description
Supplier
by weight
A
Deionised Water
45.65
A
Sequestrene NA3T
Ciba-Geigy
0.05
A
Incromide LR
Croda Inc.
5.00
A
Standapol ES-2
Henkel
28.00
A
Velvetex BA-35
Henkel
8.00
A
Polysorbate 20
ICI
1.50
B
Hydrolysed Oat Protein
Ceapro Inc.
8.00
B
Oat Extract
Ceapro Inc./
3.20
DRAGOCO Gerberding &
Co, AG
B
Oat Beta Glucan
Ceapro Inc./
0.20
DRAGOCO Gerberding &
Co, AG
C
Fragrance
0.20
C
Kathon CG
Rohn and Haas
0.20
Add ingredients in phase A one at a time with medium agitation at room temperature. Ensure each ingredient is dissolved before adding next. The solution should be clear before going onto phase B. In phase B, add ingredients one at a time to phase A with mixing. Add ingredients in phase C one at a time to the mixing phase AB. Adjust the pH with a 50% solution of citric acid until the pH is 6.5.
To use, the product may be either applied directly to the animal or alternatively, mixed with water in a suitable vessel and applied to the animal by sponging. The product rinses easily ensuring that all surfactant is removed after bathing.
The completed shampoo effectively reduced pruritus in animals. Further, the shampoo reduced shedding and scaling.
EXAMPLE 10
Soothing Formula for Veterinary Use in Treating Otitis
Table 8 presents an example of a pharmaceutical cleansing formula falling within the scope of the present invention with amounts provided expressed as weight percent.
TABLE 8
Ingredient
% Formula
Deionised water
46.0
Butylene glycol
48.85
Oat Extract
4.0
Lactic Acid
0.8
Malic Acid
0.2
Methyl Paraben
0.15
The ingredients were added one at a time to a mixing vessel with stirring. Ensure each ingredient is dissolved before adding next. The pH of the finished product was adjusted to 4.0 using 50% malic acid.
The product is for use in cleaning ears in dogs, puppies, cats, and kittens.
To clean the ear, fill the canal with cleanser, flip the ear pinna over, and massage. Take cotton balls and thoroughly remove exudate and dry the accessible portion of the canal. Repeat daily until ear is clean, treat weekly afterwards or as directed by the veterinarian.
Clinical trial results proved the product to be superior in reducing redness associated with otitis and to effectively reduce irritation, promoting the healing of the animal.
Thus, novel methods for producing liquid oat extracts and compositions containing liquid oat extracts are disclosed. Although preferred embodiments of the subject invention have been described in some detail, it is understood that obvious variations can be made without departing from the spirit and scope of the invention defined by the appended claims. | A simple and efficient method for the production of stable, clear, high-potency oat extracts is disclosed. The method employs the use of differential dissociation constants and ultrafiltration to stabilise extracts, prevent hazing, and prevent the loss of functional activity as an anti-irritant and anti-oxidant. Also disclosed are compositions of oat extracts derived from whole oat grains and oatmeal. Further disclosed are compositions of oat extracts for use in cosmetic, nutraceutical, therapeutic medical and veterinary preparations. | 0 |
[0001] This application is a continuation of U.S. patent application Ser. No. 10/152,640 entitled “Delivery of Anti-Migraine Compounds Through an Inhalation Route,” filed May 20, 2002, Rabinowitz and Zaffaroni, which claims priority to U.S. provisional application Serial. No. 60/294,203, entitled “Thermal Vapor Delivery of Drugs,” filed May 24, 2001, Rabinowitz and Zaffaroni and to U.S. provisional application Serial No. 60/317,479, entitled “Aerosol Drug Delivery,” filed Sep. 5, 2001, Rabinowitz and Zaffaroni; the entire disclosures of which are hereby incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to the delivery of anti-migraine compounds through an inhalation route. Specifically, it relates to aerosols containing lidocaine, verapamil, diltiazem, isometheptene, or lisuride that are used in inhalation therapy.
BACKGROUND OF THE INVENTION
[0003] There are a number of compositions currently marketed for the treatment of migraine headaches. The compositions contain at least one active ingredient that provides for observed therapeutic effects. Among the active ingredients given in such anti-migraine compositions are lidocaine, verapamil, diltiazem, isometheptene, and lisuride.
[0004] It is desirable to provide a new route of administration for lidocaine, verapamil, diltiazem, isometheptene, and lisuride that rapidly produces peak plasma concentrations of the compounds. The provision of such a route is an object of the present invention.
SUMMARY OF THE INVENTION
[0005] The present invention relates to the delivery of anti-migraine compounds through an inhalation route. Specifically, it relates to aerosols containing lidocaine, verapamil, diltiazem, isometheptene, or lisuride that are used in inhalation therapy.
[0006] In a composition aspect of the present invention, the aerosol comprises particles comprising at least 5 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride. Preferably, the particles comprise at least 10 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride. More preferably, the particles comprise at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent or 99.97 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride.
[0007] Typically, the aerosol has a mass of at least 10 μg. Preferably, the aerosol has a mass of at least 100 μg. More preferably, the aerosol has a mass of at least 200 μg.
[0008] Typically, the particles comprise less than 10 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride degradation products. Preferably, the particles comprise less than 5 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride degradation products. More preferably, the particles comprise less than 2.5, 1, 0.5, 0.1 or 0.03 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride.
[0009] Typically, the particles comprise less than 90 percent by weight of water. Preferably, the particles comprise less than 80 percent by weight of water. More preferably, the particles comprise less than 70 percent, 60 percent, 50 percent, 40 percent, 30 percent, 20 percent, 10 percent, or 5 percent by weight of water.
[0010] Typically, at least 50 percent by weight of the aerosol is amorphous in form, wherein crystalline forms make up less than 50 percent by weight of the total aerosol weight, regardless of the nature of individual particles. Preferably, at least 75 percent by weight of the aerosol is amorphous in form. More preferably, at least 90 percent by weight of the aerosol is amorphous in form.
[0011] Typically, where the aerosol comprises lidocaine, the aerosol has an inhalable aerosol drug mass density of between 5 mg/L and 100 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 10 mg/L and 60 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 20 mg/L and 40 mg/L.
[0012] Typically, where the aerosol comprises verapamil, the aerosol has an inhalable aerosol drug mass density of between 0.5 mg/L and 50 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 1 mg/L and 20 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 2 mg/L and 10 mg/L.
[0013] Typically, where the aerosol comprises diltiazem, the aerosol has an inhalable aerosol drug mass density of between 2 mg/L and 50 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 5 mg/L and 45 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 10 mg/L and 40 mg/L.
[0014] Typically, where the aerosol comprises isometheptene, the aerosol has an inhalable aerosol drug mass density of between 5 mg/L and 200 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 10 mg/L and 120 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 20 mg/L and 100 mg/L.
[0015] Typically, where the aerosol comprises lisuride, the aerosol has an inhalable aerosol drug mass density of between 0.01 mg/L and 1.0 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 0.05 mg/L and 0.7 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 0.1 mg/L and 0.5 mg/L.
[0016] Typically, the aerosol has an inhalable aerosol particle density greater than 10 6 particles/mL. Preferably, the aerosol has an inhalable aerosol particle density greater than 10 7 particles/mL or 10 8 particles/mL.
[0017] Typically, the aerosol particles have a mass median aerodynamic diameter of less than 5 microns. Preferably, the particles have a mass median aerodynamic diameter of less than 3 microns. More preferably, the particles have a mass median aerodynamic diameter of less than 2 or 1 micron(s).
[0018] Typically, the geometric standard deviation around the mass median aerodynamic diameter of the aerosol particles is less than 3.0. Preferably, the geometric standard deviation is less than 2.5. More preferably, the geometric standard deviation is less than 2.2.
[0019] Typically, the aerosol is formed by heating a composition containing lidocaine, verapamil, diltiazem, isometheptene, or lisuride to form a vapor and subsequently allowing the vapor to condense into an aerosol.
[0020] In a method aspect of the present invention, one of lidocaine, verapamil, diltiazem, isometheptene, or lisuride is delivered to a mammal through an inhalation route. The method comprises: a) heating a composition, wherein the composition comprises at least 5 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride, to form a vapor; and, b) allowing the vapor to cool, thereby forming a condensation aerosol comprising particles, which is inhaled by the mammal. Preferably, the composition that is heated comprises at least 10 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride. More preferably, the composition comprises at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent, 99.9 percent or 99.97 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride.
[0021] Typically, the particles comprise at least 5 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride. Preferably, the particles comprise at least 10 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride. More preferably, the particles comprise at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent, 99.9 percent or 99.97 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride.
[0022] Typically, the condensation aerosol has a mass of at least 10 μg. Preferably, the aerosol has a mass of at least 100 μg. More preferably, the aerosol has a mass of at least 200 μg.
[0023] Typically, the particles comprise less than 10 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride degradation products. Preferably, the particles comprise less than 5 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride degradation products. More preferably, the particles comprise 2.5, 1, 0.5, 0.1 or 0.03 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride degradation products.
[0024] Typically, the particles comprise less than 90 percent by weight of water. Preferably, the particles comprise less than 80 percent by weight of water. More preferably, the particles comprise less than 70 percent, 60 percent, 50 percent, 40 percent, 30 percent, 20 percent, 10 percent, or 5 percent by weight of water.
[0025] Typically, at least 50 percent by weight of the aerosol is amorphous in form, wherein crystalline forms make up less than 50 percent by weight of the total aerosol weight, regardless of the nature of individual particles. Preferably, at least 75 percent by weight of the aerosol is amorphous in form. More preferably, at least 90 percent by weight of the aerosol is amorphous in form.
[0026] Typically, the particles of the delivered condensation aerosol have a mass median aerodynamic diameter of less than 5 microns. Preferably, the particles have a mass median aerodynamic diameter of less than 3 microns. More preferably, the particles have a mass median aerodynamic diameter of less than 2 or 1 micron(s).
[0027] Typically, the geometric standard deviation around the mass median aerodynamic diameter of the aerosol particles is less than 3.0. Preferably, the geometric standard deviation is less than 2.5. More preferably, the geometric standard deviation is less than 2.2.
[0028] Typically, where the aerosol comprises lidocaine, the delivered aerosol has an inhalable aerosol drug mass density of between 5 mg/L and 100 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 10 mg/L and 60 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 20 mg/L and 40 mg/L.
[0029] Typically, where the aerosol comprises verapamil, the delivered aerosol has an inhalable aerosol drug mass density of between 0.5 mg/L and 50 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 1.0 mg/L and 20 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 2 mg/L and 10 mg/L.
[0030] Typically, where the aerosol comprises diltiazem, the delivered aerosol has an inhalable aerosol drug mass density of between 2 mg/L and 50 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 5 mg/L and 45 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 10 mg/L and 40 mg/L.
[0031] Typically, where the aerosol comprises isometheptene, the delivered aerosol has an inhalable aerosol drug mass density of between 5 mg/L and 200 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 10 mg/L and 120 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 20 mg/L and 100 mg/L.
[0032] Typically, where the aerosol comprises lisuride, the delivered aerosol has an inhalable aerosol drug mass density of between 0.01 mg/L and 1.0 mg/L. Preferably, the aerosol has an inhalable aerosol drug mass density of between 0.05 mg/L and 0.7 mg/L. More preferably, the aerosol has an inhalable aerosol drug mass density of between 0.1 mg/L and 0.5 mg/L.
[0033] Typically, the delivered aerosol has an inhalable aerosol particle density greater than 10 6 particles/mL. Preferably, the aerosol has an inhalable aerosol particle density greater than 10 7 particles/mL or 10 8 particles/mL.
[0034] Typically, the rate of inhalable aerosol particle formation of the delivered condensation aerosol is greater than 10 8 particles per second. Preferably, the aerosol is formed at a rate greater than 10 9 inhalable particles per second. More preferably, the aerosol is formed at a rate greater than 10 10 inhalable particles per second.
[0035] Typically, the delivered condensation aerosol is formed at a rate greater than 0.5 mg/second. Preferably, the aerosol is formed at a rate greater than 0.75 mg/second. More preferably, the aerosol is formed at a rate greater than 1 mg/second, 1.5 mg/second or 2 mg/second.
[0036] Typically, where the condensation aerosol comprises lidocaine, between 5 mg and 100 mg of lidocaine are delivered to the mammal in a single inspiration. Preferably, between 10 mg and 60 mg of lidocaine are delivered to the mammal in a single inspiration. More preferably, between 20 mg and 40 mg of lidocaine are delivered in a single inspiration.
[0037] Typically, where the condensation aerosol comprises verapamil, between 0.5 mg and 50 mg of verapamil are delivered to the mammal in a single inspiration. Preferably, between 1.0 mg and 20 mg of verapamil are delivered to the mammal in a single inspiration. More preferably, between 2.0 mg and 10 mg of verapamil are delivered in a single inspiration.
[0038] Typically, where the condensation aerosol comprises diltiazem, between 2.0 mg and 50 mg of diltiazem are delivered to the mammal in a single inspiration. Preferably, between 5 mg and 45 mg of diltiazem are delivered to the mammal in a single inspiration. More preferably, between 10 mg and 40 mg of diltiazem are delivered in a single inspiration.
[0039] Typically, where the condensation aerosol comprises isometheptene, between 5 mg and 200 mg of isometheptene are delivered to the mammal in a single inspiration. Preferably, between 10 mg and 120 mg of isometheptene are delivered to the mammal in a single inspiration. More preferably, between 20 mg and 100 mg of isometheptene are delivered in a single inspiration.
[0040] Typically, where the condensation aerosol comprises lisuride, between 0.1 mg and 1.0 mg of lisuride are delivered to the mammal in a single inspiration. Preferably, between 0.05 mg and 0.7 mg of lisuride are delivered to the mammal in a single inspiration. More preferably, between 0.1 mg and 0.5 mg of lisuride are delivered in a single inspiration.
[0041] Typically, the delivered condensation aerosol results in a peak plasma concentration of lidocaine, verapamil, diltiazem, isometheptene, or lisuride in the mammal in less than 1 h. Preferably, the peak plasma concentration is reached in less than 0.5 h. More preferably, the peak plasma concentration is reached in less than 0.2, 0.1, 0.05, 0.02, 0.01, or 0.005 h (arterial measurement).
[0042] In a kit aspect of the present invention, a kit for delivering lidocaine, verapamil, diltiazem, isometheptene, or lisuride through an inhalation route to a mammal is provided which comprises: a) a composition comprising at least 5 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride; and, b) a device that forms a lidocaine, verapamil, diltiazem, isometheptene, or lisuride aerosol from the composition, for inhalation by the mammal. Preferably, the composition comprises at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent, 90 percent, 95 percent, 97 percent, 99 percent, 99.5 percent, 99.9 percent or 99.97 percent by weight of lidocaine, verapamil, diltiazem, isometheptene, or lisuride.
[0043] Typically, the device contained in the kit comprises: a) an element for heating the lidocaine, verapamil, diltiazem, isometheptene, or lisuride composition to form a vapor; b) an element allowing the vapor to cool to form an aerosol; and, c) an element permitting the mammal to inhale the aerosol.
BRIEF DESCRIPTION OF THE FIGURE
[0044] [0044]FIG. 1 shows a cross-sectional view of a device used to deliver lidocaine, verapamil, diltiazem, isometheptene, or lisuride aerosols to a mammal through an inhalation route.
DETAILED DESCRIPTION OF THE INVENTION
[0045] Definitions
[0046] “Aerodynamic diameter” of a given particle refers to the diameter of a spherical droplet with a density of 1 g/mL (the density of water) that has the same settling velocity as the given particle.
[0047] “Aerosol” refers to a suspension of solid or liquid particles in a gas.
[0048] “Aerosol drug mass density” refers to the mass of lidocaine, verapamil, diltiazem, isometheptene, or lisuride per unit volume of aerosol.
[0049] “Aerosol mass density” refers to the mass of particulate matter per unit volume of aerosol.
[0050] “Aerosol particle density” refers to the number of particles per unit volume of aerosol.
[0051] “Amorphous particle” refers to a particle that does not contain more than 50 percent by weight of a crystalline form. Preferably, the particle does not contain more than 25 percent by weight of a crystalline form. More preferably, the particle does not contain more than 10 percent by weight of a crystalline form.
[0052] “Condensation aerosol” refers to an aerosol formed by vaporization of a substance followed by condensation of the substance into an aerosol.
[0053] “Diltiazem” refers to 3-(acetyloxy)-5-[2-(dimethylamino)-ethyl]-2,3-dihydro-2-(4-methoxyphenyl)-1,5-benzothiazepin-4(5H)-one.
[0054] “Diltiazem degradation product” refers to a compound resulting from a chemical modification of diltiazem. The modification, for example, can be the result of a thermally or photochemically induced reaction. Such reactions include, without limitation, oxidation and hydrolysis.
[0055] “Inhalable aerosol drug mass density” refers to the aerosol drug mass density produced by an inhalation device and delivered into a typical patient tidal volume.
[0056] “Inhalable aerosol mass density” refers to the aerosol mass density produced by an inhalation device and delivered into a typical patient tidal volume.
[0057] “Inhalable aerosol particle density” refers to the aerosol particle density of particles of size between 100 nm and 5 microns produced by an inhalation device and delivered into a typical patient tidal volume.
[0058] “Isometheptene” refers to 6-methylamino-2-methylheptene.
[0059] “Isometheptene degradation product” refers to a compound resulting from a chemical modification of isometheptene. The modification, for example, can be the result of a thermally or photochemically induced reaction. Such reactions include, without limitation, oxidation and hydrolysis.
[0060] “Lidocaine” refers to 2-(diethylamino)-N-(2,6-dimethyl-phenyl)acetamide.
[0061] “Lidocaine degradation product” refers to a compound resulting from a chemical modification of lidocaine. The modification, for example, can be the result of a thermally or photochemically induced reaction. Such reactions include, without limitation, oxidation and hydrolysis. An example of a degradation product is 2,6-dimethylaniline (C 8 H 11 N).
[0062] “Lisuride” refers to N′-[(8α)-9,10-didehydro-6-methylergolin-8-yl]-N,N-diethylurea.
[0063] “Lisuride degradation product” refers to a compound resulting from a chemical modification of lisuride. The modification, for example, can be the result of a thermally or photochemically induced reaction. Such reactions include, without limitation, oxidation and hydrolysis.
[0064] “Mass median aerodynamic diameter” or “MMAD” of an aerosol refers to the aerodynamic diameter for which half the particulate mass of the aerosol is contributed by particles with an aerodynamic diameter larger than the MMAD and half by particles with an aerodynamic diameter smaller than the MMAD.
[0065] “Rate of aerosol formation” refers to the mass of aerosolized particulate matter produced by an inhalation device per unit time.
[0066] “Rate of inhalable aerosol particle formation” refers to the number of particles of size between 100 nm and 5 microns produced by an inhalation device per unit time.
[0067] “Rate of drug aerosol formation” refers to the mass of aerosolized lidocaine, verapamil, diltiazem, isometheptene, or lisuride produced by an inhalation device per unit time.
[0068] “Settling velocity” refers to the terminal velocity of an aerosol particle undergoing gravitational settling in air.
[0069] “Typical patient tidal volume” refers to 1 L for an adult patient and 15 mL/kg for a pediatric patient.
[0070] “Vapor” refers to a gas, and “vapor phase” refers to a gas phase. The term “thermal vapor” refers to a vapor phase, aerosol, or mixture of aerosol-vapor phases, formed preferably by heating.
[0071] “Verapamil” refers to α-[3-[[2-(3,4-dimethoxyphenyl)ethyl]-methylamino]-propyl]-3,4-dimethoxy-α-(1-methylethyl)benzeneacetonitrile.
[0072] “Verapamil degradation product” refers to a compound resulting from a chemical modification of verapamil. The modification, for example, can be the result of a thermally or photochemically induced reaction. Such reactions include, without limitation, oxidation and hydrolysis.
[0073] Formation of Lidocaine, Verapamil, Diltiazem, Isometheptene, or Lisuride Containing Aerosols
[0074] Any suitable method is used to form the aerosols of the present invention. A preferred method, however, involves heating a composition comprising lidocaine, verapamil, diltiazem, isometheptene, or lisuride to form a vapor, followed by cooling of the vapor such that it condenses to provide a lidocaine, verapamil, diltiazem, isometheptene, or lisuride comprising aerosol (condensation aerosol). The composition is heated in one of four forms: as pure active compound (i.e., pure lidocaine, verapamil, diltiazem, isometheptene, or lisuride); as a mixture of active compound and a pharmaceutically acceptable excipient; as a salt form of the pure active compound; and, as a mixture of active compound salt form and a pharmaceutically acceptable excipient.
[0075] Salt forms of lidocaine, verapamil, diltiazem, isometheptene, or lisuride are either commercially available or are obtained from the corresponding free base using well known methods in the art. A variety of pharmaceutically acceptable salts are suitable for aerosolization. Such salts include, without limitation, the following: hydrochloric acid, hydrobromic acid, acetic acid, maleic acid, formic acid, and fumaric acid salts.
[0076] Pharmaceutically acceptable excipients may be volatile or nonvolatile. Volatile excipients, when heated, are concurrently volatilized, aerosolized and inhaled with lidocaine, verapamil, diltiazem, isometheptene, or lisuride. Classes of such excipients are known in the art and include, without limitation, gaseous, supercritical fluid, liquid and solid solvents. The following is a list of exemplary carriers within the classes: water; terpenes, such as menthol; alcohols, such as ethanol, propylene glycol, glycerol and other similar alcohols; dimethylformamide; dimethylacetamide; wax; supercritical carbon dioxide; dry ice; and mixtures thereof.
[0077] Solid supports on which the composition is heated are of a variety of shapes. Examples of such shapes include, without limitation, cylinders of less than 1.0 mm in diameter, boxes of less than 1.0 mm thickness and virtually any shape permeated by small (e.g., less than 1.0 mm-sized) pores. Preferably, solid supports provide a large surface to volume ratio (e.g., greater than 100 per meter) and a large surface to mass ratio (e.g., greater than 1 cm 2 per gram).
[0078] A solid support of one shape can also be transformed into another shape with different properties. For example, a flat sheet of 0.25 mm thickness has a surface to volume ratio of approximately 8,000 per meter. Rolling the sheet into a hollow cylinder of 1 cm diameter produces a support that retains the high surface to mass ratio of the original sheet but has a lower surface to volume ratio (about 400 per meter).
[0079] A number of different materials are used to construct the solid supports. Classes of such materials include, without limitation, metals, inorganic materials, carbonaceous materials and polymers. The following are examples of the material classes: aluminum, silver, gold, stainless steel, copper and tungsten; silica, glass, silicon and alumina; graphite, porous carbons, carbon yarns and carbon felts; polytetrafluoroethylene and polyethylene glycol. Combinations of materials and coated variants of materials are used as well.
[0080] Where aluminum is used as a solid support, aluminum foil is a suitable material. Examples of silica, alumina and silicon based materials include amphorous silica S-5631 (Sigma, St. Louis, Mo.), BCR171 (an alumina of defined surface area greater than 2 m 2 /g from Aldrich, St. Louis, Mo.) and a silicon wafer as used in the semiconductor industry. Carbon yarns and felts are available from American Kynol, Inc., New York, N.Y. Chromatography resins such as octadecycl silane chemically bonded to porous silica are exemplary coated variants of silica.
[0081] The heating of the lidocaine, verapamil, diltiazem, isometheptene, or lisuride compositions is performed using any suitable method. Examples of methods by which heat can be generated include the following: passage of current through an electrical resistance element; absorption of electromagnetic radiation, such as microwave or laser light; and, exothermic chemical reactions, such as exothermic solvation, hydration of pyrophoric materials and oxidation of combustible materials.
[0082] Delivery of Lidocaine, Verapamil, Diltiazem, Isometheptene, or Lisuride Containing Aerosols
[0083] Lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosols of the present invention are delivered to a mammal using an inhalation device. Where the aerosolis a condensation aerosol, the device has at least three elements: an element for heating a lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing composition to form a vapor; an element allowing the vapor to cool, thereby providing a condensation aerosol; and, an element permitting the mammal to inhale the aerosol. Various suitable heating methods are described above. The element that allows cooling is, in it simplest form, an inert passageway linking the heating means to the inhalation means. The element permitting inhalation is an aerosol exit portal that forms a connection between the cooling element and the mammal's respiratory system.
[0084] One device used to deliver the lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosol is described in reference to FIG. 1. Delivery device 100 has a proximal end 102 and a distal end 104 , a heating module 106 , a power source 108 , and a mouthpiece 110 . A lidocaine, verapamil, diltiazem, isometheptene, or lisuride composition is deposited on a surface 112 of heating module 106 . Upon activation of a user activated switch 114 , power source 108 initiates heating of heating module 106 (e.g, through ignition of combustible fuel or passage of current through a resistive heating element). The lidocaine, verapamil, diltiazem, isometheptene, or lisuride composition volatilizes due to the heating of heating module 106 and condenses to form a condensation aerosol prior to reaching the mouthpiece 110 at the proximal end of the device 102 . Air flow traveling from the device distal end 104 to the mouthpiece 110 carries the condensation aerosol to the mouthpiece 110 , where it is inhaled by the mammal.
[0085] Devices, if desired, contain a variety of components to facilitate the delivery of lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosols. For instance, the device may include any component known in the art to control the timing of drug aerosolization relative to inhalation (e.g., breath-actuation), to provide feedback to patients on the rate and/or volume of inhalation, to prevent excessive use (i.e., “lock-out” feature), to prevent use by unauthorized individuals, and/or to record dosing histories.
[0086] Dosage of Lidocaine, Verapamil, Diltiazem, Isometheptene, or Lisuride Containing Aerosols
[0087] Lidocaine, verapamil, diltiazem, isometheptene, or lisuride are given at strengths of 30 mg, 40 mg, 30 mg, 65 mg, and 0.2 mg respectively for the treatment of migraine headaches. As aerosols, 10 mg to 50 mg of lidocaine, 10 mg to 60 mg of verapamil, 10 mg to 50 mg of diltiazem, 5 mg to 200 mg of isometheptene, and 0.05 mg to 0.4 mg lisuride are generally provided for the same indication. A typical dosage of a lidocaine, verapamil, diltiazem, isometheptene, or lisuride aerosol is either administered as a single inhalation or as a series of inhalations taken within an hour or less (dosage equals sum of inhaled amounts). Where the drug is administered as a series of inhalations, a different amount may be delivered in each inhalation. The dosage amount of lidocaine, verapamil, diltiazem, isometheptene, or lisuride in aerosol form is generally no greater than twice the standard dose of the drug given orally.
[0088] One can determine the appropriate dose of lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosols to treat a particular condition using methods such as animal experiments and a dose-finding (Phase I/II) clinical trial. One animal experiment involves measuring plasma concentrations of drug in an animal after its exposure to the aerosol. Mammals such as dogs or primates are typically used in such studies, since their respiratory systems are similar to that of a human. Initial dose levels for testing in humans is generally less than or equal to the dose in the mammal model that resulted in plasma drug levels associated with a therapeutic effect in humans. Dose escalation in humans is then performed, until either an optimal therapeutic response is obtained or a dose-limiting toxicity is encountered.
[0089] Analysis of Lidocaine, Verapamil, Diltiazem, Isometheptene, or Lisuride Containing Aerosols
[0090] Purity of a lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosol is determined using a number of methods, examples of which are described in Sekine et al., Journal of Forensic Science 32:1271-1280 (1987) and Martin et al., Journal of Analytic Toxicology 13:158-162 (1989). One method involves forming the aerosol in a device through which a gas flow (e.g., air flow) is maintained, generally at a rate between 0.4 and 60 L/min. The gas flow carries the aerosol into one or more traps. After isolation from the trap, the aerosol is subjected to an analytical technique, such as gas or liquid chromatography, that permits a determination of composition purity.
[0091] A variety of different traps are used for aerosol collection. The following list contains examples of such traps: filters; glass wool; impingers; solvent traps, such as dry ice-cooled ethanol, methanol, acetone and dichloromethane traps at various pH values; syringes that sample the aerosol; empty, low-pressure (e.g., vacuum) containers into which the aerosol is drawn; and, empty containers that fully surround and enclose the aerosol generating device. Where a solid such as glass wool is used, it is typically extracted with a solvent such as ethanol. The solvent extract is subjected to analysis rather than the solid (i.e., glass wool) itself. Where a syringe or container is used, the container is similarly extracted with a solvent.
[0092] The gas or liquid chromatograph discussed above contains a detection system (i.e., detector). Such detection systems are well known in the art and include, for example, flame ionization, photon absorption and mass spectrometry detectors. An advantage of a mass spectrometry detector is that it can be used to determine the structure of lidocaine, verapamil, diltiazem, isometheptene, or lisuride degradation products.
[0093] Particle size distribution of a lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosol is determined using any suitable method in the art (e.g., cascade impaction). An Andersen Eight Stage Non-viable Cascade Impactor (Andersen Instruments, Smyrna, Ga.) linked to a furnace tube by a mock throat (USP throat, Andersen Instruments, Smyrna, Ga.) is one system used for cascade impaction studies.
[0094] Inhalable aerosol mass density is determined, for example, by delivering a drug-containing aerosol into a confined chamber via an inhalation device and measuring the mass collected in the chamber. Typically, the aerosol is drawn into the chamber by having a pressure gradient between the device and the chamber, wherein the chamber is at lower pressure than the device. The volume of the chamber should approximate the tidal volume of an inhaling patient.
[0095] Inhalable aerosol drug mass density is determined, for example, by delivering a drug-containing aerosol into a confined chamber via an inhalation device and measuring the amount of active drug compound collected in the chamber. Typically, the aerosol is drawn into the chamber by having a pressure gradient between the device and the chamber, wherein the chamber is at lower pressure than the device. The volume of the chamber should approximate the tidal volume of an inhaling patient. The amount of active drug compound collected in the chamber is determined by extracting the chamber, conducting chromatographic analysis of the extract and comparing the results of the chromatographic analysis to those of a standard containing known amounts of drug.
[0096] Inhalable aerosol particle density is determined, for example, by delivering aerosol phase drug into a confined chamber via an inhalation device and measuring the number of particles of given size collected in the chamber. The number of particles of a given size may be directly measured based on the light-scattering properties of the particles. Alternatively, the number of particles of a given size is determined by measuring the mass of particles within the given size range and calculating the number of particles based on the mass as follows: Total number of particles=Sum (from size range 1 to size range N) of number of particles in each size range. Number of particles in a given size range=Mass in the size range/Mass of a typical particle in the size range. Mass of a typical particle in a given size range=π*D 3 *φ/6, where D is a typical particle diameter in the size range (generally, the mean boundary MMADs defining the size range) in microns, φ is the particle density (in g/mL) and mass is given in units of picograms (g −12 ).
[0097] Rate of inhalable aerosol particle formation is determined, for example, by delivering aerosol phase drug into a confined chamber via an inhalation device. The delivery is for a set period of time (e.g., 3 s), and the number of particles of a given size collected in the chamber is determined as outlined above. The rate of particle formation is equal to the number of 100 nm to 5 micron particles collected divided by the duration of the collection time.
[0098] Rate of aerosol formation is determined, for example, by delivering aerosol phase drug into a confined chamber via an inhalation device. The delivery is for a set period of time (e.g., 3 s), and the mass of particulate matter collected is determined by weighing the confined chamber before and after the delivery of the particulate matter. The rate of aerosol formation is equal to the increase in mass in the chamber divided by the duration of the collection time. Alternatively, where a change in mass of the delivery device or component thereof can only occur through release of the aerosol phase particulate matter, the mass of particulate matter may be equated with the mass lost from the device or component during the delivery of the aerosol. In this case, the rate of aerosol formation is equal to the decrease in mass of the device or component during the delivery event divided by the duration of the delivery event.
[0099] Rate of drug aerosol formation is determined, for example, by delivering a lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosol into a confined chamber via an inhalation device over a set period of time (e.g., 3 s). Where the aerosol is pure lidocaine, verapamil, diltiazem, isometheptene, or lisuride, the amount of drug collected in the chamber is measured as described above. The rate of drug aerosol formation is equal to the amount of lidocaine, verapamil, diltiazem, isometheptene, or lisuride collected in the chamber divided by the duration of the collection time. Where the lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosol comprises a pharmaceutically acceptable excipient, multiplying the rate of aerosol formation by the percentage of lidocaine, verapamil, diltiazem, isometheptene, or lisuride in the aerosol provides the rate of drug aerosol formation.
[0100] Utility of Lidocaine, Verapamil, Diltiazem, Isometheptene, or Lisuride Containing Aerosols
[0101] The lidocaine, verapamil, diltiazem, isometheptene, or lisuride containing aerosols of the present invention are typically used for the treatment of migraine headaches.
[0102] The following examples are meant to illustrate, rather than limit, the present invention.
[0103] Lidocaine, verapamil hydrochloride, diltiazem hydrochloride, and lisuride are commercially available from Sigma (www.sigma-aldrich.com). The preparation of isometheptene is described in U.S. Pat. Nos. 2,230,753 and 2,230,754.
EXAMPLE 1
General Procedure for Obtaining Free Base of a Compound Salt
[0104] Approximately 1 g of salt (e.g., mono hydrochloride) is dissolved in deionized water (˜30 mL). Three equivalents of sodium hydroxide (1 N NaOH aq ) is added dropwise to the solution, and the pH is checked to ensure it is basic. The aqueous solution is extracted four times with dichloromethane (˜50 mL), and the extracts are combined, dried (Na 2 SO 4 ) and filtered. The filtered organic solution is concentrated using a rotary evaporator to provide the desired free base. If necessary, purification of the free base is performed using standard methods such as chromatography or recrystallization.
EXAMPLE 2
General Procedure for Volatilizing Compounds from Halogen Bulb
[0105] A solution of drug in approximately 120 μL dichloromethane is coated on a 3.5 cm ×7.5 cm piece of aluminum foil (precleaned with acetone). The dichloromethane is allowed to evaporate. The coated foil is wrapped around a 300 watt halogen tube (Feit Electric Company, Pico Rivera, Calif.), which is inserted into a glass tube sealed at one end with a rubber stopper. Running 90 V of alternating current (driven by line power controlled by a variac) through the bulb for 5 s or 3.5 s affords thermal vapor (including aerosol), which is collected on the glass tube walls. Reverse-phase HPLC analysis with detection by absorption of 225 nm light is used to determine the purity of the aerosol. (When desired, the system is flushed through with argon prior to volatilization.) To obtain higher purity aerosols, one can coat a lesser amount of drug, yielding a thinner film to heat. A linear decrease in film thickness is associated with a linear decrease in impurities.
[0106] The following aerosols were obtained using this procedure: lidocaine aerosol (7.3 mg, 99.5% purity); verapamil aerosol (1.41 mg, 96.2% purity); diltiazem aerosol (1.91 mg, 97.1% purity); and, lisuride aerosol (0.2 mg, 100% purity).
EXAMPLE 3
Particle Size, Particle Density, and Rate of Inhalable Particle Formation of Lidocaine Aerosol
[0107] A solution of 12.2 mg lidocaine in 100 μL dichloromethane was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were sealed with parafilm, which was punctured with fifteen needles for air flow. The third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within 1 s, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with collection of the aerosol terminated after 6 s. The aerosol was analyzed by connecting the 1 L flask to an eight-stage Andersen non-viable cascade impactor. Results are shown in table 1. MMAD of the collected aerosol was 2.4 microns with a geometric standard deviation of 2.1. Also shown in table 1 is the number of particles collected on the various stages of the cascade impactor, given by the mass collected on the stage divided by the mass of a typical particle trapped on that stage. The mass of a single particle of diameter D is given by the volume of the particle, πD 3 /6, multiplied by the density of the drug (taken to be 1 g/cm 3 ). The inhalable aerosol particle density is the sum of the numbers of particles collected on impactor stages 3 to 8 divided by the collection volume of 1 L, giving an inhalable aerosol particle density of 4.2×10 6 particles/mL. The rate of inhalable aerosol particle formation is the sum of the numbers of particles collected on impactor stages 3 through 8 divided by the formation time of 6 s, giving a rate of inhalable aerosol particle formation of 7.0×10 8 particles/second.
TABLE 1 Determination of the characteristics of a lidocaine condensation aerosol by cascade impaction using an Andersen 8-stage non-viable cascade impactor run at 1 cubic foot per minute air flow. Mass Particle size range Average particle collected Number of Stage (microns) size (microns) (mg) particles 0 9.0-10.0 9.5 0.1 2.2 × 10 5 1 5.8-9.0 7.4 0.3 1.4 × 10 6 2 4.7-5.8 5.25 0.1 1.3 × 10 6 3 3.3-4.7 4.0 0.7 2.1 × 10 7 4 2.1-3.3 2.7 0.9 8.7 × 10 7 5 1.1-2.1 1.6 1.0 4.7 × 10 8 6 0.7-1.1 0.9 0.5 1.3 × 10 9 7 0.4-0.7 0.55 0.2 2.3 × 10 9 8 0-0.4 0.2 0.0 0
EXAMPLE 4
Drug Mass Density and Rate of Drug Aerosol Formation of Lidocaine Aerosol
[0108] A solution of 10.4 mg lidocaine in 100 μL dichloromethane was spread out in a thin layer on the central portion of a 3.5 cm×7 cm sheet of aluminum foil. The dichloromethane was allowed to evaporate. The aluminum foil was wrapped around a 300 watt halogen tube, which was inserted into a T-shaped glass tube. Both of the openings of the tube were sealed with parafilm, which was punctured with fifteen needles for air flow. The third opening was connected to a 1 liter, 3-neck glass flask. The glass flask was further connected to a large piston capable of drawing 1.1 liters of air through the flask. Alternating current was run through the halogen bulb by application of 90 V using a variac connected to 110 V line power. Within seconds, an aerosol appeared and was drawn into the 1 L flask by use of the piston, with formation of the aerosol terminated after 6 s. The aerosol was allowed to sediment onto the walls of the 1 L flask for approximately 30 minutes. The flask was then extracted with acetonitrile and the extract analyzed by HPLC with detection by light absorption at 225 nm. Comparison with standards containing known amounts of lidocaine revealed that 3.1 mg of >99% pure lidocaine had been collected in the flask, resulting in an aerosol drug mass density of 3.1 mg/L. The aluminum foil upon which the lidocaine had previously been coated was weighed following the experiment. Of the 10.4 mg originally coated on the aluminum, 10.2 mg of the material was found to have aerosolized in the 6 s time period, implying a rate of drug aerosol formation of 1.7 mg/s. | The present invention relates to the delivery of anti-migraine compounds through an inhalation route. Specifically, it relates to aerosols containing lidocaine, verapamil, diltiazem, isometheptene, or lisuride that are used in inhalation therapy. In a method aspect of the present invention, lidocaine, verapamil, diltiazem, isometheptene, or lisuride is administered to a patient through an inhalation route. The method comprises: a) heating a composition of lidocaine, verapamil, diltiazem, isometheptene, or lisuride, to form a vapor; and, b) allowing the vapor to cool, thereby forming a condensation aerosol comprising particles with less than 5% drug degradation products. In a kit aspect of the present invention, a kit for delivering lidocaine, verapamil, diltiazem, isometheptene, or lisuride through an inhalation route is provided which comprises: a) a thin coating of a lidocaine, verapamil, diltiazem, isometheptene, or lisuride composition and b) a device for dispensing said thin coating as a condensation aerosol. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 08/584,942 abandoned, filed Jan. 16, 1996.
TECHNICAL FIELD
This invention relates to novel chemical formulations useful for simultaneous cleaning and disinfecting surfaces, especially porous surfaces, such as acoustic ceiling tiles in hospitals and other medical and dental facilities, etc., where at least a virtual 100% kill rate of bacteria and fungi is desired. More particularly, the present invention relates to potentiated disinfectant cleaning solutions comprising as active working ingredients a quaternary ammonium compound, a compatible surfactant other than a quaternary ammonium compound, such as a non-ionic or amphoteric surface active agent, and a solution of hydrogen peroxide. The active ingredients are present in minimal proportional ranges sufficient to achieve a virtual 100 percent kill of the microbes, e.g., bacteria and fungi present.
Furthermore, the invention relates to processes of disinfecting contaminated surfaces/substrates with the foregoing anti-microbial cleaning solutions wherein virtually 100% of bacteria and fungi are destroyed, resulting in the restoration and extension of the useful life of the treated surfaces/substrates.
BACKGROUND OF THE INVENTION
Disinfection of building interiors and other surfaces is a major concern in hospitals and other health care facilities where the presence of unwanted bacteria may be detrimental to the health of patients and workers. Health care facilities are not alone in their concern for elimination of harmful bacteria and fungi. Surfaces harboring undesirable microorganisms can pose a health threat in schools, office buildings and homes. For that reason, it is highly desirable to disinfect all surfaces in such facilities to remove as many harmful organisms as possible.
A common building surface of particular concern is ceiling tiles. Because of their porosity, ceiling tiles are particularly susceptible to harboring harmful bacteria and other microorganisms, and they are especially difficult to clean. In many instances, cleaning and disinfecting the tiles involves removing the tiles and exposing them to time consuming treatments with bactericidal agents. Even after such treatment significant amounts of bacteria and fungi can remain in the tiles and replicate.
Cleaning compositions exist which can achieve high kill rates of some harmful microorganisms. However, these compositions tend to have relatively high concentrations of toxic ingredients. Safe application of these compositions often requires special handling procedures and precautions. These can include use of protective equipment, such as safety goggles, gloves, coveralls, face masks, and the like. In many cases, additional ventilation of the space being disinfected is essential during and after application of these compositions.
Hydrogen peroxide (H 2 O 2 ) has been proposed as a bactericide and has been used for many years as a topical antiseptic, especially as a 3% aqueous solution. Addition of ferric or cupric ions, potassium dichromate, cobaltous sulfate, or manganous sulfate is known to enhance the bactericidal action of H 2 O 2 .
However, H 2 O 2 suffers from the disadvantage that by itself it is relatively inefficient and is not a potent fungicide. Further, H 2 O 2 especially at higher concentrations is irritating to the skin, eyes, and mucous membranes. Health and safety hazards associated with the use of solutions containing H 2 O 2 increase as the concentration of H 2 O 2 in the solutions increases. It is therefore desirable that disinfecting solutions contain the lowest possible concentrations of H 2 O 2 .
Processes and compositions for the disinfection of aqueous media employing hydrogen peroxide are disclosed in U.S. Pat. No. 4,311,598 to Verachtert. The disinfectant comprises a combination of hydrogen peroxide, a soluble copper salt, such as copper sulphate and an autoxisable reducing agent such as ascorbic acid or sodium sulphite. While these compositions appear to be relatively effective in killing bacteria in some aqueous solutions, they are not efficacious fungicides. Nor has their efficacy on surfaces been demonstrated.
Quaternary ammonium compounds, usually tetrasubstituted ammonium salts, have been reported for use as bacteristats, bactericides, and algaecides. Those used as bacteristats and bactericides have required relatively high levels to be effective or have required prolonged contact times.
Examples of references describing the use of quaternary ammonium compounds include U.S. Pat. No. 5,373,025 to Gay which discloses a sanitizer for swimming pools, spas and hot tubs comprising a quaternary ammonium compound and a copper ion source.
Examples of publications disclosing sanitizers combining peroxides with quaternary ammonium compounds include U.S. Pat. No. 5,348,556 to Minns et al. This patent discloses an aqueous composition which cleans and sanitizes carpets, and the like. In general, the compositions contain peroxide in concentrations of about 3% to about 30%, in combination with a volatile ammoniated substance, including tetra butyl ammonium hydroxide, in an amount of about 0.1% to 5%. However, the Minns et al patent does not disclose a fungicide, nor are the compositions disclosed as providing at least a virtual 100% kill rate of bacteria.
U.S. Pat. No. 4,397,757 to Bright et al discloses bleaching and detergent compositions containing hydrogen peroxide and quaternary ammonium activators. While the compositions of the Bright et al patent are disclosed to be effective as whiteners and cleaners, such compositions are not intended to provide high kill rates of bacteria and fungi.
Other patents of interest employing quaternary ammonium compounds are U.S. Pat. Nos. 4,941,989 and 5,320,805 both to Kramer et al. Each of the Kramer patents discloses a variety of compositions, all characterized as prepared from alkaline water soluble “per salts”, preferably from 10 to 90% by weight sodium percarbonate (2Na 2 CO 3 .3H 2 O 2 ); from a fraction of a percent to about 30% by weight of a positively charged phase transfer agent, preferably a quaternary ammonium salt, and a surfactant within a range of about 0.25 to 20% by weight.
According to the Kramer et al patents, the alkaline per salt is dissolved in an aqueous solution of the positively charged quaternary ammonium phase transfer agent to extract a proton from the per salt. According to the express teachings of Kramer et al, in order for the reaction to occur the aqueous medium is required to have a rather high pH of at least 9.5. This high pH is readily attained because per salts, such as sodium percarbonate also yield alkaline sodium carbonate when in water. Such aqueous compositions will typically have pHs in the range of 10 to 11, or more.
While such solutions, according to the Kramer patents, yield hydroperoxide ions, HO 2 − , to become associated with the positively charged quarternary ammonium ion, it was found that any residual molecular hydrogen peroxide which might otherwise remain in the alkaline solution rapidly breaks down as observed by the prompt release of oxygen bubbles.
Accordingly, the instability of hydrogen peroxide when present in alkaline media severally limits shelf-life and the ability to premix antimicrobial solutions with per salts, like sodium percarbonate (Kramer at al), and be able to store and ship product, and maintain high antimicrobial activity.
As previously pointed out, the patents of Kramer et al disclose various types of compositions prepared with per salts, etc., including creams, bulk powders, tablets, soaps and also solutions. While sodium percarbonate has a listed solubility in water of about 120 gm/L at 20° C. the preparation of true solutions, i.e., liquid having a single phase, according to the protocols of the Kramer et al patents by dissolving the granular/solid sodium percarbonate salt in the liquid components were found not to yield true solutions, i.e. liquid with a single phase. Instead, the liquid yields two distinct phases possibly resulting from incompatibilities with other active ingredients in solution, such as the quaternary ammonium compound or surfactant. Hence, these inventors found in attempting to replicate the working examples in accordance with the disclosures of the Kramer et al patents relating to the preparation of solutions with sodium percarbonate, an alkaline pH of at least 10 to 11 resulted in the evolution of oxygen gas, demonstrating the lack of stability and shelf-life, and rapid dissipation of important antimicrobial activity through premature evolution of oxygen bubbles. Furthermore, the liquid compositions of Kramer et al resulted in multi-phase compositions, rather than true single phase solutions when prepared according to the protocols of the working examples.
Accordingly, a need remains for dual action anti-bacterial and anti-fungal solutions which can be readily prepared as true solutions and which are storage stable retaining substantially all their anti-microbial activity even after prolonged periods of storage, and are capable of achieving at least a virtual 100% kill rate for both bacteria and fungi while requiring very low concentrations of potentially corrosive, toxic and other active ingredients. Such disinfectant cleaning solutions should be effective in the restoration of treated surfaces/substrates as to extend their useful lives and avoid the need for more costly replacements.
SUMMARY OF THE INVENTION
For purposes of this invention, the terms and expressions below appearing in the specification and claims are intended to have the following meanings:
“Disinfectant” refers to any antimicrobial agent which destroys or irreversibly inactivates infectious or other undesirable bacteria, pathogenic fungi on surfaces or inanimate objects.
“Surfactant” (surface-active-agent) is generally intended to refer to a substance which when dissolved in water or other aqueous solution reduces the surface or interfacial tension between it and another substance or material. However, for purposes of this invention, the term—surfactant—as appearing in the specification and claims is intended to specifically include only nonionic surfactants, amphoteric surfactants and cationic surfactants other than quaternary ammonium compounds and salts thereof. Surfactants for purposes of this invention do not include negatively charged anionic type surface active agents or other compounds which are incompatible in solution with the disinfecting quaternary ammonium compound component of the potentiated disinfectant cleaning solutions of this invention. In this connection, amphoteric surfactants is intended to include those surface active agents which exhibit cationic properties when in solutions of this invention.
“Virtual 100% kill” refers to an effective kill of essentially all target organisms existing in a sample, material or substrate to be disinfected and cleaned. This expression is hereby distinguished from the expression “actual 100% kill”, which is taken to mean a kill of precisely 100% of target organisms. Hence, the expression—virtual 100% kill—means the destruction of slightly less than 100% of the target microbes, i.e., between 96% and 100%.
“Storage stable” as appearing in the specification and claims is intended to mean the disinfectant cleaning solutions have good shelf life, remain as solutions and retain the substantial part of their original antimicrobial properties after preparation of the solutions and during extended periods of storage in sealed polymeric containers under ambient temperature conditions.
“Working solution” as appearing in the claims and specification is intended to mean the prepared solution in ready-to-use format and concentration for applying to a surface for disinfection and cleaning.
In accordance with the invention a principal object is to provide for storage stable potentiated disinfectant cleaning compositions in the form of aqueous solutions. “Solutions” as appearing in the specification and claims is intended to mean a single phase liquid. This excludes multiphase systems or mixtures, such as dispersions of solid particles suspended in a liquid phase, or precipitated solids which separate out of a liquid phase, or mixtures of immiscible liquids, such as emulsions containing separate phases or layers.
The active ingredients of the aqueous working solutions comprise a disinfectant quaternary ammonium compound or salt thereof; a surfactant as previously defined and hydrogen peroxide introduced into the working solution as a solution of hydrogen peroxide. Use of alkaline per salts, such as sodium percarbonate should be avoided because their highly alkaline pH facilitates the decomposition of hydrogen peroxide in solution shortening shelf life, dissipates antimicrobial activity, and for other reasons discussed supra.
The above active ingredients are present in minimal proportional ranges sufficient to achieve at least a virtual 100 percent kill of bacteria and fungi present. Unexpectedly, it was found the combined effect of the foregoing active ingredients together in the same composition effectively enhances both the fungicidal and bactericidal activity beyond the mere additive effects of the individual ingredients used alone or in sub-combinations. Advantageously, the potentiated activity of the disinfectant cleaning solutions of the invention allows for a significant reduction in the proportional ranges of active ingredients otherwise required in such disinfectant compositions. The very low concentration of active ingredients in the working solutions of the invention minimizes the risks of chemical contamination to the environment and hazards of toxicity to personnel applying the compositions, importantly without incurring trade-offs in cleaning and disinfecting performance.
The storage stable aqueous solutions of the invention also have a pH which maintains the shelf-life stability of the working solutions, and in particular, maintains the stability of the hydrogen peroxide, so oxygen is not readily released from solution. The preferred pH for maintaining shelf life stability is approximately a neutral pH of about 7, however, the pH may be somewhat acidic, i.e., in the range of 6 to 7. Likewise, the solutions may also be mildly alkaline, generally in the range of 7 to 7.5, but preferably not above 8. Thus, the pH is generally in the range of about 6 to 8, but more preferably, in the range of about 6.5 to about 7.5.
The quaternary ammonium compounds can be tetrasubstituted ammonium salts, such as a halide salt, e.g., chloride, bromide. However, practically any quaternary ammonium compound possessing some antimicrobial activity, and particularly antibacterial, antifungal and even some antiviral activity, and which is soluble and stable in aqueous solutions with the other active ingredients is suitable.
As previously stated, the surfactant component is intended to include most non-ionic, amphoteric and cationic types. The cationic type can include surfactants other than quaternary ammonium compounds and which are suitable for use in an aqueous system. Surprisingly, the inventors discovered the surfactant ingredient contributes to the potentiated disinfecting action of the compositions, but in addition, imparts detergency properties to the compositions by aiding in dispersing of unwanted foreign matter, such as soil particulates, grease, etc., from the substrate being cleaned.
The hydrogen peroxide ingredient is selected from solutions of hydrogen peroxide, usually from concentrated solutions, like 30%, 40%, or more by weight.
As previously stated, it is an object of the invention to provide for storage stable, potentiated disinfectant cleaning solutions. Working solutions comprise minimal concentrations of the above ingredients to achieve at least a virtual 100% kill of microorganisms. More specifically, the working solutions contain quaternary ammonium compound in an amount ranging from about 0.05% to about 5.0%; surfactant or detergent in an amount from about 0.05% to about 3.5%, and hydrogen peroxide solution in an amount sufficient to provide a working strength solution from about 0.05% to about 10%. Unless stated otherwise, the concentrations of ingredients are based on percent-by-weight.
It is yet a further object of the invention to provide disinfectant cleaning solutions having potentiated bactericidal and fungicidal properties, wherein the working strength solution comprises at least 0.05% by weight hydrogen peroxide prepared from a solution of hydrogen peroxide; as little as about 500 ppm of a dialkyl dimethyl ammonium chloride, N-alkyl dimethyl benzyl ammonium chloride, and from about 0.05% percent to about 3.0% percent of a detergent composition comprising a non-ionic surfactant. The dialkyl dimethyl ammonium chloride is preferably didecyl dimethyl ammonium chloride.
It is still a further object of the invention to provide methods for simultaneously disinfecting and cleaning a surface or substrate so it is free or virtually free of bacteria and fungi, and cleaned of unwanted foreign matter. The method comprises the steps of:
(i) providing a storage stable working disinfectant and cleaning solution comprising a quaternary ammonium compound in an amount ranging from about 0.05% to about 5.0%; surfactant or detergent in an amount from about 0.05% to about 3.5%, and hydrogen peroxide solution in an amount sufficient to provide a working solution with about 0.05 and about 10% of the hydrogen peroxide, and the balance water;
(ii) contacting a surface with a sterilizing amount of the disinfectant cleaning solution of step(i) to provide a surface which is free or virtually free of bacteria and fungi, i.e., at least a virtual 100% kill of bacteria and fungi, and other unwanted foreign matter, such as soil particulates.
The method may be utilized in cleaning, disinfecting and restoring the original appearance to a wide variety of porous and non-porous substrates, particularly surfaces such as brick; cinder block; including wood, plastic and aluminum type siding; fiberglass; concrete and ceiling tiles of various types, to name but a few. The disinfectant cleaning solutions are especially noteworthy in their ability to penetrate, especially porous surfaces, and thereby effectively sterilize the entire substrate, especially in the case of wood based siding products, and acoustical ceiling tiles.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention, disinfectant cleaning solutions have been discovered which effectively achieve at least a virtual 100% disinfection and cleaning of surfaces while minimizing the required concentrations of potentially hazardous or toxic ingredients. Table 1 below provides a representative list of bacteria and fungi against which the formulations of the invention were tested for efficacy. As can be seen from the kill rates shown for each organism the formulations of the invention have achieved at least a virtual 100% kill of practically all bacteria and fungi tested, and in many instances achieved an actual 100% kill.
TABLE 1
Organism
Class
% Kill
Bacillus spp.
Bacteria
100
Serratia marcescens
Bacteria
100
Staphylococcus spp.
Bacteria
100
Pasteurella
Bacteria
100
multicoda
Proteus spp.
Bacteria
100
Pseudomonas spp.
Bacteria
100
Aspergillus niger
Fungi
98
Ulocladium
Fungi
100
Fusarium
Fungi
98
Aspergillus glaucus
Fungi
98
Aspergillus flavus
Fungi
98
Penicillium
Fungi
100
Trichophyton
Fungi
100
Aspergillus
Fungi
95
versicolor
Stachybotrys
Fungi
99
Trichophyton
Fungi
100
mentagrophytes
Acremonioum
Fungi
100
cephalosporum
Phoma
Fungi
100
The water clear potentiated disinfectant cleaning formulations are prepared from a solution of hydrogen peroxide in a sufficient amount to provide a hydrogen peroxide concentration from about 0.05% by weight; a surfactant in an amount from about 0.05%; a quaternary ammonium compound such as didecyl dimethyl ammonium chloride, N-alkyl (C 12 ) dimethyl benzyl ammonium chloride, etc., in an amount from about 0.05% and the balance water.
The hydrogen peroxide component of the solution is the oxidant, and is derived from a solutions of hydrogen peroxide, 30 to 40 percent aqueous solutions, for example.
The surfactant may include most commercially available compounds from the classes of non-ionic and amphoteric types, and also includes cationic type surfactants other than quaternary ammonium compounds. Non-ionic types are especially preferred. One particularly suitable non-ionic surfactant, an alkyl phenol ethoxylate is available from the Buffalo Soap Company under product name 201C, and comprises nonyl phenol ethoxylate as the principal ingredient. Other useful non-ionic surfactants include the ethylene oxide/propylene oxide copolymers, and more specifically the ethylene diamine reacted block copolymers available from BASF under the trademarks Tetronic and Pluronic. Other nonionic types include the ethoxylated fatty alcohols containing from 11 to 15 carbon atoms and from 3 to 40 moles of ethylene oxide available from Union Carbide under the trademark Tergitol, and so on. Examples of amphoteric surfactants which are useful as detergents are the imidazolinium derivatives prepared from 2-alkyl-1-(2-hydroxyethyl)-2-imidazolines and sodium chloracetate. This class of surfactants is commercially available from Rhone-Poulenc under such trademarks as Miranol. Also included in this group of amphoteric surfactants are the betaines or sultaines available from Lonza, Inc., under the trademark Lonzaine.
Useful, cationic surfactants other than quaternary ammonium compounds are the polyoxyethylated cationic surfactants. Also included are the amines consisting of aliphatic and mono-, di- and polyamines derived from fatty and rosin acids. They include mainly primary, secondary and tertiary monoamines with C 18 alkyl and alkenyl chains. They are commercially available as acetates, oleates, and so on. Other useful cationic surfactants other than quaternary ammonium compounds include the oxygen-containing amines. This group includes amine oxides, ethoxylated alkylamines, 1-(2-hydroxyethyl)-2-imidazolines, and alkoxylates of ethylenediamine.
Most any quaternary ammonium compound, and especially those known to possess some biocidal activity may be used in the formulations of the invention. In one particularly preferred embodiment a tetrasubstituted ammonium salt, such as a quaternary ammonium halide salt can be utilized. The quaternary ammonium halide salt may be selected from the group consisting of a dialkyl-dimethyl ammonium chloride, an alkyl dimethyl benzyl ammonium chloride, an alkyl dimethyl ethyl benzyl ammonium chloride, and mixtures thereof. In one especially preferred embodiment of the invention, the dialkyl dimethyl ammonium chloride salt is didecyl dimethyl ammonium chloride (DDAC) and n-alkyl(C 12 ,C 14 ,C 16 ) dimethyl benzyl ammonium chloride available under the trademark Uniquat® QAC from Lonza, Inc. Fair Lawn, N.J.
The formulations of the invention may be provided in ready-to-apply, i.e., working solutions diluted with water, or alternatively, may be furnished as concentrates to be later diluted with water at the site to be decontaminated.
The solutions can be applied to a surface, such as ceiling tile by first placing the solution into a reservoir on a spray applicator machine. The suggested temperature of the solution during treatment is typically between about 20° C. and about 60° C. The solution may then be applied to ceiling tiles, for instance, at a consistent pressure of about 110 psi using a fan nozzle tip having a tip angle of about 25 degrees. The tip is preferably held at a distance of about 8 inches to about 12 inches from the surface to be disinfected.
The recommended water temperature, pressure consistency, angle of the tip and application distance are optimized to properly allow penetration of the surface while preserving important attributes of the ceiling tiles, such as acoustic properties, flame retardant and esthetic features.
As previously mentioned, the solutions and methods of cleaning according to the invention are especially desirable in the renewal of ceiling tiles, such as fiberglass type since they can be disinfected, sanitized and simultaneously cleaned in the same treatment process by the removal of dust and other undesirable particulate matter deposited therein as airborne dirt, as well as grease, bacteria, fungi, and so on, which normally builds up over a period of time due to closed, artificial environments and constant recirculation of air through forced air ventilation heating and cooling systems of buildings. Acoustical ceiling tiles, for example, can function as repositories of potentially toxic bacteria, fungi and even viruses which can contaminate and reinfect the working environment of office buildings, schools, hospitals, etc. Heretofore, the only alternative was to replace literally thousands of ceiling tiles of hospitals which have become soiled and infected with microbes with totally new tiles at very significant cost. Hence, the solutions and methods of the invention are especially advantageous in providing a more economic alternative to the costly option of installing new ceiling tiles.
The following specific examples demonstrate the invention, however, it is to be understood they are for illustrative purposes only and do not purport to be wholly definitive as to conditions and scope.
EXAMPLES
In order to illustrate the potentiated effect of the solutions of the invention a series of tests was conducted wherein each of the ingredients was tested singly and in various combinations with other ingredients at increasing levels of concentration. The results demonstrate that the disinfectant cleaning solutions of the invention achieve superior kill rates to those formulations used heretofore, and with higher rates of kill than would otherwise be expected based on test results of individual ingredients of the solution.
Bactericidal Test Protocol
Tests were performed using E. Coli (TB1 strain). The protocol consisted of growing the bacteria to stationary phase by incubating at 37° C. with agitation overnight. Tryptic Soy, a nutrient rich source, was used as the growth media. Tryptic Soy agar plates were used to simulate disinfectant efficacy on a porous surface. To this end, 0.2 ml of a disinfectant test solution was spread plated to uniformly cover the agar surface. The plates were allowed to set at room temperature (25° C.) in order for the test solution to be absorbed into the media.
For each test, a 0.1 ml aliquot of the stationary phase E. Coli culture was spread plated onto the agar. Dual controls were used consisting of a positive control for testing the viability of the organism used in the experiments wherein 0.1 ml of the E. Coli culture was spread plated onto untreated plates, i.e. plates not having any disinfectant test solution. A negative second control was also used for testing the sterility of the media used in the experiments wherein disinfectant test solution treated plates were incubated in the absence of E. Coil.
In each case, test and control plates were incubated for 18 to 24 hours at 37° C., the optimal temperature for bacterial growth.
Following incubation, test plates were scored by comparison to control plates. The positive control plates were scored as 100% growth or 0% kill. Test plates were scored relative to these values, and the data recorded.
Fungicidal Test Protocol
Penicillium spp. was grown to confluence by incubating cultures at 25° C. on Sabaroud dextrose media which was chosen as a typical nutrient rich source for supporting fungal growth. Sabaroud dextrose agar plates also simulate disinfectant efficacy on a porous surface. For each test, 0.2 ml of the disinfectant test solution was spread plated to uniformly cover the agar surface. The plates were allowed to set at room temperature (25° C.) in order for the test solution to be absorbed into the media.
A 0.1 ml aliquot of the fungal spores resuspended in the dextrose broth was spread plated onto the agar surface. Dual controls were also used, consisting first of a positive control for testing the viability of the organism used in the experiments wherein 0.1 ml of the penicillium culture was spread plated onto untreated plates, i.e., plates not have disinfectant test solution. A negative control was also used for testing the sterility of the media used in the experiments. This control consisted of test plates treated with disinfectant test solution which were incubated in the absence of Penicillium.
In each case, test and control plates were incubated for 5 days at 25° C., the optimal temperature for penicillium growth.
Following incubation, test plates were test scored by direct comparison to control plates. The positive control plates were scored as 100% or 0% kill. Test plates were scored relative to these values, and the data recorded.
Peroxide Alone
A first series of tests was conducted using solutions of H 2 O 2 and water. Solutions having increasing concentrations of H 2 O 2 were prepared and efficacy of the solution against bacteria and fungi was tested according to the protocols described above. Each test was repeated twice at every concentration level of H 2 O 2 tested. The results are shown in Table 2, below.
TABLE 2
Component:
Anti-Bacterial
Anti-Fungal
% H 2 O 2
Activity (% Kill)
Activity (% Kill)
0
0
0
2.5
70, 70, 50
20, 20
5.0
75, 80, 50
60, 70
7.5
85, 70, 75
95, 70
10
90, 100, 75
80, 90
15
95, 100, 75
95, 90
20
95, 100, 80
80, 95
25
90, 95, 80
80, 95
30
95, 100, 90
80, 90
35
100, 100, 80
95, 99
The test data indicate that high kill rates (>95%) of bacteria were not achieved until solutions containing H 2 O 2 only were applied at high concentrations in the range of 30 to 35%. Similarly, high kill rates of fungi (>95%) were not achieved until H 2 O 2 concentrations of 35% were applied. Thus, kill levels of both bacteria and fungi did not approach the virtual 100% level until H 2 O 2 concentrations of at least 35% were applied.
Surfactant Alone
A second series of tests was conducted using solutions of a non-ionic surfactant. The specific non-ionic surfactant used in the tests was polyoxyethylene fatty acid esters formula RCOO(CH 2 CH 2 O)NH, wherein R is a long chained alkyl group. This surfactant is available from the Buffalo Soap Corporation under the product designation of Detergent #201C.
Multiple solutions having increasing concentrations of surfactant were prepared. Efficacy of the solutions against bacteria and fungi was tested according to the protocols described above. Each solution was tested twice at each concentration of surfactant. The results are shown in Table 3, below.
TABLE 3
Component
Anti-Bacterial
Anti-Fungal
% 201C
Activity (% Kill)
Activity (% Kill)
0
0
0
2.5
0, 0
0, 0
5.0
0, 0
0, 0
7.5
0, 0
0, 0
10
0, 0
0, 0
15
0, 0
0, 0
20
15, 15
0, 0
25
25, 20
0, 0
30
35, 25
0, 20
35
40, 30
0, 20
As the results in Table 3 indicate, solutions containing surfactant alone at concentrations even as high as 35% failed to achieve significant kill rates of either bacteria or fungi.
Quaternary Ammonium Compounds
Four commercially available quaternary ammonium compounds were tested individually to determine the efficacy of each against bacteria and fungi. The specific quaternary ammonium compounds tested were: BTC® 885, dialkyl dimethyl ammonium chloride and n-alkyl dimethyl benzyl ammonium chloride; BTC 1010, didecyl dimethyl ammonium chloride; BTC 2125, n-alkyl dimethyl benzyl ammonium chloride and n-alkyl dimethyl ethyl benzyl ammonium chloride and BTC 835, an n-alkyl dimethyl benzyl ammonium chloride. These compounds are available from the Stepan Company of Northfield, Ill.
Quat. A Alone
A series of tests was conducted according to the protocols above using a preparation comprising the quaternary ammonium compound, dialkyl dimethyl ammonium chloride and n-alkyl dimethyl benzyl ammonium chloride, available under the trade name BTC 885, hereinafter referred to as Quat. A. BTC 885 comprises the following active ingredients: n-Alkyl (50% C 14 , 40% C 12 , 10% C 16 ) dimethyl benzyl ammonium chloride in the proportion of 20%; n-octyl decyl dimethyl ammonium chloride in the proportion of 15.0%; di-n-octyl dimethyl ammonium chloride in the proportion of 7.5%; di-n-decyl dimethyl ammonium chloride in the proportion of 7.5%; inert ingredients in the proportion of 50%.
Solutions having increasing concentrations of Quat. A were prepared and the efficacy of the solutions against bacteria and fungi was tested according to the protocols described above. Each test was repeated twice at every concentration level of H 2 O 2 tested. The results are shown in Table 4, below.
TABLE 4
Component
Anti-Bacterial
Anti-Fungal
Quat. A ppm
Activity (% Kill)
Activity (% Kill)
0
0
0
50
0, 0
0, 0
100
0, 0
0, 0
250
0, 10
20, 60
500
0, 20
40, 60
750
20, 30
60, 60
1000
25, 35
80, 75
1500
30, 35
80, 80
2000
40, 40
80, 90
2500
60, 40
80, 90
3000
75, 40
80, 80
4000
85, 70
80, 90
5000
90, 90
80, 80
Solutions of Quat. A alone at all concentrations tested, up to 5000 ppm, failed to achieve kill rates of fungi and bacteria >90%.
Quat B. Alone
A series of tests was conducted according to the above protocols using a preparation comprising the quaternary ammonium compound, didecyl dimethyl ammonium chloride (DDAC), available under the trade name BTC-1010 from the Steppan Company, referred to herein as Quat B. The composition of DDAC is: didecyl dimethyl ammonium chloride in the proportion of 50%; and inert ingredients in the proportion of 50%.
Solutions having increasing concentrations of Quat. B were prepared and efficacy of the solutions against bacteria and fungi was tested according to the above protocols. Each test was repeated twice at every concentration level of Quat. B tested. The results are shown on Table 5, below.
TABLE 5
Component
Anti-Bacterial
Anti-Fungal
Quat. B ppm
Activity (% Kill)
Activity (% Kill)
0
0
0
50
0, 5
0, 10
100
0, 10
20, 20
250
0, 15
30, 20
500
15, 25
50, 30
750
40, 30
60, 40
1000
75, 35
90, 50
1500
90, 40
90, 60
2000
98, 60
90, 60
2500
98, 70
90, 60
3000
99, 90
90, 70
4000
100, 95
90, 80
5000
100, 99
90, 85
Solutions of Quat. B alone provided at least a virtual 100% kill of bacteria when used at concentrations of 2000 ppm or greater. However, the solutions failed to provide a virtual 100% kill of fungi at any of the concentrations tested.
Quat C. Alone
A series of tests was conducted according to the above protocols using a preparation comprising a quaternary ammonium compound mixture available from the Steppan Company under the trademark BTC 2125 M, referred to herein as Quat. C. The active ingredients consisted of: n-alkyl (60% C 14 , 30% C 18 , 5% C 12 , and 5%C 18 ) dimethyl benzyl ammonium chloride.
Solutions having increasing concentrations of Quat.C were prepared and efficacy of the solutions against bacteria and fungi were tested according to the protocols described above. The results are shown on Table 6, below.
TABLE 6
Component
Anti-Bacterial
Anti-Fungal
Quat. C ppm
Activity (% Kill)
Activity (% Kill)
0
0
0
50
0, 0
0, 0
100
0, 0
0, 10
250
0, 5
0, 20
500
15, 20
0, 20
750
40, 25
0, 20
1000
75, 20
15, 20
1500
90, 25
N/A, 30
2000
98, 30
20, 30
2500
98, 30
30, 50
3000
99, 30
65, 50
4000
100, 30
75, 50
5000
100, 40
85, 50
Solutions of Quat. C alone achieved a virtual 100% kill rate or better on bacteria with concentrations of 2000 ppm or more. However, the same solutions were ineffective in achieving a virtual 100% kill rate for fungi.
Quat.D Alone
A series of tests was conducted using a quaternary ammonium compound comprising n-alkyl dimethyl benzyl ammonium chloride available from the Steppan Company under the trademark BTC 835, hereinafter referred to as Quat.D. Active ingredients in this product are: n-alkyl (50% C 14 , 40% C 12 , 10% C 16 )dimethyl benzyl ammonium chloride in the proportion of 50% and inert ingredients in the proportion of 50%.
Solutions having increasing concentrations of Quat.D were prepared and the efficacy of the solutions against bacteria and fungi was tested according to the protocols described above. Each test was repeated twice at every concentration level of Quat. D tested. The results are shown in Table 7, below.
TABLE 7
Component
Anti-Bacterial
Anti-Fungal
Quat. D ppm
Activity (% Kill)
Activity (% Kill)
0
0
0
50
0
10
100
0
20
250
5
30
500
10
35
750
15
50
1000
20
50
1500
25
70
2000
30
80
2500
40
80
3000
40
80
4000
90
95
5000
95
95
Solutions of Quat. D provided relatively high kill rates of bacteria and fungi only at concentrations of 5000 ppm. But, even at concentrations of 5000 ppm a virtual 100% kill of bacteria and fungi was not achieved.
Peroxide Combined with Surfactant
A series of tests was conducted using a solution comprising H 2 O 2 in combination with the non-ionic surfactant 201C described above. H 2 O 2 concentrations of 5%, 15% and 25% were tested three times, each test using different concentrations of the surfactant. The results are shown on Table 8, below.
TABLE 8
Anti-Bacterial
Anti-Fungal
% H 2 O 2
% 201C
Activity (% Kill)
Activity (% Kill)
0
0
0
0
5
0
100
80
15
0
100
90
25
0
100
95
0
25
20
10
5
25
100
60
15
25
100
90
25
25
100
95
0
50
50
30
5
50
100
90
15
50
100
95
25
50
100
99
In the first series of tests test (0 to 25% peroxide), no surfactant was present. As expected, antifungal activity did not reach virtual 100% kill even in the presence of relatively high concentrations of H 2 O 2 (25%).
In the second series of tests the surfactant was present in concentration levels of 25%. These surfactant concentration levels did not significantly improve antibacterial or anti-fungal efficacy relative to the first test. That is, a virtual 100% kill of fungi was not achieved.
In the third series of tests a virtual 100% kill of both bacteria and fungi was achieved, but with very high concentrations of peroxide (25%) and surfactant levels of 50%.
Peroxide Combined with Quat. B
In this series of tests H 2 O 2 concentration levels of 0%, 5%, 15% and 35% were repeatedly tested in combination with increasing levels of Quat. B: 0 ppm, 250 ppm, 500 ppm, 1000 ppm, 2500 ppm and 5000 ppm. The results are shown in Table 9, below.
TABLE 9
QUAT B
Anti-Bacterial
Anti-Fungal
% H 2 O 2
(ppm)
Activity (% Kill)
Activity (% Kill)
0
0
0
0
5
0
100
90
15
0
100
90
35
0
100
95
0
250
20
0
5
250
80
40
15
250
100
90
35
250
100
95
0
500
25
20
5
500
100
40
15
500
100
90
35
500
100
95
0
1000
60
20
5
1000
100
80
15
1000
100
80
35
1000
100
90
0
2500
95
60
5
2500
100
80
15
2500
100
80
35
2500
100
90
0
5000
100
60
5
5000
100
90
15
5000
100
80
35
5000
100
90
As the data indicates, solutions of hydrogen peroxide alone and solutions of Quat. B alone, the latter at higher concentrations, were able to achieve in many instances a 100% kill of bacteria. However, neither solutions of hydrogen peroxide and Quat. B alone or combinations of both hydrogen peroxide and Quat. B together were able to provide a virtual 100% kill of fungi.
Surfactant Combined with Quat. B
In this series of tests surfactant (201C) concentrations levels of 0%, 25% and 50% were tested in combination with increasing levels of Quat B: 0 ppm, 250 ppm, 500 ppm, 1000 ppm, 2500 ppm and 5000 ppm. The results are shown on Table 10, below.
TABLE 10
Quat B
Anti-Bacterial
Anti-Fungal
% 201C
(ppm)
Activity (% Kill)
Activity (% Kill)
0
0
0
0
0
250
20
40
0
500
20
40
0
1000
40
50
0
2500
95
80
0
5000
95
80
25
0
0
0
25
250
20
10
25
500
20
20
25
1000
30
70
25
2500
75
95
25
5000
90
95
0
0
15
30
50
250
20
30
50
500
20
25
50
1000
25
60
50
2500
40
80
50
5000
100
95
As the results indicate virtual 100% kill of bacteria did not occur until the highest concentration levels (50% surfactant and 5000 ppm Quat B) were applied. However, even at such levels of surfactant and quaternary ammonium compound a virtual 100% kill of both bacteria and fungi was not achieved.
Peroxide, Surfactant and Quaternary Ammonium Compound Together
In order to demonstrate the performance of the disinfectant cleaning compositions of the instant invention a series of tests was conducted with solutions comprised of the following: surfactant in the proportion of 3.75%; Quat. B in proportions ranging from 500 ppm to 1000 ppm; and H 2 O 2 solution in proportions ranging from 0% to 3.75%. The mixtures were tested for efficacy against bacteria and fungi according to the protocol described above. The results are shown on Table 11, below.
TABLE 11
QUAT B
Anti-Bacterial
Anti-Fungal
% H 2 O 2
% 201C
(ppm)
Activity (% Kill)
Activity (% Kill)
0
3.75
500
80
0
1
3.75
500
80
0
2
3.75
500
80
100
3
3.75
500
95
100
3.75
3.75
500
95
100
5
3.75
500
100
100
7.5
3.75
500
100
100
10
3.75
500
100
100
3.75
3.75
0
100
0
3.75
3.75
250
100
20
3.75
3.75
500
100
80
3.75
3.75
750
100
100
3.75
3.75
1000
100
100
The results indicate that virtual 100% kill of both bacteria and fungi was achieved with H 2 O 2 levels as low as about 3.75%, surfactant levels as low as about 3.75% and Quat. B. levels from as low as about 500 to as low as about 750 ppm.(depending on level of H 2 O 2 )
Conclusion
The test results indicate that the percentage of peroxide required to be present in a disinfectant to achieve at least a virtual 100% kill of both bacteria and fungi can be significantly reduced by combining the peroxide with a surfactant and a quaternary ammonium compound. The test results further indicate the advantageous effect of combining the ingredients according to the present invention to achieve superior kill rates of bacteria and fungi over individual ingredients alone, or in subcombinations of such ingredients.
While the invention has been described in conjunction with various embodiments, they are illustrative only. Accordingly, many alternatives, modifications and variations will be apparent to persons skilled in the art in light of the foregoing detailed description. The foregoing description is intended to embrace all such alternatives and variations falling within the spirit and broad scope of the appended claims. | Potentiated compositions and methods for disinfection of porous surfaces, such as ceiling tiles contaminated with bacteria and fungi permits renewal without requiring replacement tiles. The compositions, preferably water clear aqueous solutions, comprise synergistic combination of quaternary ammonium compound, a surfactant, and a hydrogen peroxide solution at very low concentrations than otherwise required if used alone. The active components are present in minimal proportional ranges sufficient to achieve a virtual 100 percent kill of bacteria and fungi present on surfaces. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application claims priority to U.S. Provisional Patent Application Ser. No. 61/021,257 filed on Jan. 15, 2008, which is herein incorporated by reference.
BACKGROUND
For the past 150 years, lighting technology has been mainly limited to incandescence and fluorescence. While derivative technologies such as high-intensity discharge (HID) lamps have emerged, none have achieved energy efficiencies exceeding 25%, with incandescent lighting achieving an efficiency of less than 2%. With the advent of commercial light emitting diodes (LEDs) in the 1960s, however, the door was opened for a different and exciting form of lighting technology. Unlike conventional lighting, LEDs consume less electricity and have largely avoided the parasitic by-products of its predecessors, namely heat. Early LEDs were red in color, with yellow and orange variants following soon thereafter. To produce white light, however, a blue LED was needed. In 1993, Shuji Nakamura of Nichia Chemical Industries produced a blue LED using gallium nitride (GaN). With this development, it was now possible to create white light by combining the light of separate LEDs (red, green, and blue), or by creating white LEDs themselves by means of doping.
Solid state lighting (SSL) refers to a type of lighting that utilizes LEDs, organic light-emitting diodes (OLEDs), or polymer light-emitting diodes (PLEDs) as sources of illumination rather than electrical filaments or gas. Unlike traditional lighting, SSL creates visible light with very little heat or parasitic energy dissipation. Additionally, the solid-state nature provides for greater resistance to shock, vibration, and wear, thereby increasing lifespan significantly. SSL has been described by the United States Department of Energy as a pivotal emerging technology that promises to alter lighting in the future. It is the first new lighting technology to emerge in over 40 years and, with its energy efficiencies and cost savings, has the potential to be a very disruptive technology in the marketplace as well.
A single LED can produce only a limited amount of light, and only a single color at a time. To produce the white light necessary for SSL, light spanning the visible spectrum (red, green, and blue) must be generated in correct proportions. To achieve this effect, three approaches may be used for generating white light with LEDs: wavelength conversion, color mixing, and most recently homoepitaxial ZnSe.
Wavelength conversion involves converting some or all of the LED's output into visible wavelengths. There are a number of techniques that may be used for wavelength conversion. One method is to deposit a yellow phosphor on a blue LED. This is considered an inexpensive method for producing white light. Blue light produced by an LED excites a phosphor, which then re-emits yellow light. This balanced mixing of yellow and blue lights results in the appearance of white light.
Wavelength conversion may also be accomplished by providing additional phosphors on a blue LED. This is similar to the process involved with yellow phosphors, except that each excited phosphor re-emits a different color. Similarly, the resulting light is combined with the originating blue light to create white light. The resulting light, however, has a richer and broader wavelength spectrum and produces a higher color-quality light, albeit at an increased cost.
Yet another technique to accomplish wavelength conversion is by using an ultraviolet (UV) LED coated with doped phosphors which, upon excitation, emit light in the red, green and blue wavelengths. The UV light is used to excite the different phosphors, which are doped at measured amounts. The colors are mixed resulting in a white light with the richest and broadest wavelength spectrum.
Another technique for wavelength conversion uses a thin layer of nanocrystal particles, called quantum dots, containing 33 or 34 pairs of atoms, primarily cadmium and selenium, which are coated on top of a blue LED. The blue light excites the quantum dots, resulting in a white light with a wavelength spectrum similar to UV LEDs.
Color mixing involves utilizing multiple colored LEDs in a lamp and adjusting the intensity of each LED to produce white light. For example, the lamp may contain a minimum of two LEDs (blue and yellow), but can also have three (red, blue, and green) or four (red, blue, green, and yellow). As no phosphors are used, there is no energy lost in the conversion process, thereby exhibiting the potential for higher efficiency. The intensity of the LEDs are configured such that the combination of the emitted light results in white light.
Wavelength conversion provides benefits versus color mixing. A SSL device contains many LEDs placed close together in a lamp to amplify their illuminating effects. This is because an individual LED produces only a limited amount of light, thereby limiting its effectiveness as a replacement light source. In the case where white LEDs are utilized in SSL, this is a relatively simple task, as all LEDs are of the same color and can be arranged in any fashion. When using the color-mixing method, however, it is more difficult to generate equivalent brightness when compared to using white LEDs in a similar lamp size. Furthermore, degradation of different LEDs at various times in a color-mixed lamp can lead to an uneven color output. Because of the inherent benefits and greater number of applications for white LED based SSL, most designs focus on utilizing them exclusively.
Currently, there is no SSL available that can be offered as a true replacement for incandescent or fluorescent lamps, even though several manufacturers have gone forward with the introduction of such products. White LEDs produced today are too expensive to be considered affordable, and the lumens produced by the LEDs today are not as bright as traditional lighting. Based on research conducted by the United States Department of Energy (DOE) and the Optoelectronics Industry Development Association (OIDA), it is expected that by the year 2025, SSL will be the preferred method of illumination in homes and offices.
What is apparent to the end user is the low color rendering index (CRI) of current LEDs. The CRI is widely used to measure how accurately a lighting source renders the color of objects. For example, sunlight and incandescent lamps have a CRI of 100, while fluorescent lamps generally have a CRI>75. The current generation of LEDs, which employs mostly blue LED chip and yellow phosphor, has a CRI of about 70, which is much too low for widespread use in lighting, particularly indoor lighting applications. In order for SSL to effectively replace incandescent lamps, more research must be done on developing alternatives to the techniques currently used that address these concerns.
There are several advantages to the use of the nano-silicon converter in a white LED. Silicon nanoparticles play a dual role of UV blockers and down converters of the UV radiation emitted by the LED. Silicon nanoparticles are highly absorbant of the UV with a quantum conversion larger than 50%. In fact, silicon nanoparticles may act as a total UV filter, resulting in a safe light source. The silicon nanoparticles stay cool because they convert the UV radiation to visible light. The silicon nanoparticles are highly photostable under UV excitation giving a long safe working lifetime.
Further, a film comprised of silicon nanoparticles acts an excellent antireflection coating preventing light from going back into the LED housing causing damage due to heating or direct interaction. The silicon nanoparticle film is transparent in the visible allowing the visible light to go through.
The nanoparticles within each color group are identical, allowing the formation of high optical quality films of closely-packed nanoparticles (solid density). This is beneficial because the emission, transmission and losses of wavelength converter depends sensitively on thickness uniformity and composition of the converter on the chip.
The nanoparticles can be functionalized (doped) to shift their luminescence under the same UV source. Producing a Si—C termination on the particles, for example, shift the spectrum to the silicon carbide emission. This may provide means to improve on filling the white spectrum to achieve a high CRI ratio in the upper nineties.
SUMMARY
The white light emitting diode of the present disclosure includes an ultraviolet/blue light emitting diode (LED) and a converter layer disposed upon an active region of the ultraviolet/blue light emitting diode. The converter layer includes a cascade of silicon nanoparticles configured to fluoresce when exposed to light from the ultraviolet/blue light emitting diode such that the combination of wavelengths of light emitted from the ultraviolet/blue light emitting diode and emitted by fluorescence of the converter layer produces white light. The converter layer includes a number of silicon nanoparticle sublayers, wherein each sublayer is configured to emit fluoresced light in a predetermined wavelength range of the visible spectrum.
For example, the converter layer may have a first sublayer of silicon nanoparticles configured to emit fluoresced light having a first wavelength such that the light emitted from the first sublayer is in the red portion of the visible spectrum. The converter layer may also have a second sublayer of silicon nanoparticles configured to emit fluoresced light having a second wavelength such that the light emitted from the second sublayer is in the green portion of the visible spectrum. Additionally, the converter layer may have a third sublayer of silicon nanoparticles configured to emit fluoresced light having a third wavelength such that the light emitted from the third sublayer is in the blue portion of the visible spectrum. The combination of the wavelengths of the emitted light from the first, second, and third sublayers along with the light emitted from the LED producing white light.
The white LED of the present disclosure may also include a dichroic film layer located between the UV/blue LED and the converter layer. The dichroic film allows UV radiation and visible light emitted from the UV/blue LED to pass through while reflecting visible light emitted by the converter layer away from the LED.
The white LED of the present disclosure may be produced by providing a UV/blue LED and providing a converter layer of silicon nanoparticles onto an active surface of the UV/blue light emitting diode. The converter layer is produced by providing a colloidal suspension of silicon nanoparticles in isopropyl alcohol, spreading the colloidal suspension onto the active surface of the LED, and allowing the isopropyl alcohol to evaporate, resulting in a layer of closely-packed nanoparticles. This process may be repeated to produce a number of sublayers.
BRIEF DESCRIPTION OF THE DRAWINGS
The present disclosure will be described hereafter with reference to the attached drawings which are given as a non-limiting example only, in which:
FIG. 1 is a schematic cross-sectional representation of the LED of the present disclosure; and
FIGS. 2-5 show the down converted spectrum under UV in the range 330-400 nm of a variety of silicon nanoparticle populations.
DETAILED DESCRIPTION
The white light emitting diode (LED) 10 of the present disclosure includes a gallium nitride (GaN) ultraviolet (UV)/blue LED 12 and a wavelength converter 14 disposed on an active region of the UV/blue LED, as shown in FIG. 1 . The converter layer 14 includes one or more nanoparticle sublayers 16 , 18 , 20 in a cascade configuration. The nanoparticles in sublayers 16 , 18 , and 20 allow blue visible light emitted by the LED to pass through while absorbing the UV radiation emitted by the LED. The absorbed UV radiation excites the nanoparticles which then fluoresce light in wavelengths of the visible spectrum. The nanoparticle sublayers are configured such that wavelengths of fluoresced light combine to produce white light.
In the exemplary embodiment shown, wavelength converter 14 is configured such that each sublayer 16 , 18 , 20 is tuned to a different section of the spectrum by choice of the size of the nanoparticle, namely red 16 , green 18 , and blue 20 resulting in a red-green-blue (RGB) wavelength converter. The wavelength converter 14 is configured in a cascade arrangement to produce red light, which is then transmitted through the blue and green layers; green light, which is transmitted through the blue layer; and blue light; the combination being white light 22 .
In the exemplary embodiment of FIG. 1 , the wavelength converter 14 includes a first sublayer 16 having relatively large silicon nanoparticles tuned to fluoresce light in the red wavelengths of the visible spectrum. Wavelength converter 14 also includes a second sublayer 18 having relatively mid-sized silicon nanoparticles tuned to fluoresce light in the green wavelengths of the visible spectrum. Wavelength converter 14 also includes a third sublayer 20 having relatively small silicon nanoparticles tuned to fluoresce light in the blue wavelengths of the visible spectrum.
FIGS. 2-5 gives the down converted spectrum under UV in the range 330-400 nm of a variety of silicon nanoparticle populations, showing that it is possible to cover the entire visible spectrum of the solar white light (from 400 nm-750 nm) with the device of the present disclosure. In addition, the primary blue component from the GaN LED can be used to further enrich the mixture of emitted light.
The emerging colored light from the sublayers 16 , 18 , 20 along with some of the remaining LED blue mix together, resulting in a white light with the richest and broadest wavelength spectrum. The thickness of the sublayers are chosen in conjunction with their characteristics absorption/conversion/eye sensitivity to achieve the feel of a sunlight light source.
The white LED of the present disclosure is produced by starting with a gallium nitride (GaN) LED. A colloidal suspension of silicon nanoparticles is prepared in isopropyl alcohol. The active region of the GaN LED is then covered with a layer of silicon nanoparticles by spreading a volume of the particle colloid on the active face. The isopropyl alcohol is allowed to dry under ambient conditions, resulting in the formation of a thin layer of closely packed particles. The response of the GaN LED is measured before the particle layer is formed and after it has been coated. Additional volume of the colloid is then placed on the device and another measurement is taken. This procedure is repeated several times to allow direct correlation of the response with the increase in the thickness of the nanoparticle active layer.
The nanoparticles may also be mixed or functionalized with organic pigments to broaden the color composition. The particles may boost the interaction of UV with the pigment by energy transfer or cascade excitation.
The active nanoparticle sublayers not only improve the conversion of UV radiation to visible light but also act as a filter that protects an end user from the UV radiation emitted from the GaN LED. Also, the nanoparticle film acts as an anti-reflecting coating that stops the UV radiation from reflecting back to the LED, which, if it happens, may cause some damage and shorten the working life of the overall device. Less UV radiation striking back upon the LED device reduces the heat generated in the device and hence prolongs the working life.
In addition to the evaporation-based method for deposit of silicon nanoparticles on the GaN LED, other methods such as spin coating, or electrodeposition may be used. Moreover, alternative methods may be used to dry the nanoparticle colloidal suspension including mild heating and ultraviolet drying, in addition to drying under ambient conditions, as previously described herein.
The down conversion spectra of single silicon nanoparticle color samples in colloids was recorded under irradiation from a 365 nm Hg source. The conversion efficiency of thin films of single color samples was examined under irradiation from a 365 nm Hg source.
Because fluorescence of the silicon nanoparticle sublayers 16 , 18 , 20 is radiated in all directions equally, half of the response of the particles to the UV irradiation escapes backward, toward the LED. This visible fluoresced light may be reflected away from the LED, and thus increase the visible light output of the white LED of the present disclosure, by using a dichroic thin film 24 . This may be done by placing an appropriate coating between the nanoparticles of the wavelength converter 14 and the LED 12 , as shown in FIG. 1 , which allows UV light to pass through the dichroic film 24 while reflecting the photoluminescence to the outside, away from the LED. Thus efficiency of the LED is further improved by eliminating this loss by redirecting this light outward.
The foregoing is considered as illustrative only of the principles of the claimed invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the claimed invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the claimed invention. | Multiple films of red-green-blue (RGB) luminescent silicon nanoparticles are integrated in a cascade configuration as a top coating in an ultraviolet/blue light emitting diode (LED) to convert it to a white LED. The configuration of RGB luminescent silicon nanoparticle films harnesses the short wavelength portion of the light emitted from the UV/blue LED while transmitting efficiently the longer wavelength portion. The configuration also reduces damaging heat and/or ultraviolet effects to both the device and to humans. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Application No. 62/232,465 filed Sep. 25, 2015, the disclosure of which is herein incorporated by reference in its entirety for all purposes.
BACKGROUND
[0002] The United States, and other countries, have high numbers of avoidable traffic fatalities that happen when automobile passengers and drivers do not put on their seatbelts, and are involved in automobile accidents. Every state has enacted laws requiring automobile occupants to wear their seatbelts when the automobile is in motion. This has reduced the number of avoidable traffic deaths, but the number of avoidable traffic deaths is still very high. Safety belt use in automobiles increased from 55% in 1994 to 82% in 2005, but still thousands of Americans suffered avoidable deaths in automobile crashes.
[0003] The National Highway Traffic Safety Administration states that in 2004, 31,693 people died in automobile crashes in the United States. 55% of these were not wearing safety belts at the time. In 2009, 2.3 million adult Americans were treated in rooms for injuries that resulted from their not wearing their safety belts, and motor vehicles are presently the main cause of death for people aged 5-34 in the United States.
[0004] Regular safety belt use is the most effective, and cheapest, way to reduce deaths and injuries resulting from automobile crashes.
[0005] Numerous government agencies and private companies have noticed this problem. For example, seventy-fiver percent of passengers who are in an automobile crash, and who have safety belts buckled, survive the crash. Safety belts reduce deaths and injuries in automobile crashes by about 50%.
[0006] Air bags also provide protection but are not a substitute for seat belts, and air bags can also be dangerous to children because of the force with which they deploy.
[0007] Police officers and others often will not know whether occupants of a vehicle are wearing safety belts until an automobile crash happens. Clearly an invention is needed which warns police officers and others that the occupants of an automobile are not wearing safety belts.
[0008] In addition, when making a traffic stop, law enforcement officers often have to manually write down the license plate number of a vehicle, and then check this number by typing it into a computer, and then wait for a response from the computer, which will tell the officer who the registered owner of the vehicle is, whether or not the vehicle is insured, whether the vehicle has been stolen, and other information about the vehicle. This approach has problems, however, because the officer will often not be able to check the information about the vehicle until he has stopped it and spoken to the passengers. If the passengers are criminals, then they could hurt the officer if he or she approaches the vehicle without knowing that they are criminals. Police officers have been killed during “routine” traffic stops, when the vehicles being stopped were stolen or occupied by criminals. An invention is needed which will allow a police officer or other law enforcement officer to check the information connected to a vehicle's license plate or vehicle identification number (VIN number) without having to physically stop the vehicle.
[0009] Insurance companies also often cannot tell, after the fact, whether an injured vehicle crash victim was wearing a safety belt. This is important for assigning “fault” for purposes of injury. Insurance companies also need a better method of encouraging their insured to “buckle up” and wear their safety belts when inside a moving vehicle. An invention is needed which can help insurance companies to reconstruct which occupants of a vehicle were wearing safety belts when a crash happens. There is also a need for an invention that will tell insurance companies whether their insured are wearing their safety belts.
SUMMARY
[0010] To address the foregoing problems, in whole or in part, and/or other problems that may have been observed by persons skilled in the art, the present disclosure provides methods, processes, systems, apparatus, instruments, and/or devices, as described by way of example in implementations set forth below.
[0011] According to one embodiment, a device is provided for communicating one or more pieces of information about a vehicle to a police officer or other law enforcement employee, wherein said pieces of information are selected from the group consisting of: a. vehicle ID number, b. identity of vehicle owner, c. whether or not registration fees for the vehicle have been paid, and d. insurance information about the vehicle, and wherein such communication happens through the device transmitting said information via a wireless method to a computer device in the possession of said police officer or other law enforcement employee, and wherein said device includes a computer memory on which is stored said pieces of information. In some embodiments the device is encased in a reinforced case that may be attached to the bumper of the vehicle. In other embodiments, said device also includes a component that flashes. In other embodiments, the pieces of information stored in said computer memory may be updated by a user with the appropriate authorization.
[0012] According to another embodiment, a system is provided for informing individuals outside a vehicle about whether the occupants of the vehicle are wearing their safety belts while the vehicle is moving, comprising: one or more monitoring sensors, each of which is capable of sensing whether a seatbelt has been buckled and whether the automobile is moving; a transmitting mechanism attached to each of the monitoring sensors; and a broadcast mechanism which has an impact-resistant outer surface; wherein said transmitting mechanisms are each capable of transmitting information to the broadcast mechanism. In some embodiments the information is selected from the group consisting of: whether the safety belt monitored by the monitoring sensor is fastened, whether there is a vehicle occupant sitting in the seat associated with said safety belt, and when said vehicle is moving and one or more of said safety belts is not fastened when an occupant is sitting in the seat associated with said safety belt. In another embodiment the broadcast mechanism is located on the outside of the vehicle. In another embodiment, said broadcast mechanism includes a flashing light that flashes when said vehicle is moving. In another embodiment, the broadcast mechanism receives a signal from one or more of said transmitting mechanisms that one or more of said seatbelts is unfastened when an occupant is occupying the seat associated with said seatbelt. In another embodiment, the flashing light has the logo of an automobile maker in its center.
[0013] According to another embodiment, a process is provided for communicating one or more pieces of information about a vehicle to police officers by making said information available in a device with a computer memory and a wireless transmitting capability, so that said device is capable of transmitting said pieces of information to a computer or equivalent machine possessed by said police officer; where said information is one or more pieces of information selected from the group consisting of: a. vehicle ID number; b. identity of vehicle owner; c. whether or not registration fees for the vehicle have been paid; and d. insurance information about the vehicle; and wherein said device is encased in a reinforced case. In some embodiments the device is attached to the bumper of the vehicle. In other embodiments, the device includes a flashing light, particularly wherein the flashing light flashes red. In other embodiments, said computer memory can be reprogrammed to reflect changes in said pieces of information. In other embodiments, magnetic sensors are electronically coupled to said device, wherein said sensors inform said device of whether a person has sat in one of the seats inside the vehicle and has not fastened the seatbelt. In other embodiments, said device has a flashing light attached, wherein said flashing light flashes when a person has sat in one of the seats inside the vehicle and has not fastened the seatbelt.
[0014] Other devices, apparatus, systems, methods, features and advantages of the invention will be or will become apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the invention, and be protected by the accompanying claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] The invention can be better understood by referring to the following figures. The components in the figures are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. In the figures, like reference numerals designate corresponding parts throughout the different views.
[0016] FIG. 1A shows one possible embodiment of the broadcast mechanism ( 1 ).
[0017] FIG. 1B shows another possible embodiment of the broadcast mechanism ( 1 ).
[0018] FIG. 2 is a “cut-away” view of an automobile, with views of the way that the monitoring sensors ( 3 ) are placed inside the seat belt couplings ( 4 ).
[0019] FIG. 3 is a “cut-away” view of an automobile from the top, with the monitoring sensors ( 3 ) inside the seats next to the seatbelts.
[0020] FIG. 4 is a “cut-away” view of the automobile from FIG. 3 , with passenger occupants.
[0021] FIG. 5 shows the back of an automobile with one possible location for the broadcast mechanism ( 1 ), upon the back of the automobile near the license plate.
[0022] FIG. 6 shows the interior of a police car, with a police officer monitoring the broadcast from the broadcast mechanism of an automobile.
[0023] FIG. 7 is a “close-up” view of the police officer's laptop screen, and what the police officer will see there.
[0024] FIG. 8 is a cross-section of one possible embodiment of a broadcast mechanism ( 1 ). The chip ( 6 ) can be seen, and is connected to a computer memory ( 7 ).
DETAILED DESCRIPTION
[0025] As used herein, the terms “seatbelt” or “safety belt” are interchangeable. In addition, although reference is made to police officers or other law enforcement employees, it is to be understood that the device, systems, and processes described herein may be used to convey information to any individual outside of the vehicle.
[0026] The basic design of the invention includes a device (The “broadcast mechanism”) ( 1 ) positioned on the outside of a vehicle, such as an automobile. The device may be protected by an impact resistant covering. The broadcast mechanism may also include a flashing light ( 2 ), which only flashes when the vehicle is moving and one of the occupants of the vehicle has taken off his or her safety belt. Inside the flashing light, the logo of the automobile maker may be provided, and may serve to make the flashing light more noticeable.
[0027] The broadcast mechanism may include a computer chip ( 6 ), and a computer memory ( 7 ), and a component (The “reception component”) capable of receiving electronic signals via radio waves or another technology. The reception component receives electronic signals from sensors inside the safety belt mechanisms of the vehicle, or alternatively inside the seats of the vehicle. They may be placed in other locations within the vehicle, as long as they are capable of monitoring whether vehicle occupants have fastened their seatbelts. These chips are referred to herein as the monitoring sensors ( 3 ).
[0028] Each of the monitoring sensors are capable of confirming whether the person sitting in the seat with the seatbelt mechanism that this particular monitoring sensor is examining, has fastened his or her safety belt. The monitoring sensor may directly confirm this, or may be connected to a computer chip, referred to herein as the monitoring chip.
[0029] In one possible design, the monitoring sensors ( 3 ) are included in the seatbelt couplings, as illustrated in the drawings. Each of the monitoring sensors ( 3 ) have a transmitting mechanism ( 5 ) that is capable of transmitting information to the broadcast mechanism ( 1 ).
[0030] When the vehicle is in motion and the seatbelt that one of the monitoring sensors ( 3 ) is attached to is fastened, the transmitting mechanism ( 5 ) attached to that monitoring sensor transmits this information to inform the broadcast mechanism ( 1 ) that the seatbelt is fastened. If the seatbelt is not fastened, the transmission mechanism will inform the broadcast mechanism, and the computer chip in the broadcast mechanism will cause the flashing light to flash. This is true of each of the monitoring sensors. In another possible design, the monitoring sensors can send signals to the monitoring chip(s), which the monitoring chip will use to determine whether the occupant has fastened his or her safety belt. The signals may be sent by either a wired or a wireless connection.
[0031] The monitoring chips send electronic signals to the reception component, and when the vehicle is moving and one of the occupants has not fastened his or her safety belt, the monitoring chips informs the reception component. The reception component then communicates with the computer chip, which activates a flashing light, which is visible to law enforcement officers and others outside the vehicle. The law enforcement officers who are watching will then know that one of the vehicle's occupants has unbuckled his or her safety belt, and will pull the vehicle over to issue that occupant a warning or citation.
[0032] In particular embodiments, the broadcast mechanism is impact resistant, includes a flashing light, and the light only flashes when one of the seatbelts in the vehicle is not fastened and the vehicle is in motion, and that the broadcast mechanism be capable of communicating either directly or indirectly with the monitoring sensors.
[0033] The monitoring sensors may also be located in another area of the automobile, where they are capable of sensing whether the seatbelts in the vehicle are not fastened, while the vehicle is in motion. For example, the monitoring sensors can be located in the seats.
[0034] The monitoring sensors may also each involve a computer chip themselves, or may rely on another, simpler mechanism for discerning whether the seatbelts are fastened.
[0035] The monitoring sensors could also potentially work by sensing the proximity of components of the seat belt buckle to the sensor, when such proximity is only possible if the seatbelt is buckled.
[0036] The monitoring sensors could also function based on magnetically sensing when metal is near, when such metal will only be near enough to a monitoring sensor to trigger that sensor when the seatbelt is buckled. The monitoring sensors could also work in other ways as will be appreciated by those of skill in the art.
[0037] The broadcast mechanism also may have a shape other than the shapes shown in the drawings.
[0038] The broadcast mechanism is capable of storing and broadcasting other information.
[0039] For example, the broadcast mechanism can include a computer memory ( 7 ) connected to the chip ( 6 ), which will store information such as the vehicle owner, vehicle registration information, VIN number, and license plate number of the vehicle, and insurance information. The computer memory ( 7 ) can also store additional information about the owner of the vehicle, and this information can be the information that an officer would get by “running the vehicle's license plates”.
[0040] Police patrol officers can then be equipped with radio receivers or other devices that can monitor the broadcasts created by the broadcast device. The receiver can he connected to an officer's laptop, with the ability to transmit information between the receiver and the laptop, so that the officer can simply press a button on his laptop and learn the information that he would get by running the license plates of the automobile. The transmissions from the broadcast instrument can be encrypted so that they can only be read by police vehicles. The technology for these encrypted communications, and to build a receiver of the type needed, which will be connected to the officer's laptop, already exists and is well-known in the prior art.
[0041] The information in the computer memory can be encrypted or otherwise protected so that only the State Department of Motor Vehicles or another authorized government entity can change it.
[0042] In another embodiment of the invention, the computer memory can be stored in another area of the automobile, where it is more physically protected, and can be connected to a means for transmitting information to the computer chip in the broadcast mechanism. The broadcast mechanism can then broadcast this information. This makes the information less vulnerable to tampering.
[0043] In another embodiment of the invention, the information stored in the computer memory will be simply a code that a police officer can use to unlock a database, accessible over the internet, and accessible only to police officers, where the information that the officer would get by “running the automobile's plates” is stored. This will reduce the chances of the information such as the vehicle's VIN number, etc. being tampered with.
[0044] In all of the embodiments listed above, the information such as the vehicle owner, vehicle registration information, VIN number, and license plate number of the vehicle, and insurance information can be encrypted so that it can only be changed by the State Department of Motor Vehicles or another authorized government entity. Certain embodiments of the invention also carry additional protections, as noted above.
[0045] In all of the embodiments listed above, a police officer will be able to get substantial information about an automobile quickly and easily, without the officer leaving his own automobile. This is an improvement over current technology, where an officer has to follow an automobile closely to read its license plates, or alternatively stop the automobile, before being able to “run its plates”.
[0046] The computer memory could also include other information, if desired.
[0047] The computer memory could also be configured to store information for a period of time about whether one of the occupants of the automobile had failed to buckle his or her safety belt at the time that the automobile was been moving. This may help an insurance company for assessing fault if the automobile is involved in a crash.
[0048] It is possible to create an embodiment of the invention that only informs police officers when the vehicle is in motion and one of the seatbelts is not fastened, and does not broadcast information such as the vehicle's VIN number, etc. Likewise, it is possible to create an embodiment of the invention that only broadcasts information such as the vehicle's VIN number, etc., and does not inform police officers when the vehicle is in motion and one of the occupants has not fastened his or her seatbelt.
[0049] In another embodiment of the invention, there are direct wire connections between the monitoring sensors and the broadcast mechanism.
[0050] In another embodiment of the invention, the broadcast mechanism ( 1 ) only broadcasts information such as the VIN number, insurance information, etc. in response to an electromagnetic beam such as a radio beam from a police car. This beam can contain encrypted identifying information, so that the chip ( 6 ) recognizes the electromagnetic beam as coming from a police car. This reduces the possibility of “hackers” monitoring the information that is being broadcast by the broadcast mechanism.
[0051] In still another embodiment of the invention, the broadcast mechanism ( 1 ) can broadcast a picture showing which passenger has not fastened his or her seatbelt. The broadcast mechanism can broadcast this information only in response to an electromagnetic beam from a police car, or can broadcast this information whenever the vehicle is in motion, or can be pre-programmed to broadcast this information in some other set of circumstances.
[0052] The technology to make the broadcast mechanism impact-resistant is presently available in the prior art.
[0053] Whether or not the vehicle is moving can be sensed by the monitoring sensors ( 3 ) in some embodiments. Alternatively, it can be sensed by the computer chip ( 6 ) or some other component of the broadcast mechanism ( 1 ) in some embodiments. This information can also be sensed by some other component of the vehicle and communicated to either the monitoring sensors ( 3 ) or the broadcast mechanism ( 1 ) in other embodiments.
[0054] Insurance companies will have an additional use for the device described herein, because they will be able to directly monitor which of their insured is actually wearing safety belts. They can then give reduced insurance rates to drivers who wear safety belts.
[0055] This invention can also be used on trucks, jeeps, or any other type of vehicle that has seatbelts.
[0056] Turning now to the figures, FIG. 1A shows one possible embodiment of the broadcast mechanism ( 1 ). It will be placed on the back of an automobile, near the license plate. The flashing light ( 2 ) is shown in the center of the broadcast mechanism. It will only flash when the vehicle that it is attached to is being driven, and one of the seats is occupied, and the seatbelt is not fastened. A logo is in the center of the flashing light in this drawing. This is for demonstration purposes only. The logo of any vehicle manufacturer can be placed in the center of the flashing light. Here, the broadcast mechanism ( 1 ) is roughly in the shape of a square with rounded corners.
[0057] FIG. 1B shows another possible embodiment of the broadcast mechanism ( 1 ). It will be placed on the back of an automobile, near the license plate. The flashing light ( 2 ) is shown in the center of the broadcast mechanism. It will only flash when the vehicle that it is attached to is being driven, and one of the seats is occupied, and the seatbelt is not fastened. A logo is in the center of the flashing light in this drawing. This is for demonstration purposes only. The logo of any vehicle manufacturer can be placed in the center of the flashing light. Here, the broadcast mechanism ( 1 ) is roughly in the shape of an Octagon.
[0058] FIG. 2 is a “cut-away” view of an automobile, with views of the way that the monitoring sensors ( 3 ) are placed inside the seat belt couplings ( 4 ). Several monitoring sensors ( 3 ) can be seen. Each of them is next to one of the seat belt couplings ( 4 ) that it is intended to be inserted into. Each monitoring sensor ( 3 ) also includes a transmitting mechanism ( 5 ) that has the ability to transmit to the broadcast mechanism ( 1 ) and inform the broadcast mechanism of whether the seatbelt related to that particular monitoring sensor ( 3 ) is fastened or not.
[0059] FIG. 3 is a “cut-away” view of an automobile from the top, with the monitoring sensors ( 3 ) inside the seats next to the seatbelts. The monitoring sensors ( 3 ) are able to communicate with the broadcast mechanism ( 1 ) and each monitoring sensor can inform the broadcast mechanism of whether the seatbelt related to the seat where that that monitoring sensor is located is fastened, or not.
[0060] FIG. 4 is a “cut-away” view of the automobile from FIG. 3 , with passenger occupants. In this embodiment, the passenger sits in the seat, the pressure on the seat informs the sensor that someone is sitting in the seat, and the sensor waits for the “click” created by the seatbelt fastening, to discern that the seatbelt applicable to that seat has been fastened. The sensor sends this information wirelessly to the broadcast mechanism ( 1 ). If the automobile has started moving and one of the seatbelts is not fastened, the flashing red light ( 2 ) will flash to make a warning of this.
[0061] FIG. 5 shows the back of an automobile with one possible location for the broadcast mechanism ( 1 ), upon the back of the automobile near the license plate. The flashing light ( 2 ) can also be seen.
[0062] FIG. 6 shows the interior of a police car, with a police officer monitoring the broadcast from the broadcast mechanism of an automobile. The police car is receiving a beam from the broadcast component ( 1 ) on the back of an automobile. The broadcast includes a visual depiction that contains information about which of the passengers is not wearing a safety belt. Furthermore, the broadcast includes information about the vehicle such as vehicle ID number, etc. This information is displayed on the in-vehicle laptop of the police officer.
[0063] FIG. 7 is a “close-up” view of the police officer's laptop screen, and what the police officer will see there. There is a schematic of the automobile, which pinpoints exactly which passenger does not have his seatbelt fastened. There is also other information about the automobile.
[0064] FIG. 8 is a cross-section of one possible embodiment of a broadcast mechanism ( 1 ). The chip ( 6 ) can be seen, and is connected to a computer memory ( 7 ). They are both safe from automobile crashes because they are inside the impact-resistant surface of the broadcast mechanism ( 1 ). The chip is also connected to the flashing light ( 2 ) and causes it to flash when the vehicle is moving and one of the seatbelts for an occupied seat is not fastened.
[0065] It will be understood that terms such as “communicate” and “in . . . communication with” (for example, a first component “communicates with” or “is in communication with” a second component) are used herein to indicate a structural, functional, mechanical, electrical, signal, optical, magnetic, electromagnetic, ionic or fluidic relationship between two or more components or elements. As such, the fact that one component is said to communicate with a second component is not intended to exclude the possibility that additional components may be present between, and/or operatively associated or engaged with, the first and second components.
[0066] It will be understood that various aspects or details of the invention may be changed without departing from the scope of the invention. Furthermore, the foregoing description is for the purpose of illustration only, and not for the purpose of limitation—the invention being defined by the claims. | A device is provided for communicating one or more pieces of information about a vehicle to a police officer or other law enforcement employee, wherein said pieces of information are selected from the group consisting of: a. vehicle ID number, b. identity of vehicle owner, c. whether or not registration fees for the vehicle have been paid, and d. insurance information about the vehicle, and wherein such communication happens through the device transmitting said information via a wireless method to a computer device in the possession of said police officer or other law enforcement employee, and wherein said device includes a computer memory on which is stored said pieces of information. Systems and processes utilizing said device are also provided. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Non-applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH AND DEVELOPMENT
[0002] Non-applicable
THE NAMES OF THE PARTIES TO A JOINT RESEARCH AGREEMENT
[0003] Non-applicable
INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC
[0004] Non-applicable
BACKGROUND OF THE INVENTION
[0005] 1. Field of the Invention
[0006] The present invention relates generally to the field of microscopic inspection of membranes, and more particularly to compositions and methods to characterize (identify, locate and measure) microscopic defects in membranes.
[0007] 2. Description of the Related Art Including Information Disclosed Under 37 CFR 1.97 and 37 CFR 1.98
[0008] Membranes are generally useful to separate components of a mixture by selectively allowing transit of certain component(s) and not others. Membranes are widely used in commercial and industrial applications such as water purification via filtration or reverse osmosis, food and drug processing, and energy-related applications like battery and fuel cell technology.
[0009] Generally, a membrane is used to discriminately allow passage of liquid and filter particulate. In some cases, the membrane's specifications are geared to allow passage of some particulate dissolved in a liquid while blocking passage of other particles. The most common particulate membranes filtered in commercial applications are selected macromolecules, bacterial pathogens, viruses, salts, colloids, and other impurities.
[0010] Structurally, membranes are barriers which serve the function of blocking or retaining contaminants and allowing passage of less contaminated, or non-contaminated fluid. Accordingly, and in light of the potentially devastating consequences to large populations which could result from failure of membranes used in large scale water purification applications, it is essential to inspect regularly the blocking properties and thus the integrity of membranes.
[0011] The prior art discloses multiple and, in some cases, costly methods of membrane inspection and identification of membrane defects. Bubble point test methodology is used for membrane defect identification in the broadest range of defect sizes. That type of testing is very expensive and time consuming. The basic commercial equipment required for bubble point testing is priced at approximately $10,000 and requires a trained professional to operate, which amounts to approximately $10,000 per test. The existing equipment requires membrane filtration modules to be taken out of service and pressurized to a nominal operating pressure of 600 psi in order to adequately test a filtration system to a 50 nm size range with water as the solvent.
[0012] In fact, in an effort to obtain improved approaches for identifying defects in membranes used for water purification, the US Environmental Protection Agency Office of Water has supported development of technology that utilizes nanoparticles made of gold. In the gold-based technology, the gold particles can be detected by use of anodic stripping voltammetry—a method that requires additional costly and complex equipment, and trained technicians. The use of such a complex electrochemical methods is also severely limited in terms of limit of detection (250,000 gold particles particle per mL of liquid). A further limitation of that method for use as a qualitative or quantitative membrane defect characterization tool is the tendency for small gold particles to agglomerate into larger scale particles. In short, implementation of the gold particle process is expected to be very expensive due to the use of a precious metal. That method is further limited by its inability to detect membrane defects in the 15-50 nm range.
[0013] In contrast, the method of the present invention utilzes a simple visual detection of fluorescent solutions which require very low (less than parts per billion) detection limits. In fact, the method of this invention can detect a single fluorescent particle. The cost of implementing and using the method of the present invention is relatively low, in part because it does not require using a precious metal or training on complex equipment.
[0014] Membranes are also inspected, and their integrity is evaluated using other techniques. Another known way of testing membranes is to apply a pressure differential across the membrane and measure the time decay of the differential. Air, an inert gas or a vacuum can be used to generate the pressure differential. Pressure differential techniques require complex equipment and a considerable investment of time and therefore are very costly. In some cases, the process in which the membrane is being used must be interrupted to perform the evaluation, which adds to the cost and makes the process less efficient. More traditionally, analysis of the filtered fluid provides a qualitative picture of membrane quality.
[0015] More recently, Rajagopalan, et al., U.S. Pat. No. 7,011,758 disclosed and claimed a method for testing the integrity of a membrane which comprises placing a magnetically susceptible material in a fluid upstream of the membrane and collecting the material downstream. Rajagopalan's method uses a magnetic field to collect the magnetic material and a sensor to detect it.
[0016] The membrane evaluation techniques of the prior art have numerous shortcomings. For the most part, those techniques provide qualitative information only. In other words, and contrary to the method of the present invention, those techniques give an indication that there is a membrane defect, but do not quantify the extent of it. In fact, the prior art does not disclose a single technique which can pinpoint the place on the membrane where a defect may exist or define whether the membrane complies with performance specifications.
BRIEF SUMMARY OF THE INVENTION
[0017] The chemical composition of the present invention, which is also known as NANOGLO™, enables rapid and cost-effective characterization (identification and location) of microscopic defects in membranes such as pinholes, cracks or fissures. Applicant developed the method disclosed and claimed herein as part of an effort to identify cost-effective manufacturing and quality-control for their proprietary developmental membranes. The present invention, however, has been found to have wide spectrum applicability on a number of different types of porous and non-porous membranes that are used for diverse applications in various industries. Those membranes include, but are not limited to, membranes made from (1) fluorinated polymers; (2) non-fluorinated, non polar materials; and (3) non-fluorinated, polar materials.
[0018] The method of the present invention allows rapid, simple and highly accurate integrity tests to be performed on membranes used in a variety of filtering, purification or manufacturing processes.
[0019] The method of the present invention uses brightly fluorescing silica or silsesquioxane spheres prepared with pre-determined definitive and uniform sizes ranging from 15 nanometers (nm) and up to 50 microns (50,000 nm, or the thickness of a human hair). The spheres' uniform controlled size allows them to be used to characterize defects or holes in membranes based on a size exclusion mechanism. The spheres used in the method of this invention are engineered to glow brightly when exposed to ultraviolet light in order to allow visual or highly sensitive fluorescence spectroscopy or microscopy to characterize the passage of the particles through defects or holes in a membrane and even identify where the defect is located (by the residence of fluorescence particles on the membrane).
[0020] If NANOGLO™ spheres in a liquid carrier pass through a microscopic defect or hole in a membrane, they will generate a distinct fluorescent glow, which acts as an optical signature in the liquid that passes through the membrane. The intensity of the fluorescence corresponds to the magnitude and/or number of defects. The pre-determined size and color of the spheres provide a quantitative indication of the size of the defect.
[0021] For example, the smallest NANOGLO™ spheres of 15 nanometers would identify membrane defects that would allow passage of a retro virus. Larger spheres are capable of identifying defects large enough to allow larger viruses (20-100 nm) or even bacterial pathogens (100 nm-120 microns) to pass through membranes.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0022] FIG. 1 is a table of dynamic light scattering (DLS) data on the size of particles with standard deviations.
[0023] FIG. 2 is a table that shows a correlation between the sample numbers and the specific monomer.
[0024] FIG. 3 is a table depicting the results of an aggregation study based on light scattering of particles of 1,2-bis(4-triethoxysilyl)phenyl)ethene monomer over an eight month period.
[0025] FIG. 4 is a scanning electron microscope (SEM) image of 1.0 mol % 1,2-bis(4-triethoxysilyl)phenyl)ethane fluorescent silica.
[0026] FIG. 5 is a table that shows the absorption-emission spectra for solutions of the monomers and their silica nanoparticles.
DETAILED DESCRIPTION OF THE INVENTION
[0027] The NANOGLO™ spheres of the present invention comprise a pre-determined fluorescent monomer incorporated into a silica (SiO 2 ) or a silsesquioxane (RSiO 1.5 ) nanoparticle by co-polymerizing a silica, silsesquioxane or bridged silsesquioxane monomer with a small (<1%) quantity of a second, highly fluorescent monomer. The majority of each particle is silica, derived from tetraalkoxysilane monomers (Si(OR′) 4 where R′ is a methyl or ethyl group), polysilsesquioxane, derived from monomers (RSi(OR′) 3 where R is methyl, vinyl, or chloromethyl and R′ is a methyl or ethyl group), or bridged polysilsesquioxanes, derived from monomers (R′O) 3 Si—R—Si(OR′) 3 where R is a arylene or alkylene bridging group. The fluorescent monomers used in connection with the NANOGLO™ spheres of this invention are bridged silane monomers with the general chemical structure of (R′O) 3 Si—R—Si(OR′) 3 where the R bridging group is a fluorescent organic group. The fluorescent silica or silsesquioxane particles are prepared from the mixtures of the silica or silsesquioxane monomer and the fluorescent monomer through a modified Stober process. The resulting particle sizes can be confirmed by using dynamic light scattering (DLS). In the preferred embodiment of the invention, the particles are between 15-1000 nanometers in diameter as shown in FIG. 1 . Sample 1 in FIG. 1 represents non-fluorescent silica which was synthesized to allow a comparison to silica particles which fluoresce.
[0028] After the modified Stober process takes place, all particles are then repeatedly centrifuged resulting in pure fluorescent silica or silsesquioxane nanoparticles. Concentrations of 1.0 mol % (Samples 2-5 in FIG. 1 ) and 0.1 mol % (Sample 6-9 in FIG. 1 ) can be used as comparisons.
[0029] FIG. 2 shows a correlation between the sample numbers and the specific monomer. The chemical structures of the fluorescent monomers that have or could be used, correlated to the sample numbers in FIGS. 1 and 2 , are set forth below.
[0000]
[0030] These monomers can be used in synthetic protocols to yield differently colored particles in a variety of colors (e.g., blue, violet, orange, yellow, green).
[0031] In an alternative embodiment of the invention, 250 nm particles, as confirmed using DLS, were synthesized using 1,2-bis(4-triethoxysilyl)phenyl)ethene monomer 2 (1 mol %) and tetraethoxysilane. The aggregation of particles, which is a predictor of shelf life, was determined by examining multiple measurements over an eight-month time period as shown in FIG. 3 . In all embodiments of the invention, Scanning Electron Microscopy (SEM) was used to confirm spherical geometry and size for the initially synthesized particles. As a way to illustrate the usefulness of SEM, FIG. 4 shows a SEM image of 1.0 mol % 1,2-bis(4-triethoxysilyl)phenyl)ethane fluorescent silica.
[0032] Monomer synthesis, as set forth above, produced very distinct fluorescent violet, blue, yellow, green and orange dyes that were bonded within the silica or silsesquioxane matrix. The monomers used do not have to be 100% pure, but purity can be increased via recrystallization.
[0033] Interestingly, changing the concentration of fuorescent monomer does not appear to affect the fluorescent intensity of the particles significantly. In contrast, adding monomer 8, results in a change in color of the particles from dark red to red as the concentration of fluorescent monomer decreases. That change is due to the reduction of the eximer emission which is taking place, which results from the decrease in concentration. Monomers 3 and 4 exhibit the greatest intensity and there is little visible change in intensity resulting from changes in the concentration of fluorescent monomer.
[0034] NANOGLO™ spheres in the lowest size range (15 nm) can be introduced into a membrane filtration system to test for defects that could allow harmful microbes to pass through. If passage is detected then additional spheres of progressively larger size are introduced to the membrane filtration system in order to define the upper limits of the defect or fissure size. Importantly, the NANOGLO™ spheres have been engineered, using more hydrophobic silsesquioxanes rather than silica, to have “non-sticking” characteristics, so that spheres will not stick to the surface of membranes and promote fouling or blockage of the defect, which enables determination of the magnitude of the defect.
[0035] The differently sized spheres of the present invention can be manufactured in multiple distinct colors (e.g., blue, violet, orange, yellow, green) using the different fluorescent dyes, which allows for a faster and simpler test protocol. For example, multiple simultaneous tests can take place using the different sized particles each with a different color (color coded spheres of different sizes), where a particular color corresponds to a particular size. Such method allows much simpler, visual testing, location and characterization of membrane defects.
[0036] Another variation of the method of the present invention utilizes food and drug-safe fluorescent dyes of particular color which (in addition to the inert materials of the spheres, themselves) enhances the utility of the method in food and drug processing applications. The silica nano particle “encapsulation” of such colored fluorescent additives eliminates the need for subsequent sterilization and cleaning equipment following characterization of defects in a membrane being used as part of a particular food or drug processing protocol.
Monomer Synthesis
[0037] 4,4′-Bis(4-(triethoxysilyl)styryl)biphenyl (4). To a three neck 25 mL round bottom, (triethoxysilyl)styrene (1.006 g, 3.8 mmol) was added. To this solution, a magnetic stir bar and 4,4′-dibromophenyl (1.176 g, 3.8 mmol) were added, followed by anhydrous toluene (10 ml). To this solution, tri-o-tolylphosphine (0.085 g, 2.6×10 −5 mol) along with palladium acetate (0.015 g, 4.45×10 −5 mol) were added. To the solution, triethylamine (1.35 g, 1.33 mmol) was added. This solution was stirred and heated at 105° C. After an hour, an additional amount of (triethoxysilyl)styrene (0.9006 g, 3.4 mmol) was added along with additional anhydrous toluene (10 mL). The solution was allowed to react for 24 hours. The brown solution was vacuumed suctioned through CELITE® to remove palladium. The solution was removed in vacuo yielding compound 4, a yellow solid.
[0038] 9,10-Bis(4-(triethoxysilyl)styryl)anthracene (6). To a three neck 25 mL round bottom, (triethoxysilyl)styrene (1.508 g, 5.6 mmol) was added. To this solution, a magnetic stir bar aND 9,10-dibromoanthracene (0.946 g, 2.8 mmol) were added followed by anhydrous toluene (10 mL). To this solution, tri-o-tolylphosphine (0.082 g, 2.6×10 −5 mol) and palladium acetate (0.016 g, 4.45×10 −5 mol) were added. To the solution, triethylamine (1.35 g, 1.33 mmol) was added. This solution was stirred and heated at 105° C. After an hour, additional anhydrous toluene (18 mL) was added. The solution was allowed to react for 24 hours. The brown solution was vacuumed suctioned through CELITE® to remove palladium. The solvent was removed in vacuo yielding compound 6, an orange solid.
[0039] N,N′-Bis(3-triethoxysilylpropyl)-perylene-3,4:9,10-tetracarboxdiimide (8). A 0.786 g (2.00 mmol) sample of 3,4,9,10-perylene-tetracarboxylic dianhydride was added to a 250 mL three neck round bottom, followed by 70 mL of dry ethanol. The round bottom was repeatedly evacuated and flushed with argon. After the mixture stirred for 30 minutes under argon, it was heated in an oil bath to 105° C. A 4.43 g (0.020 mol) sample of 3-aminopropyltriethoxysilane (APTES) was added dropwise through a septum. The red reaction mixture was stirred for 24 hours under reflux and under an inert atmosphere. After the mixture was cooled to room temperature, the red precipitate was collected by suction filtration and washed thoroughly with cold ethanol. The red solid was dried in a vacuum oven to yield compound 8 (0.955 g, 59%).
[0040] N,N′-Bis(3-triethoxysilylpropyl)-naphthalene-1,4:5,8-tetracarboxdiimide (10). A 0.536 g (0.002 mol) sample of 1,4,5,8-naphthalene-tetracarboxylic dianhydride was added to a 250 mL three neck round bottom, followed by 100 mL of dry ethanol. The round bottom was repeatedly evacuated and flushed with argon. After the mixture stirred for 30 minutes under argon, it was heated in an oil bath to 105° C. A 4.43 g (0.020 mol) sample of 3-aminopropyltriethoxysilane (APTES) was added dropwise through a septum to the opaque brown solution changing it to a transparent brown solution. The reaction mixture was stirred for 72 hours under reflux and under an inert atmosphere. After the mixture was cooled to room temperature, the brown solution was roto-vaped and dried in vacuo yielding compound 10.
[0041] 4,4′-Dibromostilbene. To a three neck 50 ml round bottom, 4-bromostyrene (14.490 g, 0.0786 mol) was added. To the solution, a magnetic stir bar along with dichloromethane (DCM) (10 mL) were added. To the solution, Grubb's catalyst (0.500 mg, 5.8×10 −4 mol) along with DCM (25 mL) was added. The solution was allowed to react for 24 hours at room temperature. The precipitate was filtered and placed into a vial for storage.
Nanoparticles Synthesis
[0042] Fluorescent nanoparticles are prepared by co-polymerizing a fluorescent monomer (<1 mol %) with a dilutent monomer (>99 mol %) under Stober conditions (monomer, excess water, ammonium hydroxide in ethanol) to afford monodisperse particles whose size can be controlled by varying the concentration of ammonium hydroxide, among other variables. Silica nanoparticles are prepared by the copolymerization of a silica precursor such as tetramethoxysilane or tetraethoxysilane with the fluorescent monomer. More hydrophobic nanoparticles can be prepared by copolymerizing silsesquioxane monomers, MeSi(OR′) 3 (R′=methyl or ethyl) or (R′O) 3 SiRSi(OR′) 3 (R′=methyl or ethyl, R=phenylene, methylene, ethylene, ethenylene, hexylene, octylene, or octafluorooctylene).
[0043] Fluorescent violet silica (150 nm in diameter). To a 20 mL scintillation vial, ethanol (7 mL) and ammonium hydroxide (1 mL) were added followed by a magnetic stir bar. The solution was vigorously stirred for 30 minutes at room temperature. To a separate 20 mL scintillation vial, fluorescent monomer 2 along with ethanol (8 mL) were added [ FIG. 5 ]. A magnetic stir bar was then added to the vial and vigorously stirred at room temperature. After 5 minutes, tetraethyl orthosilicate (TEOS; 0.4 mL, 1.79 mmol) was added and the solution was stirred for 30 minutes under the same conditions. After 30 minutes, the stir bar was removed from the first vial and the solution was poured quickly into the second vial and capped. The solution was allowed to stir for at least 24 hours at room temperature. After 24 hours, a diluted sample of silica was tested using DLS. The colloidal silica solution was centrifuged at 4000 rpm for 1 hour and the supernatant was checked for residual fluorescent monomer using long wave ultraviolet light.
[0044] Fluorescent violet silica (250 nm in diameter). To a 20 mL scintillation vial, ethanol (2.3 mL), 2 M ammonia (3.75 ml), and 18.3 MΩ water (0.16 mL) were added followed by a magnetic stir bar. The solution was vigorously stirred for 30 minutes at room temperature. To a separate 20 mL scintillation vial, 1,2-bis(4-triethoxysilyl)phenyl)ethene monomer 2 along with ethanol (2.3 mL) were added. A magnetic stir bar was then added to the vial and vigorously stirred at room temperature. After 5 minutes, tetraethyl orthosilicate (TEOS; 0.38 mL, 1.70 mmol) was added and the solution was stirred for 30 minutes under the same conditions. After 30 minutes, the stir bar was removed from the first vial and the solution was poured quickly into the second vial and capped. The solution was allowed to stir for at least 24 hours at room temperature. After 24 hours, a diluted sample of silica was tested using DLS. The colloidal silica solution was centrifuged at 4000 rpm for 1 hour and the supernatant was checked for residual fluorescent monomer using long wave ultraviolet light. Absorption-emission spectra for solutions of the monomers and their silica nanoparticles are shown in FIG. 5 . | The chemical composition and method of the invention enable characterization of microscopic defects in membranes such as pinholes, cracks or fissures. The present invention, however, can be used to characterize defects on different types of porous and non-porous membranes used for diverse applications in various industries.
It uses brightly fluorescing silica or silsesquioxane spheres prepared with pre-determined definitive and uniform sizes (15 nm-50 microns). The spheres' uniform, controlled size allows them to be used to characterize defects or holes in membranes based on a size exclusion mechanism. The spheres used are engineered to glow brightly when exposed to ultraviolet light in order to allow visual or highly sensitive fluorescence spectroscopy or microscopy to characterize the passage of the particles through defects or holes in a membrane and even identify where the defect is located. | 2 |
TECHNICAL FIELD
[0001] The present invention relates to a method of manufacturing a chlorous acid aqueous solution by chlorine dioxide adsorption.
BACKGROUND ART
[0002] Chlorous acid aqueous solution has drawn attention as a food additive. However, a chlorous acid aqueous solution is problematic in that the manufacture thereof is difficult, and even if the manufacture were possible, the storage in normal condition is not possible.
[0003] Meanwhile, the inventors have discovered a method of manufacture of a chlorous acid aqueous solution and have confirmed a sterilizing effect on E. coli , which has led to the filing of a patent application (Patent Literature 1).
CITATION LIST
Patent Literature
[0004] [PTL 1] International Publication No. WO 2008/026607
SUMMARY OF INVENTION
Solution to Problem
[0005] The present invention has discovered, and provides, a technique related to a novel method of manufacturing a chlorous acid aqueous solution.
[0006] In one aspect, the present invention provides a method of trapping (capturing or adsorbing) chlorine dioxide gas (ClO 2 ) with one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof to create a transitional state and delay a decomposition reaction, such that chlorous acid (HClO 2 ) can be stably maintained in water over a long period of time. A preferred embodiment of these methods can utilize a further addition of one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof to the above-described aqueous solution.
[0007] Examples of the above-described inorganic acid include carbonic acid, phosphoric acid, boric acid, and sulfuric acid. Further, examples of inorganic acid salt include carbonate, hydroxide, phosphate, and borate. More specifically, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate or the like may be used as the carbonate; sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide or the like may be used as the hydroxide; disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate or the like may be used as the phosphate; and sodium borate, potassium borate or the like may be used as the borate. Furthermore, examples of the above-described organic acid include succinic acid, citric acid, malic acid, acetic acid, lactic acid and the like. Further, the following are suitable as the organic acid salt: sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, calcium lactate and the like.
[0008] The present invention also provides the following.
[0000] (1) A method of manufacturing a chlorous acid aqueous solution, comprising the step of: adsorbing (trapping) chlorine dioxide (ClO 2 ) to aqueous solution A comprising one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof.
(2) The method of item 1, further comprising the step of adding the chlorine dioxide in the presence of hydrogen peroxide.
(3) The method of item 1 or 2, wherein a pH of the aqueous solution A is 11.0 or less and 6.0 or greater.
(4) The method of any one of items 1 to 3, wherein a pH of the aqueous solution A is 10.8 or less and 10.2 or greater.
(5) The method of any one of items 1 to 4, wherein TAL of the aqueous solution A is 20 to 2000, wherein the TAL is found by an amount of 0.1N-HCl titration from an initial pH at or below pH of 11.0 to a pH of 4, where the TAL is TAL of the aqueous solution prior to blowing in chlorine dioxide gas, and the aqueous solution prepared after blowing in is a chlorous acid aqueous solution. The aqueous solution at this time has a reduced TAL relative to aqueous solution A. A specific buffering agent (aqueous solution B) as designated in the present invention is added to the aqueous solution to stabilize chlorous acid and chlorite ions. The reason for keeping the initial pH of aqueous solution A low and limiting the range of TAL is to eliminate strong alkaline buffering power unique to sodium hydroxide and to limit an aqueous solution to having buffering power to weakly acidic region to weakly alkaline region.
(6) The method of any one of items 1 to 5, wherein the chlorine dioxide (ClO 2 ) is provided as gas.
(7) The method of any one of items 1 to 6, comprising, after the step of adding, a step of further adding aqueous solution B comprising one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof.
(8) The method of any one of items 1 to 7, wherein the inorganic acid is carbonic acid, phosphoric acid, boric acid, or sulfuric acid.
(9) The method of any one of items 1 to 8, wherein the inorganic acid salt is carbonate, hydroxide, phosphate, or borate.
(10) The method of item 9, wherein the carbonate is sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate.
(11) The method of item 9, wherein the hydroxide is sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide.
(12) The method of item 9, wherein the phosphate is disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, or potassium dihydrogen phosphate.
(13) The method of item 9, wherein the borate is sodium borate or potassium borate.
(14) The method of any one of items 1 to 13, wherein the organic acid salt is succinic acid, citric acid, malic acid, acetic acid, or lactic acid.
(15) The method of any one of items 1 to 14, wherein the organic acid salt is sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, or calcium lactate.
(16) The method of any one of items 4 to 15, wherein a pH of a liquid after adding the aqueous solution B is 3.2 or greater and less than 7.0.
(17) The method of any one of items 4 to 16, wherein a pH of a liquid after adding the aqueous solution B is 4.0 or greater and less than 7.0.
(18) The method of any one of items 4 to 17, wherein a pH of a liquid after adding the aqueous solution B is 5.0 or greater and less than 7.0.
(19) The method of any one of items 1 to 18, wherein the chlorine dioxide is present at a concentration of 0.8 to 1.0%.
(20) A chlorous acid aqueous solution manufactured by a method comprising the step of trapping chlorine dioxide (ClO 2 ) with aqueous solution A comprising one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof.
(21) The chlorous acid aqueous solution of item 20, wherein the method further comprises a step of adding the chlorine dioxide in the presence of hydrogen peroxide.
(22) The chlorous acid aqueous solution of item 20 or 21, wherein a pH of the aqueous solution A is 11.0 or less and 6.0 or greater.
(23) The chlorous acid aqueous solution of any one of items 20 to 22, wherein a pH of the aqueous solution A is 10.8 or less and 10.2 or greater.
(24)
[0009] The chlorous acid aqueous solution of any one of items 20 to 22, wherein the chlorine dioxide (ClO 2 ) is provided as gas.
[0010] Additional embodiments and advantages of the present invention are recognized by those skilled in the art who read and understand the following detailed description as needed.
Advantageous Effects of Invention
[0011] According to the present invention, a technique is provided for stabilizing chlorous acid, which is a useful substance, in an aqueous solution for a long period of time, such that the possibility of utility has improved as a chlorous acid aqueous solution that is convenient for handling in a wide range of applications in not only the food industry, but also in many fields such as welfare and nursing facilities and medical facilities.
BRIEF DESCRIPTION OF DRAWINGS
[0012] FIG. 1 shows a schematic diagram of a manufacturing plant used in the Examples. Each symbol represents the following: 1 : chlorous acid aqueous solution manufacturing tank; 2 : gas washing device; 3 : chlorine dioxide gas storage tank; 4 : air pump; 5 : air flow spigot.
[0013] FIG. 2 shows the UV spectrum in Example 1. A double peak is observed.
[0014] FIG. 3 shows the UV spectrum in Example 2. A double peak is observed.
[0015] FIG. 4 shows the UV spectrum in Example 3. A double peak is observed.
[0016] FIG. 5 shows the UV spectrum in Example 4. A double peak is observed.
[0017] FIG. 6 shows the UV spectrum in Example 5. A double peak is observed.
[0018] FIG. 7 shows the UV spectrum in Example 6. A double peak is observed.
[0019] FIG. 8 shows the stability of the chlorous acid aqueous solutions manufactured in Examples 2 and 4 compared to the control, which was conducted in Example 7. The horizontal axis indicates the number of days, and the vertical axis indicates the chlorous acid concentration.
DESCRIPTION OF EMBODIMENTS
[0020] The present invention is described hereinafter. Throughout the entire specification, a singular expression should be understood as encompassing the concept thereof in the plural form, unless specifically noted otherwise. Thus, singular articles (e.g., “a”, “an”, “the” and the like in case of English) should also be understood as encompassing the concept thereof in the plural form unless specifically noted otherwise. Further, the terms used herein should be understood as being used in the meaning that is commonly used in the art, unless specifically noted otherwise. Thus, unless defined otherwise, all terminologies and scientific technical terms that are used herein have the same meaning as the terms commonly understood by those skilled in the art to which the present invention pertains. In case of a contradiction, the present specification (including the definitions) takes precedence.
[0021] As used herein “chlorous acid aqueous solution” refers to an aqueous solution comprising chlorous acid (HClO 2 ) that is used as a sterilizing agent. The chlorous acid aqueous solution of the present invention creates a transitional state and delays a decomposition reaction, such that chlorous acid (HClO 2 ) can be stably maintained over a long period of time. When a sample of chlorous acid aqueous solution is measured with a spectrophotometer, the presence of a chlorous acid aqueous solution can be confirmed when an absorbent section comprising an acidic chlorite ion (H + +ClO 2 − ) representing a peak near 260 nm and an absorbent section comprising chlorine dioxide (ClO 2 ) representing a peak near 350 nm can be simultaneously confirmed between wavelengths 240 to 420 nm in the UV spectrum, i.e., when a double peak is exhibited. In such a case, it is understood that a cyclic reaction involving the main constituent chlorous acid (HClO 2 ), chlorine dioxide (ClO 2 ), and acidic chlorite ion (H + +ClO 2 − ) is simultaneously in progress.
[0022] As used herein, the term “chlorous acid aqueous solution” may encompass a “chlorous acid aqueous solution formulation”. A chlorous acid aqueous solution formulation can be manufactured by using a chlorous acid aqueous solution manufactured by the manufacturing method of the present invention and blending in aqueous solution B. A representative constitution of a chlorous acid aqueous solution formulation that can be mixed and used is 60.00% (w/v) chlorous acid aqueous solution (5% product) (chlorous acid concentration is 50000 ppm), 1.70% (w/v) potassium dihydrogen phosphate, 0.50% (w/v) potassium hydroxide, and 37.8% purified water (sold under the name “AUTOLOC Super” by the Applicant), but the constitution is not limited thereto. When this constitution of mixture is used, the chlorous acid aqueous solution may be 0.25% (w/v) to 75% (w/v), potassium dihydrogen phosphate may be 0.70% (w/v) to 13.90% (w/v), and potassium hydroxide may be 0.10% (w/v) to 5.60% (w/v). It is also possible to use sodium dihydrogen phosphate instead of potassium dihydrogen phosphate, and sodium hydroxide instead of potassium hydroxide.
[0023] As used herein, “stability” of a chlorous acid aqueous solution refers to a state of maintaining chlorous acid (HClO 2 ).
[0024] As used herein, “antimicrobial (action)” refers to suppression of growth of pathogenic, harmful, or infectious microorganisms such as mold, microbes, or viruses. A substance having antimicrobial action is referred to as an antimicrobial agent.
[0025] As used herein, “sterilizing (action)” refers to killing of pathogenic, harmful, or infectious microorganisms such as mold, microbes, or viruses. A substance having sterilizing action is referred to as a sterilizing agent.
[0026] As used herein, “microbe-removing (action)” refers to removal of pathogenic, harmful, or infectious microorganisms such as mold, microbes, or viruses. A substance having microbe-removing action is referred to as a micro-removing agent.
[0027] As used herein, “disinfecting (action)” refers to disinfection of pathogenic, harmful, or infectious microorganisms such as mold, microbes, or viruses. A substance having disinfecting action is referred to as a disinfecting agent.
[0028] Antimicrobial action, sterilizing action, microbe-removing action, and disinfecting action are collectively referred to as germicidal (action), which is used herein as a broad concept encompassing antimicrobial (action), sterilizing (action), microbe-removing (action), and disinfecting (action) unless specifically noted otherwise. Thus, substances having antimicrobial action, sterilizing action, microbe-removing action, or disinfecting action collectively referred herein as a “sterilizing agent”, which is understood as an agent also having action corresponding to antimicrobial action, sterilizing action, microbe-removing action, and disinfecting action in general use herein.
[0029] As used herein, an article used with a manufactured chlorous acid aqueous solution is any article that can be impregnated with the chlorous acid aqueous solution to be used in sterilization or the like, including medical devices. Examples thereof include, but are not limited to, a sheet, film, patch, brush, nonwoven fabric, paper, fabric, absorbent cotton, sponge and the like. Further, any material may be used, as long as a chlorous acid aqueous solution can be impregnated therein.
[0030] As used herein, “TAL” is used to measure alkalinity of a sample by titrating 0.1 mol/L hydrochloric acid-standard acid solution until a sample has a pH of 4.0, wherein alkalinity (TAL) is 1 when 1 mL of 0.1 mol/L hydrochloric acid is required to make 100 g of sample to have a pH of 4.0. A pH of 4.0 is the second neutralization point for sodium carbonate.
(Chlorous Acid Aqueous Solution and Manufacturing Example Thereof)
[0031] The chlorous acid aqueous solution used in the present invention has a feature and function that was discovered by the inventors.
[0032] The present invention relates to a method that is different from known manufacturing methods, such as those described in Patent Literature 1.
[0033] Specifically, conventional techniques added and reacted sulfuric acid or an aqueous solution thereof, with an aqueous sodium chlorate solution, in an amount and concentration at which the pH value of the aqueous sodium chlorate solution can be maintained from 2.3 to 3.4 to generate chloric acid, and then added hydrogen peroxide in an amount equivalent to or greater than the amount required for a reduction reaction of the chloric acid. However, the feature of the present invention is accomplished by providing a method of manufacturing chlorous acid comprising the step of adding chlorine dioxide gas (ClO 2 ), instead of adding hydrogen peroxide to chloric acid, to one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof (aqueous solution A). Use of chlorine dioxide gas (gas) is beneficial in that it generates chlorite ions with a high level of alkalinity and lowers the pH to neutral or lower, and then some of the chlorite ions transition to a state of chlorous acid to create a transitional state, resulting in delaying a decomposition reaction, such that chlorous acid (HClO 2 ) can be stably maintained over a long period of time. Such an effect can be accomplished by trapping chlorine dioxide (ClO 2 ) with aqueous solution A comprising one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof. The expression “trap” may refer to adsorption, capture or the like, preferably any manipulation leading to co-existence of gaseous chlorine dioxide with one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof. Examples of such a manipulation generally include, but are not limited to, a method of directly blowing in gas into aqueous solution A, a method of adsorption by spraying aqueous solution A like a mist from the top and releasing chlorine dioxide gas from the bottom, air blast and the like. Although not wishing to be bound by any theory, the chlorous acid aqueous solution of the present invention manufactured by using a manufacturing plant as shown in FIG. 1 (see Examples 1 to 6) is demonstrated as exhibiting a stable sterilizing effect at least under refrigerated condition (4° C.) for 10 days as shown in Example 7. Thus, the present invention is understood as providing a manufacturing method of stable chlorous acid in an aqueous solution, the so-called chlorous acid aqueous solution.
[0034] A chlorous acid aqueous solution formulation can be manufactured by mixing in aqueous solution B with a chlorous acid aqueous solution manufactured by the manufacturing method of the present invention. A representative constitution of such a formulation that can be mixed and used is, for example, 60.00% (w/v) chlorous acid aqueous solution (5% product) (chlorous acid concentration is 50000 ppm), 1.70% (w/v) potassium dihydrogen phosphate, 0.50% (w/v) potassium hydroxide, and 37.8% purified water (sold under the name “AUTOLOC Super” by the Applicant), but the constitution is not limited thereto. When this constitution of mixture is used, the chlorous acid aqueous solution may be 0.25% (w/v) to 75% (w/v), potassium dihydrogen phosphate may be 0.70% (w/v) to 13.90% (w/v), and potassium hydroxide may be 0.10% (w/v) to 5.60% (w/v). It is also possible to use sodium dihydrogen phosphate instead of potassium dihydrogen phosphate, and sodium hydroxide instead of potassium hydroxide. Although this agent reduces the deterioration of chlorous acid due to contact with an organic matter under acidic conditions, the sterilizing effect is maintained. In addition, very little chlorine gas is generated. The agent also has a feature of generating an insignificant amount of chlorine gas, thus reducing amplification of chlorine odor generated from reacting chlorine with an organic matter.
[0035] Conventional manufacturing methods generate a chlorous acid aqueous solution by adding and reacting sulfuric acid or an aqueous solution thereof, with an aqueous sodium chlorate solution, in an amount and concentration at which the pH value of the aqueous sodium chlorate solution can be maintained at 3.4 or lower to generate chloric acid, and then adding hydrogen peroxide in an amount equivalent to or greater than the amount required for a reduction reaction of the chloric acid. The present invention is significantly different in terms of the use of chlorine dioxide gas. A difference is also found in the use of chlorine dioxide gas creating a transitional state and delaying a decomposition reaction, such that chlorous acid (HClO 2 ) can be stably maintained over a long period of time. In addition, the present invention is characterized in that a raw material for generating chlorine dioxide gas does not need to be specified by utilizing chlorine dioxide as the raw material. For instance, chlorine dioxide gas is generated in addition to acidified sodium chlorite (ASC) when sodium chlorite is added to acid. However, such chlorine dioxide gas can be utilized to manufacture a chlorous acid aqueous solution. Sodium chlorite is a highly alkaline substance that is integrated with an alkaline substance to be stable. Sodium chlorite needs to be in a state of acidified sodium chlorite (ASC) to exert an effect for use as a sterilizing agent. However, use of this method can also lead to manufacture of a chlorous acid aqueous solution, which is a liquid product, by using as a raw material, a gasified chlorine dioxide separately generated from acidified sodium chlorite, which is a liquid product. Furthermore, due to the electrolysis process in the manufacture of a chlorous acid aqueous solution from sodium chloride, there was a risk of bromide ions in the sodium chloride changing into a carcinogenic substance bromic acid and contaminating the chlorous acid aqueous solution. However, since the manufacturing method of the present invention uses chlorine dioxide gas which is gas, such a risk of carcinogenic substance contamination has been eliminated. Use of chlorine dioxide gas as a raw material is characterized in further facilitating the manufacture of chlorous acid aqueous solution because there would be no need to consider the preceding process. In addition, since generation of chlorine dioxide gas is not preferable in a manufacturing method from sodium chlorite, it is considered desirable to increase alkalinity. A pH closer to is considered more preferable. Thus, a method of manufacturing sodium chlorite is recognized as performing the complete opposite of the present method, which manufactures a chlorous acid aqueous solution by using aqueous solution A, which is neutral to weakly alkaline, e.g., pH of 6.0 to the order of 11.0 shown in the present invention.
[0036] In one embodiment, the chlorine dioxide gas (ClO 2 ) is provided as gas. In a specific embodiment, chlorine dioxide gas (ClO 2 ) is gas that is used with a concentration of 0.8 to 1.0% (e.g., the acceptable range is 0.9%±0.1%). One preferred concentration is 0.88%, but is not limited thereto. Gas with a high concentration is dangerous due to its explosiveness. Thus, such gas is diluted with nitrogen gas or the like for use.
[0037] In one embodiment, the chlorine dioxide gas is added in the presence of hydrogen peroxide (H 2 O 2 ). In another embodiment, the aqueous solution A may contain hydrogen peroxide, and the chlorine dioxide gas is trapped with aqueous solution A containing hydrogen peroxide. Coexistence of chlorine dioxide gas with hydrogen peroxide (H 2 O 2 ) suppresses the generation of chlorate ions and generates chlorous acid (HClO 2 ) through the so-called “cyclic reaction” where chlorite ions, chlorous acid, and aqueous chlorine dioxide are simultaneously present.
[0038] A preferred embodiment comprises, after the step of adding, the step of further adding one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof. This is because the pH or the like can be adjusted to adjust the transitional state by further adding a step in this manner.
[0039] Further, in another embodiment, carbonic acid, phosphoric acid, boric acid, or sulfuric acid can be used as inorganic acid in the above-described method, but phosphoric acid is preferred. Although not wishing to be bound by any theory, the present invention is demonstrated as being able to be maintained within a suitable range of pH with a high buffering effect in a state of chlorous acid while retaining a sterilizing effect by using especially phosphoric acid.
[0040] Furthermore, in another embodiment, carbonate, hydroxide, phosphate, or borate can be used as inorganic acid salt, but phosphate is preferred. Although not wishing to be bound by any theory, the present invention is demonstrated as being able to be maintained within a suitable range of pH with a high buffering effect in a state of chlorous acid while retaining a sterilizing effect by using especially phosphate.
[0041] Further, in another embodiment, sodium carbonate, potassium carbonate, sodium bicarbonate, or potassium bicarbonate may be used as carbonate, but sodium carbonate is preferred. This is because pH has buffering power at a weakly alkaline region and weakly acidic region, such that chlorous acid can be advantageously stabilized in this region.
[0042] Furthermore, in another embodiment, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide may be used as hydroxide, but potassium hydroxide or sodium hydroxide is preferred. Although not wishing to be bound by any theory, such hydroxides can be used to increase chlorous acid content. Meanwhile, use of a divalent salt may be advantageous because desalination is possible in combined use with phosphoric acid such that the amount of salt to chlorous acid and chlorite ions can be reduced.
[0043] Furthermore, in another embodiment, disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, or potassium dihydrogen phosphate may be used as the phosphate. Preferably, dipotassium hydrogen phosphate can be used. Although not wishing to be bound by any theory, this is because these phosphates can have buffering power in a useful pH region exerting the most sterilization power, which is a pH from 5 to less than 7. This can be advantageous because chlorous acid can be stable in this pH region.
[0044] Further, in another embodiment, sodium borate or potassium borate can be used as borate.
[0045] Furthermore, in another embodiment, succinic acid, citric acid, malic acid, acetic acid, lactic acid can be used as organic acid. Succinic acid can be preferably used. Although not wishing to be bound by any theory, succinic acid can have buffering power from a pH of less than 6 to 4. Drastic gasification of chlorine dioxide can be suppressed within this range of pH. However, pH tends to drastically decrease when pH is less than 5, in which case use of organic acid with a buffering power with a pH from 3 to less than 4 such as citric acid is desirable.
[0046] Furthermore, in another embodiment, sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, or calcium lactate can be used as organic acid salt.
[0047] In one embodiment, the advantageous initial pH of a buffering agent with chlorine dioxide blown therein is generally, but not limited to, 11.0 or less and 6.0 or greater, and more preferably 10.8 or less and 10.2 or greater. When the initial pH is 10.8 or less and 10.2 or greater, the available chlorine concentration ultimately attained increases while suppressing generation of chlorite and the yield is improved. As used herein, pH values are rounded to indicate one significant digit. For instance, when the actual measured value is a pH of 10.83, this value is shown as a pH of 10.8.
[0048] Normally, such a pH may be 11.0 or greater, where available chlorine concentration ultimately attained increases and the yield is improved. However, use of sodium hydroxide (caustic soda) or the like is not preferable because the use would generate sodium chlorite, which is contradictory to the objective of the present invention. Although not wishing to be bound by any theory, when sodium chlorite is manufactured, chlorine dioxide gas is adsorbed to an aqueous solution in which hydrogen peroxide is added to a high concentration of sodium hydroxide. The pH of the aqueous solution prior to adsorption to chlorine dioxide gas is strongly alkaline with a pH of 11.3 or greater and 12 or greater in practice. The recovery rate would be nearly 100%. Thus, one adsorption tank is sufficient (generally two or more adsorption tanks are required as the recovery rate is low for chlorous acid aqueous solution), where the generated product is not chlorous acid aqueous solution but sodium chlorite. Thus, such a pH suitable for the objective of the present invention may be any condition that chlorine dioxide gas could have. A typical example includes, but is not limited to, a pH of 6.0 to 11.0 and preferably 10.2 to 10.8. Examples of a preferably pH as an upper limit include, but not limited to, 11.2, 11.1, 11.0, 10.9, 10.8, 10.7, 10.6, 10.5, 10.4, 10.3, 10.2, 10.1, 10.0, 9.9, 9.8, 9.7, 9.6, 9.5, 9.4, 9.3, 9.2, 9.1, 9.0 and the like. Examples of preferred upper limits of pH include a value less than 11, value less than 10.5, value less than 10, value less than 9.5, value less than 9, value less than 8.5, value less than 8, value less than 7.5, value less than 7, value less than 6.5 and the like. Examples of preferred low limit of pH include, but are not limited to, 6.0, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7.0, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10.0, 10.1, 10.2 and the like. Examples of preferred lower limit of pH include a value greater than 6, value greater than 6.5, value greater than 7, value greater than 7.5, value greater than 8, value greater than 8.5, value greater than 9, value greater than 9.5, value greater than 10 and the like. Any combination of such upper limits and lower limits can be suitable and used in the present invention. Examples of preferred combinations of an upper limit and lower limit include 6.0 to 6.5, 6.0 to value less than 6.5, 6.0 to 9.0, 6.0 to value less than 9.0, 6.0 to 10.0, 6.0 to value less than 10.0, 6.0 to 11.0, 6.0 to value less than 11.0, value greater than 6.0 to value of 6.5, value greater than 6.0 to value of 9.0, value greater than 6.0 to value of 10.0, value greater than 6.0 to value of 11.0, value greater than 6.0 to value less than 6.5, value greater than 6.0 to value less than 9.0, value greater than 6.0 to value less than 10.0, value greater than 6.0 to value less than 11.0, 7.0 to 9.0, 7.0 to value less than 9.0, 7.0 to 10.0, 7.0 to value less than 10.0, 7.0 to 11.0, 7.0 to value less than 11.0, value greater than 7.0 to value of 9.0, value greater than 7.0 to value of 11.0, value greater than 7.0 to value less than 9.0, value greater than 7.0 to value less than 11.0 and the like.
[0049] When chlorine dioxide gas is adsorbed to a low concentration aqueous alkaline solution in the manufacture of a chlorous acid aqueous solution, a small buffer zone appears between pH of 6 and 8 (normal sodium chlorite does not have such a buffer zone). A buffering agent for retaining a potent buffering power in this pH region is required to maintain what is in this buffer region in a state of chlorous acid or chlorite ion for a long period of time. Thus, a buffering agent and a range of pH that fit this condition are preferably selected.
[0050] Although the sodium chlorite content can be increased more with stronger buffering power from pH 14 to pH of 10, the manufacturing method of the present invention is for manufacturing an aqueous solution that maintains a cyclic reaction of chlorous acid, chlorine dioxide and chlorite ion. Thus, there is no need to raise the initial pH of aqueous solution A, which is strongly alkaline required to manufacture sodium chlorite, to a pH of 11.0 or greater. Since the present invention is not a method of manufacturing sodium chlorite, it is preferable to avoid a condition under which sodium chlorite is produced. Although not wishing to be bound by any theory, it is important for the present invention to enhance buffering power from the neutral to the weakly acidic region, and thus TAL (provided that the initial value is pH of 11.0 or less) was employed as an indicator thereof. When the pH of the manufactured chlorous acid aqueous solution is low, a buffering agent may be newly added to raise the pH. In one embodiment, when the manufactured chlorous acid aqueous solution is used and mixed with a buffering agent, the pH range may be 3.2 to 7.0.
[0051] Although there is currently no concentration that is necessarily optimal as the concentration of the blown in chlorine dioxide gas, one embodiment can use gas with a concentration of 0.8 to 1.0% and a specific example can use gas with a concentration of 0.88%. Although not wishing to be bound by any theory, gas with a high concentration is dangerous due to its explosiveness. Thus, such gas is generally diluted with nitrogen gas or the like for use.
[0052] A conventional method of manufacturing an aqueous solution (chlorous acid aqueous solution) comprising chlorous acid (HClO 2 ) that can be used as a sterilizing agent would generate chlorous acid (HClO 2 ) by adding hydrogen peroxide (H 2 O 2 ), to an aqueous solution of sodium chlorate (NaClO 3 ), in an amount required to produce chlorous acid by a reducing reaction of chloric acid (HClO 3 ) obtained by adding sulfuric acid (H 2 SO 4 ) or an aqueous solution thereof to an aqueous solution of sodium chlorate (NaClO 3 ) so that the aqueous solution of sodium chlorate is in an acidic condition. The basic chemical reaction of this method of manufacturing is represented by the following formula A and formula B.
[0000] [Chemical 1]
[0000] 2NaClO 3 +H 2 SO 4 →2HClO 3 +Na 2 SO 4 (formula A)
[0000] HClO 3 +H 2 O 2 →HClO 2 +H 2 O+O 2 ↑ (formula B)
[0053] Formula A indicates that chloric acid is obtained while sodium ions are removed by adding sulfuric acid (H 2 SO 4 ) or an aqueous solution thereof in an amount and concentration at which the pH value of an aqueous sodium chlorate (NaClO 3 ) solution can be maintained within acidity. Next, formula B indicates that chloric acid (HClO 3 ) is reduced with hydrogen peroxide (H 2 O 2 ) to produce chlorous acid (HClO 2 ).
[0000] [Chemical 2]
[0000] HClO 3 +H 2 O 2 →2ClO 2 +H 2 O+O 2 ↑ (formula C)
[0000] 2ClO 2 +H 2 O 2 →2HClO 2 +O 2 ↑ (formula D)
[0000] 2ClO 2 +H 2 O HClO 2 +HClO 3 (formula E)
[0000] 2HClO 2 H 2 O+Cl 2 O 3 (formula F)
[0054] At this time, chlorine dioxide gas (ClO 2 ) is generated (formula C). However, coexistence with hydrogen peroxide (H 2 O 2 ) results in the production of chlorous acid (HClO 2 ) through the reactions in formulae D-F. The present invention utilizes the reactions after the chlorine dioxide gas (ClO 2 ). Although not wishing to be bound by any theory, when this reaction was taken out and utilized, it was unexpectedly found that it is possible to create a transitional state and delay a decomposition reaction, such that chlorous acid (HClO 2 ) can be stably maintained over a long period of time.
[0055] Meanwhile, the property of the produced chlorous acid (HClO 2 ) is such that it is decomposed early into chlorine dioxide gas or chlorine gas due to the presence of chloride ion (Cl − ), hypochlorous acid (HClO) and other reduction substances or a decomposition reaction occurring among a plurality of chlorous acid molecules. Thus, it is necessary to prepare chlorous acid (HClO 2 ) such that the state of being chlorous acid (HClO 2 ) can be maintained for a long period of time in order to be useful as a sterilizing agent.
[0056] In this regard, chlorous acid (HClO 2 ) can be stably maintained over a long period of time by adding one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof to the chlorous acid (HClO 2 ), chlorine dioxide gas (ClO 2 ) or an aqueous solution containing them obtained by the above-described method to create a transitional state and delay a decomposition reaction. Although not wishing to be bound by any theory, the present invention further demonstrates that a transitional state is created and a decomposition reaction is delayed such that chlorous acid (HClO 2 ) can be stably maintained over a long period of time by using, for example, a phosphoric acid buffering agent. Furthermore, although not wishing to be bound by any theory, the present invention demonstrates that a longer and more stable transitional state can be created and chlorous acid (HClO 2 ) can be maintained over a longer period of time by delaying a decomposition reaction when using potassium salt (potassium hydroxide, potassium phosphate salt (e.g., tripotassium phosphate, dipotassium hydrogen phosphate, or potassium dihydrogen phosphate)) as metal, in comparison to cases using sodium salt (e.g., sodium hydroxide, sodium phosphate salt (disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate) as metal.
[0057] In one embodiment, it is possible to utilize chlorous acid (HClO 2 ), chlorine dioxide gas (ClO 2 ), or an aqueous solution containing them obtained by the above-described method, to which one of an inorganic acid and inorganic acid salt, specifically phosphate, carbonate and hydroxide, particularly phosphate and hydroxide, two or more types thereof or a combination thereof is added.
[0058] In another embodiment, it is possible to utilize an aqueous solution to which one of an inorganic acid and inorganic acid salt, specifically phosphate, carbonate and hydroxide, particularly phosphate and hydroxide, two or more types thereof or a combination thereof is added, to which one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof is added.
[0059] Additionally, in another embodiment, it is possible to utilize an aqueous solution manufactured by the above-described method, to which one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof is added.
[0060] Examples of inorganic acid include, but are not limited to, carbonic acid, phosphoric acid, boric acid, and sulfuric acid, while phosphoric acid is preferable. Further, examples of inorganic salt include, but are not limited to, carbonate and hydroxide as well as phosphate and borate, where phosphate is preferable. More specifically, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, or the like may be used as the carbonate; sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, or the like may be used as the hydroxide; disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, or the like may be used as the phosphate; and sodium borate, potassium borate, or the like may be used as the borate, which is preferably, but not limited to, potassium salt. Furthermore, examples of the above-described organic acid include succinic acid, citric acid, malic acid, acetic acid, lactic acid and the like. Further, sodium succinate, potassium succinate, sodium citrate, potassium citrate, sodium malate, potassium malate, sodium acetate, potassium acetate, sodium lactate, potassium lactate, calcium lactate or the like is suitable as the organic acid salt.
[0061] When an acid and/or a salt thereof is added, a transitional state, such as Na + +ClO 2 − <->Na—ClO 2 , K + +ClO 2 − <->K—ClO 2 , or H + +ClO 2 − <->H—ClO 2 can be temporarily created to delay the progression of chlorous acid (HClO 2 ) to chlorine dioxide (ClO 2 ), which enables the manufacture of an aqueous solution comprising chlorous acid (HClO 2 ) that maintains chlorous acid (HClO 2 ) for a long period of time and generates a small amount of chlorine dioxide (ClO 2 ). Although not wishing to be bound by any theory, it was demonstrated in the present invention that such an effect of maintaining is enhanced by using a phosphoric acid buffering agent. Although not wishing to be bound by any theory, it was further demonstrated in the present invention that such an effect of maintaining is further enhanced by using potassium salt relative to a case of using sodium salt or the like.
[0062] The following represents the decomposition of chlorite in an acidic solution in the above-described chemical formula 2.
[0000] [Chemical 3]
[0000] 5ClO 2 − +4H + →4ClO 2 +5Cl − +2H 2 O (a)
[0000] (5NaClO 2 +4CH 3 COOH→4ClO 2 +4CH 3 COONa+NaCl+2H 2 O) 3ClO 2 − →2ClO 3 − Cl − (b)
[0000] (3NaClO 2 →2NaClO 3 +NaCl) Autodecomposition ClO 2 − Cl − +2O (c)
[0063] As represented in the formula, the rate of decomposition of an aqueous sodium chlorite solution in terms of pH is higher when pH is lower, i.e., when acidity is stronger. That is, the absolute rates of the reactions (a), (b), and (c) in the above-described formula increase. For example, although the ratio accounted for by reaction (a) decreases for a lower pH, the total decomposition rate changes significantly, i.e., increases. Thus, the amount of generated chlorine dioxide (ClO 2 ) increases with the decrease in pH. Thus, the lower the pH value results in earlier sterilization or bleaching. However, stimulatory and harmful chlorine dioxide gas (ClO 2 ) renders an operation difficult and negatively affects the health of a human being. Further, a reaction from chlorous acid to chlorine dioxide progresses quickly, resulting in the chlorous acid becoming unstable. In addition, the time a sterilization power is maintained is very short.
[0064] In this regard, when the above-described inorganic acid, inorganic acid salt, organic acid or organic acid salt is added to an aqueous solution comprising chlorous acid (HClO 2 ), pH values are adjusted within the range of 3.2 to 8.5, or within a preferred range such as pH 3.2 to 7.0 or pH 5.0 to 7.0 in accordance with the objective, from the viewpoint of balancing suppression of chlorine dioxide generation and sterilizing power.
[0065] When a spectrometric measurement of a sample can simultaneously identify an absorbent section comprising an acidic chlorite ion (H + +ClO 2 − ) representing a peak near 260 nm and an absorbent section comprising chlorine dioxide (ClO 2 ) representing a peak near 350 nm between wavelengths 240 to 420 nm, it is possible to recognize presence of the chlorous acid aqueous solution of the present invention, i.e., the presence of chlorous acid (HClO 2 ). This is because a cyclic reaction involving the main constituent chlorous acid (HClO 2 ), chlorine dioxide (ClO 2 ), and acidic chlorite ion (H + +ClO 2 − ) is simultaneously in progress as shown in the following Chemical Formula 4.
[0000]
[0066] Conversion of chlorous acid (HClO 2 ) to chlorine dioxide (ClO 2 ) results in a single peak only near 350 nm.
[0067] It has already been found that pH can be further stabilized at this time by directly adding a buffering agent or by first adjusting the pH with sodium carbonate or the like and then adding another buffering agent.
[0068] Thus, in one aspect, the present invention provides a sterilizing agent comprising a chlorous acid aqueous solution, metal hydroxide, and metal phosphate.
[0069] Although not wishing to be bound by any theory, it was discovered that the present invention unexpectedly maintains a sterilizing effect while achieving an effect of long-term storage/stability because a combination of chlorine dioxide and one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof creates a transitional state and delay a decomposition reaction such that chlorous acid (HClO 2 ) can be stably maintained in water over a long period of time. Examples of preferable ranges of pH include, but are not limited to, 3.2 or higher to less than 7.0, about 5.0 to about 7.5, about 5.0 to about 7.0, about 5.5 to about 7.0, about 5.0 to about 6.0, and the like. Examples of the lower limit include, but are not limited to, about 5.0, about 5.1, about 5.2, about 5.3, about 5.4, about 5.5, and the like, and examples of the upper limit include, but are not limited to, about 7.5, about 7.4, about 7.3, about 7.2, about 7.1, about 7.0, about 6.9, about 6.8, about 6.7, about 6.5, about 6.4, about 6.3, about 6.2, about 6.1, about 6.0, about 5.9, about 5.8, about 5.7, about 5.6, about 5.5, and the like. The optimal pH includes, but is not limited to, about 5.5. When “about” is used for a pH value herein, the range is intended to span 0.05 in both directions when the significant digit is the first decimal point. For example, about 5.5 is understood as referring to 5.45 to 5.55. For the purpose of distinction from sodium chlorite, pH is preferably, but not limited to, less than 7.0 in the present invention.
[0070] In another aspect, although not wishing to be bound by any theory, use of potassium salt is preferable in the present invention because the property of being readily dissociable in an aqueous solution by using potassium as metal in a phosphoric acid buffering agent relative to sodium or the like was found to be effective in maintaining chlorous acid, and the use was found to enhance an effect of maintaining the created transitional state for a long period of time and delaying the progression from chlorous acid (HClO 2 ) to chlorine dioxide (ClO 2 ).
[0071] Preferable metal hydroxide includes sodium hydroxide and/or potassium hydroxide. Preferable metal phosphate includes sodium phosphate (e.g., disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate) and/or potassium phosphate (e.g., tripotassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate; especially potassium dihydrogen phosphate), and still preferably, potassium hydroxide and potassium phosphate (e.g., tripotassium phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate; especially potassium dihydrogen phosphate), where the above are non-limiting examples.
[0072] In a preferred embodiment, sodium hydroxide and potassium hydroxide are 0.1 N to 1.0 N and buffer pH of sodium phosphate and potassium phosphate is 5.0 to 7.5, especially pH of 5.0 to 7.0. This is because the effect of long term storage/stability is unexpectedly enhanced more than the previously-expected levels at these constitution and pH.
[0073] In one aspect, the present invention provides a chlorous acid aqueous solution manufactured by a method comprising the step of trapping chlorine dioxide (ClO 2 ) with aqueous solution A comprising one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof. In a preferred embodiment, the chlorous acid aqueous solution is manufactured by the method further comprising the step of adding the chlorine dioxide in the presence of hydrogen peroxide. In another preferred embodiment, the pH of the aqueous solution A is 11.0 or less and 6.0 or greater in the method. In still another preferred embodiment, the pH of the aqueous solution A is 10.8 or less and 10.2 or greater in the method. In another embodiment, the chlorine dioxide (ClO 2 ) is provided as gas in the method.
[0074] In one aspect, the present invention provides an article impregnated with the sterilizing agent of the present invention. An article that can be used as the article of the present invention is any article that can be impregnated with a chlorous acid aqueous solution to be used in sterilization or the like, including medical devices. Examples thereof include, but are not limited to, a sheet, film, patch, brush, nonwoven fabric, paper, fabric, absorbent cotton, sponge and the like.
[0075] Thus, the present invention provides, in one aspect, a kit for manufacturing a chlorous acid aqueous solution, comprising ( 1 ) a container comprising chlorine dioxide and (2) a container comprising one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof.
[0076] In one preferred embodiment, the kit further comprises another (3) container comprising one of an inorganic acid, inorganic acid salt, organic acid, and organic acid salt, two or more types thereof or a combination thereof. (2) and (3) may be the same or different.
[0077] According to the present invention, chlorous acid (HClO 2 ) can be stably maintained over a long period of time. Although not wishing to be bound by any theory, this is because it is understood that use of chlorine dioxide can create a transitional state and delay a decomposition reaction. Thus, a chlorous acid aqueous solution manufactured by the present manufacturing method is considered to have a longer lifespan compared to conventional chlorous acid aqueous solutions.
[0078] According to the present invention, chlorous acid having a high level of sterilizing power can be stabilized for a long period of time. Thus, an aqueous solution comprising chlorous acid (so-called chlorous acid aqueous solution), which was generally difficult to distribute as a product, can now be distributed to the market and popularized in the society as a highly safe, useful and simple sterilizing agent.
[0079] Any reference document cited herein, such as a scientific article, patent or patent application, is incorporated herein by reference in the same manner as the entire content of each document is specifically described.
[0080] As described above, the present invention has been explained while presenting preferable embodiments to facilitate understanding. Hereinafter, the present invention is explained based on the Examples. However, the aforementioned explanation and the following Examples are provided solely for exemplification, not for limiting the present invention. Thus, the scope of the present invention is not limited to the Embodiments or Examples that are specifically described herein. The scope of the present invention is limited solely by the scope of the claims.
EXAMPLES
[0081] When necessary, animals used in the following Examples were handled in compliance with the Declaration of Helsinki. For reagents, the specific products described in the Examples were used. However, the reagents can be substituted with an equivalent product from another manufacturer (Sigma, Wako Pure Chemical, Nacalai Tesque, or the like). There are cases herein where an abbreviation “CAAS” is used for a chlorous acid aqueous solution. However, they are synonymous.
(Production Condition of Chlorous Acid Aqueous Solution)
[0082] The chlorous acid aqueous solution used in the following Examples is produced as explained below.
[0083] (Example of Manufacturing Plant)
[0084] An example of a manufacturing plant used is shown in FIG. 1 .
[0085] Each of the numbers in FIG. 1 is the member shown in the following Table.
[0000]
TABLE 1
Number
Name
1
Chlorous acid aqueous solution manufacturing tank
2
Gas washing device
3
Chlorine dioxide gas storage tank
4
Air pump
5
Air flow spigot
[0086] The chlorine dioxide gas used (made by the Applicant) has a concentration of 0.88%, and the acceptable range is preferably 0.9%±0.1%. Gas with a high concentration is dangerous due to its explosiveness. Thus, such gas is diluted with nitrogen gas or the like for use. Further, the flow rate can be adjusted with 5, which is set at 210 ppm/minute (210 ppm/min±40 ppm/min (660 mg·ClO 2 /min to 530 mg·ClO 2 /min)) in the present Example.
[0087] (Blending Examples for Each Solution)
[0088] Blending examples of each solution that can be used in the present manufacturing example are described below.
[0000]
TABLE 2
Table of blended ingredients a (CAAS A-1)
Name of raw material
Blended amount
(1)
Tap water
731.88
g
(2)
Sodium hydroxide
2.5
g
(3)
Dipotassium hydrogenphosphate
139.36
g
(4)
Sodium carbonate
53
g
(5)
Sodium tetraborate (decahydrate)
7.63
g
(6)
35% hydrogen peroxide
30
g
Total
1000
g
[0000]
TABLE 3
Table of blended ingredients b (CAAS A-2)
Name of raw material
Blended amount
(1)
Tap water
738.64
g
(2)
Potassium hydroxide
44.8
g
(3)
Dipotassium hydrogenphosphate
139.36
g
(4)
Succinic acid
47.2
g
(5)
35% hydrogen peroxide
30
g
Total
1000
g
[0000]
TABLE 4
Table of blended ingredients c (CAAS A-3)
Name of raw material
Blended amount
(1)
Tap water
969
g
(2)
Sodium hydroxide
1
g
(3)
35% hydrogen peroxide
30
g
Total
1000
g
[0000]
TABLE 5
Table of blended ingredient d (gas washing solution)
Name of raw material
Blended amount
(1)
Tap water
910
g
(2)
Sodium hydroxide
60
g
(3)
35% hydrogen peroxide
30
g
Total
1000
g
Example 1
Manufacturing Example 1 of Chlorous Acid Aqueous Solution (CAAS A-1)
[0089] In Example 1, a chlorous acid aqueous solution was manufactured according to the following procedure based on the conditions for CAAS A-1 in (Production condition of chlorous acid aqueous solution).
[0090] (Method)
[0000] (1) Table of blended ingredient d was loaded into 2.
(2) Table of blended ingredient a was loaded into 1. The pH of the aqueous solution A was 10.8.
(3) A tank containing 0.9%±0.1% chlorine dioxide gas was prepared for 3.
(4) 4 was put into operation.
(5) 5 was released open to allow chlorine dioxide gas to flow into 1 at a flow rate of 210 ppm/minute (210 ppm/min±40 ppm/min (660 mg·ClO 2 /min to 530 mg·ClO 2 /min)).
(6) 5 was closed after the gas has flowed in for 15 minutes.
(7) 4 was stopped.
(8) The mixture was left standing for 15 minutes.
(9) 4 was again put into operation, and (4)-(8) were repeated 3 to 4 times (actual total time of chlorine dioxide gas flowing in was 45 to 60 minutes).
(10) The liquid in 1 was named chlorous acid aqueous solution A-1.
[0091] (Results)
[0092] The test results for the manufactured product are shown below.
[0000]
TABLE 6
Chlorous acid aqueous solution A-l
Tested item
Specification
Result
Potassium
When potassium
When potassium
permanganate
permanganate
permanganate solution
solution (1→300) is
(1→300) was added to 5
added to 5 ml of the
ml of the present
present product
product (1→20), the
(1→20), the mixture
mixture turned reddish
turns reddish purple.
purple. When 1 ml of
When 1 ml of sulfuric
sulfuric acid (1→20)
acid (1→20) is added
was added thereto, the
thereto, the mixture
mixture turned light
turns light yellow.
yellow.
UV spectrum
An aqueous solution
An aqueous solution of
of the present
the present product had
product has maximum
maximum absorbance
absorbance sections
sections at
at wavelengths 258 to
wavelengths 258 to 262
262 nm and 346 to 361
nm and 346 to 361 nm.
nm.
Potassium
When potassium iodide
When potassium iodide
iodide starch
starch paper is
starch paper was
paper
immersed in the
immersed in the present
present product, the
product, the potassium
potassium iodide
iodide starch paper
starch paper changes
changed to a blue color
to a blue color and
and then the color
then the color fades.
faded.
Chlorous acid
. . .
58285 ppm
concentration
[0093] The UV spectrum is shown in FIG. 2 . The UV spectrum, as shown, has a double peak, confirming that a chlorous acid aqueous solution with a sterilizing effect retained is correctly manufactured.
Example 2
Manufacturing Example 1 of Chlorous Acid Aqueous Solution Formulation (CAAS A-1)
[0094] In Example 2, a chlorous acid aqueous solution formulation was manufactured according to the following procedure by using CAAS A-1 in Example 1.
[0095] Aqueous solution B was made based on the following.
[0000]
TABLE 7
Name of raw material
Blended amount
(1)
CAAS A-1
686.28
g
(2)
Dipotassium hydrogenphosphate
14.00
g
(3)
Ion exchange water
299.72
g
Total
1000
g
[0096] The pH at this time was 6.4.
[0000]
TABLE 8
Chlorous acid aqueous solution formulation A-1
Tested item
Specification
Result
Potassium
When potassium
When potassium
permanganate
permanganate
permanganate solution
solution (1→300) is
(1→300) was added to 5
added to 5 ml of the
ml of the present
present product
product (1→20), the
(1→20), the mixture
mixture turned reddish
turns reddish purple.
purple. When 1 ml of
When 1 ml of sulfuric
sulfuric acid (1→ 20)
acid (1→20) is added
was added thereto, the
thereto, the mixture
mixture turned light
turns light yellow.
yellow.
UV spectrum
An aqueous solution
An aqueous solution of
of the present
the present product had
product has maximum
maximum absorbance
absorbance sections
sections at
at wavelengths 258 to
wavelengths 258 to 262
262 nm and 346 to 361
nm and 346 to 361 nm.
nm.
Potassium
When potassium iodide
When potassium iodide
iodide starch
starch paper is
starch paper was
paper
immersed in the
immersed in the present
present product, the
product, the potassium
potassium iodide
iodide starch paper
starch paper changes
changed to a blue color
to a blue color and
and then the color
then the color fades.
faded.
Chlorous acid
. . .
40000 ppm
concentration
[0097] The UV spectrum is shown in FIG. 3 . The UV spectrum, as shown, has a double peak, confirming that a chlorous acid aqueous solution with a sterilizing effect retained is correctly manufactured.
Example 3
Manufacturing Example 2 of Chlorous Acid Aqueous Solution (CAAS A-2)
[0098] In Example 3, a chlorous acid aqueous solution was manufactured according to the following procedure based on the conditions for CAAS A-2 in (Production condition of chlorous acid aqueous solution).
[0099] (Method)
[0000] (1) Table of blended ingredient d was loaded into 2.
(2) Table of blended ingredient b was loaded into 1. The pH of the aqueous solution A was 8.0.
(3) A tank containing 0.9%±0.1% chlorine dioxide gas was prepared for 3.
(4) 4 was put into operation.
(5) 5 was released open to allow chlorine dioxide gas to flow into 1 at a flow rate of 210 ppm/minute (210 ppm/min±40 ppm/min (660 mg·ClO 2 /min to 530 mg·ClO 2 /min)).
(6) 5 was closed after the gas had flowed in for 15 minutes.
(7) 4 was stopped.
(8) The mixture was left standing for 15 minutes.
(9) 4 was again put into operation, and (4)-(8) were repeated 2 to 3 times (actual total time of chlorine dioxide gas flowing in was 30 to 45 minutes).
(10) The liquid in 1 was considered a chlorous acid aqueous solution.
[0100] The test results for the manufactured product are shown below.
[0000]
TABLE 9
Table of blended ingredient b Chlorous acid aqueous solution
A-2
Tested item
Specification
Result
Potassium
When potassium
When potassium
permanganate
permanganate
permanganate solution
solution (1→300) is
(1→300) was added to 5 ml
added to 5 ml of the
of the present
present product
product (1→20), the
(1→20), the mixture
mixture turned reddish
turns reddish purple.
purple. When 1 ml of
When 1 ml of sulfuric
sulfuric acid (1→20)
acid (1→20) is added
was added thereto, the
thereto, the mixture
mixture turned light
turns light yellow.
yellow.
UV spectrum
An aqueous solution
An aqueous solution of
of the present
the present product had
product has maximum
maximum absorbance
absorbance sections
sections at
at wavelengths 258 to
wavelengths 258 to 262 nm
262 nm and 346 to 361 nm.
and 346 to 361 nm.
Potassium
When potassium iodide
When potassium iodide
iodide starch
starch paper is
starch paper was
paper
immersed in the
immersed in the present
present product, the
product, the potassium
potassium iodide
iodide starch paper
starch paper changes
changed to a blue color
to a blue color and
and then the color
then the color fades.
faded.
Chlorous acid
. . .
43093 ppm
concentration
[0101] The UV spectrum is shown in FIG. 4 . The UV spectrum, as shown, has a double peak, confirming that a chlorous acid aqueous solution with a sterilizing effect retained is correctly manufactured.
Example 4
Manufacturing Example 2 of Chlorous Acid Aqueous Solution Formulation (CAAS A-2)
[0102] In Example 4, a chlorous acid aqueous solution formulation was manufactured according to the following procedure by using CAAS A-2 in Example 3.
[0103] Aqueous solution B was made based on the following.
[0000]
TABLE 10
Name of raw material
Blended amount
(1)
Chlorous acid aqueous solution A-2
928.22 g
(2)
Potassium dihydrogenphosphate
17.32 g
(3)
Ion exchange water
54.46 g
Total
1000 g
[0104] The pH at this time was 6.0.
[0000]
TABLE 11
Chlorous acid aqueous solution formulation A-2
Tested item
Specification
Result
Potassium
When potassium
When potassium
permanganate
permanganate
permanganate solution
solution (1→300) is
(1→300) was added to 5 ml
added to 5 ml of the
of the present
present product
product (1→20), the
(1→20), the mixture
mixture turned reddish
turns reddish purple.
purple. When 1 ml of
When 1 ml of sulfuric
sulfuric acid (1→20)
acid (1→20) is added
was added thereto, the
thereto, the mixture
mixture turned light
turns light yellow.
yellow.
UV spectrum
An aqueous solution
An aqueous solution of
of the present
the present product had
product has maximum
maximum absorbance
absorbance sections
sections at
at wavelengths 258 to
wavelengths 258 to 262 nm
262 nm and 346 to 361 nm.
and 346 to 361 nm.
Potassium
When potassium iodide
When potassium iodide
iodide starch
starch paper is
starch paper was
paper
immersed in the
immersed in the present
present product, the
product, the potassium
potassium iodide
iodide starch paper
starch paper changes
changed to a blue color
to a blue color and
and then the color
then the color fades.
faded.
Chlorous acid
. . .
40000 ppm
concentration
[0105] The UV spectrum is shown in FIG. 5 . The UV spectrum, as shown, has a double peak, confirming that a chlorous acid aqueous solution with a sterilizing effect retained is correctly manufactured.
Example 5
Manufacturing Example 3 of Chlorous Acid Aqueous Solution (CAAS A-3)
[0106] In Example 5, a chlorous acid aqueous solution was manufactured according to the following procedure based on the conditions for CAAS A-3 in (Production condition of chlorous acid aqueous solution).
[0107] (Method)
[0000] (1) Table of blended ingredient d was loaded into 2.
(2) Table of blended ingredient c was loaded into 1. The pH of the aqueous solution A was 11.0.
(3) A tank containing 0.9%±0.1% chlorine dioxide gas was prepared for 3.
(4) 4 was put into operation.
(5) 5 was released open to allow chlorine dioxide gas to flow into 1 at a flow rate of 210 ppm/minute (210 ppm/min±40 ppm/min (660 mg·ClO 2 /min to 530 mg·ClO 2 /min)).
(6) 5 was closed after the gas had flowed in for 15 minutes.
(7) 4 was stopped.
(8) The mixture was left standing for 15 minutes.
(9) 4 was again put into operation, and (4)-(8) were repeated 1 to 2 times (actual total time of chlorine dioxide gas flowing in was 15 to 30 minutes).
(10) The liquid in 1 was considered a chlorous acid aqueous solution.
[0108] The test results for the manufactured product are shown below.
[0000]
TABLE 12
Chlorous acid aqueous solution A-3
Tested item
Specification
Result
Potassium
When potassium
When potassium
permanganate
permanganate
permanganate solution
solution (1→300) is
(1→300) was added to 5 ml
added to 5 ml of the
of the present
present product
product (1→20), the
(1→20), the mixture
mixture turned reddish
turns reddish purple.
purple. When 1 ml of
When 1 ml of sulfuric
sulfuric acid (1→20)
acid (1→20) is added
was added thereto, the
thereto, the mixture
mixture turned light
turns light yellow.
yellow.
UV spectrum
An aqueous solution
An aqueous solution of
of the present
the present product had
product has maximum
maximum absorbance
absorbance sections
sections at
at wavelengths 258 to
wavelengths 258 to 262 nm
262 nm and 346 to 361 nm.
and 346 to 361 nm.
Potassium
When potassium iodide
When potassium iodide
iodide starch
starch paper is
starch paper was
paper
immersed in the
immersed in the present
present product, the
product, the potassium
potassium iodide
iodide starch paper
starch paper changes
changed to a blue color
to a blue color and
and then the color
then the color fades.
faded.
Chlorous acid
. . .
13000 ppm
concentration
[0109] The UV spectrum is shown in FIG. 6 . The UV spectrum, as shown, has a double peak, confirming that a chlorous acid aqueous solution with a sterilizing effect retained is correctly manufactured.
Example 6
Manufacturing Example 3 of Chlorous Acid Aqueous Solution Formulation (CAAS A-3)
[0110] In Example 6, a chlorous acid aqueous solution formulation was manufactured according to the following procedure by using CAAS A-3 in Example 5.
[0111] Aqueous solution B was made based on the following.
[0000]
TABLE 13
Raw material
Blend ratio
Chlorous acid aqueous solution A-3
75.0%
Potassium dihydrogenphosphate
1.4%
Potassium hydroxide
0.6%
Purified water
23.0%
Total
100.0%
[0112] The pH at this time was 6.8.
[0113] The test results for the manufactured product are shown below.
[0000]
TABLE 14
Chlorous acid aqueous solution formulation A-3
Tested item
Specification
Result
Potassium
When potassium
When potassium
permanganate
permanganate
permanganate solution
solution (1→300) is
(1→300) was added to 5 ml
added to 5 ml of the
of the present
present product
product (1→20), the
(1→20), the mixture
mixture turned reddish
turns reddish purple.
purple. When 1 ml of
When 1 ml of sulfuric
sulfuric acid (1→20)
acid (1→20) is added
was added thereto, the
thereto, the mixture
mixture turned light
turns light yellow.
yellow.
UV spectrum
An aqueous solution
An aqueous solution of
of the present
the present product had
product has maximum
maximum absorbance
absorbance sections
sections at
at wavelengths 258 to
wavelengths 258 to 262 nm
262 nm and 346 to 361 nm.
and 346 to 361 nm.
Potassium
When potassium iodide
When potassium iodide
iodide starch
starch paper is
starch paper was
paper
immersed in the
immersed in the present
present product, the
product, the potassium
potassium iodide
iodide starch paper
starch paper changes
changed to a blue color
to a blue color and
and then the color
then the color fades.
faded.
Chlorous acid
. . .
10000 ppm
concentration
[0114] The UV spectrum is shown in FIG. 7 . The UV spectrum, as shown, has a double peak, confirming that a chlorous acid aqueous solution with a sterilizing effect retained is correctly manufactured.
Example 7
Sterilization Power Test/Stability Test
[0115] The following experiment was conducted to examine the effects of CAAS formulations A-1 to A-2 manufactured in Examples 2 and 4.
[0116] For stability, a compound (called “ASC” herein) in which 1N hydrochloric acid was added to 6% sodium chlorite to adjust the pH to 2.3 to 2.9 was used as a control. ASC, together with 2 types of chlorous acid aqueous solution manufactured in Examples 2 and 4, was sealed and stored at 4° C. in a dark room to examine the stability.
[0117] In the test to examine the sterilization effect, a change over time in sterilization effects immediately after manufacture, on day 5, and day 10 was examined. The sterilization effect on E. coli was assessed by a carbolic acid coefficient.
[0118] To examine the chlorous acid concentration, iodometric titration was performed on ASC and the 2 types of chlorous acid aqueous solution manufactured in Examples 2 and 4 on day 1, day 5, and day 10 to find the chlorous acid concentration.
[0119] The results thereof are shown below.
[0000]
TABLE 15-1
Sterilization effect examination table
(ASC) Immediately after manufacture
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
0.015%
150 ppm
−
−
−
−
0.010%
100 ppm
−
−
−
−
0.008%
80 ppm
−
−
−
−
0.007%
70 ppm
−
−
−
−
0.006%
60 ppm
−
−
−
−
0.005%
50 ppm
+
−
−
−
0.004%
40 ppm
+
−
−
−
0.003%
30 ppm
+
+
+
−
0.002%
20 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 15-2
Sterilization effect examination table (ASC) Day 5
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
+
+
+
+
1.500%
15000 ppm
+
+
+
+
1.000%
10000 ppm
+
+
+
+
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
0.005%
50 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 15-3
Sterilization effect examination table (ASC) Day 10
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
+
+
+
+
1.500%
15000 ppm
+
+
+
+
1.000%
10000 ppm
+
+
+
+
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
0.005%
50 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 16-1
Sterilization effect examination table (A-1) Immediately after manufacture
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
0.015%
150 ppm
−
−
−
−
0.010%
100 ppm
−
−
−
−
0.008%
80 ppm
−
−
−
−
0.007%
70 ppm
−
−
−
−
0.006%
60 ppm
−
−
−
−
0.005%
50 ppm
−
−
−
−
0.004%
40 ppm
+
+
−
−
0.003%
30 ppm
+
+
+
+
0.002%
20 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 16-2
Sterilization effect examination table (A-1) Day 5
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
0.015%
150 ppm
−
−
−
−
0.010%
100 ppm
−
−
−
−
0.008%
80 ppm
−
−
−
−
0.007%
70 ppm
−
−
−
−
0.006%
60 ppm
−
−
−
−
0.005%
50 ppm
−
−
−
−
0.004%
40 ppm
+
+
−
−
0.003%
30 ppm
+
+
+
−
0.002%
20 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 16-3
Sterilization effect examination table (A-1) Day 10
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
0.015%
150 ppm
−
−
−
−
0.010%
100 ppm
−
−
−
−
0.008%
80 ppm
−
−
−
−
0.007%
70 ppm
−
−
−
−
0.006%
60 ppm
−
−
−
−
0.005%
50 ppm
−
−
−
−
0.004%
40 ppm
+
+
−
−
0.003%
30 ppm
+
+
+
+
0.002%
20 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 17-1
Sterilization effect examination table (A-2) Immediately after manufacture
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
0.015%
150 ppm
−
−
−
−
0.010%
100 ppm
−
−
−
−
0.008%
80 ppm
−
−
−
−
0.007%
70 ppm
−
−
−
−
0.006%
60 ppm
−
−
−
−
0.005%
50 ppm
−
−
−
−
0.004%
40 ppm
−
−
−
−
0.003%
30 ppm
+
+
−
−
0.002%
20 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 17-2
Sterilization effect examination table (A-2) Day 5
Carbolic acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
15 min.
0.015%
150 ppm
−
−
−
−
0.010%
100 ppm
−
−
−
−
0.008%
80 ppm
−
−
−
−
0.007%
70 ppm
−
−
−
−
0.006%
60 ppm
−
−
−
−
0.005%
50 ppm
−
−
−
−
0.004%
40 ppm
−
−
−
−
0.003%
30 ppm
+
+
−
−
0.002%
20 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0000]
TABLE 17-3
Sterilization effect examination table (A-2) Day 10
Carbolic acid
concentration
Contact time
%
ppm
1 min.
15 min.
10 min.
15 min.
2.070%
20000 ppm
−
−
−
−
1.500%
15000 ppm
+
−
−
−
1.000%
10000 ppm
+
+
−
−
0.700%
7000 ppm
+
+
+
+
0.500%
5000 ppm
+
+
+
+
0.300%
3000 ppm
+
+
+
+
0.100%
1000 ppm
+
+
+
+
0.010%
100 ppm
+
+
+
+
Chlorous acid
concentration
Contact time
%
ppm
1 min.
5 min.
10 min.
5 min.
0.015%
150 ppm
−
−
−
−
0.010%
100 ppm
−
−
−
−
0.008%
80 ppm
−
−
−
−
0.007%
70 ppm
−
−
−
−
0.006%
60 ppm
−
−
−
−
0.005%
50 ppm
−
−
−
−
0.004%
40 ppm
−
−
−
−
0.003%
30 ppm
+
+
−
−
0.002%
20 ppm
+
+
+
+
0.001%
10 ppm
+
+
+
+
0.000%
0 ppm
+
+
+
+
[0120] The advantage in using gaseous chlorine dioxide (gas) includes the following: a transitional state is created and a decomposition reaction is delayed such that chlorous acid (HClO 2 ) can be stably maintained over a long period of time.
[0121] FIG. 8 shows a graph of results summarizing the above.
[0122] As shown in Tables 15-1 to 15-3 and FIG. 8 , the chlorous acid aqueous solution concentration in the control, ASC, has nearly disappeared on day 5, and the sterilization effect on E. coli has also disappeared. Meanwhile, as shown in Tables 16-1 to 16-3, 17-1 to 17-3 and FIG. 8 , the chlorous acid aqueous solution concentration of chlorous acid aqueous solution formulation A-1 and chlorous acid aqueous solution formulation A-2 dramatically decreased immediately after manufacture, but stabilized thereafter despite with a gradual decrease. The sterilization effect on E. coli was also maintained. Since there is hardly any difference in the sterilization effect when data for immediately after manufacture and day 10 are compared, it is understood as a manufacturing method of a chlorous acid aqueous solution which can stably exhibit a sterilizing effect for at least 10 days. Although not wishing to be bound by any theory, this has demonstrated that a chlorous acid aqueous solution manufactured by the manufacturing method of the present invention creates a transitional state and delays a decomposition reaction such that chlorous acid (HClO 2 ) is stably maintained in an aqueous solution over a long period of time.
[0123] As described above, the present invention is exemplified by the use of its preferred Embodiments and Examples. However, the present invention is not limited thereto. Various embodiments can be practiced within the scope of the structures recited in the claims. It is understood that the scope of the present invention should be interpreted solely based on the claims. Furthermore, it is understood that any patent, any patent application, and references cited herein should be incorporated herein by reference in the same manner as the content are specifically described herein.
INDUSTRIAL APPLICABILITY
[0124] An aqueous solution comprising a chlorous acid aqueous solution obtained by the present invention can be utilized in applications such as sterilizing agents as well as deodorants, bleaching agents, blood stain removing agents, and the like. | The present invention addresses the problem of providing a novel technique for producing aqueous chlorous acid. The present invention provides a method for producing chlorous acid, which comprises a step of adding chlorine dioxide (ClO 2 ) to one or more components independently selected from an inorganic acid, an inorganic acid salt, an organic acid and an organic acid salt or a combination of two or more of the aforementioned components. In the method, chlorine dioxide (ClO 2 ) is provided in the form of a gas. The method also comprises, subsequent to the above-mentioned addition step, a step of further adding one or more components independently selected from an inorganic acid, an inorganic acid salt, an organic acid and an organic acid salt or a combination of two or more of the aforementioned components. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. application Ser. No. 13/504,741, entitled “ENHANCED GENE EXPRESSION IN ALGAE” filed Apr. 27, 2012, which issued as U.S. Pat. No. 8,476,019, on Jul. 2, 2013, and which is a national phase of PCT/US2010/055012, entitled “ENHANCED GENE EXPRESSION IN ALGAE” filed Nov. 1, 2010, which claims the priority benefit under 35 U.S.C. §119(e) of U.S. Provisional Application Ser. No. 61/256,921, entitled “ENHANCED GENE EXPRESSION IN ALGAE” filed Oct. 30, 2009, which are both incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the field of molecular biology and in particular to the expression of transgenes in algae.
2. Description of the Background
Transgenes are foreign DNA sequences introduced into genomes, in the case of eukaryotic cells within the chromosomes. These genes are usually transcribed as any other gene of the host. Transcription is generally controlled by the chromatin structure that packs the chromosome's DNA into tight bundles in eukaryotic organisms called nucleosomes. As the chromatin structure around a specific gene relaxes, the DNA of the particular gene becomes accessible to the transcription machinery of the cell. Staining indicates that actively transcribed genes in eukaryotes are more loosely incorporated in nucleosomes and more prevalent in euchromatin. In some instances, transgenes are incorporated into the host's chromosome but fail to be expressed due to unfavorable chromatin structures. This phenomenon is called “gene silencing.” The ability to control how tightly a nucleosome is packed can help enhance the expression of transgenes in host cells. In mammalian cells, it has been proposed that coupling transgene expression with increased availability of a histone “tail” modifying gene, p300 (also known as a histone acetyl transferase, or “HAT”; in the family of CREB binding proteins, or “CBP”), can increase the expression level, presumably because the acetyl transferase activity causes a looser histone-DNA association and allows transcription factors access to the genes. T. H. J. Kwaks et al., J. Biotechnology, 115:35-46 (2005).
Microalgae encompass a broad range of organisms, mostly unicellular aquatic organisms. The unicellular eukaryotic microalgae (including green algae, diatoms, and brown algae) are photosynthetic and have a nucleus, mitochondria and chloroplasts. The chromatin structure in algae is distinct from other eukaryotes. The chromatin in algae stains heavily, indicating a more compact nucleosome structure and tight association of the DNA to the histones. These differences in chromatin structure of microalgae, particularly in green algae, suggest distinct mechanism of histone chromatin regulation of gene expression.
These differences in eukaryotic microalgae chromatin structure may be the factor behind the observation that stable nuclear transgene expression in microalgae is difficult and transient due to chromatin mediated gene silencing. H. Cerutti, A. M. J., N. W. Gillham, J. E. Boynton, Epigenetic silencing of a foreign gene in nuclear transformants of Chlamydomonas , The Plant Cell 9:925-945 (1997). When genetic constructs comprising a mammalian derived anti-apoptotic gene and a fluorescent reporter gene were previously introduced by the present inventors in algae, the expression levels were low and no expression of the fluorescence gene was detected, thus confirming that transgenes are difficult to express in algae.
Algae are considered an important source of healthy nutrients for human consumption and are important as biomass and biofuels. Genetic engineering and stable (over multiple generations) expression of transgenes would open new horizons and greatly enhance the value and desirability to beneficially culture algae. However, as noted above, stable and sufficiently high level of gene expression has been difficult to achieve. A method to improve transgene expression in algae and make that expression stable would be very useful. Such an approach would need to account for the uniquely robust histone mediated gene silencing of microalgae including green algae.
SUMMARY OF THE INVENTION
In accordance to one embodiment, the invention provides a system for enhanced gene expression in algae, the system comprising:
an algae compatible transcriptional promoter functionally upstream of a coding sequence for a gene expression enhancer (GEE) fusion protein, wherein the fusion protein comprises an algae derived p300 functionally fused to the DNA binding protein, wherein at least the portion of the coding sequence of the DNA binding protein domain is codon optimized for improved expression in an algae; at least one transgene functionally downstream of an algae compatible transcriptional promoter; and at least one DNA region that is a binding site for the DNA binding protein, in vicinity of at least one of said transcriptional promoters; wherein said system resides in an algae.
In a preferred embodiment, the DNA binding protein is LexA DNA Binding domain. In another preferred embodiment, the p300 part of the GEE fusion protein is from Chlamydomonas reinhardtii . In a more preferred embodiment, only a HAT domain of the p300 protein is part of the GEE fusion protein. The p300 or only the HAT domain of p300 may be derived from homologs of other microalgae including green algae in addition to Chlamydomonas reinhardtii.
In accordance to another embodiment, the transgene is codon modified for improved expression in algae. In a preferred embodiment, the transgene or gene of interest (GOI) is a fluorescence-Bcl-x L fusion gene. The fusion protein may include a fluorescence-Bcl-x L construct (e.g. YFP-Bcl-x L fusion or a Venus-Bcl-x L fusion). In another preferred embodiment, the transgene is the YFP/Venus gene, not necessarily part of a fusion protein. Venus is an enhanced yellow fluorescent protein (YFP) that is stable over a wide range of pH, folds quickly, and emits at 30-fold the intensity of conventional YFP. Nagai T., Ibata K., Park E. S., Kubota M., Mikoshiba K. and Miyawaki A. (2002). A variant of yellow fluorescent protein with fast and efficient maturation for cell-biological applications. Nature Biotechnol, 20, 87-90.
In accordance to another embodiment, the system further comprises at least one selective marker such as an antibiotic resistance marker. In a preferred embodiment, the GEE fusion protein and the at least one transgene are introduced into the system on one vector and structurally arranged to be expressed from one bidirectional promoter region and comprising DNA binding sites in the vicinity of both promoters. In a more preferred embodiment, the GEE fusion protein and the transgene are introduced in the system on separate vectors, each comprising a selective marker and the selective markers are not the same. When separate vectors, both the GEE vector and the vector for the gene of interest (GOI) will contain selective markers. When the GEE is introduced on a separate vector from the vector for the GOI, the GEE vector may be used to generate a stable algae cell line that will serve as the recipient for the second vector expressing the GOI. This stable GEE algae cell line will function to enhance the expression of the second vector containing the GOI.
In accordance to yet another embodiment, the algae compatible transcriptional promoters are hsp70, rbcS, nitA, actin, tubA2 or a combination thereof.
In accordance to another yet embodiment, the GEE fusion protein comprises a DNA binding domain functionally fused to an algae derived p300 homologue having at least 80% identity over the HAT region to the p300 from Chlamydomonas reinhardtii . Preferably, the GEE fusion protein comprises a DNA binding domain functionally fused to the HAT domain of the HAT region to the p300 from Chlamydomonas reinhardtii . It is noteworthy that the p300 from mammalian species is much larger in size and is much less that 50% similar to Chlamydomonas reinhardtii p300.
The invention also provides a method of expressing a gene in algae at higher levels, comprising:
transforming algae with at least one vector comprising:
an algae compatible transcriptional promoter functionally upstream of a coding sequence for a gene expression enhancer (GEE) fusion protein, wherein the fusion protein comprises an algae derived p300 functionally fused to the DNA binding protein, wherein at least the portion of the coding sequence of the DNA binding protein domain is codon optimized for improved expression in an algae;
at least one transgene functionally downstream of an algae compatible transcriptional promoter; and at least one DNA region that is a binding site for the DNA binding protein, in vicinity of at least one of said transcriptional promoters; selecting a transformed algae cell; and detecting the expression of said GEE gene and/or said transgene in algae.
In a preferred embodiment, the DNA Binding protein is the LexA binding domain, and more preferably the p300 is from Chlamydomonas reinhardtii . More preferably yet, the GEE fusion protein comprises the LexA binding domain functionally fused with the HAT domain of the p300 protein from Chlamydomonas reinhardtii.
In accordance to another embodiment, the transgene is a YFP-Bcl-x L fusion protein or a Venus-Bcl-x L fusion protein.
In accordance to yet another embodiment, the GEE fusion protein and said transgene are transformed in algae on separate vectors, first selecting a vector stably expressing the GEE fusion protein and then transforming the selected algae with the vector comprising the transgene.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the features of a vector in accordance to one embodiment of the present invention. The direction of transcription is indicated by arrows. The figure indicates certain structural components, as discussed herein elsewhere. The linear drawing provides further details of the respective region of the vector: a fused LexA-p300 protein coding region and a coding region of a GOI. In this embodiment, these two coding regions are transcribed in opposite directions (thus the “bidirectional” nomenclature). These two coding regions are separated by a locus comprising LexA binding sites.
FIGS. 2A and 2B illustrate another embodiment of the invention. FIG. 2A is a vector expressing a LexA-p300 fusion protein. FIG. 2B illustrates a vector expressing another gene which is advantageously introduced in algae (“gene of interest or “GOI”). In accordance to this embodiment, each of the LexA-p300 fusion and the GOI have, at or near their 5′-ends, LexA binding site(s).
FIG. 3 compares the putative p300 protein from algae ( Chlamydomonas reinhardtii (“Chlamy”) with known p300 proteins from the indicated phylogenetically representative species. The lighter colored section of each bar represents the histone acetylase (HAT) domain. The HAT domains are aligned for visualization purposes. These lighter bars include numbers that are indicative of the percent identity of the HAT domain of each protein proteins within each panel, with the indicated percentages of identity of each HAT protein to the p300 HAT domain of the p300 protein from Chlamy. The figure is drawn to scale, both in respect to the overall size of the p300 proteins and the location of the HAT domain within the protein.
DETAILED DESCRIPTION
Expression of transgenes in the algae is difficult. H. Cerutti, A.M.J. et al., The Plant Cell 9:925-945 (1997). Likewise, when the present inventors transformed a microalgae with a construct expressing a yellow florescence protein (“YFP”) fused to a cancer suppressing Bcl-x L gene (the transcription driven by the rubisco promoter (rcbS2) and relying on a heat shock translational enhancer (HSP70)), the transformed microalgae failed to produce fluorescence. However, transformants which survived marginally longer and were morphological affected (the result of limited expression of the Bcl-x L gene) were observed. It is expected that that gene silencing contributed to the poor expression of the transgenes in algae.
The present invention provides an effective method to increase transgene expression in algae, preferably a green algae, more preferably a microalgae. A preferred algae of the invention is an unicellular, photosynthetic algae. A yet more preferred algae is the microalgae. The GOI transgene expressed in the algae in accordance to the invention is expressed to a higher level. The expression is increased by at least 50%, preferably about two to at least five fold, relative to the expression of the same transgene engineered in the algae without the benefit of the present invention. In respect of fluorescence transgenes, the expression is increased sufficiently to allow monitoring the fluorescence signal. More preferably, the fluorescence signal is monitored in Chlamydomonas.
The transgene is introduced in algae. In accordance with an embodiment of the present invention, the transgene is placed on a vector. The vector is a nucleic acid structure used to introduce a cassette containing a DNA sequence into an algae chromosome. The vector is introduced in the nucleus of a host algae cell and the transgene is transcribed/translated in the algae. Methods of transformation of algae are well known to artisans skilled in the art. For example, a vector construct may be introduced via electroporation, via plasmid conjugation, and via particle bombardment. The transformed algae are recovered on a solid nutrient media or in liquid media. Elizabeth H Harris, Chlamydomonas As A Model Organism , Annual Review of Plant Physiology and Plant Molecular Biology 52:363-406 (2001) and EMBO Practical Course: Molecular Genetics of Chlamydomonas , Laboratory protocols. Geneva, Sep. 18-28, 2006.
A preferred vector of the invention is a plasmid capable of integrating the DNA sequence of interest into a chromosome of the algae. There are a large numbers of vectors known and characterized. A preferred vector of the invention is pSP124. Lumbreras et al., Efficient foreign gene expression in Chlamydomonas reinhardtii mediated by an endogenous introns, The Plant Journal 14(4):441-447 (1998).
Methods of engineering vectors are well known in the art. The vector backbone may include genes encoding transformation markers, to indicate transformation of the host cell with the vector. A transformation marker may be a selective marker gene used to select cells in which the vector is present from normal cells without the vector. Selective markers are well known to artisans skilled in the art. Commonly used selective markers include genes that confer resistance to specific antibiotics such as bleomycin. Only cells containing the vector grow in media containing the antibiotic. Other vector backbones may also include marker genes that merely indicate which cells were transformed. When such markers are used, cells with and without the vector will grow but the cells containing the vector can be distinguished from those not having the vector because they display a specific characteristic conferred by the vector, e.g., color. A commonly used transformation marker gene is the yellow or green fluorescence gene. Cells containing a vector with such a gene will be yellow or green. Other common transformation markers include various luciferase genes. Cells containing the luciferase genes emit light.
Any effective combination of gene expression regulatory features compatible with expression of genes in the algae nucleus can be incorporated in the vector. The plasmid may include different types of promoters, for example constitutive promoters or inducible promoters. Preferred transcriptional promoters in accordance to the invention include the hsp70 (“heat shock protein” promoter), rbcS (“rubisco small subunit” promoter) and tubA2 (“actin” promoter). The vector employs suitable translational enhancer elements, generally referred to as 5′untranslated regions or “5′UTR.” Preferred enhancers in accordance to the invention are the tubA2 intron 1, the HSP70 enhancer, and the rcbS2 intron 1. The vector of the invention includes also effective translational terminators, 3′UTR. Examples of preferred 3′-UTR sequences include the tubA2, HSP70, and rcbS2 3′UTR. Other effective promoters, transcription enhancers and terminators may, in particular combinations, may produce satisfactorily high and stable expression.
Some of these options are illustrated in FIGS. 1 and 2 . The features selected to be exemplified in FIGS. 1 and 2 include the promoter and 3′UTR regions of the Chlamy genes: tubA2 encoding actin (Tubulin); rbcS2 encoding the rubisco small subunit; or nitA encoding nitrate reductase. Furthermore, the hsp70A/rbcS2 tandem promoter is a preferred driver of transgene expression. Schroda M., Beck C. F. and Vallon A., Sequence elements within an hsp70 promoter counteract transcriptional transgene silencing in Chlamydomonas . Plant J. 31:445-455 (2002). This chimeric promoter contains the enhancer region of the nucleo-cytoplasmic-localized 70 kD heat shock protein gene (NCBI GenBank ID: M76725; by 572-833) and the promoter from the nuclear rubisco small subunit gene (NBCI GenBank ID: X04472; bp 934-1142). Additionally, the first intron (bp 1307-1451) and 3′-untranslated region (bp 2401-2632) of the rbcS2 gene may be included to further promote stable transgene expression.
In accordance with an embodiment of the present invention, one or more vectors are used to introduce a cassette that contains a gene of interest (“GOI”) and a gene silencing inhibitor into the nucleus DNA of algae, e.g., a Chlamy nucleus. The GOI can be any gene desirably expressed in algae. Viable genes of interest include genes involved in controlling algae's metabolic pathways. For example, in one embodiment of the present invention the Bcl-x L gene can be inserted and expressed in the algae's nucleus. Bcl-x L is an abbreviation for B-cell lymphoma extra-large; it is known to be an inhibitor of apoptosis (programmed cell death). Boise L. H. et al., Bcl - x, a bcl -2- related Gene that Functions as a Dominant Regulator of Apoptotic Cell Death , Cell 74:597-608 (1993). In another embodiment genes affecting lipid or isoprenoid production pathways are desirably introduced. Due to Bcl-x L 's ability to inhibit apoptosis, its expression allows algae cells to live longer. A longer lifespan for microalgae enables the use of microalgae in various industrial applications such as photobioreactors.
A gene silencing inhibitor is also introduced into the algae. A gene silencing inhibitor is a peptide that induces relaxation of nucleosomes in the algae's nucleus. Gene silencing inhibitors include histone acetyl transferases (HATs) and other peptides that modify elements of the nucleosome, causing the chromatin structure to relax and to allow transcription factors to access the gene of interest. HAT proteins and the HAT domains of p300 and of other HAT proteins are known to cause histone acetylation and can be utilized in the invention. In accordance to the invention the domain responsible for the acetylation activity or the whole protein is deployed. See Fukuda H, et al., Brief Funct. Genomic Proteomic, 5(3):190-208 (2006); Renthal W. and Nestler E. J., Semin Cell Dev Biol. 20(4):387-94 (Epub 2009); and Lin Y. Y. et al., Genes Dev., 22(15):2062-74 (2008).
One preferred embodiment of the present invention utilizes a p300 protein as a gene silencing inhibitor. More preferably, a Chlamy derived p300 protein is utilized. In a yet more preferred embodiment, the Chlamy p300 protein is the homologue detailed in FIG. 3 . In a further more preferred embodiment, only the HAT domain of the Chlamy p300 gene is utilized. See FIG. 3 and relevant portion of SEQ ID NO 4.
FIG. 3 shows an alignment comparison of the Chlamy p300 with phylogenetically distinct other p300 homologues. The lighter colored section of each bar represents the histone acetylase (HAT) domain. The HAT domains are aligned for visualization purposes. These lighter bars include numbers that are indicative of the percent identity of the HAT domain of each protein proteins with the indicated percentages of identity of each HAT protein to the p300 HAT domain of the p300 protein from Chlamy. FIG. 3 is drawn to scale, both in respect to the overall size of the p300 proteins and the location of the HAT domain within the protein.
Table 1, exemplifies the highly conserved nature of the p300 proteins and particularly conserved nature of the HAT domains.
TABLE 1
Comparison of HAT domain identity within each phylogenetic clade.
- 100%
- 100%
- 100%
- 100%
V. carteri - 85%
G. max - 91%
A. gambiae - 92%
M. mulatta - 100%
O. sativa - 91%
C. floridanus - 89%
O. cuniculus - 100%
S. bicolor - 90%
R. norvegicus - 99%
P. trichocarpa - 88%
H. musculus - 99%
Microalgae
Higher Plants
Insects
Mammals
The bolded organism at the top of each column is the representative species to which all other percent identities are based.
Indeed, the percent identity between plant and mammalian p300 homologues is also very high, typically at least about 80%. See US Patent Publication US2003/0145349. However, the homology of the Chlamy p300 homologue to other organisms is lower. Likewise, the p300 full protein of Chlamydomonas reinhardtii is 11.5% identical and further 9.9% similar to the mouse p300 protein; 9.1% identical and a further 4.7% similar to the Drosophila p300 protein; and 23.6% identical and a further 9.9% similar to the Arabidopsis p300 protein. The Chlamy derived protein has N-terminal or C-terminal regions which are shorter and dissimilar in their location visa-vie the HAT domain to these of the mammalian or plant p300 proteins. See FIG. 3 . This is suggestive of proteins with overall distinct functions and phylogeny.
The various proteins p300 homologues in FIG. 1 and described herein elsewhere are:
C. reinhardtii p300/HAT Protein ID: 159467703 from NCBI Database. V. carteri p300/CBP Protein ID: 300256266 from NCBI Database. S. bicolor putative p300 Protein ID: C5XTZ4 from Universal Protein Resource. P. trichocarpa GenBank ID: POPTR — 007s15090 from Joint Genome Institute Database. G. max Protein ID: PF02135 from Joint Genome Institute Database. A. thaliana HAC1/p300/CBP GenBank ID: NM — 106550.3 from NCBI Database. O. saliva p300/CBP Protein ID: 108792657 from NCBI Database. D. melanogaster CBP/HAT Genbank ID: NM — 079903.2 from NCBI Database. A. gambiae HAT Protein ID: 158289391 from NCBI Database. C. floridanus CBP Protein ID: 307172990 from NCBI Database. M. musculus E1A/BP/p300 GenBank ID: NM — 177821.6 from NCBI Database. O. cuniculus p300 Protein ID: 291410334 from NCBI Database. R. norvegicus p300 Protein ID: XP — 576312.3 from NCBI Database. M. mulatta p300 HAT Protein ID: XP — 001102844.1 from NCBI Database. H. sapiens p300 Protein ID: NP — 001420.2 from NCBI Database.
In another preferred embodiment of the present invention, the gene silencing inhibitor is functionally tethered or, preferably, fused to a DNA binding protein or domain thereof (the tethered/fused protein or its/their gene hereinafter are referred to as the gene expression enhancer unit, or “GEE”). The DNA binding protein or domain binds to a particular DNA sequence (Binding Site or “BS”), bringing the gene silencing inhibitor to its histone target at a location in the vicinity of the BS and thereby inducing relaxation of the nucleosome at that genetic location. As the nucleosome relaxes, the nearby DNA sequence is exposed to transcription factors and is more actively transcribed.
In accordance to a preferred embodiment, the invention requires the expression in an algae protein that binds specific DNA sequences, which sequences can be engineered upstream of any GOI for expression in algae. The DNA binding protein/domain can be any protein having known DNA binding sites can be used. Examples of proteins targeting specific DNA motifs applicable to this invention include the Gal4 protein and Early Growth Response Protein 1. DNA binding site motifs for these proteins are known. Likewise, the binding domains of these as well as the LexA protein are known and are preferentially used, instead of the full-length protein. See for example Young, K., Biol. Reprod., 58:302-311 (1998) and Joung, J. et al., Proc. Natnl. Acad. Sci., 97:7382-7 (2000). The DNA binding site (BS) for Gal4 is 5′-CGGAGGACAGTCCTCCG-3′ (SEQ ID NO 10).
LexA is a preferred example of a DNA binding protein. LexA is a gene of bacterial origin. LexA proteins or genes are not known in algae. Thus, it is unlikely that the Chlamy genome will contain the DNA binding sequence of LexA. The function of LexA in the context of the invention is to bind a particular DNA sequence (binding site, “BS”). LexA binding sites are found upstream promoters in a number of microorganisms. A consensus BS sequence for LexA is CTGTATATATATACAG. SEQ ID NO 9. The binding domain of the LexA protein is known and, for the purpose of the invention, it is preferred to employ only the binding domain. Protein ID: 2293118 from NCBI Database: MKALTARQQEVFDLIRDHISQTGMP PTRAEIAQRLGFRSPNAAEEHLKALARKGVIEIVSGASRGIRLLQEEEEGLPLVGRVAAG EPLLAQQHIEGHYQVDPSLFKPNADFLLRVSGMSMKDIGIMDGDLLAVHKTQDVRNGQ VVVARIDDEVTVKRLKKQGNKVELLPENSEFKPIVVDLRQQSFTIEGLAVGVIRNGDWL EFPGIRRPWRPLESTCSQANSGRISYDL (SEQ ID NO 11).
As noted above, the DNA binding protein or domain thereof, preferably the LexA domain, is constructed to translate in a protein allowing the DNA binding domain and a nucleosome relaxation protein to act in concert. Any nucleosome relaxation protein might be used. Preferably, as noted above, a Chlamy p300 domain is used.
Without being limited to a single mechanism of action, it is proposed that one partner binds to the DNA, the other acetylates nearby histones, thereby creating a looser association between the DNA and the histones at that site. Therefore any method to render the DNA binding domain and the acetylase domain spatially close to each other is preferred. A fused protein is more preferred. The order of the two units (N-terminal proximity) within the fusion protein is not critical. However, in the p300-LexA binding domain example, it is preferred that LexA binding domain is at the N-terminal end of the fusion. “Functional” fusion proteins are designed. By way of example, certain linker regions are introduced to allow flexibility, orientation or simply “dead” protein sequence corresponding to strategically placed genetic engineering features such as primers and restriction enzyme sites.
Preferably, the GEE can be a p300 peptide homolog and the DNA binding domain can be LexA binding domain, creating a p300-LexA binding domain fusion protein and its gene construct. Preferably, that fusion is an algae p300-LexA binding domain fusion. More preferably, the fusion is the Chlamy p300-LexA fusion. Alternatively, the fusion comprises select domains of the Chlamy p300-LexA proteins. See SEQ ID NO 4. Yet more preferably, the fusion, at the nucleic acid level, comprises a LexA sequence modified in its codon usage for higher yield when expressed in algae. Preferably, the whole of the GEE fusion protein gene was designed for preferred codon usage in algae, even if part of the gene (p300) is an algae derived gene, as provided by SEQ ID NO 1 and SEQ ID NO 3. Indeed, the transgene (GOI) and other genes in the system preferably are codon optimized based on codon frequency in algae.
It should be noted that other algae p300 homologues or their acetylasehistone acetyltransferase (HAT) domains may be preferentially used in the invention. However, these preferred homologues must be at least about 60% identical to the Chlamy p300, preferably at least about 70% identical, at least about 80% identical, at least about 85% identical, at least about 90% identical or more. A p300 homologue from V. carteri (algae) was recently identified. It has about 85% identity to the Chlamy p300, over the HAT domains.
The LexA-p300 fusion DNA (SEQ ID 1) is the nucleotide sequence encoding a fusion protein (exemplary GEE) comprising the LexA binding domain and the full length Chlamy p300 sequence, all of the fusion designed to reflect preferred codon usage in algae. It was adapted to the nuclear codon usage of C. reinhardtii according to the table provided by the Kazusa Codon Usage Database (Species ID: 3055), using Gene Designer software from DNA 20. The sequence up to nucleotide 690 is that of the LexA DNA binding domain and the fell length C. reinhardtii p300 sequence begins at nucleotide 700. A 3-amino acid peptide linker (GVL) connects LexA binding domain and p300, which represents the DNA restriction site PpuMI (9 bp). The LexA gene sequence is codon-optimized for C. reinhardtii nuclear expression using AA sequence from Protein ID: 2293118 from NCBI Database:
SEQ ID NO 1
1
ATGAAGGCTCTGACCGCTCGCCAGCAGGAGGTGTTTGATCTGATTCGGGA
51
CCATATCAGCCAAACGGGCATGCCCCCTACGCGCGCGGAGATCGCGCAAC
101
GGCTGGGCTTCCGCTCCCCGAACGCGGCTGAGGAGCACCTGAAGGCGCTG
151
GCGCGCAAGGGTGTGATTGAGATCGTCTCCGGCGCGTCGCGGGGCATTCG
201
GCTGCTGCAGGAGGAGGAGGAGGGTCTGCCTCTGGTGGGGCGGGTGGCTG
251
CGGGCGAGCCCCTGCTGGCCCAGCAGCACATTGAGGGCCACTACCAAGTG
301
GACCCGTCCCTCTTCAAGCCGAACGCCGATTTCCTGCTGCGCGTCAGCGG
351
TATGAGCATGAAGGACATCGGCATCATGGACGGTGACCTGCTGGCCGTGC
401
ATAAGACGCAGGACGTGCGCAACGGCCAAGTGGTCGTCGCCCGCATCGAT
451
GACGAGGTGACCGTGAAGCGCCTGAAGAAGCAGGGGAACAAGGTCGAGCT
501
GCTGCCCGAGAACAGCGAGTTCAAGCCCATCGTGGTGGATCTGCGCCAGC
551
AATCCTTCACCATCGAGGGCCTGGCGGTGGGCGTGATCCGCAACGGCGAC
601
TGGCTGGAGTTCCCGGGCATCCGCCGCCCGTGGCGCCCTCTGGAGTCCAC
651
GTGCTCGCAGGCCAACTCCGGCCGCATTAGCTACGACCTGGGGGTCCTTA
701
TGGTGCCGATGGGCGCGCCCGCTATGCCCATGGGCAACAACGGCTCGCCC
751
ATGCTGAACGGCATGGGTATGTTCAACGCCCCGCAGCAGACCGTGCCCAA
801
CGGCGGGCCGGGTGGCGTGAACCCCATGGGCCAGGTGCCGGCGATGCCTG
851
CGCCGATCCCCAACGGCGGTCTGCCCGGTATGAACGCTGCCGGCGGTGCC
901
GACGATCCTGCGAAGCAGCGGGAGCAATCGATCCAGAAGCAGCAGCGCTG
951
GCTGCTGTTCCTGCGGCACTGCGCGAAGTGCCGGGCTCCCGGCGAGGACT
1001
GCCAGCTGAAGTCCCAGTGCAAGTTCGGCAAGCAGCTGTGGCAGCACATC
1051
CTGTCGTGCCAAAACCCGGCCTGCGAGTACCCGCGCTGCACCAACTCCAA
1101
GGATCTGCTCAAGCACCACCAGAAGTGCCAGGAGCAGACCTGCCCCGTGT
1151
GCATGCCGGTGAAGGACTACGTGAAGAAGACGCGCCAGGCGACCCAACAG
1201
CAGCAACAAATGCAGCAACAACAGCAAATCCAGCAACAGCAACAACAACA
1251
AATGCAACAGCAACAGATGCAACAGCAGCAGCTCCAGCAGCAGCAGATGC
1301
AACAACAACAGCAGATGCAGCAGCAGCAACAGCCCGGCGTGGGCGCCAAC
1351
TTCATGCCCACCCCGCCCATGATGCCGAACGGCATGTTCCCTCAACAGCA
1401
GCCCCAGCAGGCGATGCGCCTGAACGCCAACGGCCTCGGCGGCCAGAAGC
1451
GCCCCCACGAGATGATGGGTATGTCCAGCGGCGGCATGGACGGTATGAAC
1501
CAGATGGTGCCCGTCGGCGGCGGCGGCATGGGCATGTCGATGCCGATGGG
1551
TATGAACAACCCCATGCAGGGCGGTATGCCCCTGCAGCCTCCGCCCCAGG
1601
TGCAGGCTCCCGGTCAGGGCCCCATGATGAGCGCCCCTCAGCAGCAACAG
1651
CAGCAACCGGCCCCTAAGCGGGCGAAGACCGACGATGTGCTGCGCCAGAA
1701
CACGGGCACCAGCCTCCTGGAGACGTTCGACGCCAAGCAGATCCGCGTGC
1751
ACGTGGACCTGATCCGCGCTGCCGCGGTGACCCAGAAGGCCCAGCAGCCT
1801
CCCCCGGCTAACCCCGACGACGCGTGCAAGGTCTGCGCGCTGACGAAGCT
1851
GTCGTTCGAGCCCCCGGTGATTTACTGCTCGAGCTGCGGCCTGCGCATCA
1901
AGCGCGGCCAGATCTTCTACAGCACGCCTCCGGACCACGGCAACGACCTG
1951
AAGGGTTACTTCTGCCACCAGTGCTTCACCGACCAGAAGGGCGAGCGCAT
2001
CCTGGTGGAGGGCGTCTCGATCAAGAAGAGCGACCTGGTGAAGCGCAAGA
2051
ACGATGAGGAGATCGAGGAGGGGTGGGTGCAGTGCGACCACTGCGAGGGC
2101
TGGGTGCACCAGATTTGCGGCATGTTCAACAAGGGCCGGAACAACACGGA
2151
CGTCCACTACCTGTGCCCTGACTGCCTGGCCGTGGGCTACGAGCGCGGCC
2201
AGCGCCAGAAGACGGAGGTCCGCCCCCAGGCGATGCTCGAGGCGAAGGAT
2251
CTGCCCACGTCCCGGCTGTCCGAGTTTATTACGGAGCGCCTGAACCGCGA
2301
GCTGGAGAAGGAGCACCACAAGCGGGCTGAGCAGCAGGGCAAGCCGCTGC
2351
ACGAGGTGGCGAAGCCCGAGCCCCTGACCGTGCGGATGATCAACTCCGTG
2401
ATGAAGAAGTGCGAGGTCAAGCCGCGCTTCCACGAGACGTTCGGCCCCAC
2451
CGACGGCTACCCCGGGGAGTTCGGCTACCGGCAGAAGGTGCTGCTGCTGT
2501
TCCAAAGCCTGGACGGTGTCGACGTGTGCCTGTTCTGCATGTACGTGCAG
2551
GAGTACGGCAAGGACTGCCCTGCGCCCAACACCAACGTGGTGTACCTGTC
2601
GTATCTGGACTCCGTCAAGTACTTCCGCCCTGAGATTCCCTCGGCCCTGG
2651
GCCCTGCCGTGTCGCTGCGCACCTTCGTGTACCACCAACTCCTGATCGCC
2701
TACGTGGAGTTTACCCGCAACATGGGTTTTGAGCAGATGTACATTTGGGC
2751
GTGCCCGCCGATGCAAGGCGACGACTACATCCTGTACTGCCACCCGACCA
2801
AGCAGAAGACGCCGCGCTCGGACCGCCTGCGCATGTGGTACATTGAGATG
2851
CTGAAGCTGGCGAAGGAGGAGGGTATCGTGAAGCACCTGAGCACGCTGTG
2901
GGATACGTACTTCGAGGGCGGTCGCGACCACCGGATGGAGCGCTGCTCGG
2951
TCACGTACATTCCGTACATGGAGGGCGACTACTGGCCCGGCGAGGCTGAG
3001
AACCAGCTCATGGCCATTAACGACGCGGCCAAGGGCAAGCCTGGGACCAA
3051
GGGTGCGGGCAGCGCCCCGAGCCGCAAGGCCGGTGCCAAGGGCAAGCGCT
3101
ACGGCGGTGGCCCCGCCACGGCTGATGAGCAGCTGATGGCCCGCCTCGGT
3151
GAGATCCTGGGCGGGAACATGCGGGAGGACTTCATTGTGGTCCACATGCA
3201
GGTGCCCTGCACGTTCTGCCGCGCTCACATTCGGGGTCCGAACGTGGTGT
3251
ACCGCTATCGGACGCCGCCTGGCGCGACCCCTCCCAAGGCTGCCCCCGAG
3301
CGCAAGTTCGAGGGCATCAAGCTGGAGGGCGGTGGCCCCAGCGTGCCCGT
3351
GGGCACCGTCTCGAGCCTGACGATCTGCGAGGCGTGCTTTCGCGACGAGG
3401
AGACGCGCACGCTGACCGGCCAACAGCTGCGCCTGCCCGCTGGCGTGTCG
3451
ACCGCTGAGCTCGCGATGGAGAAGCTGGAGGAGATGATCCAGTGGGACCG
3501
CGACCCTGACGGCGACATGGAGAGCGAGTTCTTCGAGACGCGGCAGACCT
3551
TCCTGTCGCTGTGCCAGGGCAACCACTACCAGTTCGACACCCTCCGCCGC
3601
GCTAAGCACTCGTCGATGATGGTGCTCTACCACCTGCACAACCCCCACTC
3651
GCCGGCGTTCGCGTCCTCGTGCAACCAGTGCAACGCCGAGATCGAGCCGG
3701
GCAGCGGCTTTCGCTGCACCGTGTGCCCCGACTTCGACATGTGCGCCAGC
3751
TGCAAGGTCAACCCTCATAAGCGCGCCCTGGACGAGACGCGCCAGCGGCT
3801
GACCGAGGCCGAGCGCCGGGAGCGCAACGAGCAGCTGCAGAAGACCCTCG
3851
CCCTGCTGGTGCACGCCTGCGGCTGCCACAACAGCGCGTGCGGCTCCAAC
3901
AGCTGCCGCAAGGTGAAGCAGCTGTTCCAGCACGCGGTCCACTGCCAGAG
3951
CAAGGTGACCGGGGGCTGCCAGCTGTGCAAGAAGATGTGGTGCCTGCTGA
4001
ACCTGCACGCCAAGTCCTGCACCCGCGCGGACTGCCCGGTGCCGCGCTGC
4051
AAGGAGCTGAAGGAGCTGCGCCGGCGCCAAACGAACCGGCAGGAGGAGAA
4101
GCGCCGGGCGGCCTACGCCGCTATGCTGCGCAACCAGATGGCCGGCAGCC
4151
AGGCTCCGCGCCCCATGTAA.
LexA-p300 Fusion Protein (SEQ ID NO 2) is the respective protein sequence encoded by the nucleic acid sequence of SEQ ID NO 1. The LexA binding domain is the sequence up to and including amino acid 230 and the full-length p300 HAT domain sequence begins at amino acid 234. A 3-amino acid peptide linker (GVL) connects LexA binding domain and p300, which represents the DNA restriction site PpuMI (9 bp):
SEQ ID NO 2
1
MKALTARQQEVFDLIRDHISQTGMPPTRAEIAQRLGFRSPNAAEEHLKAL
51
ARKGVIEIVSGASRGIRLLQEEEEGLPLVGRVAAGEPLLAQQHIEGHYQV
101
DPSLFKPNADFLLRVSGMSMKDIGIMDGDLLAVHKTQDVRNGQVVVARID
151
DEVTVKRLKKQGNKVELLPENSEFKPIVVDLRQQSFTIEGLAVGVIRNGD
201
WLEFPGIRRPWRPLESTCSQANSGRISYDLGVLMVPMGAPAMPMGNNGSP
251
MLNGMGMFNAPQQTVPNGGPGGVNPMGQVPAMPAPIPNGGLPGMNAAGGA
301
DDPAKQREQSIQKQQRWLLFLRHCAKCRAPGEDCQLKSQCKFGKQLWQHI
351
LSCQNPACEYPRCTNSKDLLKHHQKCQEQTCPVCMPVKDYVKKTRQATQQ
401
QQQMQQQQQIQQQQQQQMQQQQMQQQQLQQQQMQQQQQMQQQQQPGVGAN
451
FMPTPPMMPNGMFPQQQPQQAMRLNANGLGGQKRPHEMMGMSSGGMDGMN
501
QMVPVGGGGMGMSMPMGMNNPMQGGMPLQPPPQVQAPGQGPMMSAPQQQQ
551
QQPAPKRAKTDDVLRQNTGTSLLETFDAKQIRVHVDLIRAAAVTQKAQQP
601
PPANPDDACKVCALTKLSFEPPVIYCSSCGLRIKRGQIFYSTPPDHGNDL
651
KGYFCHQCFTDQKGERILVEGVSIKKSDLVKRKNDEEIEEGWVQCDHCEG
701
WVHQICGMFNKGRNNTDVHYLCPDCLAVGYERGQRQKTEVRPQAMLEAKD
751
LPTSRLSEFITERLNRELEKEHHKRAEQQGKPLHEVAKPEPLTVRMINSV
801
MKKCEVKPRFHETFGPTDGYPGEFGYRQKVLLLFQSLDGVDVCLFCMYVQ
851
EYGKDCPAPNTNVVYLSYLDSVKYFRPEIPSALGPAVSLRTFVYHQLLIA
901
YVEFTRNMGFEQMYIWACPPMQGDDYILYCHPTKQKTPRSDRLRMWYIEM
951
LKLAKEEGIVKHLSTLWDTYFEGGRDHRMERCSVTYIPYMEGDYWPGEAE
1001
NQLMAINDAAKGKPGTKGAGSAPSRKAGAKGKRYGGGPATADEQLMARLG
1051
EILGGNMREDFIVVHMQVPCTFCRAHIRGPNVVYRYRTPPGATPPKAAPE
1101
RKFEGIKLEGGGPSVPVGTVSSLTICEACFRDEETRTLTGQQLRLPAGVS
1151
TAELAMEKLEEMIQWDRDPDGDMESEFFETRQTFLSLCQGNHYQFDTLRR
1201
AKHSSMMVLYHLHNPHSPAFASSCNQCNAEIEPGSGFRCTVCPDFDMCAS
1251
CKVNPHKRALDETRQRLTEAERRERNEQLQKTLALLVHACGCHNSACGSN
1301
SCRKVKQLFQHAVHCQSKVTGGCQLCKKMWCLLNLHAKSCTRADCPVPRC
1351
KELKELRRRQTNRQEEKRRAAYAAMLRNQMAGSQAPRPM*.
LexA-p300 HAT domain DNA (SEQ ID NO 3) is a nucleic acid sequence corresponding to a gene encoding the LexA binding domain-acetyl-transferase (HAT) domain of the Chlamy p300 protein. Similarly, the LexA binding domain is the sequence up to and including nucleotide 690 and the p300 HAT domain sequence begins at nucleotide 700. A 3-amino acid peptide linker (GVL) connects LexA binding domain and p300, which represents the DNA restriction site PpuMI (9 bp).
SEQ ID NO 3
1
ATGAAGGCTCTCACCGCTCGCCAACAGGAGGTCTTTGATCTGATTCGCGA
51
CCACATCTCGCAGACCGGCATGCCGCCGACCCGGGCGGAGATTGCTCAGC
101
GGCTGGGCTTCCGGAGCCCCAACGCGGCCGAGGAGCACCTGAAGGCCCTC
151
GCGCGCAAGGGGGTGATCGAGATTGTCTCCGGCGCTAGCCGCGGCATCCG
201
CCTGCTGCAGGAGGAGGAGGAGGGCCTGCCGCTGGTCGGGCGGGTCGCGG
251
CCGGGGAGCCTCTGCTGGCCCAGCAGCACATCGAGGGCCACTACCAAGTG
301
GACCCCTCGCTGTTTAAGCCCAACGCGGACTTCCTGCTCCGGGTGTCGGG
351
CATGAGCATGAAGGACATCGGCATCATGGACGGCGACCTCCTGGCGGTGC
401
ACAAGACCCAGGACGTGCGCAACGGCCAGGTGGTCGTCGCGCGGATTGAC
451
GACGAGGTGACCGTGAAGCGGCTGAAGAAGCAGGGCAACAAGGTCGAGCT
501
GCTGCCCGAGAACTCGGAGTTCAAGCCTATCGTGGTCGACCTGCGCCAGC
551
AGTCCTTCACCATCGAGGGCCTGGCCGTGGGGGTCATCCGCAACGGTGAC
601
TGGCTGGAGTTCCCCGGCATCCGGCGCCCGTGGCGGCCGCTGGAGTCCAC
651
CTGCAGCCAGGCGAACTCCGGCCGCATCTCCTACGATCTGGGGGTCCTTG
701
AGGTGGCCAAGCCGGAGCCGCTGACCGTGCGGATGATCAACAGCGTGATG
751
AAGAAGTGCGAGGTCAAGCCCCGCTTCCACGAGACGTTCGGTCCGACCGA
801
CGGTTACCCCGGGGAGTTCGGCTACCGGCAGAAGGTGCTCCTCCTGTTCC
851
AGTCCCTCGACGGCGTCGACGTGTGCCTGTTCTGCATGTACGTGCAGGAG
901
TACGGGAAGGACTGCCCGGCGCCCAACACGAACGTGGTGTACCTGAGCTA
951
CCTGGACTCCGTCAAGTATTTCCGCCCCGAGATTCCCAGCGCCCTGGGCC
1001
CTGCGGTGAGCCTGCGGACCTTCGTGTACCACCAGCTCCTGATTGCGTAC
1051
GTGGAGTTCACGCGCAACATGGGCTTCGAGCAGATGTACATTTGGGCGTG
1101
CCCCCCCATGCAGGGGGACGACTATATCCTGTATTGCCATCCCACGAAGC
1151
AGAAGACCCCGCGCTCGGACCGCCTGCGCATGTGGTACATCGAGATGCTG
1201
AAGCTGGCTAAGGAGGAGGGCATCGTGAAGCACCTGTCGACGCTGTGGGA
1251
CACCTACTTCGAGGGCGGTCGCGACCACCGGATGGAGCGCTGCAGCGTGA
1301
CCTACATCCCCTACATGGAGGGCGACTACTGGCCTGGCGAGGCCGAGTAA.
LexA-p300 HAT domain AA (SEQ ID NO 4) is an exemplary GEE protein sequence of a LexA binding domain-Chlamy p300 protein, where the Chlamy p300 is limited to the histone acetyl-transferase (HAT) domain of the Chlamy p300 enzyme. The LexA binding domain is the sequence up to and including amino acid 230 and the p300 HAT domain sequence begins at amino acid 234. The 3-amino acid peptide linker (GVL) connects LexA binding domain and p300:
SEQ ID NO 4
1
MKALTARQQEVFDLIRDHISQTGMPPTRAEIAQRLGFRSPNAAEEHLKAL
51
ARKGVIEIVSGASRGIRLLQEEEEGLPLVGRVAAGEPLLAQQHIEGHYQV
101
DPSLFKPNADFLLRVSGMSMKDIGIMDGDLLAVHKTQDVRNGQVVVARID
151
DEVTVKRLKKQGNKVELLPENSEFKPIVVDLRQQSFTIEGLAVGVIRNGD
201
WLEFPGIRRPWRPLESTCSQANSGRISYDLGVLEVAKPEPLTVRMINSVM
251
KKCEVKPRFHETFGPTDGYPGEFGYRQKVLLLFQSLDGVDVCLFCMYVQE
301
YGKDCPAPNTNVVYLSYLDSVKYFRPEIPSALGPAVSLRTFVYHQLLIAY
351
VEFTRNMGFEQMYIWACPPMQGDDYILYCHPTKQKTPRSDRLRMWYIEML
401
KLAKEEGIVKHLSTLWDTYFEGGRDHRMERCSVTYIPYMEGDYWPGEAE*.
Codon-optimized Venus gene sequence is a preferred embodiment:
SEQ ID NO 5
1
ATGGTGTCGAAGGGTGAGGAGCTGTTTACCGGTGTCGTGCCTATTCTGGT
51
GGAGCTCGACGGCGACGTCAACGGGCACAAGTTTTCGGTGTCCGGCGAGG
101
GTGAGGGGGACGCGACGTACGGCAAGCTCACGCTGAAGCTGATCTGCACC
151
ACCGGCAAGCTGCCCGTCCCCTGGCCGACGCTGGTGACCACCCTGGGCTA
201
CGGCCTGCAGTGCTTCGCCCGCTACCCGGACCACATGAAGCAGCACGACT
251
TCTTCAAGTCGGCCATGCCCGAGGGGTACGTGCAGGAGCGCACGATCTTC
301
TTTAAGGACGATGGCAACTACAAGACCCGCGCTGAGGTGAAGTTCGAGGG
351
CGATACGCTGGTGAACCGCATCGAGCTCAAGGGCATCGACTTCAAGGAGG
401
ACGGCAACATCCTGGGTCACAAGCTGGAGTACAACTACAACTCCCACAAC
451
GTGTACATCACGGCGGATAAGCAGAAGAACGGCATCAAGGCCAACTTTAA
501
GATTCGCCATAACATCGAGGACGGCGGCGTGCAGCTCGCCGACCACTACC
551
AGCAGAACACCCCGATCGGCGACGGCCCCGTGCTGCTGCCCGATAACCAC
601
TACCTCAGCTACCAGTCGGCCCTGTCCAAGGATCCCAACGAGAAGCGCGA
651
TCACATGGTCCTCCTGGAGTTCGTGACCGCCGCTGGCATCACCCTGGGCA
701
TGGACGAGCTGTACAAGTAA.
SEQ ID NO 6 is the protein encoded by the nucleic acid of SEQ ID NO 5. The Venus AA sequence:
SEQ ID NO 6
1
MVSKGEELFTGVVPILVELDGDVNGHKFSVSGEGEGDATYGKLTLKLICT
51
TGKLPVPWPTLVTTLGYGLQCFARYPDHMKQHDFFKSAMPEGYVQERTIF
101
FKDDGNYKTRAEVKFEGDTLVNRIELKGIDFKEDGNILGHKLEYNYNSHN
151
VYITADKQKNGIKANFKIRHNIEDGGVQLADHYQQNTPIGDGPVLLPDNH
201
YLSYQSALSKDPNEKRDHMVLLEFVTAAGITLGMDELYK*.
SEQ ID NO 7 is a nucleic acid encoding a Venus-Bcl-x L fusion of the invention. It was designed to represent preferred codon usage in algae. The sequence up to and including nucleotide 717 represents Venus. A 3-amino acid peptide linker (GVL) connects Venus and Bcl-x L , which represents the DNA restriction site PpuMI (9 bp). Bcl-x L begins at nucleotide 726.
SEQ ID NO 7
1
ATGGTGTCGAAGGGTGAGGAGCTGTTTACCGGTGTCGTGCCTATTCTGGT
51
GGAGCTCGACGGCGACGTCAACGGGCACAAGTTTTCGGTGTCCGGCGAGG
101
GTGAGGGGGACGCGACGTACGGCAAGCTCACGCTGAAGCTGATCTGCACC
151
ACCGGCAAGCTGCCCGTCCCCTGGCCGACGCTGGTGACCACCCTGGGCTA
201
CGGCCTGCAGTGCTTCGCCCGCTACCCGGACCACATGAAGCAGCACGACT
251
TCTTCAAGTCGGCCATGCCCGAGGGGTACGTGCAGGAGCGCACGATCTTC
301
TTTAAGGACGATGGCAACTACAAGACCCGCGCTGAGGTGAAGTTCGAGGG
351
CGATACGCTGGTGAACCGCATCGAGCTCAAGGGCATCGACTTCAAGGAGG
401
ACGGCAACATCCTGGGTCACAAGCTGGAGTACAACTACAACTCCCACAAC
451
GTGTACATCACGGCGGATAAGCAGAAGAACGGCATCAAGGCCAACTTTAA
501
GATTCGCCATAACATCGAGGACGGCGGCGTGCAGCTCGCCGACCACTACC
551
AGCAGAACACCCCGATCGGCGACGGCCCCGTGCTGCTGCCCGATAACCAC
601
TACCTCAGCTACCAGTCGGCCCTGTCCAAGGATCCCAACGAGAAGCGCGA
651
TCACATGGTCCTCCTGGAGTTCGTGACCGCCGCTGGCATCACCCTGGGCA
701
TGGACGAGCTGTACAAGGGGGTCCTTATGAGCCAGAGCAACCGGGAGCTG
751
GTGGTGGACTTCCTGAGCTACAAGCTGAGCCAAAAGGGCTATAGCTGGTC
801
GCAGTTCTCCGACGTCGAGGAGAACCGGACCGAGGCCCCCGAGGGGACCG
851
AGTCCGAGATGGAGACGCCGAGCGCGATTAACGGCAACCCGAGCTGGCAC
901
CTGGCGGACTCCCCTGCCGTGAACGGCGCGACCGGCCACAGCTCCAGCCT
951
GGACGCGCGCGAGGTCATCCCGATGGCGGCCGTGAAGCAGGCCCTCCGCG
1001
AGGCCGGCGACGAGTTCGAGCTGCGCTATCGCCGCGCTTTCTCGGACCTG
1051
ACCAGCCAGCTGCACATCACCCCCGGCACGGCTTACCAAAGCTTCGAGCA
1101
GGTGGTGAACGAGCTGTTCCGCGACGGCGTGAACTGGGGTCGCATCGTGG
1151
CGTTCTTCAGCTTCGGCGGTGCGCTGTGCGTGGAGAGCGTCGACAAGGAG
1201
ATGCAGGTGCTGGTGTCGCGCATTGCGGCTTGGATGGCCACCTACCTGAA
1251
CGACCACCTGGAGCCCTGGATTCAGGAGAACGGCGGCTGGGACACCTTCG
1301
TCGAGCTGTACGGCAACAACGCTGCGGCGGAGAGCCGCAAGGGCCAAGAG
1351
CGGTTCAACCGCTGGTTCCTCACGGGGATGACCGTGGCGGGCGTCGTCCT
1401
GCTGGGCAGCCTGTTCTCGCGGAAGTAA.
Venus-Bcl-x L Protein (SEQ ID NO 8) is the protein fusion encoded by the nucleic acid of SEQ ID NO 7. The underlying Bcl-x L protein sequence (233 AA) is encoded by the DNA sequence GenBank ID: 20336334 from NCBI Database:
SEQ ID NO 8
1
MVSKGEELFTGVVPILVELDGDVNGHKFSVSGEGEGDATYGKLTLKLICT
51
TGKLPVPWPTLVTTLGYGLQCFARYPDHMKQHDFFKSAMPEGYVQERTIF
101
FKDDGNYKTRAEVKFEGDTLVNRIELKGIDFKEDGNILGHKLEYNYNSHN
151
VYITADKQKNGIKANFKIRHNIEDGGVQLADHYQQNTPIGDGPVLLPDNH
201
YLSYQSALSKDPNEKRDHMVLLEFVTAAGITLGMDELYKGVLMSQSNREL
251
VVDFLSYKLSQKGYSWSQFSDVEENRTEAPEGTESEMETPSAINGNPSWH
301
LADSPAVNGATGHSSSLDAREVIPMAAVKQALREAGDEFELRYRRAFSDL
351
TSQLHITPGTAYQSFEQVVNELFRDGVNWGRIVAFFSFGGALCVESVDKE
401
MQVLVSRIAAWMATYLNDHLEPWIQENGGWDTFVELYGNNAAAESRKGQE
451
RFNRWFLTGMTVAGVVLLGSLFSRK*.
Example 1
An Exemplary Vector of the Invention
FIG. 1 illustrates a construct in accordance to the invention. The starting vector is pSP124. See V. Lumbreras, D. R. S. and S. Purton, Plant J., 14(4):441-447 (1998). Features of the vector are listed in FIG. 1 , i.e. the two regions indicated in FIG. 1 to be part of the backbone vector, pSP124.
None pSP124 sequences are preferably engineered as individual synthetic DNA fragments and strung together via restriction enzyme sites, by well-known techniques. Alternative approaches and mixtures of approaches are available. For example, some features are optionally introduced as PCR products or “cut and pasted” from other available constructs. Typically, sequencing and/or other assays (e.g. size analysis, hybridization) are used to verify the resultant vector.
As an example, one section of the insert is created by synthesis of a region having a BamHI site and ending with an EcoRI site (“Synthetic — 1”). This region provides a transcriptional enhancer region, two LexA binding motifs, a rubisco transcriptional promoter (including the first intron of rbcS2), a YFP-Bcl-x L fusion protein, and a rubisco 3′UTR. The YFP and Bcl-x L coding regions were designed in this instance to reflect the preferred codon usage in algae.
Another region incorporated is prepared by high fidelity PCR and effectively provides the p300 (HAT) gene (“Genomic PCR”). Flanking the genomic PCR fragment are two additional regions prepared by synthetic DNA (“Synthetic — 2”). The region transcriptionally upstream of the p300 gene provides the LexA binding domain coding sequence downstream of transcriptional promoters and two LexA binding sites. The Synthetic — 2 region provides a 3′UTR. Combined, the Synthetic — 2 and Genomic regions create a complete transcription unit encoding a LexA-p300 fusion protein (GEE).
Effectively, FIG. 1 and these explanations provide an example of the features of a construct of the invention and illustrate methods of creating the features within an algae compatible plasmid. Two transcriptional units face opposing directions and each have two LexA binding sites, creating an opportunity for the LexA-p300 to bind at any of four sites and affect transcription levels of either transcriptional unit. A third transcriptional unit provides a selection marker, bleomycin-resistance.
It will be recognized by a skilled artisan that other design approaches are available, including the incorporation within the vector of additional or different genes incorporated for expression, different gene expression control features, other restriction sites, change the number of LexA-BS, and so on, without changing the concept behind the creation of this vector, namely to effectively increase the levels of expression of the genes located in vicinity of a DNA-BS, in the presence of a GEE that recognizes/binds the BS.
Example 2
Additional Exemplary Vectors
Two vectors are constructed which are in most respects identical, but for the presence of a GEE unit. The vectors are otherwise the same to each other and similar to the vector of FIG. 2A . The use of these vectors in parallel allows testing of the p300 activity and the role of LexA in otherwise identical genetic backgrounds. The use of two vectors also allows for modulation of the GEE activities by such additional engineering, for example, as addition of other genes, addition of multiple copies of GEE and so on.
Notably, “LexA BS” does not refer to any limit of the number of binding sites; anything from one BS to many BS are possibly located at the indicated position. Practically speaking, it is unlikely to utilize more than about 8 BS, as benefit from additional sites would be unlikely. Preferably, about 2 to 6 BS are located in the region at or near the 5′end of genes desirably expressed, more preferably there are 2-4 BS.
Example 3
Characterization of GEE Efficacy with a Bidirectional Promoter
Experiment 1. Use the bidirectional construct with YFP reporter in the position of the GOI and either one of two variants of the GEE construct: [1] in which the LexA-p300 chimeric gene is driven in the opposite direction ( FIG. 1 ) or [ 2 ] in which only LexA is driven in the opposite direction which serves as a control.
Algae are transformed with the two constructs and selected on appropriate antibiotic containing selection media (e.g. media containing bleocin). After selection, 100 colonies from transformation for each construct are chosen to analyze the expression of the YFP transgene by assaying mRNA expression using rtPCR, protein expression with Western blot, and single cell fluorescence by flow cytometry and fluorescent microscopy. The clonal populations are passaged for 2, 4, 6, and 10 generations. The frequency of high-level expression of YFP are compared between the LexA-p300 and LexA only clones. The LexA-p300 GEE increases expression and maintains a higher level of nuclear transgene expression over time.
Example 4
Characterization of GEE Efficacy Using Distinct Plasmids
Generate two sets of stable clones: Set one is a stable cell line with the incorporated transgene encoding the LexA-p300 fusion ( FIG. 2A ) that is then transformed with a plasmid that expresses the YFP vector ( FIG. 2B ). Set two is a stable cell line with the incorporated transgene encoding the LexA only (related to FIG. 2A with the exception of the p300 fusion partner) that is then transformed with a plasmid that expresses the YFP vector ( FIG. 2B ).
Select for stable cell lines and characterize the YFP expression over time by assaying mRNA expression by rtPCR, western blot to determine protein expression, and assay of single cell fluorescence by flow cytometry and fluorescent microscopy. The clonal populations will be passaged for 2, 4, 6, and 10 generations. Similarly, the frequency of high-level expression of YFP are compared between the LexA-p300 and LexA only clones. The LexA-p300 GEE increases expression and maintains a higher level of nuclear transgene expression over time.
The invention described above should be read in conjunction with the accompanying claims and drawings. The description of embodiments and examples enable one to practice various implementations of the invention and they are not intended to limit the invention to the preferred embodiment, but to serve as a particular example of the invention. Those skilled in the art will appreciate that they may readily use the conception and specific embodiments disclosed as a basis for modifying or designing other methods and systems for carrying out the same purposes of the present invention.
All references, including publications, patent applications, patents, and website content cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and was set forth in its entirety herein.
The websites mentioned herein were last visited on Oct. 30, 2010.
The use of the terms “a” and “an” and “the” and similar references in the context of describing the invention are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. The word “about,” when accompanying a numerical value, is to be construed as indicating a deviation of up to and inclusive of 10% from the stated numerical value. The use of any and all examples, or exemplary language (“e.g.” or “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. NO language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention. | The invention provides eukaryotic unicellular algae engineered to express a nucleosome alteration protein fused to a protein with affinity to the DNA binding site acting in coordination. An example is a LexA-p300 fusion protein, where the p300 is derived from Chlamydomonas . The LexA binding domain guides the p300 to the binding site and the p300 loosens the nucleosome structure by acetylating histones within proximity of the transgene, thus remodeling the local chromatin structure to allow for high-level expression. | 2 |
[0001] This application claims the benefit of priority under 35 U.S.C. 119(e) to provisional application 60/463,510 filed Apr. 16, 2003.
BACKGROUND OF THE INVENTION
[0002] Sport fishing is enjoyed by millions of people every year and many fish are caught and release each year by anglers. However a significant portion of sport fishermen catch and keep the fish they have caught.
[0003] Removing the fish from the ecosystem denies future anglers the opportunity to catch and release the same fish. Larger fish are particularly susceptible to being kept. These larger fish represent an opportunity for increasing the fish population through their potential offspring, offspring that could be increased through the practice of catch and release.
[0004] Fish tagging, especially by fish hatcheries, biologists, and scientists is known. However, past tagging practice has had several limitations. Many fish die when they are young fingerlings and the tagging effort is wasted. Those tagged fish that are recovered are often removed from the ecosystem by the angler. Even if the fish is returned, the tag is often removed as evidence that the fish was caught, or to provide the data needed to specifically identify the fish caught. Even when the tagged fish is returned the data from the fish is narrowly distributed. Often, the tagging information is not provided back to the person or organization that did the initial tagging. Another limitation of previous tagging efforts is that they have not sufficiently encouraged the releasing of fish caught during recreational fishing. A method that encourages recreational and/or professional anglers to tag fish, record data on the fish and make that data available to others remains lacking in the art. The previous methods of tagging provided inadequate motivation to anglers to release the fish with the tag intact and/or record information about the fish to share with others.
[0005] Individuals and organizations have studied fish using various tags. However, the expense of tagging, the limited return rate of information and the lack of funding have all limited the use of fish tagging in spite of its value as a fish management tool.
[0006] While rewards for the return of tags in general have been contemplated, such efforts without a broader business strategy are too expensive and inefficient. A tagged fish may not be recaptured for years. Further, the tag and/or the fish are often kept to validate the data provided. A public database of tagging information has previously been incompatible with a reward system since the database would include the tag number.
[0007] A number of fish tagging mechanisms are known. All of the art disclosed herein is incorporated by reference. U.S. Pat. No. 1,742,649, issued to Eastman, discloses a band-type identification tag and method of banding fish for identification and conservation.
[0008] U.S. Pat. No. 4,790,090, issued to Sharber, discloses a fish tag having an invasive cellularly adhering point of attachment. Sharber teaches invasive anchoring of a fish tag by initial mechanical attachment and subsequent assimilation with the flesh of the fish through cellular adhesion, impregnation or ingrowth (absorption by the fish body).
[0009] U.S. Pat. No. 4,920,670, issued to Amick, discloses a fish tag including a monofilament having a retention member on one end and a flexible indicia bearing tube positioned about the monofilament.
[0010] U.S. Pat. No. 3,545,405, issued to Jefferts, discloses an identifying tag which is capable of being implanted in a macro-organism, such as a fish. The tag disclosed by Jefferts comprises a small metallic body having on their surface thereof coded information in the form of a predetermined pattern which is imparted on the surface of the body by a high-energy heat source, such as a laser.
[0011] U.S. Pat. No. 4,713,315, issued to Smith, discloses a wire tag etching system.
[0012] U.S. Pat. No. 4,750,490, issued to Haw et al., discloses a method for tagging fish for identification including an identification tag that is shallowly implanted within transparent or semi-transparent tissues of respective specimens wherein markings on the tag remain visible. Haw et al. teaches a method which includes implanting a tag, releasing the tagged fish into a body of water, subsequently capturing the fish and optically reading the detectable markings through the transparent tissue. In an alternate embodiment, Haw et al. contemplates removing the tag from the fish and reading the detectable markings upon removal of the tag.
[0013] U.S. Pat. No. 4,333,072 issued to Beigel, discloses an identification device including one method of radio frequency identification (RFID). Beigel discloses technical details that may be helpful in the manufacture of an RFID device.
[0014] U.S. Pat. No. 5,214,409 issued to Beigel, discloses an identification device including multi-memory electronic identification tags that have read only and read-write memory used and created by various means. Beigel discloses technical details that may be helpful in the manufacture of an RFID device.
[0015] U.S. Pat. No. 5,235,326 issued to Beigel et al, discloses an identification device including other sensors as part of the tag. Beigel discloses technical details that may be helpful in the manufacture of an RFID device.
[0016] Current catch and release programs and tag utilization methods lack the proper incentives to motivate people to tag fish, record the data of tagged fish, share the data with others and importantly, release the fish back into the ecosystem. When a fish is caught, the angler releasing the fish loses all contact with the fish and does not have an efficient, long-term organized means to learn about the fish's past or what may happen to “his (or her)” fish in the future. The angler also receives very little recognition for his action, especially when returning an average size fish that may one day grow to trophy proportions. Accordingly, there exists a need for a method for tracking fish, collecting data, and encouraging catch and release fishing.
[0017] There are numerous objectives of the present invention that may be achieved. Achieving even one objective may be sufficient for the business method to succeed. One objective of the present invention is to encourage the public to gain more information concerning the importance of catch and release of fish. An objective of the present invention is to encourage the release of fish caught by sport fishermen, especially the release of trophy size fish.
[0018] Another objective of the present invention is to better inform people about fish and the fishermen that release them. An objective of the present invention is to provide a method of doing business that encourages the practice of catch and release. Another objective of the present invention is to provide a method for the angler to maintain an interest in the fish by tagging it. The angler may also learn of future anglers that catch the same fish. Each angler may reinforce the benefits of catch and release to one another and help build an angling community commitment to catch and release fishing. It is a further objective to create camaraderie among catch and release anglers that can be used to encourage others to practice catch and release fishing. An objective of the present invention is to gather data on fish. It is a further objective to provide a means for encouraging communication between anglers on fishing, fishing methods and fish as a natural resource. It is also an objective of the present invention to raise the awareness of catch and release fishing in the angling community and change the way people think about fishing. At least some of the fish caught fishing, especially trophy and near trophy fish, are better tagged, and released, rather than mounted on a wall, or fried for dinner.
SUMMARY OF THE INVENTION
[0019] The present business method includes providing an incentive to people, especially recreational and professional anglers, to release the fish they catch, and encourage other to do so as well. This incentive may be provided by a combination of fish tagging, data availability, data updating and angler communication. The method further provides generally reliable data for fish research. The method may also provide a motive for the purchase of equipment and supplies to tag fish. A motive to visit a particular web site that can provide a platform for marketing other products and services may also be provided by the method.
[0020] The present invention may include a business method for encouraging the release of fish caught by recreational anglers. The method may be used to identify the released fish. The method may also be used by people other than recreational anglers. The method may be used for the identification of birds, reptiles, and mammals where subsequent capture is possible, and the next capturer is not expected to be by the same individual or organization that completed the original capture.
[0021] The present invention may include a method of recording fish and/or fishing information such as location, weight, time, lure/bait used, weather, fishing method, water temperature depth and any other pertinent details each time the fish is caught. Information on the angler may also be part of the database. The information may include e-mail, number of fish caught that day, number of tagged fish caught, number of fish caught and/or tagged over an extended period of time, and any other desired information. Generally, this is more information than would otherwise be reliably memorized or conveniently recorded upon an appropriate size tag.
[0022] With the present invention, freshwater, saltwater, and fly fishing anglers (hereinafter angler(s)) or other individuals such as those that raise and/or release fish for stocking purposes may be provided with an apparatus and/or method to enable the angler to quickly and easily tag a fish with a tag which is attached to the fish. Preferably, the tag remains affixed for the life of the fish. Once tagged, if the fish is caught again, the information about the fish and/or the second angler may be added to the data already recorded and previously made available. The information obtained provides data about the movements and habits of the tagged fish and/or the angling community.
[0023] The apparatus according to the present invention may include a suitable fish tag having an identification sequence that can be obtained by the subsequent individual (angler) that catches the fish. The identification sequence is used to identify the fish and correlate that fish with additional data available in a searchable and updateable database. At least a portion of the identification sequence is also used as a semi-secret code to limit data entry on a fish to those that have caught the fish, and have the entire identification sequence. The data set of data on the fish is preferably part of a widely accessible database, such as an Internet accessible database that contains information on many fish tagged with a unique identification sequence. The method also has applicability to local databases such as those used by a fishing guide service, state fisheries agencies or private lakes.
[0024] In a preferred embodiment, the tag according to the present invention may be inserted into the fish. The tag is preferable non-toxic, since the fish may be eaten by other fish or predators. The identification sequence is preferably obtainable from an internal tag through the use of a device such as a reader, which does not require removing the tag.
[0025] Alternatively, the tag with the identification sequence may be external to the fish. The identification sequence may be imprinted, engraved or otherwise obtainable from the tag. The tag would include the identification sequence. The tag may also identify the internet wed address where further data can be obtained. The tag may be removed but preferably, it would remain attached to the fish. The tagging system may alternatively include a combination of an internal and external tag. The external tag may let the casual angler know that there is an internal tag. This may encourage the release of the fish and provide notice that if they chose to eat the fish, they should look for the internal tag before consumption.
[0026] The invention may include a kit. The kit may include a tag insertion device, tag reader for reading the identification sequence on the tag, a selection of tags, a data recording means, and/or combinations thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The instant invention is described with particular reference to the following drawings.
[0028] [0028]FIG. 1A is an illustration of a fish tag in accordance with the present invention.
[0029] [0029]FIG. 1B is an illustration of a fish tag in accordance with the present invention.
[0030] [0030]FIG. 2 is an illustration of a tag being read by a tag reader.
[0031] [0031]FIG. 3 is an illustration of a fish tag in accordance with the present invention.
[0032] [0032]FIG. 4 shows a tag being inserted into a fish with an insertion device.
[0033] [0033]FIG. 5 is a sample database data screen of a particular fish.
DETAILED DESCRIPTION OF THE INVENTION
[0034] The subheadings contained within the detailed description of the invention are intended ONLY to assist the reader. Each aspect may be closely related with other aspects of the invention, therefore a particular aspect of the present invention may be further described and disclosed elsewhere in the application. Each aspect of the present invention can be fully understood only within the entire text of the disclosure.
[0035] Definitions
[0036] As used herein the following terms are used consistent with their common usage and the following specific applications.
[0037] “Read” refers to obtaining the identification sequence.
[0038] “Scanned” refers to examining a tag by something other than the human eye, such as with a tag reader to read a tag.
[0039] “Identification sequence” is used herein to represent any combination of signals, characters, symbols, marks or other indicia that may be read by the human eye or scanned with the assistance of a machine. Indicia individually or in combination define an identification sequence, identifier, or code.
[0040] “Data” is used herein as at least one element of information. This element of information is generally part of a data set.
[0041] “Data set” is used herein as a collection of data, usually regarding a particular item of interest such as a fish. The collection of data may include many pieces of data.
[0042] “Database” is used herein as a collection of data and or data sets. The database may include many searchable and sortable data and/or data sets.
[0043] “User” refers to angler or person that catches the fish and/or the person entering data into the database.
[0044] The Tag
[0045] The tag used on the fish should remain useable for at least a year, preferably more than five years. The tag may be attached internally to the fish, external to the fish, or a combination thereof. The tag may comprise an internal component and/or an external component. RFID tags may come in any variety of shapes and sizes. The tag is preferably small and easily inserted into a fish. A small tag is one less than about 15 mm long and less than about 8 mm wide. The tag is preferably non-toxic to the fish and to any predator (including human) that might latter catch and eat the fish. More preferably the tag is a color that would enable a person Cleaning or eating the fish to find and remove the tag prior to eating it.
[0046] The tag may include any information acquisition or transmission technology. The tag may include a radio frequency identification (RFID), barcode, magnetic stripe, voice data entry and/or other automatic identification technologies.
[0047] RFID technology includes a sensing device (tag reader) which transmits a radio frequency signal to a specially designed RFID tag, which responds with another radio message. The RFID system may include the RFID active or RFID passive transponders (the tag) and the RFID reader. The RFID reader emits a frequency magnetic (electromagnetic) field via its antenna. When a RFID transponder passes within range, it is excited, causing it to transmit its data back to the RFID reader. Transmission and reception may occur nearly simultaneously.
[0048] As shown in FIG. 1 the RFID tag 60 may include an antenna 61 , a transceiver 62 , and a transponder 63 electronically programmed with the identification sequence. The tag components, including the antenna 61 , transceiver 62 and transponder 63 may be incased in a casing 64 . The casing may be any material known in the art. The antenna 61 emits radio signals to activate the tag 60 and read and write data to it. The antenna 61 acts as a conduit between the tag 60 and a tag reader 40 shown in FIG. 2 (AKA a transceiver/decoder). The antenna 61 may be available in any variety of strengths, shapes and sizes. The tag 60 may be packaged with the tag reader 40 (FIG. 2).
[0049] RFID tags may be categorized as either active or passive. Active RFID tags are powered by an internal power source such as a battery. The active RFID tags are typically both readable and writable. They can have data read from them or written (added) to them. The data may be rewritten and/or modified. An active tag's memory size may vary between about 1 kilobyte and about 2 megabytes. An active RFID tag may be used to add information about the fishes capture to the RFID tag, in addition or instead of adding the information to the internet accessible data base. This encoded data added to the tag would then become part of the RFID tag data immediately available when the fish was caught again.
[0050] Passive RFID tags operate without a separate external power source and obtain operating power generated from the reader. Passive tags are consequently much lighter than active tags, less expensive, and may offer a very long (many years) operational lifetime. The trade off is that they have shorter read ranges than active tags and require a higher-powered reader. Read-only tags are typically passive and are programmed with a unique set of data (usually 32 to 128 bits) that cannot be modified. Read-only tags most often operate as an identification sequence into a database. Linear barcodes similarly reference a database containing modifiable information. The general uniqueness of each identification sequence correlated or linked to data in a database controlled by a company, individual, or service provider. Unknown individuals do not have access to update or change the data provided. The addition of a secure component to the identification sequence may be used to enable people unassociated with the initial fish tagging to act as a trusted party and add information into the database, if they obtain the complete identification sequence. The person is trusted to add data on that fish because that person has the entire identification code. While not everyone that catches a fish will enter data truthfully, in general the majority of the information obtained may be accurate and reliable.
[0051] RFID systems are also distinguished by their frequency ranges. Low-frequency systems operate between about 10 KHz and 750 KHz. Low-frequency systems typically have short reading ranges and lower system costs. High-frequency RFID systems typically operate above 500 MHz. High-frequency RFID systems offer read ranges greater than 50 feet and high reading speeds. High frequency RFID systems may be used however, the high-frequency RFID systems may be more expensive that lower frequency systems.
[0052] One advantage of the RFID systems is the noncontact, non-line-of-sight nature of the technology. The tag may be read through the body of the fish by a tag reader. In other embodiments, the tag may even be read through a portion of the water, reducing the need to remove the fish from the water. Depending upon the application, passive, low frequency tags may be preferred to avoid the targeting of previously caught fish by other anglers with high powered readers.
[0053] External Indication
[0054] [0054]FIG. 1B shows an external tag 20 , that includes an identification sequence 25 . The particular identification sequence 25 shown is 03OH23Z 7 SQ93762. The identification sequence 25 includes a public sequence 251 and an access sequence 252 . The particular public sequence 251 shown in 03OH23Z7. The particular access sequence 252 shown in SQ93762.
[0055] An external tag, visible on the fish, may be used in the place of an internal tag, or in addition to an internal tag. The external tag may include the identification sequence. Alternatively, the external tag could be in addition to an internal tag with a readable identification sequence. An external indication of the tag may help avoid the inadvertent double tagging of a fish. It may also help avoid taking the time to scan a fish that is not already tagged. One disadvantage to an external tag is that it may snag on underwater obstacles and may be a source of irritation or infection to the fish. An external tag is also susceptible to falling off over time. Generally, an external tag may be most preferable for fish large in proportion to the tag, and/or fish that are frequently caught. Bar codes with an identification sequence with the public sequence and the access sequence may be used on an external tag.
[0056] Tag Reader
[0057] [0057]FIG. 2 shows a tag reader 40 , reading a tag 60 , in a fish 50 . The fish has a dorsal fin 51 and a pectoral fin 52 . The tag reader 40 emits radio waves which may travel and be easily detectable anywhere from about 2 centimeters (cm) to about 35 meters (m) or more, depending upon its power output and the radio frequency used. When an RFID tag 60 passes through an electromagnetic zone created by the radio waves, the tag 60 detects the tag reader's radio wave activation signal, activates using the energy from the radio wave and transmits the identification sequence 25 . The tag reader 40 is designed to be used to obtain information such as the identification sequence 25 encoded into the tag 60 . The data may be read, transmitted or otherwise entered into a computer 70 for processing. The transfer to a computer 70 may occur during the tag reading process, or afterwards and/or elsewhere. The data may be stored in the computer by any means known in the art. The tag reader 40 may be configured as either a handheld or a fixed-mount device. The tag reader 40 may be powered by any means known in the art including solar and/or battery power. The tag reader my include a computer and/or other data recording componenet.
[0058] Preferably, the tag is read by a tag reader that will detect and/or record the tag identification sequence. More preferably, the tag reader will also record other data to minimize the amount of data reentry required. For example the tag reader (sensor) could be programmed and/or combined with other devices to provide the fish weight, length, time of day caught, Global Positioning System (GPS) location, water temperature and the like. This data could them be downloaded for inclusion into the data set and/or database being maintained. The information may alternatively be recorded by the angler by any means known in the art including pencil, pen, palm pilot, or computer, for later entry into the data set and/or database.
[0059] The tag reader may also be connectable to a GPS device, depth finder, temperature gauge, wind gauge, speed gauge, scale, or other fishing aid to allow downloading of the data to the reader, computer or other device for later entry into the database. Even more preferably, the tag reader could be used to store data about the fish, and this data could be entered electronically (digitally) downloaded into the Internet accessible database.
[0060] Information
[0061] The internal and/or external tag should include the identification sequence. The identification sequence may be established by any method and/or process known in the art. Suitable identification sequences may be alphabetical, numerical, alphanumerical, detectable signal(s) or other symbol combinations. Detectable signals may be converted to identification sequences such as alphanumerics for simplified data recording. The identification sequence can include any number of characters. The each identification sequence may preferably be random and unique. Alternatively, not every identification sequence may be unique. The particular fish information such as species and general location of the tagged fish may provide sufficient detail to allow some repetition of particular identification sequence. Other information in addition to the identification sequence may be obtainable from the external tag and/or the internal tag.
[0062] The identification sequence 25 (FIG. 1B) may be used as part of the data entered into a database. The identification sequence 25 may be in one or more parts. For example, a portion of the identification sequence 25 may be a public sequence 251 (FIG. 1B) for public identification and dissemination. The public sequence 251 would identify the fish, either by itself, or in combination with other information such as the fish species, or location.
[0063] A second part of the identification sequence may be an access sequence 252 as shown in FIG. 1B. The access sequence 252 is used to identify a person that either has been, or is, in possession of the fish tagged with the tag containing the complete identification sequence. The access sequence 252 is the portion of the identification sequence 25 required for an individual to add and/or update one or more pieces of information (data and/or dataset) on the fish in the database.
[0064] The access sequence 252 may be part of the data entered into the Internet database but it should not be readable or accessible by someone accessing the data on the Internet. The access sequence 252 is designed to ensure that people without the complete identification sequence 25 do not enter fraudulent data and/or fraudulent dataset into the database. Those that catch the tagged fish may obtain the access sequence and update and/or add data and/or a dataset to the database. The public sequence 251 may also be used to identify a specific fish, and/or correlate specific data to a specific fish. The public sequence 251 would preferably allow read only access on the Internet. Preferably, each fish would have a unique access sequence and/or public sequence.
[0065] In one example, a fish may be tagged with the identification sequence 45OH30004Q-9001. The data recorded in the database included:
[0066] Identification sequence: 45OH30004Q-*********(* indicates the access sequence is not visible on the computer monitor or other display); Fish species: large mouth bass; Weight 3.2 kg, Length: 45 cm, Bait used: Rat-L-Trap® Bleeding Shiner; Date: Mar. 13, 2002; Time: 8 am; Location: Rocky Fork Lake, Ohio; GPS location: unknown; Water Temperature: 5 degrees C; Water depth: 5 meters; Anglers e-mail: 4jeffm**re@*n**net.com. Do you want to be contacted if this fish is caught again: yes; Other information: One of 8 fish caught and tagged that day. I caught this one along the rocks on the south shore east of South Beach. Fishing has been good for the last couple of weeks.
[0067] About two years later, the fish may be caught again. The angler or other user may record the identification sequence and details about the fish. Later the angler logs onto the Internet. In order to enter data on a fish previously caught a second angler or other user must enter the correct access sequence. The second angler entered the following data:
[0068] Identification sequence: 45OH30004Q-*********(-*********(* indicates the access sequence is not visible); Fish species: large mouth bass; Weight 5.2 kg, Length: 54 cm, Bait used: night crawler; Date: May 10, 2004; Time: 1 pm; Location: Rocky Fork Lake, Ohio; GPS location: unknown; Water Temperature: 15 degrees C; Water depth: 3 meters; Anglers e-mail: NFR. Do you want to be contacted if this fish is caught again: yes; Other information: He is still there. My eight-year-old daughter caught him while we were fishing for crappies. I would have kept it, it was the biggest fish she had ever caught, but when we scanned it and found the tag we decided that it wasn't really “just ours.” I sure hope the next guy lets it go so we can read about it. It was a great day. P.S. we did eat a few crappies
[0069] Since the first angler included his e-mail, the data was sent directly to the first angler about his fish. The second angler either did not want his e-mail address on the web, or planned to change it. An NFR, or similar entry may stand for “NOT FOR RELEASE.” In this instance, at least the public sequence of the identification sequence of the fish would be linked through the Internet to the second anglers e-mail. The second angler could automatically get e-mail from the web site, whenever the data on a fish he was interested in was updated. This type of arrangement may require a fee, or an agreement to also receive e-mail from businesses that sell fishing or other outdoor equipment. The angler or other user may have a different user enter and record the data and/or data set about their fish. Typically, the first angler or user and the second angler or user are different individuals without a prior relationship. It is of course possible for the same person to catch the fish a second time.
[0070] As shown above, it may be desirable for the identification sequence to have a portion that is not kept secret. This would simplify some aspects of data sorting, should the data be published in a written format such as a book or magazine. The access sequence may also facilitate links to specific e-mail addresses or web pages. For example, identification sequence 45OH30004Q-9001 may read 45OH30004Q-****** (* blank) on the Internet. Both the public sequence and the access sequence may be unique so that someone looking for a specific fish in the public database could search by the public sequence. The information is enterable into the Internet database by those possessing both the public sequence and the access sequence for a specific fish. The published part of the identification sequence could include data as well. The public sequence above could indicate that the tag was manufactured in 2004 and sold in Ohio. The data could also be recordable into a database and used on a computer without the Internet.
[0071] Upon entering the complete identification sequence an introductory page such as the following could be displayed on the Internet web page:
[0072] Congratulations, you caught one of 2,365 fish tagged to track the fish released in Rocky Fork Lake in 2008. Our goals include learning more about fish habits, their survival, and to encourage the practice of catch and release fishing by Ohio anglers. The state fisheries department and several local businesses contributed their time and money to this project. Please provide as much information about your fish and about yourself as possible so that we can continue to provide angling opportunities at Rocky Fork and around the state. Upon completion of this information, you may be e-mailed a coupon good for 10% off your next purchase from any of the business that contributed to this effort. It is our way of saying thank you, and encouraging everyone to participate in this program and practice catch and release fishing.
[0073] Over time, the information gathered may provide information on both fish and anglers. The information on fish may include growth rates, mortality, travel, density, and the like. Information on anglers may include their total fish catch, where they fish, who they are, what equipment they use, their conservation activities and the like.
[0074] Medication
[0075] There are few opportunities other than the capture of a fish to apply a health helpful substance directly to wild and semi-wild fish. The fish tagging process may provide an opportunity to apply a health helpful substance including medication, immunization, vitamins, and/ or combinations thereof to the fish. The tag may preferably include a substance helpful to the health of the fish such as at least one medication and/or vitamin. When the tag is inserted, the health helpful substance is also applied to the fish. Combining the helpful substance with the tag minimizes the number of fish body insertions required and the time required to tag and immunize the fish. The health helpful substance may be in the tag or coated about the tag. Alternatively, the tag may be contained in a liquid solution that includes the health helpful substance.
[0076] [0076]FIG. 3 shows the tag 64 with the casing 664 and a health helpful substance 26 applied to the casing 664 . Preferably, the health helpful substance 26 may be absorbed through the tissue of the fish. The health helpful substance 26 may also help heal any wound in the fish resulting from the insertion of the tag. The health helpful substance 26 may include an antibiotic, vaccine, anti-fungal, anti-viral, anti-parasite, antibacterial, immunization, vitamin and combinations thereof. Examples of antibiotics include erythromycin, minocycline, tetracycline, penicillin, and sulfonamides. Sulfonamides include sodium sulfathiazole, sodium sulfamethazine, sodium sulfacetamide, and the like. MARACYN® and MARACYN II® by Mardel are examples of an antibiotics. Anti-fungal's include MAROXY® by Mardel, neutroflavine and the like. Anti-parasite substances include copper sulfate, trichlorfon, metronizadole, and the like. The tag may also include a sedative to relax the fish after capture. Any health helpful substance 26 may be customized for a specific fish species and/or size.
[0077] A surface treatment such as a cream or ointment may also be applied to the fish at the point of tag insertion to minimize harm to the fish. Two exemplary creams include DEBRIDE® and ORABASE®. Iodine, potassium permanganate, and/or hydrogen peroxide may also be used. Any combination of the above substances may be used, depending upon the particular desired application.
[0078] The Tagging Process
[0079] The tagging process is the process by which the tag is affixed to the fish. The tagging process may be by any means known in the art. The tagging process preferably causes minimal harm to the fish. The tagging process is designed to be done in a manner that minimizes any harm to the fish and allows the fish to be released with a reasonable expectation of survival. The fish should be handled as little as possible. Basic fish information may be gathered either before or after the fish is tagged. This information may include the fish length, weight, girth, and the like. The fish may be scanned to ensure a previous tag has not been attached internally or externally to the fish. The scanning may be visual, physical or by a tag reader. If no other tag is located, a tag may be attached to and/or inserted in the fish. Most fish are small enough that an internal tag may be inserted anywhere and it will likely be found easily by a scanner. For larger fish, a specific insertion point may be desirable and specified on the web page and/or pages associated with the tag. For example, fish over about 15 cm long may have the tag inserted near the port side of the dorsal fin.
[0080] As shown in FIG. 2, the tag 60 may preferably be inserted into the fish 50 at the base of the dorsal fin 51 . Alternatively, as shown in FIG. 4, the tag 60 may also be inserted into the fish 50 just behind the pectoral fin 52 . An insertion tool 90 may be used to insert the tag 60 . The insertion tool 90 may be any tool known in the art. The insertion tool may include a needle 91 and/or syringe 92 . Similar devices such as pumps may also be used.
[0081] The Fish Source
[0082] The fish may be hatched in captivity or captured by any means known in the art including a fishing pole, net, electric shock etc. The fish is preferably wild but may be pen raised. The fish may live in a fresh or salt-water environment.
[0083] The Data Base
[0084] One component of the business method may be a widely accessible database of fish and other data. One method of providing wide access includes an Internet web access point “web page” that is searchable and updateable by the general public. This database may be directly updateable or verified and entered by a web manager. Preferably, the public sequence 251 and the access sequence 252 controls will be sufficient to limit inappropriate use and misinformation being submitted to the database.
[0085] The database is designed to include at least one data set on at least one fish. The database is designed to be sortable, searchable, expandable, and/or changeable. It is anticipated that as fish are tagged and released the database may eventually hold information on many thousands of fish.
[0086] The data in at least one data set for a specific fish may be added, changed or updated by individuals or organizations in possession of the complete identification sequence (access sequence 252 ). Preferably this data set input may be made by computer using the Internet. More preferable this data input may be made over the Internet. Preferably, the data set may be added to the database, but previous data and or data sets may not be deleted. Preferably, any one data set may not be updated more than once a day.
[0087] The database may function utilizing any communication protocol. The Defense Advance Research Projects Agency (DARPA) originally developed Transmission Control Protocol/Internet Protocol (TCP/IP) to interconnect various defense department computer networks. The Internet, an international Wide Area Network, uses TCP/IP to connect government and educational institutions across the world. TCP/IP is also in widespread use on commercial and private networks. Communication protocol may include Hypertext Transfer Protocol (HTTP), Secure Hypertext Transfer Protocol (HTTPS), File Transfer Protocol (FTP), Wide Area Information System (WAIS) (supports retrieval of documents from databases via full-text search) and/or any Uniform Resource Locator (URL) recognizable by a browser such as Netscape or Windows Explorer. The web site www.protocols.com lists dozens of available protocols for particular applications.
[0088] The database may be maintained by a commercial entity, not for profit entity, a wildlife service organization, a guide service, or an individual. Data entry preferably adds to the data from the previous fish tagging or release. This allows a history of the fish to be maintained as each new capture and release of the fish adds to the data already recorded. As a result, after multiple captures multiple fish weights and other information may be contained in the database.
[0089] The data gathered by this approach may also provide useful information on both the fish and the anglers that catch them. The data may encourage the release of fish through participation, peer pressure, and an increased desire to help the fish population. Released fish provide future opportunities for that fish to be caught again. It also provides that fish an opportunity to breed and produce offspring which may also be caught another day, or feed other animals in the ecosystem.
[0090] Information and statistical data obtained from the database may help assess fish populations, locations, mortality, habits, growth rates and the like. The fish information may be particularly helpful on lakes where slot fishing is practiced. Slot fishing occurs when fish of a particular species and size are required by the fishing regulations to be released. Sometimes this is a minimum size but it may also be a mid-range size between a specified weight and/or length limit, thus the term “slot fish.” The slot fish that must be returned may represent the preferred fish breeding age. The tagging of slot fish may help encourage compliance with the release requirements. It can be frustrating to fish all day and catch numerous fish in the slot that cannot be kept for a fish dinner. Catching tagged fish let's the angler know that he was not the first one to catch the fish in the slot and that without the release requirement he would be catching fewer fish overall. This feedback may help build “buy-in” or acceptance by the anglers that the slot requirements are necessary for a healthy fish population. This buy-in may also make it easier to expand slot-fishing regulations to other waters that could benefit from such a restriction. Gaining the buy-in of recreational anglers for new fishing restrictions in the interest of long-term resource management is an ongoing challenge for Federal, State and local fish management organizations. Tagging may also help encourage the release of otherwise legal fish which were previously tagged. Information on the survivability of caught slot fish and/or their growth rate may be helpful in determining the optimum size for the slot-fish. The information may also help identify other conservation efforts that may be helpful to the fish population.
[0091] Information on the anglers may include where they are from, their success, travels, spending, equipment, conservation activities, identity, and the like. This information may help State and/or Federal agencies monitor the fishing success of a particular lake or region and implement policies that help both anglers and the fish population. Companies may use the information to better target their marketing efforts. Anglers may also use the information to discuss fishing, find new fishing partners and/or learn more about the fishing in their area.
[0092] The Internet structure of the present invention may preferably include at least one web site entry point to access the information on the database. The web site may be used for recording at least a portion of the tag identification sequence and at least a portion of the fish information. The web page could be located at for example, www.fishid***.net. Alternatively, the entry point may be the web page of a prominent fish research center, a web page dedicated to a particular species of fish, or angler supply store. Once on the web page, the web page may include a search routine, banners, sponsors and discussion groups. A web visitor may be able to search by state, fish type, lake, specific angler or any other data group within the database. In one embodiment, the data may be sortable or cataloged by a particular resort, agency, or guide service. The data could also be maintained by a guide service on a personal computer for their own use, although this type of database would lack many of the advantages of the Internet accessible database disclosed herein.
[0093] Preferably, at least a portion of the identification sequence (ID, fish ID, or code) is not viewable or discernable by a user on the Internet. In order to update or add data (or a data set) on a particular fish, the access sequence (complete identification sequence) must be known. This limits the number of people capable of falsely inputting data about a particular fish. A person could search a particular lake in a particular state for all the recorded large mouth bass. However, that individual could not update that bass's information without the access sequence component of the complete identification sequence for a given fish. When entering information or a data set on a particular fish, the access sequence would have to be provided. After a certain number of failures, the system may be designed to lock out the person and/or computer entering invalid identification sequences. Preferably the public sequence would be used to match the access code with the specific data or data set in the database. A particular access sequence would only allow access when entered in conjunction with the correct public sequence. Many different public sequences and access sequence combination may be used to ensure the capture of one fish would not allow the changing of multiple fish data sets.
[0094] One advantage to having a public sequence and an access sequence is the ability to share consistently and easily identified data while maintaining confidence in any new data and/or data sets added to the database. Tagging data can be shared with other interested organizations without the access sequence. Any conclusions made based upon the data can be correlated with the public sequence and independently verified.
[0095] For example, one identification sequence may be AX345G9-I9476 attached to a bass first caught in Bass Lake, Minn. In order to update a data set of information about this fish, the fish species and identification sequence be provided by a subsequent angler. A help-line could be available to override this limitation. For example, if the fish was a largemouth base and the original data entry identified it as a small mouth bass in error. Preferably, when an identification sequence and other data match is provided, the data entry fields are presented with the prior fish information already complete. Only that information that needs changing would have to be entered by the person entering the data. For example if the fish weight was 8 kg and is now 10 kg, that data may be up-dated and/or added with another data set of information about the fish and other desired data. The original data set on the fish may remain unchangeable, or be unchangeable after a certain number of days subsequent to it's entry into the database. Thus when a fish is caught, new information may be added, but old information cannot be deleted or altered.
[0096] By way of a non-limiting example, FIG. 5 shows information on a fish with a possible data entry screen 100 containing non-limiting date fields 120 . As shown in FIG. 5, this information may include a portion of the identification sequence 101 . The identification sequence 101 shows the public sequence 101 A data entry field. For a new data set entry, the public access field may be blank or pre-filled if the fish had been previously captured. There may be a blank data entry field for the access sequence 101 B. When the correct access sequence is entered, an additional or new data and/or data set 120 B on that fish may be added to the database and/or made available for data entry. The data sets 120 A and/or 120 B may also be changed. Alternatively, this data in data set 120 A could become unchangeable by an Internet user after a certain period of time. For example, data entered would not be changeable by a user 2 days after entry into the database. This may help limit the ability of one user changing the data entered on a fish by a previous user. Data set 120 A may be data for the fish when it was first caught (e.g.on about 3/13/×2). Data set 120 B is for the fish when it was later caught (e.g. on about 7/4/×4). Each data set may have multiple data fields for specific information. FIG. 5 shows several possible data fields 120 for subsequent data sets 120 A, 120 B, and others as needed (not shown). Data set categories 130 identify the appropriate data type the be entered in each data field of the data sets 120 A, 120 B. Data set categories 130 may identify data fields 120 for data such as the Identification Sequence, date caught, time caught, weather details, water temperature, fishing depth, fish species, year caught, date caught, time caught, fish weight when caught, fish length, location caught, angler information, water details, lure used, other data, a picture and the like. Further location information may include the approximate Global Positioning System (GPS) location, State caught or body of water. Angler data includes such items as their name, e-mail address and whether they would like to be automatically notified by e-mail when the fish is caught again. Other data fields of information may be provided as requested by anglers and desired by anglers and those using the database for research purposes. Other information could include the number of fish caught that day, the total number of fish released by that angle for the year, and the like. A general field for other information may also be provided. A link to other web sites and/or a picture may also be provided.
[0097] Preferably, the person entering the data may indicate whether they have a desire to receive e-mail whenever this fish is caught again. This enables an angler to receive feedback on the survival and growth of “their” fish. These reports back to the anglers that previously caught and released the fish may be preformed by the angler, the Internet site manager, automatically through software coding, or by the resort and/or guide service used by the angler. The resort of guide service may provide information on the fish and use the opportunity to suggest to the angler that they return for another fishing trip in the future. The database on the Internet is preferably sortable by at least one data field 120 . For example, a person could list all the large mouth bass tagged, or more specifically all the large mouth bass from Rocky Fork Lake tagged in the year 20xx. The sort may narrow the search with as few or as many fields desired.
[0098] In addition to a widely accessible internet database, the database may be maintained locally on a personal computer by resorts, guide services, and the like. For example, resorts and guide services could maintain their own database. When the fish is recaptured, it may provide an opportunity and/or reason for the resort and/or guide, service to notify the previous anglers that caught that fish. The resort and/or guide service may suggest that the angler return for another visit to fish. It would also help the resort or guide service protect the resources they market. The advantages of promoting catch and release may be significant enough to a resort that they would do the record keeping, data entry and fish tagging. The resort and/or guide service may even pay for the tagging and release of any fish over a certain weight. Resorts and/or guide services that depend upon the fish resources of a particular waterway are highly motivated to protect the fishing resource and may be willing to use and support this method as one tool for encouraging the release of fish, especially trophy fish.
[0099] The database may include marketing information as a component of the data maintained for public access. For example, a web site, an identification sequence and/or group of identification sequences may be associated with a sponsor or other entity that is supporting the tagging, and release of fish. The sponsor may be a business, a federal organization, state organization, non-profit organization, conservation organization, resorts, guide services and the like.
[0100] For example, in order to increase the fishing success of a particular lake, federal agencies, state agencies, local agencies and/or businesses may donate funds for tagging 2,000 fish. At least a portion of the identification sequences in the tagged fish may correspond to data sets in the database. Included in the data set associated with the public sequence and/or access sequence of the identification sequence may be marketing information from the various tagging sponsors. For example, when an angler enters the access sequence on a fish, a marketing screen may appear (pop-up) on the web site. The screen may be similar to the typical pop-up screen used on the Internet today. The marketing screen may include information such as:
[0101] Congratulations, you have caught one of 2,360 fish tagged to encourage the catch and release of fish in our area. Yours was the 236 th fish tagged. The State Fisheries Department and six local businesses contributed their time and money to encourage the conservation of this natural resource. Please update as much information on your fish as possible on this web site. The data being gathered will help encourage the release of fish and provide information to our State Fisheries Department that may help further improve the fishing in our area. Thank you for your participation in this fish management effort. If you print this screen and bring the printout with you to Bills Bait and Tackle. you can receive a free fishing lure valued up to $5.00.
[0102] The data gathered and recorded in the database may be categorized, sorted, analyzed, cross-referenced and/or manipulated to provide statistical information on fish and/or the anglers that catch them. This analysis may be maintained on the Internet, typically accessible from at least one web site. The data and information may alternatively be periodically published as a document in a book or magazine form. Alternatively, the database may also be downloadable from the Internet into a formatted document. Preferably, the user may specify the data set organization and structure. The published document could be sold and/or given away for use as a marketing tool. The marketing users may include resorts, guide services, and other organizations that want to inform previous and/or potential customers about their fishing success, and their efforts to protect the fishing resource.
[0103] RFID tags, particularly high frequency RFID tags may have particular utility with larger fish. For example, some sailfish are tagged and released. In order to subsequently remove and/or read the tag, the fish must be brought close to the boat, typically within a meter or two of the boat. Getting the sailfish this close to the boat may require exhausting the fish. The last few meters to the boat may be particularly exhausting and/or traumatic for the fish, possibly causing it to expend energy reserves it may need for long term survival. A high frequency RFID, and/or a high powered tag reader may be used to read the tag further from the boat, thus causing less stress on the fish. The tag could be read and the fish released without forcing the fish in close proximity of the boat. A database of tagged fish data could be used to extrapolate the present size of the fish from the original tagged fish weight, tagging date and/or other parameters. Tournament and guide services could release the fish early if the extrapolated data indicated the fish was not likely to place in the tournament or meet the clients trophy goals. This may save the fishermen time better spent on bigger fish and save the fish valuable energy it may need for it's continued survival.
[0104] The present invention has been shown and described herein in what is considered a practical and exemplary embodiment. It is recognized, however, that departures may be made there from within the scope of the invention and that obvious modifications will occur to a person skilled in the art. | The present invention provides a means for obtaining and maintaining reasonably reliable data on individual fish in an accessible database. The present invention also includes a method of doing business that encourages returning fish caught by anglers back into the ecosystem. The method of doing business generally relates to using unique fish identification to provide data to people and organizations trying to lean more about fish. The present invention also provides a specially coded tag with a identification sequence for use with the business method. The present invention may also comprise a kit including a suitable coded tag, a means of recording the data of fish tagged and a means for reading and recording the data from previously tagged fish. | 0 |
FIELD OF THE INVENTION
This invention relates to a method for diagnosing a pathological condition, via assaying or measuring particular T-cell subtypes in a sample taken from a patient suspected of having the pathological condition. In particular, it relates to measuring cell surface antigens of T-cells which are characteristic of particular T-cell subtypes.
RELATED PUBLICATION
Portions of the invention described herein have been presented in Kappler, et al., Science 244: 811-813 (May 19, 1989), the inventors' publication and the disclosure of which is incorporated by reference herein.
BACKGROUND AND PRIOR ART
In recent years, the mechanism by which mammalian immune systems, such as human and murine systems react to infections, foreign antigens, and to so-called "self antigens" in connection with autoimmune diseases has begun to be established. See, in this regard, Grey, et al., Scientific American 261(5): 56-64 (1989); Male, et al., Advanced Immunology (J. P. Lippincott Company, 1987), especially chapters 6 through 10.
Well known, both to the skilled artisan and to the general public is the role of antibodies, sometimes referred to as "immunoglobulin" or the less correct and older "gammaglobulin" in response to infection. Antibodies are protein molecules which are produced by B cells in response to infection. It is well known that these antibodies act to "disable" or to inactivate infectious agents in the course of combating the infection.
In order for antibodies to be produced, however, preceding events must occur which lead to stimulation of the B cells which produce the antibodies. One of the key events involved in the processes leading to antibody production is that of antigen recognition. This aspect of the immune response requires the participation of so-called "T-cells", and is less well known than the antibody response commented on supra.
Briefly, and in outline form, antigen recognition requires interaction of an "antigen presentation cell", a "processed antigen", and a T-cell. See Grey and Male, supra. The "processed antigen", in an infection, is a molecule characteristic of the pathogen which has been treated, i.e., "processed", by other cells which are a part of the immune system. The processed antigen interacts with a receptor on the surface of an antigen presented in a manner not unlike a lock fitting into a key hole or, perhaps more aptly, two pieces of a jigsaw puzzle.
The configuration of the complex of processed antigen and receptor on antigen presentation cell allows the participation of T-cells. T-cells do not join the complex unless and until the processed antigen has fit into the receptor on the antigen presentation cell. This receptor will hereafter be referred to by its scientific name, the major histocompatibility complex (MHC), or the human leukocyte antigen (HLA). Generally, MHC is used to refer to murine systems, and HLA to humans.
These receptors fall into two classes. MHC-II molecules are involved in most responses to pathogens. In contrast, MHC-I molecules are involved when the pathogen is a virus, or a malignant cell is involved. When MHC-I participation is involved, there is no antibody stimulation; rather, the interaction of MHC-I, processed antigen and T-cell leads to lysis of cells infected with the pathogen.
The foregoing discussion has focused on the events involved in responding to "infection", i.e., the presence of pathogenic foreign material in the organism. Similar mechanisms are involved in autoimmune diseases as well. In these conditions, the organism treats its own molecules as foreign, or as "self-antigens". The same type of complexing occurs as described supra, with an antibody response being mounted against the organism itself. Among the diseases in which this is a factor are rheumatoid arthritis, diabetes, systemic lupus erythematosis, and others.
The ability of the T-cell to complex with the processed antigen and MHC/HLA complex is dependent on what is referred to as the T-cell antigen receptor, referred to as "TCR" hereafter. The TCR is recognized as a heterodimer, made up of alpha (α) and beta (β) chains. Five variable elements, coded for by germline DNA and known as "Vα, Jα, Vβ, Dβ, and Jβ" as well as non-germline encoded amino acids contribute to the TCR. See, in this regard, Marrack, et al., Immunol. Today 9: 308-315 (1988); Toyonaga, et al., Ann. Rev. Immunol 5: 585-620 (1987); Davis, Ann. Rev. Immunol 4: 529-591 (1985); Hendrick, et al., Cell 30: 141-152 (1982). With respect to the binding of TCR with processed antigen and MHC, see Babbitt, et al., Nature 317: 359-361 (1985); Buus, et al., Science 235: 1353-1358 (1987); Townsend, et al., Cell 44: 959-968 (1986); Bjorkman, et al., Nature 329: 506-512 (1987).
Generally, both the alpha and beta subunits are involved in recognition of the ligand formed by processed antigen and MHC/HLA molecule. This is not always the case, however, and it has been found that so-called "superantigens" stimulate T-cells with a particular Vβ element, regardless of any other element. See Kappler, et al., Cell 49: 273-280 (1987); Kappler, et al., Cell 49: 263-271 (1987); MacDonald, et al., Nature 332: 40-45 (1988); Pullen, et al., Nature 335: 796-801 (1988); Kappler, et al., Nature 332: 35-40 (1988); Abe, et al., J. Immunol 140: 4132-4138 (1988); White, et al., Cell 56: 27-35 (1989); Janeway, et al., Immunol. Rev. 107: 61-88 (1989); Berkoff, et al., J. Immunol 139: 3189-3194 (1988), and Kappler, et al., Science 244: 811-813 (1989). This last reference discloses information which is also incorporated into the subject patent application.
The "superantigens" mentioned supra, while generally stimulating T-cells as long as they possess a Vβ element, are somewhat specific in terms of the particular form of the Vβ moiety which is present on the stimulated T cell. This feature is one aspect of the invention, i.e., the ability to assay for particular subtypes or subclasses of T-cells, based upon the cell surface antigens presented by these subclasses.
Staphylococcus aureus has long been implicated in morbidity and mortality in humans. See Bergdoll, in Feed Bourne Infections and Intoxications (Riemann and Bryan, ed., Acad. Press, N.Y.) pp. 443-494 (1979). The various toxins presented by S. aureus are responsible for most food poisoning cases, as well as severe shock, and other life threatening pathological conditions. The mechanism of action of the toxins associated with S. aureus is unknown. The primary structure of the toxins, while showing some relationship, also show some great differences in primary structure. See Betley, et al., J. Bacteriol 170: 34-41 (1988); Jones, et al., J. Bacteriol 166: 29-33 (1986); Lee, et al., J. Bacteriol 170: 2954-2960 (1988); Blomster-Hautamaa, et al., J. Biol. Chem. 261: 15783-15786 (1986). For the time being, it cannot be said with any certainty whether the various S. aureus antigens function in the same way in terms of the immunological response they generate.
The ability of S. aureus to stimulate powerful T cell proliferative responses in the presence of mouse cells bearing MHC-II type molecules is taught by, e.g., Carlson, et al. J. Immunol 140-2848 (1988); White, et al., Cell 56 27-35 (1989); Janeway, et al., Immunol. Rev. 107:61-88 (1989). White, et al., and Janeway, et al. showed that one of these proteins is not mitogenic, in that it selectively stimulates murine cells which bear particular Vβ elements. These papers, however, did not extend the study to human cells. It has now been shown, however, that certain antigens do selectively stimulate specific Vβ subclasses of human T cells, making it possible to diagnose pathological conditions by assaying for particular Vβ subtypes.
Hence, it is an object of the invention to describe a method for diagnosing a pathological condition in a human by assaying a biological sample from the subject being tested for levels of particular Vβ subtypes. These levels are then compared to normal levels, where a difference between the two is indicative of a pathological condition.
It is a further object of the invention to carry out the assaying using antibodies which are specific for the particular Vβ subtype. Especially preferred are monoclonal antibodies.
It is still another object of the invention to perform the above described assay by measuring DNA coding for specific Vβ molecules. This can be done via utilizing, e.g., the polymerase chain reaction.
How these and other objects of the invention are achieved are detailed in the disclosure which follows.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 shows the results of staphylococcal toxin stimulation of human T cells.
FIG. 2 depicts studies showing Vβ specific stimulation of T cells by toxins is donor independent.
FIG. 3 depicts a standard curve used to normalize polymerase chain reaction values (PCRs) to percentages of T cells carrying particular Vβs in mixed populations.
FIG. 4 shows autoradiograms of coamplified cDNA of human TCR transcripts following stimulation with anti-CD3 antibody or a S. aureus toxin.
FIG. 5 presents in bar graph form Vβ specific stimulation caused by S. aureus toxins in three individuals.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Example 1
This experiment used monoclonal antibodies directed against Vβ5, Vβ6, Vβ8 and Vβ12, as taught by Yssel, et al., Eur. J. Immunol. 16: 1187 (1986); Borst, et al., J. Immunol. 139: 1952 (1987); Posnett, et al., Proc. Natl. Acad. Sci. USA 83: 7888 (1986); Carrel, et al., Eur. J. Immunol 16: 649 (1986), and Bigler, et al., J. Exp. Med. 158: 1000 (1983).
T cells of a human individual were first isolated from that individual's peripheral blood. These T cells were then examined before and after stimulation with one of (i) anti-CD3 antibody, (ii) SEC2; (iii) SED, or (iv) SEE. Items (ii), (iii) and (iv) are known S. aureus molecules which act as toxins.
The anti-CD3 antibodies had been rendered stimulatory by adherence to plastic bottles. The protein was incubated on plastic surfaces for 8 hours at 4° C. Extensive washing removed non-adherent antibody. Following this, either adherent antibody or a S. aureus antigen was used to stimulate peripheral blood T cells.
Stimulation took place in the presence of irradiated, autologous, non T-cells as described by Kotzin, et al., J. Immunol. 127: 931 (1981), the disclosure of which is incorporated by reference herein.
Three days after stimulation, live cells were collected and cultured for 24 hours in recombinant human IL-2 (25 units/ml). This allows regeneration of potentially modified receptors. Of the surviving cells, about 10% were true blast cells.
The blast cell fractions were then incubated with one of (i) purified antibody to CD3 or with a monoclonal antibody to (ii) Vβ5 (mAb 1C1); (iii) Vβ6 (mAb OT145); (iv) Vβ8 (mAb MX6), or (v) Vβ12 (mAb S511). Following incubation with the mAb, the cells were stained with fluorescein-conjugated goat anti mouse IgG, following Kappler, et al., Cell 49: 173 (1987). The staining pattern was then studied on an EPICS C device, using a forward angle and 90° light scatter pattern to gate large blast cells, which were easily distinguished from small lymphocytes, and constituted 50% or more of all surviving cells in culture.
The results of the staining patterns are shown in FIG. 1. Panels A-D shows the degree of staining using the mAbs before stimulation. Panels E-H show it after stimulation with anti-CD3. Finally, panels I-L show the pattern following stimulation with SED, SEE, and SEC2.
Each anti-Vβ stained a definable percentage of the peripheral resting T cells from this donor (FIG. 1). The percentage stained ranged from 5.2% with anti-Vβ6 to 1.5% with anti Vβ12 (FIG. 1, A to D). Culture with anti-CD3 and interleukin-2 hardly changed the percentage stained with each anti-Vβ (FIG. 1, E to H) , indicating that this combination of T cell stimuli affected T cells bearing different αβ receptors similarly. Culture with the toxins had variable effects on the percentage of T cells stained with each anti-Vβ (FIG. 1, I to L) Staphylococcal entertoxin (SE) D, for example, greatly increased the percentage of T cells bearing Vβ5 in the blast population and nearly excluded cells bearing Vβ6. In contrast, T cells blasts stimulated with SEC2 were depleted of Vβ6- and Vβ8 bearing T cells and were greatly enriched in Vβ12 bearing T cells. Finally, SEE stimulated Vβ8 + T cells, while excluding cells bearing Vβ12. Reciprocal results for each of the toxins were found if the resulting T cells contaminating the blast populations were analyzed for Vβ usage. After SEE stimulation, for example, the resting T cells were selectively depleted of Vβ8 + cells. This result indicates that the toxins are stimulating most of the T cells bearing the appropriate Vβs, nor a minor population of these cells.
Five different donors were used in the experiments. These donors were HLA-typed by standard serological techniques, and their restring peripheral T cells were stained with anti-CD3 and the anti-Vβs. Each of the anti-Vβs reacted with a low but measurable percentage of peripheral blood T cells from each of the individuals (Table 1). For a particular individual these percentages were extremely reproducible from one day to another. The percentages of T cells that bore the different Vβs varied somewhat among individuals.
TABLE 1______________________________________Vβ expression on unstimulated human peripheral T cells. Percentage ofCell HLA type T cells bearingdonor A B C DR DQ Vβ5 Vβ6 Vβ8 Vβ12______________________________________BK 26 14 1.4 w1 3.9 3.3 3.2 1.3 28 38 w53 w3CW 24 7 .sup. 3 4.6 w3 2.7 2.0 4.0 1.5 31 60 .sup. 7 w52, w53LS 2 8 w7 3.6 w1 2.6 5.2 3.6 1.5 62 w52RC 1 35 w4 1.7 w1 3.2 6.1 6.5 1.2 11 37 w53 w2SL 1 8 w7 3.6 w1 3.1 4.4 3.7 1.8 63 w52 w2______________________________________
Example 2
Cells from the different donors were stimulated with anti-CD3 or the staphylococcal toxins and analyzed for CD3 and Vβ expression (FIG. 2). For each individual, results were calculated as the percentage of T cell blasts bearing a particular Vβ after stimulation divided by the percentage of T cells bearing that Vβ before stimulation. This calculation was designed to correct for variations in Vβ expression from one person to another. As before, anti-CD3 stimulated T cells bearing the different Vβs uniformly; the ratio of T cells bearing a particular Vβ before and after CD3 stimulation was close to 1. In contrast, it was clear that the staphylococcal toxins varied markedly in their ability to stimulate T cells bearing different Vβs. For example, T cells bearing Vβ5 and Vβ12 were quite rich in blasts produced by challenge with SEC3, whereas T cells bearing Vβ8 were specifically excluded from the SEC3 blasts. One or more of the toxins was a stimulus for T cells positive for each of the Vβ families (albeit weakly for Vβ6), indicating that a toxin superantigen had been identified for each of the Vβ families. Conversely, toxins could be identified which specifically failed to stimulate T cells bearing each of the Vβs.
It is remarkable that a characteristic stimulation pattern could be identified for almost each toxin. SEC2, for example, stimulated T cells bearing Vβ12 and excluded cells bearing Vβs from the other three families. This pattern was not seen with any of the other toxins. SED stimulated T cells bearing Vβ5 and Vβ12, had marginal effects on T cells bearing Vβ8, and excluded cells bearing Vβ6. Again, this pattern was unique to this toxin.
In some cases, stimulation with a given enterotoxin yielded blasts that were neither enriched nor depleted for expression of a given Vβ by comparison with the starting population. Starting and ending percentages of Vβ5-bearing cells were similar, for example, in responses to toxic shock toxin (TSST). Such a result might indicate that only some Vβ5-bearing T cells were stimulated by TSST. Perhaps the other variable components of the receptor, Vα, Jα, or Jβ, could quite often prevent interaction of this toxin with Vβ5, a phenomenon that has been noticed before for superantigen reaction with mouse T cell receptor Vβs. Alternatively, TSST may react with only one member of the Vβ5 family. Thus, in responses to TSST, the increase in blasts bearing this member may be offset by a disappearance of T cells bearing other members of the family, but also reactive with 1C1. Discrimination by superantigens among different members of Vβ families has been seen in mice, where the self superantigen Mls-1 stimulates T cells positive for Vβ8.1 but not those bearing Vβ8.2 or Vβ8.3 (Kappler, et al. Nature 332: 35 (1988), and SEC1 stimulates T cells bearing Vβ8.2 but not those bearing Vβ8.1 or Vβ8.3.
In some experiments, the percentages of T cells that stained with anti-CD4 or anti CD9 were checked before and after stimulation. The starting percentages were virtually unchanged by toxin stimulation. T cells from one donor, for example, were initially 78% CD4 + and 23% CD8 + . After stimulation with the nine different toxins the percentages in the blast of CD4 + cells ranged from 74% to 79%, and of CD8 + cells from 20% to 25%, suggesting that all these stimuli affected CD4 and CD8 cells equally. It might have been expected that the toxins, which are dependent on class II MHC for presentation would have preferentially stimulated CD4 + cells, but such is not the case.
One of the most striking features of the data in FIG. 2 is the consistency of the results from one individual to another. Thus, although the five people tested had different HLA types and different starting percentages of T cells bearing the various Vβs (Table 1), the proportional changes in Vβ expression in blasts stimulated by each toxin were almost the same from one individual to another. Although the superantigens require class II MHC for presentation, the allele of class II has much less impact on superantigen presentation than it does on recognition of conventional antigens plus MHC by T cells.
These results show that the staphylococcal toxins are not indiscriminate mitogens for human T cells, but are, in fact, Vβ-specific. This result accounts for the previously noted clonal specificity for such toxins. Although each toxin is able to stimulate only a subpopulation of all T cells in humans, they are still powerful T cell stimulants, active at low concentrations. Some or all of the toxic effects of these proteins in humans may be mediated by their ability to stimulate large numbers of human T cells. For example, the ability of these toxins to induce secretion of large quantities of lymphokines is probably secondary to their ability to stimulate, in a Vβ-specific way, a sizable percentage of T cells. It is also possible that the ability of these and other microbial-derived superantigens to stimulate populations of T cells bearing particular Vβs may be related to the differential resistance of different individuals to the effects of these toxins and also to the ability of microbial attack to induce immune consequences, such as autoimmunity, in certain individuals.
Example 3
The foregoing examples demonstrated a method for quantifying T cell subsets having particular cell surface phenotypes, using antibodies. This methodology calls for interaction between the antibody and its binding partners, i.e., the cell surface antigen, which is the Vβ molecule.
Enhanced presence of the Vβ molecules means that there has been enhanced expression of the DNA coding for the particular molecule. Thus, the following experiments deal with the measurement of the aforementioned T-cell subsets via analysis of the DNA expressing a particular Vβ subtype.
Among the methods available to the skilled artisan for analyzing DNA is the so-called polymerase chain reaction, or "PCR" as used hereafter. PCR methodology is well known to the art, as may be seen in, e.g, U.S. Pat. Nos. 4,683,195, 4,683,202 and 4,800,159, Saiki, et al., Science 239: 487-491 (1988), and Chelly, et al., Nature 333: 858-860 (1988). Given that the PCR methodology is known to the art, only the modifications to the technology used are elaborated upon.
Total RNA was prepared from anti-CD3 stimulated peripheral T cells as described supra. Two μg of total RNA was used for the synthesis of first strand cDNA using reverse transcriptase (Amersham) and random hexanucleotides. The reaction was stopped by heating for 5 minutes at 95° C. before polymerase chain reaction.
One twentieth of each cDNA samples was co-amplified using a Vβ-specific primer with a Cβ primer and two Cα primers as set forth at Table 2 with final concentration of 0.3 μM in each reaction. The amplification was performed with 2.5 U of Taq polymerase (Perkin-Elmer) and a Cetus Perkin Elmer thermocycler under the following conditions; 95° C. melting, 55° C. annealing, and 72° C. extension for 1 minute each. For quantification of amplified products, coamplification was performed with 5' 32 P-labelled reverse primers (about 5×10 5 cpm each) The amplified products were separated on 2% agarose gels, dried and exposed to X-ray film. The autoradiograms were used to identify and cut out the Vβ-Cβ and Cα bands. Each band was counted by liquid scintilation counter. In control experiments, the relative amplification efficiency was calculated essentially as described by Chelly et al., supra.
TABLE 2__________________________________________________________________________Sequences of primers used for PCRprimer sequence members.sup.a__________________________________________________________________________5' 3'Vβ1 GCACAAACAGTTCCCTGACTTGCAC 1.1, 1.2Vβ2 TCATCAACCATGCAAGCCTGACCT 2.1, 2.2, 2.3Vβ3 GTCTCTAGAGAGAAGAAGGAGCGC 3.1, 3.2Vβ4 ACATATGAGAGTGGATTTGTCATT 4.1, 4.2, 4.3Vβ5.1 ATACTTCAGTGAGACACAGAGAAAC 5.1Vβ5.2/3 TTCCCTAACTATAGCTCTGAGCTG 5.2, 5.3Vβ6 AGGCCTGAGGGATCCGTCTC 6.1, 6.2, 6.3Vβ7 CCTGAATGACCCAACAGCTCTC 7.1, 7.2Vβ8 ATTTACTTTAACAACAACGTTCCG 8.1, 8.2, 8.3, 8.4Vβ9 CCTAAATCTCCAGACAAAGCTCAC 9.1Vβ10 CTCCAAAAACTCATCCTGTACCTT 10.1, 10.2Vβ11 TCAACAGTCTCCAGAATAAGGACG 11.1, 11.2Vβ12 AAAGGAGAAGTCTCAGAT 12.1, 12.2Vβ13.1 CAAGGAGAAGTCCCCAAT 13.1.sup.bVβ13.2 GGTGAGGGTACAACTGCC 13.2.sup.cVβ14 GTCTCTCGAAAAGAGAAGAGGAAT 14.1.sup.dVβ15 AGTGTCTCTCGACAGGCACAGGCT 15.1Vβ16 AAAGAGTCTAAACAGGATGAGTCC 16.1Vβ17 CAGATAGTAAATGACTTTCAG 17.1Vβ18 GATGAGTCAGGAATGCCAAAGGAA 18.1Vβ19 CAATGCCCCAAGAACGCACCCTGC 19.1Vβ20 AGCTCTGAGGTGCCCCAGAATCTC 20.13'Cβ TTCTGATGGCTCAAACAC5'Cα GAACCCTGACCCTGCCGTGTACC3'Cα ATCATAAATTCGGGTAGGATCC__________________________________________________________________________ Notes to Table 2 The size of amplified products (Vβ bands) by Vβ and 3'Cβ primers ranged from about 170 to 220 bp. The size of the amplified cDNA (Cα band) by 5'Cα and 3'Cα primers was about 600 bp. Th 3'Cβ primer used in this study matches exactly both Cα 1 and Cα 2 DNA. The sequences of Vβ, Cβ, and Cα are from previously published reports. .sup.a Members of each Vβ family which have identical sequences as the corresponding primer are listed. .sup.b Vβ 13.1, .sup.c Vβ 13.2, and .sup.d Vβ 14.1 have also been called Vβ 12.3, 12.4, and 3.3, by Toyonaga, et al., Ann. Rev. Immunol. 5: 585-620 (1987), Kimura, et al., Eur. J. Immunol. 17: 375-383 (1987).
Among the at least 20 different families of human Vβ genes, at least 46 different members of these families have been cloned and sequenced, as reported by Toyonaga, et al., supra; Concannon, et al., Proc. Natl. Acad. Sci. USA 83: 6598-6602 (1986); Lai, et al., Nature 331: 543-546 (1988). To analyze human T cell Vβ usage, 22 different Vβ-specific oligonucleotides for use as 5' sense primers for PCR were synthesized. Their sequences, and the Vβ's which they would be expected to amplify, are shown in Table 2. All the Vβ's indicated as amplified have sequences matching their corresponding primers exactly. There may have been other Vβ genes amplified with these primers. For example, the Vβ6 primer matches Vβ6.4 except for one nucleotide, and further experiments will be needed to find out if Vβ6.4 is amplified using this primer. Altogether, all these primers would be expected to cover at least 39 of the 46 sequenced human genes. Each Vβ specific oligomer was picked to have roughly the same G+C content and to be located at relatively the same position in Vβ.
Example 4
Total RNA was prepared from human peripheral T cells stimulated by anti-CD3 antibody or one of 5 different S. aureus toxins (SEB, SEC2, SEE, exfoliating toxin (ExT), and toxic shock syndrome toxin 1 (TSST), as described in the previous examples. At the time of analysis these populations contained 50-90% T cell blasts as judged by flow cytometric analysis. A single strand complementary DNA was prepared for mRNA phenotyping, following Buus, et al., Science 235: 1353-1358 (1987); Townsend, et al., Cell 44: 959-968 (1986), and aliquots of cDNA from each sample were amplified with each of the 22 5' Vβ specific sense primers and the 3' Cβ specific antisense primer. As an internal control, TCR α chain mRNA was co-amplified in the same tube. Amplification was performed with 25 cycles, a limited number used to ensure that the amount of product synthesized was proportional to the amount of Vβ mRNA in the original preparation. The specificity of each Vβ specific primer was determined by the size of its amplified product and hybridization to the amplified products of specific probes (not shown). The amplification efficiencies of four of the primer sets (5'Cα-3'α, Vβs 2, 3, and 8-3'Cβ) were determined as described by Chelly, et al., supra. The average efficiency ranged about 46-48%. For each sample the number of counts in the Vβ band were normalized to those found in the Cα band.
It was necessary to find out whether or not the relative incorporation in this PCR reaction was proportional to the number of cells in the responding population expressing a particular Vβ element. However, two possible sources of error had to be considered. The first of these was contribution from unstimulated T cells. It was reasoned that, since mRNA levels are extremely low in unstimulated T cells compared to T cell blasts, the contribution from unstimulated cells would only become a problem when the proportion of blasts expressing a particular Vβ was very low compared to the unstimulated cells. Secondly, since all T cells have the potential to rearrange the β-locus on both chromosomes, transcription of Vβ mRNA from a non-productively rearranged chromosome in at least some T cells might confuse the analysis. Since non-functional mRNA could be expected to be at a low level due to its instability, it was reasoned that this mRNA may only present a problem in cases where a particular Vβ element was poorly expressed in the blast population.
In order to test these assumptions, the actual percentage of T cell blasts expressing Vβ5.2/3, Vβ8 and Vβ12 in the various samples using flow cytometry and anti-Vβ monoclonal antibodies was determined prior to preparing mRNA. When the normalized PCR incorporations for Vβ's 5.2/3, 8 and 12 for these samples were plotted in a log/log plot against the percentage of T cell blasts staining with these anti-Vβs monoclonal antibodies, a linear relationship was obtained (FIG. 3) with the data from three different experiments indistinguishable. This relationship was most evident for values above 1%. Below about 1% Vβ expression or a normalized PCR incorporation of about 30 the correlation was lost. It was concluded, therefore that contributions from unstimulated T cells and non-productively rearranged β-genes were insignificant when Vβ expression in the blasts was greater than 1%. Therefore, the data plotted in FIG. 3 was used as a standard curve to analyze expression of Vβ's for which antibody was not used, estimating the percent Vβ expression from the normalized PCR incorporation.
Example 5
The PCR methodology was used to analyze the expression of Vβ5.2/3, Vβ8, Vβ12 and 19 other Vβs or Vβ families in normal peripheral T cells stimulated with the various toxins. T cells stimulated with anti-CD3 were used as a control, because Examples 1 and 2 show that stimulation with anti-CD3 did not significantly change the percentages of T cells bearing particular Vβ's from that seen in the starting population. Results are shown in FIG. 4. The results of a complete analysis of the response of T cells from a single individual to five different S. aureus toxins are summarized in Table 3.
__________________________________________________________________________ Anti-CD3Normal T cells, Raw SEB SEC2% Vβ PCR % Vβ PCR % Vβ PCR % VβVβ (mAbs) value PCR mAbs value PCR mAbs value PCR mAbs__________________________________________________________________________ 1 88 3.8 20 <1.0 32 1.1 2 180 9.0 31 1.1 31 1.1 3 156 7.5 383 22.1 87 3.7 4 57 2.3 14 <1.0 11 <1.0 5.1 97 4.3 72 3.0 26 <1.0 5.2-3 3.2 105 4.7 4.4 61 2.4 3.2 46 1.7 1.2 6.1-3 160 7.8 54 2.1 88 3.8 7 211 10.8 44 1.7 89 3.8 8 4.2 168 8.2 5.3 35 1.3 0.2 28 1.0 0.2 9 55 2.2 10 <1.0 29 1.010 27 <1.0 11 <1.0 16 <1.011 37 1.3 8 <1.0 11 <1.012 1.5 51 2.0 2.4 93 4.1 4.9 120 5.5 5.913.1 181 9.0 48 1.8 172 8.513.2 67 2.7 55 2.2 115 5.214 81 3.4 137 6.5 157 7.615 33 1.2 99 4.4 94 4.116 23 <1.0 8 <1.0 13 <1.017 51 2.0 136 6.4 123 5.718 59 2.4 19 <1.0 14 <1.019 76 3.2 41 1.5 22 <1.020 80 3.4 118 5.4 186 9.3Total 91.2 66.0 63.1__________________________________________________________________________ SEE ExT TSST PCR % Vβ PCR % Vβ PCR % Vβ Vβ value PCR mAbs value PCR mAbs value PCR mAbs__________________________________________________________________________ 1 40 1.5 37 1.3 33 1.2 2 41 1.5 271 14.6 693 45.0 3 50 1.9 109 4.9 82 3.5 4 16 <1.0 22 <1.0 80 3.4 5.1 164 8.0 69 2.8 15 <1.0 5.2-3 57 2.3 1.9 98 4.3 3.8 118 5.4 4.0 6.1-3 263 14.1 152 7.3 167 8.2 7 107 4.8 108 4.9 103 4.6 8 349 19.8 15.7 32 1.1 0.8 26 <1.0 0.3 9 5 <1.0 76 3.2 39 1.4 10 24 <1.0 15 <1.0 32 1.1 11 11 <1.0 10 <1.0 12 <1.0 12 15 <1.0 0.3 20 <1.0 1.9 23 <1.0 1.4 13.1 16 <1.0 31 1.1 16 <1.0 13.2 33 1.2 30 1.0 25 <1.0 14 34 1.2 47 1.8 40 1.5 15 14 <1.0 24 <1.0 26 <1.0 16 25 <1.0 12 <1.0 12 <1.0 17 29 1.0 35 1.3 32 1.1 18 129 6.0 68 2.8 70 2.9 19 53 2.1 37 1.3 35 1.3 20 42 1.6 39 1.4 48 1.8 Total 67.0 55.1 82.4__________________________________________________________________________
Some Vβ families were used more abundantly than others by normal peripheral T cells. Members of the Vβ 2, 3, 6, 7 and 8 families and Vβ13.1 were expressed by more than 50% of total T cells. Such a finding was perhaps not unexpected for Vβ6 and Vβ8 which are part of large families of Vβ's (although the Vβ6 oligonucleotide probably primes for only 3 of the 9 members of the Vβ6 family), but is more surprising for Vβ13.1, which appears to be the product of a single gene. The uneven expression of Vβ's by human peripheral T cells did not appear to be idiosyncratic for this individual or determined by MHC, since similar frequencies were seen for 2 other unrelated human donors tested (see discussion, infra, and FIG. 5).
Complete analysis of the expression of mRNA for all 20 families of human T cell receptor Vβ genes showed clearly that all the toxins preferentially stimulated T cells expressing particular Vβ's, moreover the pattern of stimulation was different for each toxin. A number of striking new associations were found. Most dramatically Vβ2-bearing cells were highly-enriched by stimulation with TSST. About 50% of the T cells in TSST stimulated T cell blasts had Vβ2. As was shown, supra SEB stimulated T cells bearing Vβ12, but this analysis also revealed stimulation of T cells bearing Vβ3, Vβ14, Vβ15, Vβ17 and perhaps Vβ 20 by SEB. The related toxin, SEC2, also stimulated T cells expressing Vβ12, Vβ14, Vβ15, Vβ17 and Vβ20, but not those expressing Vβ3. SEE stimulated T cells bearing members of the Vβ8 family, as we have previously shown, but also increased the proportion of Vβ 5.1 + , Vβ6.1-3 + , and Vβ18 + cells.
Using this method, it was possible to estimate roughly the percentage of all the T cells in a given human cell population that could be accounted for by summing those bearing the different Vβs measured. As shown in Table 3, this percentage was about 90% for T cells stimulated with anti-CD3, suggesting that the estimate that the Vβ oligonucleotides would prime for expression of mRNA's encoded by 39 of the 46 human Vβ genes is not exaggerated, certainly not by an order of magnitude. This suggests that the 46 known Vβ sequences probably cover most of the human genes. The quantitative PCR's accounted for a lower percentage of blasts stimulated by some of the toxins, in particular, ExT. It is possible that this toxin predominantly stimulates T cells bearing Vβ's not covered by the listed primers
Some of the most dramatic associations in Table 3 were tested in two additional human individuals to see how general the phenomena were (FIG. 5). The stimulation experiments, and calculations, were identical to those used supra. In their responses to these toxins the 3 individuals behaved almost identically. For example, Vβ2 + T cells were enriched by TSST to almost the same level of 45% in every case. Similarly, in all three individuals, SEB stimulated T cells bearing Vβ3 and SEE stimulated T cells bearing Vβ8.
Example 6
The similarities between mice and humans in the T cell response to these toxins in striking. In both cases T cells bearing particular Vβ's dominate the response to each toxin. In both cases the discriminatory powers of the toxins can be particularly dramatic. For example, in humans Vβ5.1 + T cells responded to SEE, whereas cells bearing Vβ 5.2/3 did not. Similarly, it has been observed by the inventors that, in the mouse, several toxins can distinguish among the members of the Vβ 8 family. This member-specific response to superantigens has also been seen in mice for the endogeneous superantigen, Mls-1 a , which stimulates T cells bearing Vβ8.1 but not those expressing Vβ8.2 or Vβ8.3. See Kappler, et al., Nature 332: 35-40 (1988).
Extensive sequence analysis of Vβ genes from mouse and man shows that there are some homologues, both by primary sequence, and by their relative location in the Vβ gene complex. See Toyonaga, et al., Ann. Rev. Immunol. 5: 585-620 (1987); Concannon, et al., Proc. Natl. Acad. Sci. USA 83: 6598-6602 (1986); Lai, et al., Nature 331: 543-546 (1988). The stimulation patterns by the different toxins of these homologues by using data for mice Vβ stimulation by toxins was compared, following White, et al., Cell 56: 27-35 (1989). As indicated in Table 4, in some cases T cells bearing homologous Vβ's show a similar pattern of response to the toxins. ExT and especially TSST, for example, stimulated T cells bearing human Vβ2 and mouse T cells bearing the most analogous Vβ15. Human T cells expressing members of the Vβ12, 14, 15 and 17 families all showed a tendency to respond to SEB and SEC2, but not ExT or TSST. This property was shared by their closest murine relatives, mouse Vβ's 8.1, 8.2 and 8.3. However, similar response patterns by T cells bearing homologous Vβ's was not always seen. For example, T cells bearing murine Vβ3 responded to most of these toxins, however, those bearing the closest human analog, Vβ10, did not. Even with all this information in hand, a close examination of the primary amino acid sequences of the human and mouse Vβ elements has not yet revealed the essential residues responsible for toxin specificity. Thus, while tempting, complete generalization from mouse to human systems (MHC to HLA) is not indicated.
TABLE 4______________________________________Correlations Between Mouse and Human Vβ Usagein Response to S. Aureus Toxins. Enriched in Response to SEB SEC2 SEE ExT TSST______________________________________Mouse Vβ's 8.1 + ± - - - 8.2 + + - - - 8.3 + - - - -Human 14 (67) + + - - -Homologs 12 (62) + + - - -(% Homo) 13 (60) - ± - - - 15 (58) + + - - - 11 (55) - - - - - 17 (52) + + - - -Mouse Vβ 11 - - + - -Human 8 (71) - - + - -Homologs 6.1-3 (60) - - + ± ±(% Homo) 18 (55) - - + ± ±Mouse Vβ 15 - - - + +Human 2 (45) - - - ± +Homolog(% Homo)Mouse Vβ 3 + + - + +Human 19 (67) - - - - -Homologs 10 (56) - - - - ±(% Homo)______________________________________
In comparing mouse and man, the most striking difference to emerge thus far in our studies is the apparent lack of mechanisms limiting Vβ expression in humans. In the mouse, despite the potential for expression of over 20 Vβ elements in the species as a whole, various mechanisms limit Vβ expression in individual mice. In some strains large genetic deletions have eliminated about half of the Vβ gene elements. See, e.g., Behlke, et al., Proc. Natl. Acad. Sci. USA 83: 767-771 (1986). Other Vβ gene elements are often inactivated by point mutations. See Wade, et al., J. Immunol. 141: 2165-2167 (1988). Most ingeniously, in many strains of mice, self-superantigens, expressed during T cell development lead to the deletion of T cells bearing particular Vβ elements during the establishment of self tolerance. See in this regard Kappler, et al., Cell 49: 273-280 (1987); Kappler, et all, Cell 49: 263-271 (1987); macDonald, et al., Nature 332: 40-45 (1988); Pullen, et al., Nature 335: 796-801 (1988); Kappler, et al., Nature 332: 35-40 (1988); Abe, et al., J. Immunol 140: 4132-4138 (1988). It is proposed that these mechanisms which lead to limited Vβ expression in individual mice may be a protective evolutionary response to the pressure exerted by bacterial toxins, so that in a population of mice some individuals will be relatively resistant to the effects of any particular toxin superantigen. No evidence for widespread similar mechanisms in humans has emerged thus far from the limited number of individuals examined. Thus large genetic deletions have not been found nor have self-superantigens which cause elimination of T cells bearing particular Vβ been observed. A closer examination both of individual members of the Vβ families and of larger human populations, especially those with a much more widespread exposure at an early age to these types of toxins, may be required to observe some of these mechanisms at work in humans.
The foregoing examples show that a pathological condition, such as an infection, can be diagnosed by assaying a sample from a patient to determine levels of particular Vβ molecules in the sample. Increased levels of specific subtypes have been found to be linked to particular antigens, as the results show.
The term "pathological condition" as used herein is not limited to an infection; rather, it refers to any condition where an abnormal immune response has occurred. This includes, e.g., autoimmune diseases where, as has been shown supra, specific Vβ type molecules are present where they should not be, or are present in quantities above those found in normal individuals.
Increases in Vβ quantities are not the only way to diagnose pathological conditions in accordance with this invention. The art is familiar with various diseases and pathological states, such as HIV infection, where T cell levels are below those normally encountered. Correlation of particular Vβ types to conditions characterized by T cell depletion are also embraced herein.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, it being recognized that various modifications are possible within the scope of the invention. | The invention teaches a method for determining levels of T-cell surface antigens in humans, specifically, Vβ molecules. Measurement of such levels allows for diagnosis of pathological conditions, such as infections, where changes in these levels are indicative of a superantigen initiated pathological condition. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to currently pending U.S. Provisional Patent Application 60/744,850, entitled, “Molecular Detection and Quantification of Enterococci”, filed Apr. 14, 2006, the contents of which are herein incorporated by reference.
STATEMENT OF GOVERNMENT INTEREST
[0002] This invention was made with Government support under Grant No. 25000 172 00 awarded by the National Science Foundation. The Government has certain rights in the invention.
FIELD OF INVENTION
[0003] This invention relates to rapid detection of an organism, specifically, this is a method for detecting and quantifying Enterococci (a human fecal indicator organism) from sea water.
BACKGROUND OF THE INVENTION
[0004] The coastal ocean is an important economic and recreational resource that is constantly influenced by human activities. In 2003, there were more than 18,000 days of beach closings throughout the US due to high concentrations of fecal bacteria. This was an increase of more than 51% over the previous year. Health related management of recreational coastal sites is currently undertaken by monitoring fecal coliform and enterococci by membrane filtration. Elevated concentrations of enterococci in marine waters have been shown to have a strong correlation with illness (especially gastrointestinal disease) in exposed individuals therefore making enterococci the indicator organism of choice for saline waters. The problem with this type of standard indicator monitoring is that there is a lag of at least 24-48 hours between when the sample is collected and when the data become available. Changes in the water quality and potential exposures during this delay lead to management decisions and public notifications that are often times inaccurate. To improve our management abilities, we have adapted a primer pair and probe for the large subunit ribosomal RNA gene of enterococci for use in a real-time nucleic acid sequence based amplification (NASBA) assay. This region is highly conserved within all reported species of the Enterococcus genus. Using this assay, we are able to detect the equivalent to less than one enterococci colony forming unit (CFU) from a spiked sea water sample (100 ml). Further, there is a negative linear relationship (R 2 =0.9484) between CFUs obtained by membrane filtration and time to positivity (TTP) readings obtained with the NASBA assay. Therefore, quantitative estimates of enterococci are possible over at least four orders of magnitude and all positive samples amplified within forty-three minutes. By coupling this real-time NASBA assay to our existing field RNA extraction procedure and portable NASBA detection device, this technology will provide a simple, rapid (<1 hr), convenient testing format for coastal sites and greatly improve the health risk assessment of these regions.
[0005] Unlike polymerase chain reaction (PCR) based methods, NASBA is able to amplify RNA in a DNA background, and thus, only viable targets will be detected. This is important for indicator monitoring because only recent pollution events will be detected and false positive amplifications of naked DNA present in the sample will be eliminated. Indicator bacteria are chosen because of their ability to survive longer than the pathogenic organisms in question and therefore only viable bacteria should be considered as part of a risk analysis.
SUMMARY OF INVENTION
[0006] This is a method for the detection and quantification of Enterococci. Enterococci is the USEPA approved indicator organism used to monitor for fecal pollution in saline waters. Current methods rely on membrane filtration and even though the direct enumeration of these microorganisms using membrane filtration and plating has been available for years, there continue to be outbreaks associated with fecal contamination. The problem is that there is a lag of at least 24-48 hours between when the sample is collected and when the data become available. Changes in the water quality and potential exposures during this delay lead to management decisions and public notifications that are often times moot. To improve our management abilities, there is a need for rapid detection and quantification of appropriate bacterial indicators in coastal waters and sediments to ensure the safety of these resources for their multiple users. Our NASBA based method addresses this issue by quantitatively amplifying the target RNA and providing results in less than one hour.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] For a fuller understanding of the invention, reference should be made to the following detailed description, taken in connection with the accompanying drawings, in which:
[0008] The FIGURE shows sequences for primers and probe for NASBA amplification of Enterococci.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0009] NASBA primers and probes were designed based on homologous regions of the large subunit ribosomal RNA gene (The FIGURE). This region is highly conserved within all reported species of the Enterococcus genus (Haugland et al., 2005). Previous researchers (Frahm and Obst, 2003) used this region as the priming site for the development of a Taqman PCR assay for enterococci detection. The primers have been modified to best fit the NASBA amplification requirements and molecular beacon design criteria as well as minimize the cross hybridization to each other. This primer set has been tested against Enterococcus faecalis and E. faecium , and E. avium , as well as several other genera of Gram positive and Gram negative bacteria to determine the specificity of the assay and ensure that no cross reactivity occurs to non-target organisms. Data thus far indicate that the primer set is specific to the genus enterococci.
[0010] The assay sensitivity has been evaluated using serially diluted RNA isolated from enterococci cells. It is also possible to include cell extract samples from individual species as well as mixtures of all of the enterococci species available. Because ribosomal RNA tends to have a complex secondary structure, the NASBA assay was initiated by a 65° C. denaturing step for 3 minutes prior to the 41° C. amplification step (60 to 90 minutes). This initial denaturation is required for some, but not all NASBA assays and its requirement for efficient amplification of enterococci still needs to be evaluated.
[0011] Amplification inhibitors are often co-purified with natural environmental samples. We have encountered such inhibitors in our coastal water filtrates (Casper et al., 2005b). However, this inhibition tends to occur in sample volumes greater than 200 ml. For enterococci samples, the sample volume will always be less than 100 ml (as used by the DOH). Also, we will include an internal control (IC-NASBA protocol) that will be used to normalize the amplification results (Patterson et al., 2005). This approach will increase the precision of our quantification and reduce the amount of false negative results. Because the internal control molecule contains the same priming site as the target, the amplification reaction becomes competitive. Serial titrations of internal control RNA determine the optimal concentration to allow for consistent quantification of enterococci within the expected environmental concentrations (Patterson et al, 2005).
REFERENCES
[0012] The following citations are incorporated herein by reference:
Haugland R A, Siefring S C, Wymer L J, Brenner K P, Dufour A P. 2005. Comparison of Enterococcus measurements in freshwater at two recreational beaches by quantitative polymerase chain reaction and membrane filter culture analysis. Water Res. 39(4):559-68.
[0014] Frahm E, Obst U. 2003. Application of the fluorogenic probe technique (TaqMan PCR) to the detection of Enterococcus spp. And Escherichia coli in water samples. J Microb Meth 52: 123-131.
[0015] It will be seen that the advantages set forth above, and those made apparent from the foregoing description, are efficiently attained and since certain changes may be made in the above construction without departing from the scope of the invention, it is intended that all matters contained in the foregoing description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense.
[0016] It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween. Now that the invention has been described, | A primer pair and probe for the large subunit ribosomal RNA gene of enterococci for use in a real-time nucleic acid sequence based amplification (NASBA) assay. | 2 |
FIELD OF THE INVENTION
[0001] This invention relates to apparatus for extraction of tetrodotoxin. The apparatus can be used, inter alia, for batch production of tetrodotoxin or other toxins from animal tissues, for example using the method described in another application of the inventors (application Ser. No. 09/695,711, filed Oct. 25, 2000, Attorney Docket No. 3519-0111P). Twenty to one hundred kilograms of raw material can be processed at one time when puffer fish ovaries are used.
BACKGROUND OF THE INVENTION
[0002] A method for extraction of tetrodotoxin from animal tissues is described in a prior patent application of the inventors (U.S. application Ser. No. 09/695,711, filed Oct. 25, 2000, Attorney Docket No. 3519-0101P). That method comprises five steps as follows:
[0003] Step 1: Grind the tissues into small pieces, soak with an amount of water equal to 1.5 times by weight of the tissues and an amount of a weak organic acid, typically a carboxylic acid, preferably acetic acid, equal to 0.05%-1%, preferably 0.1%-0.3%, by weight of the tissue for several hours, then stir and filter quickly to obtain a lixiviated solution. Repeat this step 3-4 times in order to extract as much toxin as possible.
[0004] Step 2: Heat the lixiviated solution to 70-95° C. to coagulate and remove soluble proteins (“scleroprotein”).
[0005] Step 3: Adjust the pH of the lixiviated solution obtained in step 1 to 6.0˜7.5 using an aqueous solution of a weak base, then put the solution through a weakly acidic cation ion-exchange resin to enrich tetrodotoxin. Elute the bound tetrodotoxin with a weak acid.
[0006] Step 4: Adjust the pH of the obtained tetrodotoxin solution in step 3 to a range between 8 and 9 for a period of 2-4 hours, during which the solution is put through a column filled with active charcoal and diatomaceous silica so as to remove inorganic salts and a fraction of the alkaline amino acids. Tetrodotoxin binds the immobile phase, which is washed with de-ionized water, then the toxin is eluted with acidic ethanol solution.
[0007] Step 5: Purify and crystallize the tetrodotoxin by concentrating the solution obtained in step 4 under vacuum, then adjusting to an alkaline pH. Vacuum dry the obtained tetrodotoxin crystals, typically about 24 hours until the weight of the crystals becomes constant.
[0008] The method as described above can be run in either a batch mode or a continuous mode, but is typically run in a batch mode. The extraction system described herein is an efficient system for continuous production. A production cycle can be completed within a period of 6-7 days providing that the extraction is conducted 24 hours a day and 20-100 kg puffer fish ovaries are loaded at one time. For a load of 20 kg material, 0.8-1.2 grams tetrodotoxin can be obtained; for a load of 100 kg, 4-6 grams can be obtained.
SUMMARY OF THE INVENTION
[0009] The extraction system of this invention is named IWT-112 (See FIG. 1). An important component of the IWT-112 system is a lixiviating and filtering apparatus (“lixiviator”, device IWT-113). Additional components are a heater, an ion-exchange column, a diatomaceous silica-active carbon column, a vacuum concentrator etc. The components of the system are arranged so that liquids flow from the outlet of one device into the inlet of the next device. For continuous mode operation, it is possible to arrange the downstream components so that a batch run from the lixiviator is directed to one of several sets of series of the downstream components. Flow through the system can be driven either by gravity or by pressure differential established across each component separately or across the system as a whole or across various subsets of the components. For instance, a pressure differential can be established across the cation-exchange column and the diatomaceous silica-activated charcoal column while at the same time a vacuum is drawn on the decompression chamber of the lixiviator by an appropriate arrangement of valves and pressure and vacuum lines. Such a mode of operation might be utilized, for example, when starting a second extraction in the lixiviator while the chromatography steps are being completed on a first extraction.
[0010] Lixiviator (Device IWT-113, FIG. 2):
[0011] Device IWT-113 functions to lixiviate and filter. It is made of metals, preferably a corrosion-resistant material like stainless steel. It comprises three dismountable parts, namely a “sealing head” at the top, a “lixiviating barrel” in the middle and a “decompressing chamber” at the bottom.
[0012] The sealing head comprises a deceleration joint ( 1 ), a pressure gauge ( 2 ), a water inlet valve ( 3 ), a material filling inlet ( 4 ), a safety valve ( 14 ), a gas valve ( 15 ) and a degassing valve ( 16 ). The deceleration joint ( 1 ) transmits power to the propeller pug mill ( 8 ) by connecting a decelerating motor at a speed of 60-120 rpm so as to enable faster lixiviation and filtration by stirring. The propeller pug mill ( 8 ) can also help remove used raw material. The water inlet valve ( 3 ) is used to provide water for repeated lixiviation steps. After lixiviation, water can be supplied through the water inlet valve ( 3 ) to help pump out the used raw material from the material filling inlet while stirring.
[0013] The safety valve ( 14 ) controls the pressure inside the lixiviating barrel. The pressure is typically 0.5-1.5 kg per square centimeters while filtering. The pressure can be elevated up to 6 kg per square centimeters when necessary. The gas valve ( 15 ) maintains the pressure inside the lixiviating barrel by connecting to an air-compressing unit, whereas the degassing valve ( 16 ) functions to release the pressure inside the barrel.
[0014] The sealing head ( 6 ) is removably attached to the lixiviator. The sealing head is typically bolted on, but any removable joiner, for example a clamping device, that can seal the sealing head against the lixiviating barrel and can tolerate the pressurization can be used. A gasket for effecting a pressure seal can be inserted between the sealing head and the lixiviator barrel. The gasket material can be any typical pressure gasket material, preferably an elastomeric material that is resistant to weak acid solutions.
[0015] Filtering material ( 9 , 10 ) is mounted between the decompressing chamber and the lixiviator barrel. During the lixiviation process, the filtration can be speeded by elevating the pressure in the lixiviation barrel or reducing pressure in the decompression module. The filtering material is made from filtering paper, filtering cloth and other porous filtering material that is compatible with use between stainless steel components. “Compatible with use between stainless steel components” means that the filter material will at least not promote electromotive corrosion of the stainless steel.
[0016] The filtering material can be for example, a nylon mesh having 100 to 200 meshes per square inch, a stainless steel mesh having 40 to 60 meshes per square inch, or a porous metal plate having a pore diameter of from 2 to 10 mm, preferably from 2 to 4 mm, more preferably 2.5 to 3.5 mm. These materials can be combined in a layered arrangement. Thus, the filter material can be a combination for example, of a nylon mesh having 100 to 200 meshes per square inch, middle to high speed filtering paper, a stainless steel mesh having 40 to 60 meshes per square inch, and a porous metal plate having a pore diameter of 3 mm. A preferred arrangement is to have a metal plate on the bottom, upon which is stacked a stainless steel mesh, a filtering paper and then nylon mesh on top.
[0017] The filter is preferably installed in a frame that can be removed from the lixivating/filtering apparatus for easy cleaning and maintenance. Also, the filter is preferably mounted in an elastomeric material suitable for maintaining a pressure seal between the filter and the walls of the lixiviator barrel and/or decompression chamber.
[0018] A vacuum valve ( 13 ) is installed on the side of the decompression chamber, and a drain ( 18 ) at the bottom.
[0019] The lixiviator can be mounted on a stand ( 19 ).
[0020] A heater can be fitted to the lixiviator. The heater should be capable of heating the liquid to a desired temperature and maintaining that temperature. The heater can be an oil-bath heater or steam heater of industry standards. Alternatively, the filtered solution collecting in the decompressing chamber at the bottom of the lixiviator can be passed to a separate heated vessel.
[0021] A second filtering apparatus is connected to the outlet of the lixiviator or of the separate heated vessel. The second filtering apparatus can be integral with the separate heated vessel. The filtering material of the second filtering apparatus functions to remove precipitate from the heated filtrate. The filtering material of the second filtering apparatus can be made from material similar to that of the filter between the lixiviator barrel and decompression chamber of the lixiviator. However, the filtering material of the second filtering apparatus is more preferably one having a smaller pore size, sufficient to remove small bits of precipitated protein so that such precipitate does not interfere with subsequent chromatographic steps. The filtering material for the second filtering apparatus preferably includes a middle to high speed filtering paper, in order to separate out the smaller bits of precipitated protein. The order of the filtering material components is the same as that of the first filter. Also, rather than “mesh” type filtering material, an membrane type filter, typically made from nylon or other polymeric material, suitable for filtration driven by a pressure differential is preferred as the filter material for the second filtration apparatus.
[0022] The second filtering apparatus is preferably operable by pressure differential and therefore the second filtering apparatus and the separate heated vessel may comprise appropriate connections to pressure or vacuum lines and appropriate relief valves as needed.
[0023] Ion-exchange column (Device IWT-312):
[0024] An ion-exchange column (IWT-312) is used to remove proteins, peptides and their derivatives from the tetrodotoxin solution during enrichment and purification of tetrodotoxin. If not removed, these substances produce a high viscosity solution and also interfere with precipitation of the tetrodotoxin later in processing.
[0025] Diatomaceous Silica-active Charcoal Column (Device IWT-412):
[0026] A column comprising diatomaceous silica and activated charcoal is used to remove basic amino acids remaining in the eluate from the ion-exchange column.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] [0027]FIG. 1—Flow chart of IWT-112 TTX Extraction System.
[0028] [0028]FIG. 2—Lixiviator—Apparatus IWT-113.
[0029] [0029]FIG. 3—HPLC profile of TTX obtained in Example 1.
[0030] [0030]FIG. 4—HPLC profile of TTX obtained in Example 2.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The extraction procedure using the system of this invention comprises:
[0032] 1. Lixiviation with Water
[0033] 20-100 kg toxic tissues, for example ovaries of puffer fish, are crushed into pieces less than 1 cc 3 , and put into a IWT-113 lixiviator (See FIG. 2). The lixiviator is filled with de-ionized water to 1.5 times the weight of the ovaries and acetic acid is added to 0.1 to 1% by weight of the ovaries. The propeller pug mill is run to stir the mixture for a few hours at room temperature. The vacuum pump is run to decompress the decompression chamber and begin filtering for several minutes. Then the compressor is run to adjust the pressure at the upper part of the lixiviator to 0.5 to1 kg/cm 2 . The filtrate is collected, then heated quickly to 70-90° C. for 3-25 minutes. The filtrate is cooled and again filtered to remove the precipitate. The clarified filtrate is a yellow transparent liquid, called “first clear lixiviated liquid”.
[0034] The lixiviation is repeated as above and the second lixiviated clear liquid is collected. Repeat the lixiviation process to obtain the third and the fourth lixiviated liquids. The fourth lixiviated liquid is collected only when extremely or highly toxic tissues are used. For mildly toxic tissues, only the third lixiviated liquid is obtained.
[0035] The first, second, third (and fourth) lixiviated liquids are pooled, and the toxin content of the liquid is determined by bioassay or high performance liquid chromatography (HPLC). See, e.g. Chinese patent application 00132673.2, filed Nov. 22, 2000, or U.S. application Ser. No. ______, filed ______, Attorney Docket No. 3519-0110P.
[0036] 2. Ion-Exchange Enrichment and TTX-Separation Process
[0037] The pH of the pooled clear lixiviated liquid is adjusted to 6.0˜7.5, preferably using a strong amine base, typically ammonia. Any precipitate that forms should be removed, e.g by filtration. The clear lixiviated liquid is then put through a cation-exchange resin column (Device IWT-312). A preferred resin is a weakly acidic ammonium cation ion-exchange resin, such as D-152 (Nankai University Chemical Factory, Tianjing, P.R. China.) A typical flow rate for loading the column is 2000 to 3750 mL/hr. Thin layer chromatography (TLC) on a silica plate is used to monitor whether or not toxin leaks from the outflow. TLC can be performed on a silica gel thin-layer plate eluted with n-butanol: acetic acid: water (2:1:1). TTX can be detected by spraying the plate with 10% KOH solution after it is eluted, baking for 10 minutes at 110° C., and observing under a 365 nm ultraviolet lamp. TTX is detected as blue fluorescent spots with R f =0.38−0.40. If toxin leaks, the resin column should be replaced with a new one immediately.
[0038] After all the clear lixiviated liquid passes through the column, the column is washed with de-ionized water until there is no protein present in the outflow. The outflow can be monitored for protein content by any typical method in the art, for example by measuring absorbance of 280 nm light. The column is then eluted with a solution of 5 to 12% (by volume) of a weak organic acid, preferably acetic acid, in water, typically at a flow rate of 500 to 2500 mL/hr. The eluate is collected in fractions, preferably of about 1500 mL per portion, and each fraction is assayed for TTX content by thin layer chromatography (TLC).
[0039] 3. Purification with Active Charcoal
[0040] The eluate from the ion-exchange column that contain TTX are pooled and the pH of the solution is adjusted to 8 to 9 with a strong base, preferably aqueous ammonia. The pH is maintained for a period of 2 to 4 hours, within which time the solution is passed through a column that is packed with active charcoal and diatomaceous silica. The diatomaceous silica-active carbon column comprises two layers, with the upper layer being diatomaceous silica and the lower layer being active charcoal. The layer of diatomaceous silica has a {fraction (1/10)} to ½, preferably {fraction (1/10)}-⅕, the thickness of the layer of active charcoal.
[0041] The column is washed with de-ionized water, then eluted with an ethanol solution that contains acid (the concentration of ethanol is between 0.5% to 40%, preferably 15% to 30% by volume; the concentration of the acid is from and 0.2 to 0.6% by volume. The acid is preferably a weak organic acid, typically acetic acid. Elution of TTX from the column can be monitored by TLC.
[0042] Concentration and Crystallization
[0043] The eluate from the silica-charcoal column is concentrated by vacuum evaporation of the solvent, preferably to about {fraction (1/10)}th the volume, Or about 0.5-1 mL per kilogram raw material used. The concentrated solution is cooled to 18-25° C. (room temperature) and the pH is adjusted 8 to 9. A strong amine base, preferably ammonia, is used to adjust the pH. The solution is left standing to precipitate TTX. The crystalline TTX is collected, preferably by filtration and then washed with de-ionized water several times. The crystalline TTX is dried, for example by vacuum evaporation, and redissolved in a dilute solution of an organic acid, preferably acetic acid. The acid solution has a concentration of about 3-7%, preferably 5%, by volume of the acid. The pH is again adjusted to 8 to 9 as above and the TTX is reprecipitated, washed and dried as above. The recrystallization can be repeated, e.g. another 1 or 2 times. The TTX crystals obtained are dried to constant weight and the purity of the produc is determined by HPLC.
EXAMPLES
[0044] The following examples serve to illustrate the invention, but are in no way intended to limit the invention.
EXAMPLE 1
[0045] Twenty kilograms ovaries of puffer fish were ground into pieces less than 1 cc 3 , and put into an IWT-113 lixiviator. Thirty liters de-ionized water and 30 milliliters acetic acid were added. The propeller pug mill was started to stir the mixture for 10 hours at room temperature. Then a vacuum pump was run to enable the filtrate start flowing out from the lixiviator, followed by turning on an air compressor to speed the filtration. After filtering, another 30 liters de-ionized water was added to repeat the lixiviation process. The lixiviation process was repeated totally four times.
[0046] The filtrates were merged, and then heated at 80° C. for 5 minutes. After cooling down, the filtrates were sent into a second IWT-113 lixiviator to separate out the precipitated scleroprotein and obtain clear liquid. The pH of the clear liquid was adjusted to 7.5 using aqueous ammonia. Then the solution was put through an ion-exchange column (device IWT-312) which was a NH 4 + weakly acidic cation ion-exchange resin (D-152, (Nankai University Chemical Factory, Tianjing, P.R. China.) column having a diameter of 6 cm and a height of 1 meter, filled with resin by Nankai University Chemical Factory, Tianjing, China. After the solution all passed through, the column was washed clean with de-ionized water, then was eluted with 10% aqueous acetic acid solution to get a TTX eluate. Subsequently, strong aqueous ammonia was used to adjust the pH of the TTX eluate to 8.5. The resulting solution was put through a diatomaceous silica-active charcoal column (device IWT-412), in which a diatomaceous silica layer was placed above an active charcoal layer, and the diatomaceous silica layer was {fraction (1/15)} the thickness of the active charcoal layer. The TTX was adsorbed on the active charcoal. Then a 20% aqueous ethanol solution containing 0.2% acetic acid was used to elute TTX, and the eluate was put into a rotating evaporator to concentrate to about 15 milliliters. After cooling to 22° C., the pH of the concentrated solution was adjusted with concentrated ammonia to 9, and the solution was put into a refrigerator to be cooled further and to crystallize the TTX. The crystals were separated out and dissolved in 5% acetic acid, then the pH of the resulting solution was adjusted with strong ammonia to 9, and TTX in the solution was crystallized and precipitated again. Next, the TTX crystals were placed in a vacuum drier and were dried for 24 hours so that their weight became constant. The TTX content of the dried product was determined by high performance liquid chromatograph (HPLC) to be 85.4% (See FIG. 3). From 20 kilograms ovaries, 1210 milligrams TTX crystals were obtained, an equivalent of 6.05 grams per 100 kilograms ovaries.
EXAMPLE 2
[0047] One hundred kilograms puffer fish ovaries were ground, and 150 L water and 150 mL 0.5% acetic acid were added. The tissue was lixiviated and the remaining process steps were performed as in Example 1. 5.82 g TTX crystals of 80.0% purity by HPLC were obtained (See FIG. 4). | The invention relates to a system for extracting toxins from biological tissues. The system comprises a lixiviator, an ion-exchange column, a diatomaceous silica-active carbon column, and a vacuum concentrator. Twenty to one hundred kilograms of raw material can be processed at one time when puffer fish ovaries are used as the starting material. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of pending U.S. patent application Ser. No. 09/846,154, filed Apr. 30, 2001 now U.S. Pat. No. 6,596,875, which claims the benefit of the earlier filing date of U.S. patent application Ser. No. 09/499,596, filed Feb. 7, 2000, now abandoned, which claims the benefit of the earlier filing date U.S. Provisional Application No. 60/118,883, filed Feb. 5, 1999. Each of these prior applications is incorporated herein by reference.
ACKNOWLEDGEMENT OF GOVERNMENT SUPPORT
The United States government may have certain rights in this technology pursuant to Grant No. GM-50574, awarded by the National Institutes of Health.
FIELD
The present disclosure concerns a method for making epothilones and epothilone analogs, and compounds made by the method.
BACKGROUND
I. Introduction
Epothilones A (2) and B (4) were discovered by Höfle and coworkers while examining metabolites of the cellulose-degrading myxobacterium Sorangium cellulosum (Myxococcales) as potential antifungal agents. Höfle, G.; Bedorf, N.; Gerth, H.; Reichenbach (GBF), DE-B 4138042, 1993 ( Chem. Abstr. 1993, 120, 52841). Höfle, G.; Bedorf, N.; Steinmeth, H.; Schomburg, D.; Gerth. H.; Reichenbach, H. Angew. Chem. Int. Ed. Engl. 1996, 35, 1567.
Although the antifungal spectrum of 2 and 4 proved to be quite narrow, scientists at Merck found that these macrolides are highly cytotoxic. Bollag, D. M.; McQueney, P. A.; Zhu, J.; Hensens, O.; Koupal, L.; Liesch, J.; Goetz, M.; Lazarides, E.; Woods, C. M. Cancer Res. 1995, 55, 2325. The epothilones had powerful activity against mouse fibroblast and leukemia cells (2 ng mL −1 ) and strong immunosuppressive activity. Gerth, K., et al., Antibiot., 1996, 49, 560-563. By observing the effect of the epothilones on induction of tubulin polymerization to microtubules and noting that 2 and 4 are competitive inhibitors of Taxol with almost identical IC 50 values, it was concluded that epothilones act at the cellular level by a mechanism similar to Taxol. Bollag, D. M. Exp. Opin. Invest. Drugs 1997, 6, 867; Nicolaou, et al., Angew. Chem. Int. Ed. Engl., supra. Epothilone B (2) was particularly impressive in these assays, having a 2,000-5,000-fold higher potency than Taxol in multiple-drugresistant cell lines. Bollag, D. M.; et al., Cancer Res. 1995, supra.
After scientists from Merck reported their findings on the mode of action of epothilones in 1995, interest in these compounds increased. The Merck scientists subjected tens-of-thousands of compounds to biological assays for Taxol-like tubulin-polymerization activity. However, of the compounds assayed, only epothilones A and B proved biologically active.
II. Tubulin and Microtubules
Tubulin polymerization-depolymerization plays an important role in the cell cycle, particularly during mitosis. Tubulin, a heterodimer protein comprising globular αβ-tubulin subunits is the monomeric building block of microtubules. Microtubules are one of the fundamental structural components of the cytoskeleton in all eukaryotic cells, and help develop and maintain the shape and structure of the cell as needed. Microtubules may operate alone, or in conjunction with other proteins to form more complex structures, such as cilia, centrioles, or flagella. Nicolaou et al., at 2019, supra.
Structurally, microtubules are regular, internetworked linear polymers (protofilaments) of highly dynamic assemblies of heterodimers of α and β tubulin. Nicolaou et al., supra. When thirteen of these protofilaments are arranged parallel to a cylindrical axis they selfassemble to form microtubes. These polymers form tubes of approximately 24 nm in diameter and up to several μm in length. Nicolaou et al., supra.
Growth and dissolution of microtubules are regulated by bound GTP molecules. During polymerization, GTP molecules hydrolyze to guanosine diphosphate (GDP) and orthophosphate. The half-life of tubulin at 37° C. is nearly a full day, but that of a given microtubule may be only 10 minutes. Consequently, microtubules are in a constant state of flux to respond to the needs of the cell. Microtubule growth is promoted in a dividing or moving cell, but is more controlled in a stable, polarized cell. The regulatory control is exerted by adding (for growth) or hydrolyzing (for shrinkage) GTP on the ends of the microtubule.
Microtubules are major components of the cellular apparatus and play a crucial role in mitosis, the process during cell replication in which duplicated genetic material in the form of chromosomes is partitioned equally between two daughter cells. When cells enter mitosis, the cytoskeletal microtubule network (mitotic spindle) is dismantled by melting at the center, and two dipolar, spindle-shaped arrays of microtubules are formed outwardly from the centrosome. Nicolaou et al., at 2020, supra. In vertebrate cells, the centrosome is the primary site of microtubule nucleation (microtubule-organizing center or MTOC). At metaphase, the dynamic action of the microtubules assembles the chromosomes into an equatorial position on the mitotic spindle. At anaphase, the microtubule dynamics change and the chromosomes partition and move to the new spindle poles on the dynamic microtubules, where the new cells are being formed. Nicolaou et al., supra. By this process, the parent cell duplicates its chromosomes, which provides each of the two daughter cells with a complete set of genes. When it is time for a eukaryotic cell to divide, microtubules pull its chromosomes apart and pushes them into the two emerging daughter cells. The rate at which microtubules change their length increases by 20- to 100-fold during mitosis relative to the rate during interphase. These rapid dynamics are sensitive to tubulin-interactive agents that exert their antimitotic action at the metaphase-to-anaphase transition. Kirschner et al., Cell, 1986, 45, 329-342.
III. Anticancer Drugs that Disrupt Microtubule Dynamics
A number of anticancer drugs having diverse molecular structures are cytotoxic because they disrupt microtubule dynamics. Most of these compounds, including known chemotherapeutic agents colchicine, colcemid, podophyllotoxin, vinblastine, and vincristine, interfere with the formation and growth of microtubules and prevent the polymerization of microtubules by diverting tubulin into other aggregates. This inhibits cell proliferation at mitosis.
Vinblastine binds to the ends of microtubules. Vinblastine's potent cytotoxicity appears to be due to a relatively small number of end-binding molecules. Mitchison et al, Nature, 1984, 312, 237-242.
Colchicine first binds to free tubulin to form complexes. These complexes are incorporated into the microtubules at the growth ends in relatively low concentrations, but show profound effects on the microtubule dynamics. Toso R. J., Biochemistry, 1993, 32, 1285-1293.
Taxol disturbs the polymerization-depolymerization dynamics of microtubules in vitro by binding to the polymeric microtubules and stabilizing them against depolymerization. Cell death is the net result. Epothilones appear to act by the same mechanism and bind to the same general regions as Taxol does. Bollag et al., Cancer Res., 1995, 55, 2325-2333. Epothilones displace Taxol from its receptor, but bind in a slightly different manner to microtubules, as suggested by their action against Taxol-resistant tumor cells, which contain mutated tubulin. Each tubulin molecule of the microtubules contains a Taxol binding site. Taxol and epothilone binding markedly reduce the rate of α/β tubulin dissociation.
Merck scientists compared the effects of the epothilones and Taxol on tubulin and microtubules and reported higher potencies for both epothilones A and B as tubulin polymerization agents (epothilone B>epothilone A>Taxol). All three compounds compete for the same binding site within their target protein. The epothilones exhibit similar kinetics in their induction of tubulin polymerization, and gave rise to microscopic pictures of stabilized microtubules and damaged cells that were essentially identical to those obtained with Taxol. Epothilones are superior to Taxol as killers of tumor cells, particularly multiple drug resistant (MDR) cell lines, including a number resistant to Taxol. In some of the cytotoxicity experiments, epothilone B demonstrated a 2,000-5,000-fold higher potency than Taxol, as stated above. Moreover, in vivo experiments, carried out recently at Sloan Kettering in New York involving subcutaneous implantations of tumor tissues in mice, proved the superiority of epothilone B.
On treatment with epothilone B, cells appear to be in disarray with their nuclei fragmented in irregular shapes and the tubulin aggregated in distinct wedge-shaped bundles. By interacting with tubulin, the epothilones block nuclear division and kill the cell by initiating apoptosis.
Recently, Hamel and co-workers examined the actions of epothilones A and B with additional colon and ovarian carcinoma cell lines and compared them with the action of Taxol. Kowalski R. J., et al., J. Biol. Chem., 1997, 272, 2534-2541. Pgp-overexpressing MDR colon carcinoma lines SW620 and Taxol-resistant ovarian tumor cell line KBV-1 retained susceptibility to the epothilones. With Potorous tridactylis kidney epithelial (PtK2) cells, examined by indirect immunofluorescence, epothilone B proved to be the most active, inducing extensive formation of microtubule bundles. Nicolaouet al., at 2022, supra.
Epothilone A initiates apoptosis in neuroblastoma cells just as Taxol does. Unlike Taxol, epothilone A is active against a Pgp-expressing MDR neuroblastoma cell line (SK-N SH). And, the efficacy of epothilone was not diminished despite the increase of the Pgp level during administration of the drug.
IV. Taxol Side Effects
Taxol molecules bind to microtubules, making cell division impossible, which kills the cells as they begin to divide. Since cancer cells divide more frequently than healthy cells, Taxol damages tumors where runaway cell division occurs most profoundly. Other rapidly dividing cells, such as white blood cells and hair cells, also can be attacked. Consequently, patients taking the drug experience side effects. Chemotherapy with Taxol frequently is accompanied by immune system suppression, deadening of sensory nerves, nausea, and hair loss (neutropenia, peripheral neuropathy, and alopecia).
Taxol exhibits endotoxin-like properties by activating macrophages, which in turn synthesize proinflammatory cytokines and nitric oxide. Epothilone B, despite its similarities to Taxol in its effects on microtubules, lacked any IFN-γ-treated murine-macrophage stimulatory activity as measured by nitric oxide release, nor did it inhibit nitric oxide production. Epothilone-mediated microtubule stabilization does not trigger endotoxin-signaling pathways, which may translate in clinical advantages for the epothilones over Taxol in terms of reduced side effects.
The importance of the epothilones as therapeutic agents recently was discussed on the front page of the Jan. 27, 2000, edition of the Wall Street Journal. This article states:
But Taxol has its drawbacks. Some fast-dividing cancer cells can mutate into forms resistant to the drug. Often, patients with advanced cancer who respond at first to Taxol don't respond after several cycles of treatment because their cells become resistant, too. Despite conducting dozens of trials over the years, Bristol-Myers has been frustrated in its efforts to expand Taxol's effectiveness beyond certain breast, ovarian and lung cancers. That's why the new drugs, broadly classified as part of a family of chemicals known as the epothilones, hold such promise. In studies not yet published, Bristol-Myers and others have shown that the epothilones disrupt cell division through the same biochemical pathway as Taxol. But for reasons scientists are only beginning to understand, the new drugs are equally effective against cancer cells already resistant to Taxol, as well as cells that develop resistance over time.
V. Syntheses of Epothilones
Based on the biological activity of the epothilones and their potential as antineoplastics, it will be apparent that there is a need for an efficient method for making epothilones and epothilone analogs. Four total syntheses of 4, and several incomplete approaches, are known. See, for example: (1) Nicolaou, K. C.; Ninkovic, S.; Sarabia, F.; Vourloumis, D.; He, Y.; Vallberg, H.; Finlay, M. R. V.; Yang, Z. J. Am. Chem. Soc. 1997, 119, 7974; (2) Meng, D.; Bertinato, P.; Balog, A.; Su, D.-S.; Kamenecka, T.; Sorensen, E. J.; Danishefsky, S. J. J. Am. Chem. Soc. 1997, 119, 10073; (3) May, S. A.; Grieco, P. Chem. Commun. 1998, 1597; (4) Schinzer, D.; Bauer, A.; Schieber, J. Synlett 1998, 861; (5) Mulzer, J.; Mantoulidis, A. Tetrahedron Lett. 1996, 37, 9179; (6) Claus, E.; Pahl, A.; Jones, P. G.; Meyer, H. M.; Kalesse, M. Tetrahedron Lett. 1997, 38, 1359; (7) Gabriel, T.; Wessjohann, L. Tetrahedron Lett. 1997, 38, 1363; (8) Taylor, R. E.; Haley, J. D. Tetrahedron Lett. 1997, 38, 2061; (9) Brabander, J. D.; Rosset, S.; Bemardinelli, G. Synlett 1997, 824; (10) Chakraborty, J. K.; Dutta, S. Tetrahedron Lett. 1998, 39, 101; (11) Liu, Z.-Y.; Yu, C.-Z.; Yang, J. D. Synlett 1997, 1383; (12) Liu, Z.-Y.; Yu, C.-Z; Wang, R.-F.; Li, G. Tetrahedron Lett. 1998, 39, 5261; (13) Mulzer, J.; Mantoulidis, A.; Öhler, E. Tetrahedron Lett. 1997, 38, 7725; and (13) Bijoy, P.; Avery, M. A. Tetrahedron Lett. 1998, 39 1209.
Methods for making epothilone and epothilone analogs also have been described in the patent literature, including: (1) Schinzer et al., WO 98/08849, entitled “Method for Producing Epothilones, and Intermediate Products Obtained During the Production Process”; and (2) Reichanbach et al., WO 98/22461, entitled “Epothilone C, D, E, and F, Production Process, and Their Use as Cytostatic as well as Phytosanitary Agents.” One disadvantage associated with these prior processes for synthesizing epothilones is the lack of stereoselectivity in the production of the Z trisubstituted bond of the desepoxyepothilone. As a result, a new synthetic approach to epothilones and epothilone analogs is required which addresses this and other problems associated with syntheses of the epothilones known prior to the present disclosure.
SUMMARY
The present disclosure provides a novel method for making epothilones and epothilone analogs. The method can provide almost complete stereoselectivity with respect to producing the Z trisubstituted double bond of the desepoxyepothilone, and therefore addresses one of the disadvantages associated with methods known prior to the present disclosure.
One embodiment of the present disclosure provides compounds having the structure represented by Formula 1.
With respect to Formula 1, G is selected from the group consisting of
R substituents independently are H, lower alkyl, or a protecting group, such as a silyl group; R 1 is an aryl group, such as comprising a benzene derivative, or a heterocyclic aryl group, such as a thiazole derivative. R 2 substituents independently are selected from the group consisting of H and lower alkyl groups; Z is selected from the group consisting of the halogens and —CN; M is selected from the group consisting of O and NR 3 ; R 3 is selected from the group consisting of H, lower alkyl, R 4 CO, R 4 OCO, and R 4 SO 2 ; R 4 is selected from the group consisting of H, lower alkyl, and aryl; T is selected from the group consisting of CH 2 , CO, HCOH and protected derivatives thereof; W is H or OR; and X and Y independently are selected from the group consisting of O, NH, S, CO, and C.
In certain disclosed embodiments X and Y define a carboxylic acid derivative, such as provided by an ester, thioester, or amide bond. One example, without limitation of such an ester bond is formed where X is C═O and Y is O. In other preferred embodiments X and Y mutually comprise a triple bond.
In particular preferred embodiments, R 1 is a group according to Formula 2 where X and Y independently are selected from the group consisting of O, N, and S, and R 6 is selected from the group consisting of H and lower alkyl. A particular class of aryl group according to Formula 2 is the thiazole class.
A method for synthesizing compounds according to Formula 1 is provided. One embodiment of the method comprises providing a compound according to Formula 3.
Compounds according to Formula 3 are subjected to macrolactonization conditions to yield macrocyclic compounds according to Formula 1.
Another embodiment of the method comprises procedures for synthesizing compounds according to Formula 3. One embodiment of such procedures comprises providing a compound according to Formula 4, and a compound according to Formula 5, and coupling the compounds to form a bond between X and Y, thereby yielding a compound
according to Formula 3. In particular embodiments, coupling the compounds comprises reacting compounds having Formulas 4 and 5 by a reaction selected from the group consisting of organometallic reactions, such as transition metal-mediated coupling reactions, and amide bond-forming reactions, esterification reactions, thioesterification reactions, and the like.
One embodiment of the method comprises first providing a compound having Formula 6.
With reference to Formula 6, R is H or a protecting group; R 1 is an aryl group, such as, without limitation, benzene derivatives or the thiazole of epothilone B; R 2 -R 5 substituents independently are selected from the group consisting of H and lower alkyl groups; and R 6 , substituents independently are selected from the group consisting of H and lower alkyl groups. Compounds having Formula 6 are then converted into an epothilone or an epothilone analog. For example, in the synthesis of epothilone B the step of converting the compound can involve first removing the protecting groups, and thereafter forming an epoxide at C12-C13.
In preferred embodiments, R 1 is the thiazole shown below.
Most known epothilones have this thiazole derivative as the aryl group.
Providing compounds having Formula 6 can be accomplished in a number of ways. One embodiment comprises coupling a first compound having Formula 7,
where R is H or a protecting group and X is a functional group or chemical moiety equivalent to a carbanion at a terminal carbon of the first compound, with a second compound having Formula 8. With reference to Formula 8, R 6 substituents independently are selected from the group consisting of H and lower alkyl groups, R is H or a protecting group, and Y is an electrophilic group capable of reacting with and coupling to the terminal carbon of the first compound, for example, Y can be an aldehyde. The precursor compound is then converted into compounds having Formula 6. For example, two compounds, one having Formula 7 and the other Formula 8, can be coupled by a Wittig reaction where X is PPH 3 + and Y is a carbonyl compound, such as an aldehyde.
Compounds having Formula 6 can be provided by a second embodiment of the disclosed method. This second embodiment involves coupling a first compound having Formula 9
where R is H or a protecting group and X is a halide, with a second compound including an alkyne and having Formula 10.
With reference to Formula 10, R groups independently are H, a protecting group, or a lower alkyl group. This compound is then converted into a compound having Formula 6. This embodiment can proceed by first forming an enyne precursor compound having Formula 11 where the substituents are as stated above.
Thus, another embodiment of the present method for forming epothilones or epothilone analogs comprises forming the precursor enyne compound having Formula 11 where R 1 is H or a protecting group, or is a thiazole group according to the triene compound having Formula 12 where R groups independently are H, a protecting group, or a lower alkyl group. Compounds having Formulas 11 and/or 12 are then converted into a compound having Formula 13, where
the carbon atom numbers correspond to the numbering system stated for epothilone A.
With reference to Formula 13, R-R 7 are independently selected from the group consisting of H, lower aliphatic groups, particularly lower alkyl groups, protecting groups, or are bonded to an 0 in an epoxide or N in an aziridine. More particularly, R substituents independently are H, lower alkyl, or a protecting group; R 1 is an aryl group; R 2 is H or lower alkyl; C13 and C12 are carbons bonded together by a single bond or a double bond; R 3 and R 4 independently are H, lower aliphatic groups, or are bonded to 0 in an epoxide or to N in an aziridine; C10 and C9 are carbons in a double bond or triple bond, and, where C10 and C9 are carbons in a double bond, R5 and R6 independently are H, or lower aliphatic; and R7 substituents independently are selected from the group consisting of lower aliphatic groups. The configuration of the double bond between C10 and C9 may be cis or trans, i.e., E or Z. Compounds having Formula 13 are then converted into an epothilone or an epothilone analog.
Moreover, a compound having Formula 11 may be converted into a compound having Formula 12, such as by catalytic semi-hydrogenation. Lindlar's catalyst has proved to be an effective catalyst for conducting this catalytic semi-hydrogenation.
The disclosed embodiments of the present method differ from known synthetic pathways in a number of ways, such as by assembling the macrolide from two segments, which first are connected at C9-C10 before macrolactonization. With reference to the first disclosed embodiment of the present method, fragments were constructed around a preformed Z trisubstituted alkene to circumvent stereochemical problems afflicting known synthetic methods. The 9,10 olefin produced by coupling the two segments confers rigidity on the one portion of the epothilone macrocycle that exhibits flexibility, and hence may be expected to affect its tubulin binding properties. Moreover, this alkene provides a chemical moiety from which novel epothilone analogs can be prepared.
Epothilones, such as epothilone A, epothilone B, epothilone C, epothilone D, epothilone E, and epothilone F, can be made by the present method. The disclosed method also provides access to novel compounds. These compounds typically have Formula 13
where the substituents are as described above. Preferred compounds satisfying Formula 13 include one or more of the following: (1) R being hydrogen; (2) R 1 being the aryl thiazole side chain of the epothilones; (3) R 2 being hydrogen or methyl; (4) R 3 -R 6 being hydrogen or methyl, or R 3 and R 4 and/or R 5 and R 6 being bonded to oxygen in an epoxide; (5) R 7 being lower alkyl, particularly methyl.
Compounds having Formula 13 include several chiral centers, which allows for a plurality of diastereomers. The disclosed method is directed to all such stereoisomers.
However, naturally occurring epothilones have known stereochemistries at each of the chiral centers. As a result, preferred compounds have the same stereochemistries at each chiral center, as do the epothilones. This is illustrated below in Formula 14, which shows the stereochemistries of preferred epothilone analogs at certain chiral centers. With respect to Formula 14, certain centers are represented stereoambiguously; however, the present method provides access to compounds having defined stereochemistry at these positions. Thus, in certain embodiments of the present method, compounds having controlled stereochemistry at positions 4, 9, 10, 12, 13 and 15 can be prepared.
The present disclosure describes novel, biologically active epothilone analogs having the general structure represented by Formula 15. With reference to Formula 15, particular embodiments include compounds wherein R is H or a protecting group; R 1 is an aryl group, such as, without limitation, benzene derivatives, the thiazole derivative of epothilone B; R 2 and R 3 substituents are selected independently from the group consisting of H and lower alkyl groups; and R 4 substituents are selected independently from the group consisting of lower alkyl groups. Group Y at position 9 can comprise a heteroatom, such as an oxygen, nitrogen, or sulfur. In particular embodiments, Y is an oxygen atom, such as in an ester bond with a carbonyl at position 10 of an epothilone analog. Likewise, Y can comprise an NH group in an
amide bond or a sulfur in a thioester linkage. Group X at position 10 can comprise a carbon, such as a methylene, a methine, or a carbon bonded to a heteroatom, such as an oxygen atom. In particular embodiments, group X is a carbonyl, such as a carboxylic acid derivative. For example X can be bonded to Y in an ester, thioester or amide linkage.
The present method provides novel synthetic routes to compounds having the general structure represented by Formula 15. For example, with reference to Formula 16, Y can be a hydroxyl group, and as such, can be oxidized to provide the corresponding carboxylic acid. This compound can then be coupled, for example, with a compound having the structure represented by Formula 17.
With reference to Formulas 16 and 17, each R group independently can be H or a protecting group, with R 1 -R 4 as defined above. In particular embodiments, groups X and Y independently comprise an oxygen, nitrogen or sulfur, such as in an alkoxy group, an amine, or a sulfhydryl, respectively.
DETAILED DESCRIPTION
The process of the present method can be used to make known epothilones A, B, C, D, E and F, as well as analogs of these compounds, including the cryptothilones, which typically are dilactone or lactone-amide-type analogs of the epothilones. The cryptothilones are hybrid structures that include a portion of cryptophycins and a portion of the epothilones.
One such novel diene analog 10 has double bonds at positions C9-C10, and C12-C13. The
alkene configurations at C 9 -C10, and C12-C13 can be cis or trans (Z or E), including compounds 11 and 12.
Using compound 10 and/or 11 to make analogs of epothilones, such as the cryptothilones, provides advantages relative to prior known syntheses, as indicated above.
A method for making diene 10 and converting 10 into, for example, epothilone B, as well as other epothilones and epothilone analogs, is described below.
I. Epothilone Structures and Epothilone Analogs
Formula 1 is a generic structural formula for diene and enyne derivatives of Compound 10, and analogs of the epothilones, such as a bislactone analog.
Preferred compounds have the stereochemistries shown in Formula 14.
With reference to Formula 14, R is H, lower aliphatic, preferably lower alkyl, or a protecting group; R 1 is an aryl group; C13 and C12 are carbons bonded together by a single or double bond; R 3 and R 4 independently are H, lower alkyl, or are bonded to oxygen in an epoxide or to nitrogen in an aziridine; C10 and C9 are carbons in a single bond, double bond or triple bond, with preferred compounds having C10 and C9 bonded together by a double bond or a triple bond; if C10 and C9 are bonded together by a double bond, the configuration of the double bond may be cis or trans or E or Z; and R 5 and R 6 independently are H, lower aliphatic, preferably lower alkyl, or are bonded to heteroatoms in cyclic structures, such as to oxygen in an epoxide or to nitrogen in an aziridine.
As used herein, “lower” refers to carbon chains having 10 or fewer carbon atoms, typically less than 5 carbon atoms. “Lower aliphatic” includes carbon chains having: (a) sites of unsaturation, e.g., alkenyl and alkynyl structures; (b) non-carbon atoms, particularly heteroatoms, such as oxygen and nitrogen; and (c) all branched-chain derivatives and stereoisomers.
The phrase “protecting group” is known to those of ordinary skill in the art of chemical synthesis. “Protecting group” refers generally to a chemical compound that easily and efficiently couples to a functional group, and can be easily and efficiently removed to regenerate the original functional group. By coupling a protecting group to a first functional group of a compound other functional groups can undergo chemical or stereochemical transformation without affecting the chemistry and/or stereochemistry of the first functional group. Many protecting groups are known and most are designed to be coupled to only one or a limited number of functional groups, or are used for particular circumstances, such as reaction conditions. Theodora Greene's Protecting Groups in Organic Syntheses, (Wiley Science, 1984), and later editions, all of which are incorporated herein by reference, discuss protecting groups commonly used in organic syntheses. Examples of protecting groups used to protect hydroxyl functional groups for the syntheses of epothilones and epothilone analogs include the silyl ethers, such as t-butyl dimethyl silyl (TBDMS) ethers, and tetrahydropyranyl (THP) ethers.
The term “analog” refers to a molecule that differs in chemical structure from a parent compound, for example a homolog (differing by an increment in the chemical structure, such as a difference in the length of an alkyl chain), a molecular fragment, a structure that differs by one or more functional groups, or an ion differing in ionization state from the parent compound.
A “derivative” is a chemical substance structurally related to a parent substance and theoretically derivable from it.
“R groups” in generic structural formulas are typically recited as being independent. This means that each R group can be varied, one from another, even when designated with the same R group. Thus each R group can represent the same chemical moiety, some R groups can be the same chemical moiety, or each R group can represent a different chemical moiety.
“Aryl” refers to compounds derived from compounds having aromatic properties, such as benzene. “Aryl” as used herein also includes compounds derived from heteroaromatic compounds, such as oxazoles, imidazoles, and thiazoles.
Preferred aryl groups have Formula 2
where X and Y are independently selected from the group consisting of heteroatoms, particularly oxygen, nitrogen and sulfur, and R 6 is selected from the group consisting of lower alkyl. For the epothilones, and most epothilone analogs, the R 1 aryl group is thiazole 18 shown below.
C12 and C13 of Formula 13 are carbons bonded together by a single or double bond. Whether C12 and C13 are joined by a single or double bond determines, in part, substituents R 3 and R 4 . For example, if C12 and C13 are coupled by a single bond, then R 3 and R 4 independently are selected from the group consisting of hydrogen and lower alkyl. Moreover, if C12 and C13 are coupled by a single bond then R 3 and R 4 can be bonded to a heteroatom, such as oxygen and nitrogen, in a cyclic structure, such as an epoxide or an aziridine. Epoxide 20 and aziridine 22 are examples of these compounds.
Several chiral centers of these structures are represented stereoambiguously to indicate that the various stereoisomers are within the scope of the disclosed method. With respect to the aziridine analogs, such as aziridine 22, R 2 is selected from the group consisting of hydrogen, lower aliphatic, particularly lower alkyl, acyl, and aryl. Preferred compounds have R 2 be hydrogen or lower alkyl.
C9 and C10 of Formula 13 are carbons bonded together by a single, double or triple bond. Whether C9 and C10 are joined by a single bond, a double bond or a triple bond determines, in part, substituents R 5 and R 6 . For example, if C9 and C10 are coupled by a single bond, then R 5 and R 6 typically are selected from the group consisting of hydrogen and lower aliphatic, preferably lower alkyl. Moreover, if C9 and C10 are coupled by a single bond then R 5 and R 6 also can be bonded to a heteroatom, such as oxygen and nitrogen, in a cyclic structure, such as an epoxide or an aziridine. Epoxide 24 and aziridine 25 provide examples of these compounds.
Compounds 26-35 provide additional examples of epoxide/aziridine epothilone analogs.
II. Biological Activity
Known epothilones have significant biological activity. Novel epothilone analogs made according to the method also have been shown to have significant biological activity. For example, Tables 1 and 2 provide biological data for certain epothilones and epothilone analogs. The antiproliferative activity of cis 9,10-dehydroepothilone D and trans 9,10-dehydroepothilone D was assessed in vitro using a panel of human cancer cell lines.
As illustrated in Table 1, cis 9,10-dehydroepothilone was 20- to 30-fold less potent than natural epothilone D, and 330- to 670-fold less potent than epothilone B. Interestingly, trans 9,10-dehydroepothilone D showed biological activity very similar to that of its cis isomer in spite of an apparent difference in the conformation of these two macrolactones. Thus, the average IC 50 of trans 9,10-dehydroepothilone D for growth inhibition in the cell line panel used in this study was only 1.36-fold higher than that observed for cis 9,10-dehydroepothilone D. As noted for epothilones B and D, cis 9,10-dehydroepothilone D and trans 9,10-dehydroepothilone D retain full anti-proliferative activity against KB-8511 cells, a paclitaxel-resistant cell line overexpressing P-glycoprotein (Table 1). While the tubulin polymerization activity of cis 9,10-dehydroepothilone D and trans 9,10-dehydroepothilone D was lower than of natural epothilone D (56%, 36%, and 88%, respectively) (Table 1), it is conceivable that decreased cellular penetration may contribute to the reduction in antiproliferative potency observed for cis 9,10-dehydroepothilone D and trans 9,10-dehydroepothilone D. The absence of a clear difference in the biological profiles of cis and trans analogs of 9,10-dehydroepothilone D observed here has a parallel in results previously reported for other epothilone analogs. Thus, epothilones incorporating a trans epoxide or trans olefin at C12-C13 have been shown to possess biological activity comparable to their cis isomer.
TABLE 1
IC 50
IC 50
KB-31
KB-8511
IC 50
IC 50
IC 50
IC 50
Tubulin
(Epider-
(Epider-
A549
HCT-116
PC3-M
MCF-7
Compound
Polym. a
moid) b
moid) b,c
(lung) b
(colon) b
(prostate) b
(breast) b
95
0.17
0.16
0.16
0.34
0.32
0.29
Epothilone B
88
1.94
1.00
4.62
4.48
7.40
2.31
Epothilone D
56
59.39
28.54
109.03
101.83
146.47
72.00
9,10-cis-Dehydroepothilone D
36
103.70
70.37
109.27
109.97
146.80
95.03
trans 9,10-, trans 12,13-Dehydroepothilone D
Paclitaxel (Taxol)
53
2.67
841.80
5.19
4.88
6.62
3.26
a Tubulin polymerization data (induction of porcine tubulin polymerization) are for 5 μM compound concentration relative to the effect of Epothilone B at a concentration of 25 μM, which is defined as 100%.
b IC 50 values are expressed in nM and represent the mean of three independent experiments:
c KB8511 is a Pgp-overexpressing sub-line of the KB-31 line.
With reference to Table 2, the bislactone epothilone analog was tested as indicated under the conditions used for Table 1. The bislactone was standardized against epothilone B, epothilone D, and paclitaxel in each experiment. The data indicate that although the bislactone is less active than epothilone B and D, the analog retains useful biological activity, particularly against the paclitaxel resistant KB-8511 cells.
TABLE 2
Tubulin
IC 50 KB-31
IC 50 KB-8511
Compound
Polym.
(Epidermoid)
(Epidermoid)
21.4
25.5
25.2
Bislactone
81.4
0.24
0.15
Epothilone B
62.3
1.94
1.00
Epothilone D
Paclitaxel
38.9
2.9
661
Taken together, these data support the proposition that the C 8 -C 13 region of the epothilone perimeter is relatively tolerant of structural modification and suggest that the interaction of this segment of the molecule with tubulin is less stringently defined.
III. Method for Making Epothilones
The synthesis of epothilones can be exemplified by a working embodiment of a method for making epothilone B. Epothilone B was synthesized by coupling a first subunit with a second subunit to form a coupled intermediate for forming epothilones. One embodiment of the method comprised coupling a first subunit 36 with a second subunit 38.
A second embodiment comprised coupling a first allylic halide subunit 40 with a second alkyne subunit 42. With respect to 36, 38, 40, and 42, the R substituents are as described above.
A first embodiment of a the present method for making epothilones and epothilone analogs comprised making a suitable subunit 36 as illustrated by Scheme 1, i.e., compound 60.
Synthesis of segment 36, as represented by 60 in Scheme 1, began from (Z)-3-iodo-2-methyl-2-propen-1-ol prepared in geometrically pure form from propargyl alcohol. After protection to provide 44, the iodoalkene was converted to the corresponding cuprate, which underwent clean conjugate addition to (S)-3-acryloyl-4-benzyl-2-oxazolidinone (45, not shown) to yield 46. Hydroxylation of the sodium enolate derived from 46 with Davis oxaziridine gave 48. See, for example, Evans et al. Angew. Chem. Int. Ed Engl. 1997, 26, 2117. The configuration of 48 was confirmed by oxidative degradation to dimethyl (S)-malate. Protection of alcohol 48 as silyl ether 50, followed by exposure to catalytic potassium thioethoxide in ethanethiol provided 52, along with recovered oxazolidinone (93%). Treatment of thioester 52 with lithium dimethylcuprate furnished ketone 54, which upon Homer-Emmons condensation with phosphonate 53 (shown below) produced diene 56 in excellent yield, accompanied by 5% of its (Z,Z) isomer.
The tetrahydropyranyl ether protecting group was removed using magnesium bromide. The liberated alcohol was converted to bromide 58. Homologation of 58 to phosphonium bromide 60 using triphenylmethylenephosphorane completed the synthesis of segment 36, as represented by compound 60 in Scheme 1.
One embodiment of a segment 38, i.e., compound 74, was made as illustrated by Scheme 2. A key construction in one embodiment of a suitable segment 38 involved an aldol condensation of ketone 62 with aldehyde 64. This double stereodifferentiating reaction proceeded in good yield to give anti-Felkin product 66 as the sole stereoisomer. An important contribution to the stereoselectivity of this condensation is made by the p-methoxybenzyl (PMB) ether of 64, since the TBS protected version of this aldehyde resulted only in a 3:2 mixture of 66 and its Felkin diastereomer, respectively. The favorable outcome with 64 is consistent with chelation of the aldehyde carboxyl with both the lithium enolate from 62 and the PMB ether. After protection of 66 as tris ether 68, the terminal olefin was cleaved oxidatively to carboxylic acid 70, which was converted to its methyl ester 72. Hydrogenolysis of the PMB ether and oxidation of the resultant alcohol 74 yielded aldehyde 76.
Subunits 60 and 76 were coupled together, followed by macrolactonization, to provide the diene lactone precursor to epothilone B as shown below in Scheme 3. Wittig coupling of the ylide from 58, compound 60, with aldehyde 76 at low temperature afforded triene 78 as a single stereoisomer in excellent yield. Selective removal of the C15 silyl ether of 78 was unsuccessful. But, after saponification to carboxylic acid 80 this deprotection was readily accomplished with tetra-n-butylammonium fluoride. Macrolactonization of seco acid 82 was carried out under Yamaguchi's conditions and both silyl ethers were cleaved with acid to yield 9,10-dehydrodes-epoxyepothilone B 84.
Compounds made in this manner can be converted to epothilones using conventional chemistry. For example, selective hydrogenation of the disubstituted olefin of 84 with diimide gave the known lactone 86. Lactone 86 underwent epoxidation with dimethyldioxirane to produce 4. Epoxidation of lactone 86 to provide epothilone B (4) can be accomplished according to the method of Danishefsky et al., Angew. Chem. Int. Ed. Engl., 1997, 36, 757, which is incorporated herein by reference. Characterization data for both 86 and 4 matched those in the literature and/or of the naturally occurring product. The 1 H NMR spectrum of 4 was in excellent agreement with that provided by Professor Grieco.
Schemes 1-3 provide a convergent synthesis of epothilone B (4), which generates all seven of its asymmetric centers in a completely stereoselective fashion. In addition, clean Z configuration at the C12-C13 double bond is incorporated by this pathway. Finally, the Z olefin at C9-C10 provides a chemical moiety from which exploratory structural modifications can be made.
Scheme 4 illustrates a second embodiment of a method for making epothilones and epothilone analogs. With reference to Scheme 4, compound 76 was made as illustrated above in Scheme 2, and as discussed in more detail in Example 16. Aldehyde 76 was reacted with dimethyl diazophosphonate [J. C. Gilbert et al., J. Org. Chem. 1982, 47, 1837] in THF at −78° C. to provide alkyne 88 in approximately 80% yield. The copper (I) derivative of alkyne 88 was produced and was found to couple with allylic halide 58. This reaction was extensively investigated, and was found to proceed to product 90 best when the conditions for the reaction were as shown in Table 3, using about 5% CuI, Et 3 N, Et 2 O-DMF, and about 2.0 equivalents of 88. Conditions investigated for this coupling are summarized below in Table 3.
TABLE 3
Equivalents
of 88
Coupled With
Reagents/Conditions
Product Yield
1.1
Allylic Bromide 58
5% CuI, TBAB, K 2 CO 3 , DMF
8
1.1
Allylic Bromide 58
20% CuI, ALIQUOT 336,
11
K 2 CO 3 , DMF
1.1
Allylic Bromide 58
50% CuI, Pyrrolidine, DMF
0
1.1
Allylic mesylate 58B
(a) Ms 2 O, Et 3 N, DMF
34
(b) 10% CuI, Na 2 CO 3 , TBAB,
DMF
1.1
Allylic mesylate 58B
(a) Ms 2 O, Et 3 N, CH 2 Cl 2
42
(b) 20% CuI, Na 2 CO 3 , TBAB,
DMF
1.1
Allylic Chloride 58A
5% CuI, Et 3 N, Et 2 O-DMF
24
2.0
Allylic Chloride 58A
5% CuI, Et 3 N, Et 2 O-DMF
60
Product 90 was semi-hydrogenated over Lindlar's catalyst [Pd/CaCO 3 , Pd(OAc) 2 ]. This reaction was found to proceed best when hexanes was used as the solvent. The hydrogenated product was then saponified using NaOH and isopropyl alcohol at 45° C. to provide the corresponding seco acid 80 in approximately 66% yield. The C15 TBS ether 80 was then deprotected using TBAF and THF by warming the reaction from 0° C. to 25° C., with a yield of about 89%. The selectivity of this reaction is attributed to sterically favorable transilyation involving the carboxylate anion. The resultant silyl ester is hydrolyzed during aqueous work-up. Macrolactonization was then performed under Yamaguchi conditions. Yamaguchi et al., Bull Chem. Soc. Jpn. 1970, 52, 1989. The remaining TBS ether protecting groups were then removed using trifluoroacetic acid (TFA) in dichloromethane at 0° C. to provide compound 84. Compound 84 was then converted to 4 as discussed with respect to Scheme 3 and Examples 21, 22 and 23.
Schemes 5, 6, and 7 illustrate an embodiment of a synthesis via Stille coupling that yields epothilone derivatives containing a trans (or E) double bond between C9 and C10 (See Formula 13).
With reference to Scheme 5, compound 92 was esterified with 2-(trimethylsilyl)ethanol using Mitsunobu conditions to provide 94. Hydrogenolysis removed the p-methoxybenzyl ether from 94, and oxidation of alcohol 95 afforded an aldehyde, which was reacted with Bestmann's reagent (Müller et al. Synlett. 1996, 521) to give terminal alkyne 96. Hydrostannylation of the latter in the presence of a palladium dichloride catalyst furnished vinylstannane 98
With reference to Scheme 6, compound 48, which was prepared from compound 46 of Scheme 1, was protected as TES ether 49 by reaction with triethylsilyl triflate. The latter was advanced to alcohol 104 by a four-step sequence analogous to that used for converting 48 to 56 (see Scheme 1) and including a final step of removing the tetrahydropyranyl ether protecting group with magnesium bromide. For Stille coupling purposes, the allylic chloride 106 (prepared by chloride displacement of the corresponding mesylate prepared from compound 104) was found to be more effective than the corresponding bromide (Scheme 1).
Coupling of 98 with 106 (Scheme 7) in the presence of catalytic dipalladium tris(dibenzylideneacetone)chloroform complex and triphenylarsine (Farina and Krishnan, J. Am. Chem. Soc. 1991, 113, 9585) proceeded in high yield and gave the 9E,12E,16E-heptadecanoate 108. Exposure of 108 to tetra-n-butylammonium fluoride cleaved both the (trimethylsilyl)ethyl ester and the triethylsilyl ether but left tert-butyldimethylsilyl ethers at C3 and C7 intact. The resulting seco acid 110 underwent facile macrolactonization to 112 under Yamaguchi conditions. Subsequent removal of the remaining pair of TBS ethers with trifluoroacetic acid furnished trans 9,10, trans 12,13-dehydroepothilone D (114).
Scheme 8 illustrates an embodiment of the method that provides a conformationally constrained epothilone analog, 9,10-didehydroepothilone D (124). Compound 124 was synthesized, its conformation studied, and its tubulin polymerization and antiproliferative activity assayed by White et al. Org. Lett. 2002, 4, 995-997, which is incorporated herein by reference.
With reference to Scheme 8, allylic chloride 106 (Scheme 6) was coupled with alkyne 116 in the presence of cuprous iodide to afford dienyne 118. This dienyne was treated with TBAF to effect selective deprotection of the TES and TMSE blocking groups, yielding compound 120. The resulting hydroxy acid, 120, was lactonized under Yamaguchi conditions to furnish 122, and removal of the remaining silyl ethers using trifluoroacetic acid gave 9,10-didehydroepothilone D (124).
Scheme 9 illustrates the synthesis of a bislactone analog, 134, of the epothilones. Bislactone 134 was assayed for tubulin polymerization activity as well as antiproliferative action relative to paclitaxel and epothilones B and D. The biological data are recorded in Table 2.
As depicted in Scheme 9, allylic alcohol 104 was coupled to acid 81 via a Mitsunobu reaction to afford compound 126. The resultant ester compound was selectively deprotected to yield hydroxy acid 130, which underwent lactonization under Yamaguchi conditions to afford the bislactone 132. Cleavage of the remaining silyl ethers gave target compound 134.
Compounds 126 and 128 are used to synthesize the corresponding lactam and thiolactone epothilone analogs, respectively. The lactam and thiolactone can be prepared in analogous fashion to the bislactone 132. Amine 126 is readily available by the present method from compound 57. For example, compound 57 has been converted to the corresponding allylic halide 106 (Scheme 6). Such an allylic halide can be converted to amine 126 via the corresponding allylic azide (not shown) as is known to those of ordinary skill in the art. Similarly, compound 128 can be prepared from compound 106 via displacement of the allylic halide using thioacetic acid, and followed by removal of the acetyl moiety to provide compound 128.
Trans 9,10-dehydroepothilone 146 can be prepared according to Scheme 10 from aldehyde 76 and compound 140 via a Julia olefination. According to this route, treatment of compound 140 (available from compound 106) with a base, such as butyl lithium, forms the corresponding sulfonyl carbanion. The carbanion then reacts with aldehyde 76 to provide a β-hydroxy sulfone product (not shown). The β-hydroxy sulfone is eliminated under reductive conditions to give 9E, 12Z, 16E-heptadecanoate derivative 142. Selective removal of the triethylsilyl and trimethylsilyl ethyl ester protecting groups from 142, followed by macrolactonization under Yamaguchi conditions, provides compound 144 Removal of the remaining silyl protecting groups affords trans 9,10-dehydroepothilone 146.
IV. Examples
The following examples are provided to illustrate certain particular features of working embodiments of the disclosed method. The scope of the present invention should not be limited to those features described.
Example 1
This example describes the synthesis of compound 44 of Scheme 1. To a stirred solution of the alcohol precursor to 44 (1.03 g, 5.20 mmol) in CH 2 Cl 2 (20 mL) was sequentially added DHP (580 mg, 630 μL, 6.91 mmol), followed by PPTS (110 mg, 0.438 mmol). After 1.5 hours, the reaction was quenched with solid NaHCO 3 (5 g), filtered, concentrated in vacuo and purified by chromatography over silica gel, eluting with 30% Et 2 O/petroleum ether, to give 44 (1.42 g, 5.00 mmol, 96%) as a colorless oil: IR (neat) 2940, 1445 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.04 (s, 1H), 4.62 (t, J=3.0 Hz, 1H), 4.26 (d, J=12.1 Hz, 1H), 4.16 (d, J=12.1 Hz, 1H), 3.85-3.95 (m, 1H), 3.5-3.6 (m, 1H), 1.95 (d, J=1.5 Hz, 3H), 1.5-1.9 (m, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ 144.6, 98.4, 75.8, 72.1, 62.5, 30.7, 25.6, 22.2, 19.6; HRMS (CI) calculated for C 9 H 16 O 2 (M + H + ) 283.0195, found 283.0198.
Example 2
This example describes the synthesis of compound 46. To a stirred solution of t-BuLi (48 mL, 62.4 mmol, 1.3 M in pentane) in Et 2 O (63 mL) at −78° C. was added a solution of 44 (10.27 g, 36.4 mmol) in Et 2 O (75 mL) via syringe pump over 20 minutes. After 20 minutes, the slurry was rapidly transferred to a precooled solution of CuCN (1.58 mg, 17.7 mmol) in THF (122 mL) at −78° C. After 1 hour at −78° C. and 5 minutes at −40° C., the solution was recooled to −78° C., and a precooled solution of 42 (3.40 g, 14.7 mmol) in THF (86 mL) was added via cannula. An additional amount of THF (25 mL) was added to rinse the flask. After 30 minutes, the solution was warmed to 0° C., and after a further 10 minutes the reaction was quenched with saturated aqueous NH 4 Cl (300 mL) and extracted with Et 2 O (3×150 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 15-50% Et 2 O/petroleum ether, to give 46 (5.05 mg, 13.1 mmol, 89%) as a colorless oil: [α]D 23 +46.1 (c 2.58, CHCl 3 ); IR (neat) 1782, 1699 cm −1 ; 1 H NMR (300 MHz, CDCl 3 )δ 7.1-7.4 (m, 5H), 5.40 (t, J=7.1 Hz, 1H), 4.6-4.7 (m, 2H), 4.05-4.2 (m, 4H), 3.8-3.95 (m, 1H), 3.45-3.6 (m, 1H), 3.28 (dd, J=3.2, 13.3 Hz, 1H), 2.9-3.05 (m, 2H), 2.76 (dd, J=9.6, 13.3 Hz, 1H), 2.46 (q, J=7.3 Hz, 2H), 1.5-1.9 (m, 6H), 1.78 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 172.8 , 153.6, 135.5, 133.8, 129.6, 129.1, 127.5, 127.4, 97.8, 97.7, 66.4, 65.5, 65.4, 62.3, 55.3, 38.1, 36.0, 30.8, 25.7, 22.7, 21.9, 19.7; HRMS (FAB) calculated for C 22 H 28 NO 5 (M+H + ) 386.1968, found 386.1965.
Example 3
This example describes the synthesis of compound 48. To a stirred solution of NaHMDS (7.6 mL, 7.6 mmol, 1 M in THF) in THF (35 mL) at −78° C. was added a solution of the alcohol precursor to 46 (2.482 g, 6.41 mmol) in THF (50 mL) via syringe pump over 30 minutes. An additional amount of THF (5 mL) was added to rinse the syringe. After 20 minutes, a precooled solution of oxaziridine (2.55 g, 9.77 mmol) in THF (8 mL) was quickly added via cannula. After 6 minutes, the reaction was quenched with a solution of CSA (3.54 g, 15.2 mmol) in THF (10 mL). After 2 minutes, saturated aqueous NH 4 Cl (75 mL) was added. The mixture was allowed to warm to room temperature and was concentrated in vacuo to remove THF. The aqueous layer was extracted with Et 2 O (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 50-70% Et 2 O/petroleum ether, followed by chromatography over silica gel, eluting with 2-4% acetone/CH 2 Cl 2 , followed by trituration in 10% Et 2 O/petroleum ether to give 48 (1.84 g, 4.5 mmol, 71%) as a white foam contaminated with a small amount of the phenyl sulfonamide: [α]D 23 +37.2 (c 4.00, CHCl 3 ); IR (neat) 3476, 1781, 1699 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.1-7.4 (m, 5H), 5.40 (m, 1H), 5.05-5.15 (m, 1H), 4.55-4.7 (m, 2H), 4.05-4.3 (m, 4H), 4.02 (dd, J=3.7, 11.7 Hz, 1H), 3.8-3.95 (m, 1H), 3.79 (d, J=8.6 Hz, 1H of a diastereomer), 3.66 (d, J=8.6 Hz, 1H of a diastereomer), 3.45-3.6 (m, 1H), 3.31 (dt, J=3.0, 13.5 Hz, 1H), 2.75-2.9 (m, 1H), 2.45-2.6 (m, 2H), 1.5-1.9 (m, 9H); 13 C NMR (75 MHz, CDCl 3 ) δ 174.6, 174.3, 153.4, 153.3, 136.2, 135.5, 135.11, 135.06, 129.6, 129.2, 127.6, 123.8, 123.1, 98.1, 96.4, 70.5, 70.4, 67.1, 67.0, 65.7, 65.0, 62.4, 61.8, 55.7, 37.7, 32.6, 30.7, 30.5, 25.6, 22.2, 22.1, 19.7, 19.2; HRMS (Cl) calculated for C 22 H 28 NO 6 (M+H + ) 402.1917, found 402.1919.
Example 4
This example describes the synthesis of compound 50. To a stirred solution of 48 (1.74 g, 4.32 mmol) in CH 2 Cl 2 (22 mL) at −78° C. was added sequentially 2,6-lutidine (1.06 g, 1.15 mL, 9.87 mmol) followed by TBSOTf (2.07 g, 1.8 mL, 7.83 mmol). After 30 minutes, the reaction was quenched with saturated aqueous NH 4 Cl (100 mL) and extracted with Et 2 O (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 30-50% Et 2 O/petroleum ether, to give 50 (2.06 g, 3.90 mmol, 90%) as a colorless oil: [α]D 23 +32.3 (c 2.96, CHCl 3 ); IR (neat) 1782, 1714 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.15-7.4 (m, 5H), 5.35-5.5 (m, 2H), 4.55-4.7 (m, 2H), 4.05-4.2 (m, 2H), 4.0-4.15 (m, 2H), 3.8-3.9 (m, 1H), 3.4-3.5 (m, 1H), 3.36 (d, J=13.1 Hz, 1H), 2.7-2.8 (m, 1H), 2.71 (dt, J=1.6, 10.1 Hz, 1H), 2.45-2.55 (m, 2H), 1.5-1.8 (m, 9H), 0.92 (s, 9H), 0.91 (s, 9H of a diastereomer), 0.11 (s, 3H of a diastereomer), 0.10 (s, 3H of a diastereomer), 0.08 (s, 3H of a diastereomer), 0.07 (s, 3H of a diastereomer); 13 C NMR (75 MHz, CDCl 3 ) δ 173.9, 173.7, 153.3, 135.5, 134.9, 129.6, 129.1, 127.5, 124.0, 97.6, 96.9, 71.1, 66.7, 65.5, 65.2, 62.3, 61.9, 55.8, 37.9, 34.2, 33.7, 30.8, 30.7, 26.0, 25.7, 22.0, 21.9, 19.7, 19.4, 18.5, −4.6, −4.9; HRMS (CI) calculated for C 28 H 44 NO 6 Si (M) 518.2938, found 518.2908.
Example 5
This example describes the synthesis of compound 52. To a stirred solution of EtSH (713 mg, 850 FL, 11.5 mmol) in THF (45 mL) was added KH (106 mg, 0.93 mmol, 35% in mineral oil). After 30 minutes, the mixture was cooled to 0° C. and a solution of 50 (2.064 g, 3.99 mmol) in THF (15 mL) was added via cannula over 5 minutes. An additional amount of THF (10 mL) was added to rinse the flask. After 50 minutes at room temperature, the reaction was quenched with saturated aqueous NH 4 Cl (50 mL). Air was bubbled through the solution for 2 hours to remove excess EtSH. The solution was extracted with Et 2 O (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was crystallized by the addition of 10% Et 2 O/petroleum ether to yield the recovered auxiliary (640 mg, 3.61 mmol, 93%) as a white solid. The decanted solution was purified by chromatography over silica gel, eluting with 10-30% Et 2 O/petroleum ether, to give 52 (1.44 g, 3.50 mmol, 90%) as a colorless oil: [α]D 23 −46.1 (c 3.50, CHCl 3 ); IR (neat) 1684 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) 5.35-5.5 (m, 1H), 4.55 (bs, 1H), 3.9-4.2 (m, 3H), 3.8-3.9 (m, 1H), 3.45-3.6 (m, 1H), 2.75-2.9 (m, 2H), 2.4-2.6 (m, 2H), 1.4-1.9 (m, 6H), 1.21 (t, J=7.5 Hz, 3H), 0.93 (s, 9H), 0.09 (s, 3H), 0.06 (s, 3H of a diastereomer), 0.05 (s, 3H of a diastereomer); 13 C NMR (75 MHz, CDCl 3 ) δ 205.1, 205.0, 135.24, 135.16, 97.9, 97.4, 78.6, 65.7, 65.5, 62.3, 62.2, 34.5, 30.8, 25.9, 25.7, 22.6, 22.1, 22.0, 19.7, 19.6, 18.4, 14.8, −4.7, −4.8; HRMS (CI) calculated for C 20 H 37 NO 4 SSi (M+H + ) 401.2182, found 401.2172.
Example 6
This example describes the synthesis of compound 54. To a stirred solution of CuI (4.85 mg, 25.5 mmol) in Et 2 O (120 mL) at 0° C. was added MeLi (33.1 mL, 23.2 mmol, 1.4 M in Et 2 O). After 15 minutes, the solution was cooled to-50° C. and a solution of 52 (1.78 g, 4.64 mmol) in Et 2 O (90 mL) was added via cannula. An additional amount of Et 2 O (10 mL) was added to rinse the flask. After 30 minutes, the reaction was quenched with saturated aqueous NH 4 Cl (300 mL) and extracted with Et 2 O (4×175 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 15% Et 2 O/petroleum ether, to give 54 (1.36 g, 3.81 mmol, 82%) as a colorless oil: [α]D 23 +14.0 (c 5.00, CHCl 3 ); IR (neat) 1719 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 5.35-5.5 (m, 5H), 4.5-4.55 (m, 1H), 3.9-4.1 (m, 3H), 3.75-3.9 (m, 1H), 3.4-3.5 (m, 1H), 2.3-2.5 (m, 2H), 2.10 (s, 3H), 1.74(s, 3H), 1.4-1.9 (m, 6H), 0.87 (s, 9H), 0.00 (s, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ 211.7, 135.2, 135.1, 123.8, 123.5, 97.7, 97.3, 79.0, 65.5, 65.2, 62.2, 62.1, 33.2, 30.7, 25.8, 25.6, 25.5, 22.0, 19.6, 19.5, 18.2, −4.8, −4.9; HRMS (CI) calculated for C 19 H 37 O 4 Si (M+H + ) 357.2461, found 357.2455.
Example 7
This example describes the synthesis of compound 56. To a stirred solution of the phosphonate (1.45 g, 5.82 mmol) in THF (10 mL) at −78° C. was added n-BuLi (3.6 mL, 5.76 mmol, 1.6 M in hexanes). After 15 minutes, a solution of 54 (590 mg, 1.66 mmol) in THF (7 mL) was added via cannula. An additional amount of THF (3 mL) was added to rinse the ketone flask. After 30 minutes, the mixture was allowed to warm to room temperature over 1 hour. After an additional 30 minutes, the reaction was quenched with saturated aqueous NH 4 Cl (50 mL) and extracted with Et 2 O (4×75 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 10-20% Et 2 O/petroleum ether, to give sequentially the undesired olefin isomer (40 mg, 0.089 mmol, 5%) as a colorless oil followed by the desired product 54 (690 mg, 1.52 mmol, 92%) as a colorless oil: Minor diastereomer: [α]D 23-59.2 (c 1.26, CHCl 3 ); IR (neat) 2959, 2852, 1022 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.79 (s, 1H), 6.18, (s, 1H), 5.35-5.5 (m, 2H), 4.55-4.65 (m, 1H), 4.05-4.15 (m, 2H), 3.8-3.9 (m, 1H), 3.45-3.6 (m, 1H), 2.68 (s, 3H), 2.4-2.5 (m, 1H), 2.2-2.35 (m, 1H), 1.87 (d, J=0.9 Hz, 3H), 1.76 (s, 3H), 1.4-1.9 (m, 6H), 0.84 (s, 9H), 0.07 (s, 3H), −0.10 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 164.4, 152.9, 143.5, 133.4, 126.7, 126.5, 118.8, 115.2, 97.9, 97.6, 70.8, 70.5, 65.9, 62.4, 62.2, 34.5, 30.9, 26.0, 25.7, 22.1, 19.8, 19.7, 19.4, 18.5, 18.4, −4.7, −4.9. Major diastereomer: [α]D 23 +19.2 (c 3.45, CHCl 3 ); IR (neat) 2959, 1531, 1474 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.91 (s, 1H), 6.45, (s, 1H), 5.35-5.5 (m, 1H), 4.5-4.6 (m, 1H), 3.9-4.2 (m, 3H), 3.8-3.9 (m, 1H), 3.45-3.6 (m, 1H), 2.70 (s, 3H), 2.2-2.4 (m, 2H), 1.99 (d, J=1.0 Hz, 3H), 1.76 (s, 3H) 1.4-1.9 (m, 6H), 0.88 (s, 9H), 0.04 (s, 3H), −0.01 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 164.5, 153.4, 142.5, 142.4, 133.6, 126.2, 126.1, 119.2, 118.9, 115.3, 97.8, 97.5, 79.0, 78.9, 65.8, 65.6, 62.3, 62.2, 35.4, 35.3, 30.1, 26.9, 26.0, 25.7, 22.0, 19.7, 19.4, 18.4, 14.1, −4.5, −4.8; HRMS (CI) calculated for C 24 H 42 NO 3 SSi (M+H + ) 452.2655, found 452.2645.
Example 8
This example describes the synthesis of the alcohol precursor to compound 58. To a stirred solution of freshly prepared MgBr 2 (27.6 mmol of Mg, 23.8 mmol of BrCH 2 CH 2 Br, 50 mL of Et 2 O) was added 56 (663 mg, 1.26 mmol) in Et 2 O (5 mL) at room temperature followed by saturated aqueous NH 4 Cl (approximately 50 μL). After 3.5 hours, the solution was cooled to 0° C. and carefully quenched with saturated aqueous NH 4 Cl (50 mL). The solution was extracted with Et 2 O (4×70 mL), and the dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 30-50% Et 2 O/petroleum ether, to give the desired alcohol (459 mg, 1.26 mmol, 99%) as a colorless oil: [α]D 23-16.8 (c 3.40, CHCl 3 ); IR (neat) 3374 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.92 (s, 1H), 6.44, (s, 1H), 5.31 (t, J=7.7 Hz, 1H), 4.14 (d, J=12.2 Hz, 1H), 4.1-4.2 (m, 1H), 4.00 (d, J=12.2 Hz, 1H), 2.71 (s, 3H), 2.4-2.5 (m, 1H), 2.2-2.3 (m, 2H), 2.00 (s, 3H), 1.80 (s, 3H), 0.89 (s, 9H), 0.06 (s, 3H), 0.04 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 164.8, 153.0, 142.4, 137.7, 124.4, 119.0, 115.4, 78.4, 62.0, 35.5, 26.0, 22.2, 19.3, 18.5, 14.3, −4.5, −4.7; HRMS (CI) calculated for C 19 H 34 NO 2 SSi 368.2080. Found 368.2061.
Example 9
This example describes the synthesis of compound 58. To a stirred solution of the alcohol precursor (620 mg, 1.69 mmol) in CH 2 Cl 2 (5.5 mL) at 0° C. was added Et 3 N (360 FL, 2.58 mmol) followed by Ms 2 O (390 uL, 2.24 mmol). After 10 minutes, Me 2 CO (5.5 mL) was added followed by LiBr (890 mg, 10.3 mmol). After 1.8 hours at room temperature, the mixture was concentrated in vacuo to remove the acetone, diluted with saturated aqueous NH 4 Cl (100 mL), and extracted with Et 2 O (4×200 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 10-20% Et 2 O/petroleum ether, to give 58 (607 mg, 1.44 μmol, 84%) as a colorless oil: [α]D 23 +65.1 (c 2.95, CHCl 3 ); IR (neat) 2949, 2930, 2852, 1479, 844 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.93 (s, 1H), 6.48, (s, 1H), 5.42 (1 dt, J=1.3, 7.6 Hz, H), 4.16 (dd, J=5.4, 7.3 Hz, 1H), 4.06 (d, J=9.5 Hz, 1H), 3.90 (d, J=9.5 Hz, 1H), 2.71 (s, 3H), 2.3-2.5 (m, 2H), 2.01 (d, J=1.1 Hz, 3H), 1.83 (d, J=1.0 Hz, 3H), 0.88 (s, 9H), 0.04 (s, 3H), 0.01 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 164.6, 153.2, 142.1, 133.3, 128.2, 119.2, 115.4, 78.1, 35.7, 32.6, 26.0, 22.2, 19.4, 18.4, 13.1, −4.5, −4.8; HRMS (CI) calculated for C 19 H 33 NO 2 SSiBr (M+H + ) 430.1235, found 430.1244.
Example 10
This example describes the synthesis of compound 60. To a stirred solution of Ph 3 PMeBr (1.53 g, 4.28 mmol) in THF (16.2 mL) at −78° C. was added n-BuLi (2.7 mL, 4.32 mmol, 1.6 M in hexanes) over a period of 3 minutes. After 35 minutes, a pre-cooled solution of 58 (607 mg, 1.41 mmol) in THF (7 mL) was added dropwise to the ylide over a period of 5 minutes. An additional portion of THF (6 mL) was added to rinse the flask. After 15 minutes, the mixture was allowed to warm to −20° C. After an additional 20 minutes, the reaction was quenched with MeOH, and was concentrated in vacuo. The residue was purified by chromatography over silica gel, eluting with 0-6% MeOH/CH 2 Cl 2 , followed by dilution with CH 2 Cl 2 and an H 2 O wash to remove excess Ph 3 MeBr, to give 60 (890 mg, 1.26 mmol, 89%) as an off-white foam: [α]D 23 +6.4 (c 1.06, CHCl 3 ); IR (neat) 2959, 2930, 2853, 1440; 1 H NMR (300 MHz, CDCl 3 ) δ 7.6-7.9 (1 m, SH), 6.89 (s, 1H), 6.33, (s, 1H), 5.20 (m, 1H), 3.95 (m, 1H), 3.5-3.8 (m, 2H), 2.65 (s, 3H), 2.1-2.3 (m, 2H), 1.88 (s, 3H), 1.83 (s, 3H), 0.78 (s, 9H), −0.07 (s, 3H), −0.09 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 164.7, 153.0, 142.1, 135.6, 133.9, 130.9, 130.7, 124.7, 118.8, 117.5, 115.6, 78.2, 35.9, 26.0, 24.7, 23.7, 22.6, 21.9, 19.4, 18.3, 14.4, −4.6, −4.8; HRMS (CI) calculated for C 38 H 49 NOPSSi (M+H) 626.3042, found 626.3028.
Example 11
This example describes the synthesis of compound 66. To a stirred solution of i-Pr 2 NH (390 μL, 2.78 mmol) in THF (0.7 mL) was added n-BuLi (1.73 mL, 2.77 mmol, 1.6 M in hexanes) dropwise at −78° C. After 5 minutes, the solution was warmed to 0° C. for 45 minutes and recooled to −78° C. To the stirring solution of LDA was added a precooled solution of 62 (718 mg, 2.53 mmol) in THF (0.6 mL) dropwise via cannula over 5 minutes. An additional amount of THF (0.4 mL) was used to rinse the flask. After an additional 50 minutes at −78° C., a precooled solution of 64 (484 mg, 2.33 mmol) in THF (0.6 mL) was added dropwise via cannula. An additional amount of THF (0.4 mL) was used to rinse the flask. After 30 minutes, the reaction was quenched with saturated aqueous NH 4 Cl (20 mL) and extracted with Et 2 O (4×25 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 6-10% Et 2 O/petroleum ether, to give 66(694 mg, 1.41 mmol, 61%) as a colorless oil: [α]D 23 −25.1 (c 3.05, CHCl 3 ); IR (neat) 3483, 1695 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.25 (d, J=8.7 Hz, 2H), 6.86 (d, J=8.7 Hz, 2H), 5.65-5.85 (m, 1H), 4.9-5.1 (m, 2H), 4.44 (s, 2H), 3.93 (dd, J=4.5, 6.4 Hz, 1H), 3.80 (s, 3H), 3.55-3.65 (m, 3H), 3.46 (dd, J=6.1, 8.9 Hz, 1H), 3.15-3.25 (m, 1H), 2.05-2.2 (m, 2H), 1.8-1.9 (m, 1H), 1.18 (s, 3H), 1.11 (s, 3H), 1.05 (d, J=6.8 Hz, 3H), 0.94 (d, J=7.9 Hz, 3H), 0.89 (s, 9H), 0.07 (s, 3H), 0.06 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 221.7, 159.3, 136.5, 130.9, 129.4, 116.9, 113.9, 73.2, 73.1, 72.9, 55.4, 54.4, 41.9, 39.8, 36.4, 29.9, 26.3, 23.9, 19.3, 18.4, 14.3, 10.2, −3.3, −3.8; HRMS (CI) calculated for C 28 H 49 O 5 Si (M+H + ) 493.3349, found 493.3350.
Example 12
This example describes the synthesis of compound 68. To a stirred solution of 66 (61 mg, 0.124 mmol) in CH 2 Cl 2 (0.7 mL) at 0° C. was sequentially added Et 3 N (29 mg, 40 mL, 0.287 mmol) followed by TBSOTf (43.7 mg, 38 μL, 0.165 mmol) at 0° C. After 45 minutes, the reaction was quenched with saturated aqueous NH 4 Cl (20 mL) and extracted with Et 2 O (4×25 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 3-10% Et 2 O/petroleum ether, to give 68(66.5 mg, 0.111 mmol, 89%) as a colorless oil: [α]D 23-16.0 (c 2.92, CHCl 3 ); IR (neat) 1695 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.23 (d, J=8.6 Hz, 2 h), 6.86 (d, J=8.6 Hz, 2 h), 5.7-5.9 (m, 1H), 4.99 (d, J=6.4 Hz, 1H), 4.95 (s, 1H), 4.40 (s, 2H), 3.9-4.0 (m, 1H), 3.85 (d, J=7.3 Hz, 1H), 3.80 (s, 3), 3.58 (dd, J=5.7, 9.2 Hz, 1H), 3.27 (qn, J=7.4 Hz, 1H), 3.19 (t, J=7.4 Hz, 1H), 2.0-2.2 (m, 2H), 1.8-1.9 (m, 1H), 1.13 (s, 3H), 1.04 (s, 3H), 1.02 (3H, d, J=7.0 Hz), 0.96 (3H, d, J=6.9 Hz), 0.891 (s, 9H), 0.887 (s, 9H), 0.06 (s, 6H), 0.05 (s, 3H), 0.03 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 219.2, 159.3, 137.1, 131.0, 129.5, 116.5, 113.9, 76.5, 73.1, 71.8, 55.5, 54.2, 46.2, 39.8, 38.9, 26.5, 26.3, 25.3, 18.7, 18.4, 18.0, 17.0, 16.6, −3.0, −3.3, −3.5, −3.8; HRMS (CI) calculated for C 34 H 63 O 5 Si 2 (M+H + ) 607.4214, found 607.4212.
Example 13
This example describes the synthesis of compound 70. To a stirred solution of 68(722 mg, 1.19 mmol) in THF (9 mL) and H 2 O (8.5 mL) was sequentially added OSO 4 (400 μL, 4% in H 2 0) followed by NaIO 4 (1.065 g, 4.98 mmol). After 18 hours, the reaction was quenched with saturated aqueous Na 2 S 2 O 3 (50 mL). After 30 minutes, saturated aqueous NaCl (100 mL) was added and the mixture was extracted with Et 2 O (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo to give the aldehyde as a colorless oil: [α] D 23 −13.0 (c 4.20, CHCl 3 ); IR (neat) 1725, 1689 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 9.74 (It, J=1.2 Hz, 1H), 7.22 (d, J=8.5 Hz, 2 h), 6.85 (d, J=8.5 Hz, 2H), 4.46 (t, J=5.3 Hz, 1H), 4.39 (s, 2H), 3.82 (d, J=7.9 Hz, 1H), 3.80 (s, 3H), 3.58 (dd, J=6.0, 9.1 Hz, 1H), 3.27 (qn, J=7.4 Hz, 1H), 3.19 (dd, J=6.9, 8.9 Hz, 1H) 2.3-2.5 (m, 2H), 1.6-1.8 (m, 1H), 1.14 (s, 3H), 1.06 (s, 3H), 1.00 (d, J=7.0 Hz, 3H), 0.94 (d, J=7.0 Hz, 3H), 0.88 (s, 9H), 0.87 (s, 9H), 0.08 (s, 3H), 0.05 (s, 6H), 0.03 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 219.0, 201.5 159.3, 130.9, 129.5, 113.9, 76.8, 73.1, 71.7, 71.6, 55.4, 53.7, 49.7, 46.2, 38.8, 26.4, 26.1, 24.4, 18.7, 18.3, 17.0, 15.7, −3.4, −3.5, −3.9, −4.3; HRMS (CI) calculated for C 33 H 61 O 6 Si 2 (M+H + ) 609.4007, found 607.4005.
To a stirred solution of the crude aldehyde (1.19 mmol) prepared above in t-BuOH (16 mL) and H 2 O (15 mL) was sequentially added 2-methyl-2-butene (3 mL) followed by NaH 2 PO 4 (1.06 g, 11.6 mmol) and NaClO 2 (490 mg, 5.4 mmol). After 1 hour, the reaction was quenched with saturated aqueous NaCl (75 mL) and extracted with Et 2 O (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo to give crude 70 as a colorless oil: [α] D 23 −26.8 (c 4.20, CHCl 3 ); IR (neat) 2400-3400, 1722 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.23 (d, J=8.6 Hz, 2H), 6.85 (d, J=8.6 Hz, 2H), 4.40 (s, 2H), 4.3-4.4 (m, 1H), 3.82 (d, J=7.9 Hz, 1H), 3.80 (s, 3H), 3.58 (dd, J=5.8, 9.1 Hz, 1H), 3.32 (qn, J=7.2 Hz, 1H), 3.18 (dd, J=7.2, 8.9 Hz, 1H) 2.46 (dd, J=2.9, 16.4 Hz, 1H), 2.28 (dd, J=6.8, 16.4 Hz, 1H), 1.7-1.85 (m, 1H), 1.15 (s, 3H), 1.07 (s, 3H), 1.02 (d, J=6.9 Hz, 3H), 0.95 (d, J=7.0 Hz, 3H), 0.88 (s, 9H), 0.87 (s, 9H), 0.08 (s, 3H), 0.05 (s, 6H), 0.04 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.7, 178.0, 159.3, 130.9, 129.5, 113.9, 73.8, 73.1, 71.7, 55.5, 53.7, 46.3, 40.4, 38.9, 26.4, 26.4, 26.2, 24.0, 18.7, 18.4, 17.0, 15.8, −3.3, −3.5, −4.1, −4.4; HRMS (CI) calculated for C 33 H 61 O 7 Si 2 625.3966. Found 625.3957.
Example 14
This example describes the synthesis of compound 72. To a stirred solution of crude 70 (1.19 mmol) in PhH (20 mL) and MeOH (2.5 mL) was added TMSCHN 2 (700 μL, 1.4 mmol, 2 M in hexanes). After 45 minutes, the mixture was concentrated in vacuo and purified by chromatography over silica gel, eluting with 5-10% Et 2 O/petroleum ether, to give 72 (502 mg, 0.797 mmol, 66% over three steps) as a colorless oil: [α] D −27.1 (c 1.03, CHCl 3 ); IR (neat) 1741, 1690 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.23 (d, J=8.5 Hz, 2H), 6.86 (d, J=8.5 Hz, 2H), 4.39 (s, 2H), 4.3-4.4 (m, 1H), 3.83 (d, J=7.8 Hz, 1H), 3.80 (s, 3H), 3.66 (s, 3H), 3.58 (dd, J=5.7, 9.1 Hz, 1H), 3.31 (qn, J=7.2 Hz, 1H), 3.18 (dd, J=7.3, 9.1 Hz, 1H), 2.46 (dd, J=3.1, 16.1 Hz, 1H), 2.26 (dd, J=7.0, 16.1 Hz, 1H), 1.7-1.85 (m, 1H), 1.14 (s, 3H), 1.06 (s, 3H), 1.01 (d, J=6.9 Hz, 3H), 0.95 (d, J=6.9 Hz, 3H), 0.88 (s, 9H), 0.87 (s, 9H), 0.08 (s, 3H), 0.05 (s, 6H), 0.02 (s, 3H); 3 C NMR (75 MHz, CDCl 3 ) δ 218.5, 172.7, 159.3, 131.0, 129.5, 113.9, 74.1, 73.1, 71.8, 55.5, 53.6, 51.8, 46.3, 40.4, 38.9, 26.5, 26.2, 24.0, 18.8, 18.7, 18.4, 17.0, 15.7, −3.3, −3.5, −4.3, −4.4; HRMS (CI) calculated for C 33 H 63 O 7 Si 2 (M+H + ) 639.4112, found 639.4112.
Example 15
This example describes the synthesis of compound 74. To a stirred solution of 72 (290 mg, 0.455 mmol) in EtOH (7 mL) was added palladium on carbon (101 mg, 10% Pd) and the mixture was placed under an atmosphere of H 2 . After 0.75 hour, the H 2 atmosphere was replaced by Ar and the reaction was filtered through Celite (EtOH rinse). The liquid was concentrated in vacuo and the residue was purified by chromatography over silica gel, eluting with 10-30% Et 2 O/petroleum ether, to give 74 (216 mg, 0.418 mmol, 92%) as a colorless oil: [α] D 23 −13.2 (c 1.07, CHCl 3 ); IR (neat) 3538, 1743, 1694 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 4.40 (dd, J=2.9, 6.9 Hz, 1H), 3.93 (dd, J=2.0, 7.8 Hz, 1H), 3.67 (s, 3H), 3.6-3.7 (m, 1H), 3.5-3.6 (m, 1H), 3.31 (qn, J=7.5 Hz, 1H), 2.43 (dd, J=2.7, 16.3 Hz, 1H), 2.26 (dd, J=6.9, 16.3 Hz, 1H), 1.55-1.65 (m, 1H), 1.22 (s, 3H), 1.13 (s, 3H), 1.09 (d, J=7.0 Hz, 3H), 0.95 (d, J=7.1 Hz, 3H), 0.92 (s, 9H), 0.87 (s, 9H), 0.12 (s, 3H), 0.10 (s, 3H), 0.09 (s, 3H), 0.01 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.4, 172.8, 78.2, 73.6, 64.9, 53.9, 51.9, 47.0, 40.3, 39.8, 29.9, 26.4, 26.2, 24.1, 19.1, 18.6, 18.4, 16.1, −3.4, −3.6, −4.3, −4.4; HRMS (CI) calculated for C 26 H 51 Si 2 O 6 (M + H + ) 517.3381, found 517.3361.
Example 16
This example describes the synthesis of compound 76. To a stirred solution of 74(700 mg, 1.36 mmol) and powdered molecular sieves (1.5 g) in CH 2 Cl 2 (35 mL) was sequentially added NMO (420 mg, 3.56 mmol) followed by TPAP (137.5 mg, 106 mmol). After 1 hour, the mixture was diluted with 30% Et 2 O/petroleum ether (100 mL) and filtered through silica gel (30% Et 2 O/petroleum ether rinse). The filtrate was concentrated in vacuo to give 76 (698 mg, 1.36 mmol, 99%) as a colorless oil: [α] D 23 −32.1 (c 1.76, CHCl 3 ); IR (neat) 1746, 1690 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 9.73 (d, J=2.1 Hz, 1H), 4.41 (dd, J=3.2, 6.9 Hz, 1H), 4.08 (dd, J=2.1, 8.3 Hz, 1H), 3.67 (s, 3H), 3.25 (qn, J=7.0 Hz, 1H), 2.41 (1Hdd, J=3.3, 16.1 Hz, 1H), 2.2-2.35 (m, 2H), 1.24 (s, 3H), 1.12 (d, J=7.1 Hz, 3H), 1.10 (d, J=6.9 Hz, 3H), 1.09 (s, 3H), 0.89 (s, 9H), 0.87 (s, 9H), 0.11 (s, 3H), 0.090 (s, 3H), 0.085 (s, 3H), 0.01 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.0, 204.4, 172.6, 76.5, 73.9, 53.8, 51.9, 51.0, 46.8, 40.4, 29.9, 26.4, 24.0, 19.2, 18.6, 18.4, 15.9, 12.7, −3.4, −3.6, −4.3, −4.4; HRMS (CI) calculated for C 26 H 51 Si 2 O 6 (M+H + ) 515.3225, found 515.3218.
Example 17
This example describes the synthesis of compound 78. To LHMDS [HMDS (280 μL, 1.31 mmol) in THF (650 μL) at −78° C. was added n-BuLi (820 μL, 1.31 mmol, 1.6 M in hexanes). After 5 minutes, the solution was warmed to 0° C. and added dropwise to a stirred solution of the salt 58 (930 mg, 1.32 mmol) in THF (17 mL) at −78° C. via cannula. After 15 minutes, the solution was warmed to −30° C. After an additional 15 minutes, the solution was re-cooled to −78° C. and added dropwise to a pre-cooled solution of the 76 (520 mg, 1.03 mmol) in THF (0.6 mL) via cannula. The mixture was then allowed to warm slowly to room temperature over a period of 1 hour. After 10 minutes at room temperature, the reaction was quenched with saturated aqueous NH 4 Cl (25 mL) and was concentrated in vacuo to remove THF. The solution was extracted with Et 2 O (4×50 mL), and the dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 2-10% Et 2 O/petroleum ether, to give 78 (728 mg, 0.84 mmol, 82%) as a colorless oil: [α] D 23 +3.6 (c 1.00, CHCl 3 ); IR (neat) 1743, 1699 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.91 (s, 1H), 6.45 (s, 1H), 5.58 (t, J=9.2 Hz, 1H), 5.2-5.35 (m, 1H), 5.16 (t, J=6.6 Hz, 1H), 4.39 (1H, dd, J=3.1, 6.9 Hz), 4.09 (1H, t, J=6.6 Hz), 3.8-3.9 (m, 1H), 3.6-3.7 (m, 1H); 3.66 (s, 3H), 3.03 (qn, J=6.7 Hz, 1H), 2.70 (s, 3H), 2.65-2.75 (m, 2H), 2.3-2.5 (m, 2H), 2.15-2.35 (m, 3H), 1.99 (s, 3H), 1.64 (s, 3H), 1.19 (s, 3H), 1.06 (s, 3H), 1.03 (d, J=7.1 Hz, 3H), 1.00 (d, J=7.0 Hz, 3H), 0.92 (s, 9H), 0.88 (s, 9H), 0.86 (s, 9H), 0.08 (s, 3H), 0.07 (s, 6H), 0.04 (s, 3H), 0.00 (s, 3H), −0.01 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.0, 172.6, 164.5, 153.4, 142.5, 135.5, 131.7, 128.7, 122.2, 119.0, 115.2, 79.1, 76.1, 74.2, 53.5, 51.8, 46.4, 40.4, 37.9, 35.6, 30.9, 26.4, 26.2, 26.0, 24.0, 23.9, 19.4, 19.3, 18.7, 18.4, 14.9, 14.1, −3.3, −3.7, −4.3, −4.4, −4.7; HRMS (CI) calculated for C 46 H 86 O 6 Si 3 SN (M+H + ) 864.5484, found 864.5510.
Example 18
This example describes the synthesis of compound 80. To a stirred solution of 78 (51 mg, 59 μmol) in i-PrOH (1 mL) was added NaOH (11.5 FL, 62 μmol, 5.4 M in H 2 O), and the mixture was heated at 45° C. in a sealed tube. After 16 hours, the solution was concentrated, diluted with aqueous HCl (20 mL, 0.5 M) and extracted with Et 2 O (4×50 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 5-20% EtOAc/hexanes, to give 80 (33 mg, 34 μmol, 66%) as a colorless oil: IR (neat) 3500-2500, 1713 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.93 (s, 1H), 6.67 (s, 1H), 5.52 (t, J=9.6 Hz, 1H), 5.3-5.4 (m, 1H), 5.23 (t, J=7.4 Hz, 1H), 4.41 (dd, J=3.3, 6.6 Hz, 1H), 3.75-3.85 (m, 1H), 2.9-3.1 (m, 2H), 2.71 (s, 3H), 2.5-2.8 (m, 2H), 2.1-2.6 (m, 4H), 1.9-2.1 (m, 1H), 1.93 (s, 3H), 1.71 (s, 3H), 1.16 (s, 3H), 1.13 (s, 3H), 1.04 (d, J=7.0 Hz, 3H), 9.94 (obscured d, 3H), 0.92 (s, 9H), 0.88 (18H, s), 0.12 (s, 6H), 0.09 (s, 3H), 0.06 (s, 3H), 0.03 (s, 3H), −0.01 (s, 3H); HRMS (CI) calculated for C 45 H 84 O 6 Si 3 SN (M+H + ) 850.5327, found 850.5281.
Example 19
This example describes the synthesis of compound 82. To a stirred solution of 80(154 mg, 181 μmol) in THF (3.9 mL) at 0° C. was added TBAF (1.1 mL, 1.1 mmol, 1 M in THF). The solution was allowed to warm slowly to room temperature overnight. After 16 hours, the mixture was diluted with EtOAc, washed with saturated aqueous NH 4 Cl (50 mL), and extracted with EtOAc (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 2-5% MeOH/CH 2 Cl 2 , to give 82 (118.5 mg, 160 μmol, 89%) as a white foam: [α] D 23 −2.6 (c 3.50, CHCl 3 ); IR (neat) 3500-2500, 1709 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.95 (s, 1H), 6.70 (s, 1H), 5.56 (t, J=10.0 Hz, 1H), 5.3-5.45 (m, 1H), 5.24 (t, J=7.3 Hz, 1H), 4.35-4.45 (m, 1H), 4.16 (t, J=6.2 Hz, 1H), 3.75-3.85 (m, 1H), 3.03 (m, 2H), 2.75-2.85 (m, 1H), 2.72 (s, 3H), 2.65-2.75 (m, 1H), 2.2-2.7 (m, 5H), 1.99 (s, 3H), 1.74 (s, 3H), 1.15 (s, 3H), 1.14 (s, 3H), 1.04 (d, J=7.1 Hz, 3H), 0.98 (d, J=6.9 Hz, 3H), 0.92 (s, 9H), 0.87 (s, 9H), 0.12 (s, 3H), 0.10 (s, 3H), 0.07 (s, 3H), 0.06 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.1, 176.0, 165.1, 152.4, 141.9, 137.5, 131.6, 127.8, 120.8, 118.8, 115.1, 77.2, 76.0, 73.5, 53.6, 46.3, 40.1, 38.0, 34.1, 30.8, 26.2, 26.0, 23.7, 23.5, 19.0, 18.9, 18.7, 18.5, 18.1, 15.0, 14.6, −3.6, −4.1, −4.2, −4.6; HRMS (CI) calculated for C 39 H 70 O 6 Si 2 SN (M+H + ) 736.4462, found 736.4451.
Example 20
This example describes the synthesis of the protected alcohol precursor to compound 84. To a stirred solution of 82 (57.2 mg, 78.0 μmol) in THF (1.3 mL) at 0° C. was added Et 3 N (19 FL, 136 μmol) followed by 2,4,6-trichlorobenzoyl chloride (14 μL, 89.5 mmol). After 45 minutes, the mixture was diluted with THF (1 mL) and PhMe (1.7 mL) and was added via syringe pump to a stirring solution of DMAP (16.3 mg, 133 μmol) in PhMe (18 mL) at 75° C. over a period of 3.5 hours. After an additional 1 hour, the solution was cooled, diluted with EtOAc, washed with saturated aqueous NH 4 Cl (50 mL), and extracted with EtOAc (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 2-10% EtOAc/hexanes, to give the protected alcohol precursor to compound 84 (35.5 mg, 49.5 mmol, 63%) as a colorless oil contaminated with a small amount of an oligomer: IR (neat) 1738, 1709 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.95 (s, 1H), 6.50 (s, 1H), 5.65 (t, J=10.0 Hz, 1H), 5.3-5.45 (m, 2H), 5.11 (t, J=6.3 Hz, 1H), 4.45 (dd, J=2.8, 8.0 Hz, 1H), 3.7-3.8 (m, 1H), 3.19 (dd, J=9.5, 15.7 Hz, 1H), 3.0-3.1 (m, 1H), 2.71 (s, 3H), 2.2-2.7 (m, 6H), 2.09 (s, 3H), 1.74 (s, 3H), 1.13 (s, 3H), 1.11 (s, 3H), 1.07 (d, J=7.1 Hz, 3H), 0.99 (d, J=7.0 Hz, 3H), 0.93 (s, 9H), 0.87 (s, 9H), 0.14 (s, 3H), 0.11 (s, 3H), 0.07 (s, 3H), 0.06 (s, 3H); 3 C NMR (75 MHz, CDCl 3 ) δ 216.0, 169.9, 164.9, 152.9, 137.8, 136.5, 130.8, 126.9, 121.1, 118.9, 116.6, 106.3, 78.1, 76.4, 73.1, 54.0, 47.4, 41.2, 39.0, 31.0, 26.4, 26.3, 26.1, 24.5, 21.3, 20.5, 19.7, 19.5, 18.9, 18.3, 15.2, 14.7, −3.4, −3.5, −4.6; HRMS (CI) calculated for C 39 H 68 O 5 Si 2 SN (M+H + ) 718.4357, found 718.4354.
Example 21
This example describes the synthesis of compound 84. To a stirred solution of the protected alcohol precursor to compound 82 (16.5 mg, 23 mmol) in CH 2 Cl 2 (110 μL) at 0° C. was added TFA (100 μL). After 4.5 hours, the mixture was concentrated in vacuo and purified by chromatography over silica gel, eluting with 20-50% EtOAc/hexanes, to give 84 (9.3 mg, 19 μmol, 83%) as a colorless oil: [α] D 23 −133.0 (c 1.30, CHCl 3 ); IR (neat) 3438, 1738, 1694 cm −1 ; 1 H NMR (400 MHz, CDCl 3 ) δ 6.97 (s, 1H), 6.52 (s, 1H), 5.5-5.7 (m, 2H), 5.35-5.45 (m, 1H), 5.15 (t, J=7.1 Hz, 1H), 4.22 (dd, J=2.5, 9.4 Hz, 1H), 3.7-3.8 (m, 1H), 3.1-3.2 (m, 1H), 3.04 (dd, J=7.7, 15.3 Hz, 1H), 2.85-2.95 (m, 1H), 2.70 (s, 3H), 2.4-2.7 (m, 6H), 2.06 (s, 3H), 1.72 (s, 3H), 1.27 (s, 3H), 1.1-1.2 (obscured d, 3H×2), 1.12 (s, 3H); 13 C NMR (100.5 MHz, CDCl 3 ) δ 220.4, 170.7, 152.2, 138.1, 137.0, 132.3, 128.1, 119.0, 118.9, 115.7, 77.4, 74.1, 73.0, 52.7, 44.2, 39.1, 36.9, 31.4, 30.2, 29.7, 23.9, 21.8, 20.4, 19.0, 17.5, 16.0, 13.3; HRMS (CI) calculated for C 27 H 40 O 5 SN (M+H + ) 490.2627, found 490.2627.
Example 22
This example describes the synthesis of 86. To a stirred solution of 84 (6.6 mg, 13.5 μmol) in CH 2 Cl 2 (2 mL) at reflux was added portionwise a large excess of KO 2 CN═NCO 2 K followed by AcOH (2 equivalents) until the reaction was complete by TLC (25 hours). The KOAc precipitate was periodically removed during the course of the reaction. The solution was filtered through SiO 2 (Et 2 O rinse), concentrated in vacuo, and purified by chromatography over silica gel, eluting with EtOAc/hexanes/CH 2 Cl 2 (1:4:5-1:1:2), to give 86 (3.4 mg, 6.9 mmol, 52%) as a colorless oil: [α] D 23 −86.7 (c 0.15, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ 6.95 (s, 1H), 6.58 (s, 1H), 5.22 (d, J=8.8 Hz, 1H), 5.1-5.2 (m, 1H), 4.30 (d, J=11.2 Hz, 1H), 3.7-3.8 (m, 1H), 3.4-3.55 (m, 1H), 3.15 (q, J=4.8 Hz, 1H), 3.0-3.1 (m, 1H), 2.69 (s, 3H), 2.5-2.7 (m, 1H), 2.05-2.5 (m, 4H), 2.06 (s, 3H), 1.8-1.9 (m, 1H), 1.7-1.8 (m, 1H), 1.34 (s, 3H), 1.2-1.3 (m, 4H), 1.19 (d, J=7.0 Hz, 3H), 1.07 (s, 3H), 1.01 (d, J=6.9, 3H); 13 C NMR (100.5 MHz, CDCl 3 ) δ 220.8, 170.6, 165.2, 152.3, 139.4, 138.7, 121.1, 119.5, 115.9, 79.2, 74.4, 72.6, 53.7, 42.0, 39.9, 32.8, 32.0, 31.9, 25.6, 23.1, 19.3, 18.3, 16.1, 16.0, 13.6.
Example 23
This example describes the synthesis of compound 4. To a stirred solution of 86 (1.5 mg, 3.05 mmol) in CH 2 Cl 2 (400 mL) at −50° C. was added a solution of dimethyl dioxirane until all of the starting material had been consumed as judged by TLC. The solution was concentrated in vacuo and purified by chromatography over silica gel, eluting with 50-60% EtOAc/pentane, to give epothilone B (4) (1.2 mg, 2.4 mmol, 78%) as a colorless oil: [α] D 23 −36.7 (c 0.12, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ 6.97 (s, 1H), 6.59 (s, 1H), 5.42 (dd, J=2.8, 7.9 Hz, 1H), 4.1-4.3 (m, 2H), 3.77 (bs, 1H), 3.2-3.35 (m, 1H), 2.81 (dd, J=4.5, 7.6 Hz, 1H), 2.69 (s, 3H), 2.66 (bs, 1H), 2.4-2.55 (m, 1H), 2.36 (dd, J=2.3, 13.6 Hz, 1H), 2.1-2.2 (m, 1H), 2.09 (s, 3H), 1.85-2.0 (m, 1H), 1.6-1.7 (m, 1H), 1.35-1.55 (m, 4H), 1.37 (s, 3H), 1.28 (s, 3H), 1.17 (d, J=6.8 Hz, 3H), 1.08 (s, 3H), 1.00 (d, J=7.1 Hz); 13 C NMR (100.5 MHz, CDCl 3 ) δ 220.6, 170.5, 165.1, 151.8, 137.5, 119.7, 116.1, 74.1, 72.9, 61.6, 61.3, 53.1, 42.9, 39.2, 36.4, 32.3, 32.1, 30.8, 29.7, 22.7, 22.3, 21.4, 19.6, 19.1, 17.0, 15.8, 13.6; HRMS (CI) calculated for C 27 H 42 NO 5 S (M+H + ) 492.2784, found 492.2775.
Example 24
This example describes the synthesis of alkyne 88 as illustrated in Scheme 4. To a stirred solution of potassium tert-butoxide (0.27 mL, 1.0 M THF solution) in THF (0.5 mL) at −78° C. was added a solution of (diazomethyl)phosphonate (40.2 mg, 1.25 mmol) in THF (0.5 mL). After 5 minutes a solution of 76 (110 mg, 0.21 mmol) in THF (0.5 mL) was added dropwise, and the mixture was stirred at −78° C. for 12 hours. The mixture was then warmed to room temperature and was quenched with saturated aqueous NH 4 Cl. The aqueous layer was extracted with 3×5 mL portions of Et 2 O, and the combined organic extracts were dried (MgSO 4 ), concentrated in vacuo, and purified by chromatography (SiO 2 , 5% Et 2 O/hexane) to give 88 (85 mg, 80%) as colorless crystals: [α] D 24 −24.1 (c 1.12, CHCl 3 ); mp 52-54° C.; IR (film) 3310 2951, 2927, 2883, 2854, 1743, 1691, 1472, 1254, 1089, 990, 837, 775 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 4.45 (1H, dd, J=3.1, 7.5 Hz), 3.76 (1H dd, J=2.1, 6.4 Hz), 3.65 (1H, s), 3.33 (1H, qn, J=7.5) 2.40-2.26 (3H, m), 2.06 (1H, s), 1.24 (3H, s), 1.18 (3H, d, J=6.9 Hz), 1.17 (3H, 3H), 1.07 (3H, d, J=7.0 Hz), 0.92 (9H, s), 0.86 (9H, s), 0.08 (3H, s), 0.07 (3H, s), 0.00 (3H, s); 13 C NMR (CDCl 3 , 75 MHz) δ 218.6, 172.3, 85.6, 75.7, 73.3, 70.8, 53.9, 46.5, 32.1, 26.1, 23.7, 18.7, 18.5, 18.2, 15.8, −3.3, −3.9, −4.5, −4.7; HRMS (CI) calculated for C 27 H 52 Si 2 O 5 (M+H + ) 512.3353, found 512.3342.
Example 25
This example describes the synthesis of enyne 90 as illustrated in Scheme 4. To a stirred solution of 88 (70.0 mg, 0.135 mmol) in Et 2 O (1.0 mL) and DMF (0.4 mL) at room temperature was added Et 3 N (18.8 μL, 0.135 mmol) and CuI (25.7 mg, 0.135 mmol). After the mixture turned clear (approximately 5 minutes), a solution of 56 (29.1 mg, 0.068 mmol) in Et 2 O (1.0 mL) was added, and the mixture was stirred for 18 hours. The reaction mixture was quenched with saturated aqueous Na 2 S 2 O 3 (5 mL) and was extracted with Et 2 O (3×2 mL). The combined organic extracts were dried (MgSO 4 ), concentrated in vacua, and purified by flash chromatography over silica gel (50-60% CH 2 Cl 2 /hexanes) to give 90 (35.6 mg, 60%) as a colorless oil: [α] D 23 −16.7 (c 1.01); IR (film) 2927, 2857, 2371, 2341, 1743, 1683, 1648, 1482, 1251, 991, 837 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 6.91(1H, s), 6.46 (1H, s), 5.36 (1H, t, J=4.7 Hz), 4.45 (1H, dd, J=3.1, 6.9), 4.11 (1H, t, J=6.6), 3.76-3.72 (1H, m), 3.74-3.67 (1H, m), 3.67 (3H, s), 3.36-3.31 (1H, qn, J=6.8), 2.71 (3H, s), 2.41-2.25 (7H, m), 2.01 (3H, s), 1.80 (3H, s), 1.24 (3H, s), 1.16 (3H, s), 1.12 (3H, d, J=7.0), 1.05 (3H, d, J=6.8), 0.92 (9H, s), 0.88 (9H, s), 0.87 (9H, s), 0.09 (3H, s), 0.06 (6H, s), 0.04 (3H, s), 0.01 (3H, s), −0.00 (3H, s); 13 C NMR (CDCl 3 , 75 MHz): δ 218.0, 172.4, 164.3, 153.2, 142.5, 132.2, 122.2, 118.6, 118.9, 83.1, 80.2, 78.6, 75.9, 73.5, 53.7, 51.6, 46.3, 40.4, 35.7, 32.6, 29.7, 29.2, 26.1, 26.0, 25.8, 23.8, 21.7, 19.2, 18.9, 18.4, 18.2, 16.2, 15.7, 13.9, −3.3, −3.9, −4.4, −4.6, −4.7, −4.9; HRMS (CI) calculated for C 46 H 34 O 6 Si 3 SN (M+H + ) 862.5327, found 862.5325.
Example 26
This example describes the synthesis of methyl ester 80 from compound 90 as illustrated in Scheme 4. A suspension of 90 (10 mg, 0.011 mmol) and Lindlar's catalyst (1.35 mg, 5% Pd) was stirred at room temperature under an atmosphere of H 2 for 28 hours. The suspension was filtered through silica gel (Et 2 O rinse), concentrated in vacuo, and purified by flash chromatography over silica gel (40-60% CH 2 Cl 2 /hexane) to give 80 (6.8 mg, 68%) as a colorless oil: [α] D 24 +3.6 (c 1.00, CHCl 3 ); IR (film) 1743, 1699 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.91 (1H, s), 6.45 (1H, s), 5.58 (1H, t, J=9.2 Hz), 5.2-5.35 (1H, m), 5.16 (1H, t, J=6.6 Hz), 4.39 (1H, dd, J=3.1, 6.9 Hz), 4.09 (1H, t, J=6.6 Hz), 3.8-3.9 (1H, m), 3.6-3.7 (1H, m); 3.66 (3H, s), 3.03 (1H, qn, J=6.7 Hz), 2.70 (3H, s), 2.65-2.75 (2H, m), 2.3-2.5 (2H, m), 2.15-2.35 (3H, m), 1.99 (3H, s), 1.64 (3H, s), 1.19 (3H, s), 1.06 (3H, s), 1.03 (3H, d, J=7.1 Hz), 1.00 (3H, d, J=7.0 Hz), 0.92 (9H, s), 0.88 (9H, s), 0.86 (9H, s), 0.08 (3H, s), 0.07 (6H, s), 0.04 (3H, s), 0.00 (3H, s), −0.01 (3H, s); C NMR (75 MHz, CDCl 3 ) δ 218.0, 172.6, 164.5, 153.4, 142.5, 135.5, 131.7, 128.7, 122.2, 119.0, 115.2, 79.1, 76.1, 74.2, 53.5, 51.8, 46.4, 40.4, 37.9, 35.6, 30.9, 26.4, 26.2, 26.0, 24.0, 23.9, 19.4, 19.3, 18.7, 18.4, 14.9, 14.1, −3.3, −3.7, −4.3, −4.4, −4.7; HRMS (CI) calculated for C 46 H 86 O 6 Si 3 SN (M+H + ) 864.5484, found 864.5510.
Example 27
This example describes the saponification of methyl ester 90 to form carboxylic acid 80 as illustrated in Scheme 4. To a stirred solution of the methyl ester (51 mg, 59 μmol) in i-PrOH (1 mL) was added NaOH (11.5 μL, 62 μmol, 5.4 M in H 2 O), and the mixture was heated at 45° C. in a scaled tube. After 16 hours, the solution was concentrated, diluted with aqueous HCl (20 mL, 0.5 M) and extracted with Et 2 O (4×50 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 5-20% EtOAc/hexanes, to give acid 80 (33 mg, 34 mmol, 66%) as a colorless oil: IR (neat) 3500-2500, 1713 cm 1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.93 (s, 1H), 6.67 (s, 1H), 5.52 (t, J=9.6 Hz, 1H), 5.3-5.4 (m, 1H), 5.23 (t, J=7.4 Hz, 1H), 4.41 (dd, J=3.3, 6.6 Hz, 1H), 3.75-3.85 (m, 1H), 2.9-3.1 (m, 2H), 2.71 (s, 3H), 2.5-2.8 (m, 2H), 2.1-2.6 (m, 4H), 1.9-2.1 (m, 1H), 1.93 (s, 3H), 1.71 (s, 3H), 1.16 (s, 3H), 1.13 (s, 3H), 1.04 (d, J=7.0 Hz, 3H), 9.94 (obscured d, 3H), 0.92 (s, 9H), 0.88 (18H, s), 0.12 (s, 6H), 0.09 (s, 3H), 0.06 (s, 3H), 0.03 (s, 3H), −0.01 (s, 3H); HRMS (CI) calculated for C 45 H 84 O 6 Si 3 SN (M+H + ) 850.5327, found 850.5281.
Example 28
This example describes the deprotection of carboxylic acid 80 to form triene 82 as illustrated in Scheme 4. To a stirred solution of carboxylic acid 80 (154 mg, 181 μmol) in THF (3.9 mL) at 0° C. was added TBAF (1.1 mL, 1.1 mmol, 1 M in THF). The solution was allowed to warm slowly to room temperature overnight. After 16 hours, the mixture was diluted with EtOAc, washed with saturated aqueous NH 4 Cl (50 mL), and extracted with EtOAc (4×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and purified by chromatography over silica gel, eluting with 2-5% MeOH/CH 2 Cl 2 , to give 82 (118.5 mg, 160 μmol, 89%) as a white foam: [α] D 23 −2.6 (c 3.50, CHCl 3 ); IR (neat) 3500-2500, 1709 cm 1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.95 (s, 1H), 6.70 (s, 1H), 5.56 (t, J=10.0 Hz, 1H), 5.3-5.45 (m, 1H), 5.24 (t, J=7.3 Hz, 1H), 4.35-4.45 (m, 1H), 4.16 (t, J=6.2 Hz, 1H), 3.75-3.85 (m, 1H), 3.03 (m, 2H), 2.75-2.85 (m, 1H), 2.72 (s, 3H), 2.65-2.75 (m, 1H), 2.2-2.7 (m, 5H), 1.99 (s, 3H), 1.74 (s, 3H), 1.15 (s, 3H), 1.14 (s, 3H), 1.04 (d, J=7.1 Hz, 3H), 0.98 (d, J=6.9 Hz, 3H), 0.92 (s, 9H), 0.87 (s, 9H), 0.12 (s, 3H), 0.10 (s, 3H), 0.07 (s, 3H), 0.06 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.1, 176.0, 165.1, 152.4, 141.9, 137.5, 131.6, 127.8, 120.8, 118.8, 115.1, 77.2, 76.0, 73.5, 53.6, 46.3, 40.1, 38.0, 34.1, 30.8, 26.2, 26.0, 23.7, 23.5, 19.0, 18.9, 18.7, 18.5, 18.1, 15.0, 14.6, −3.6, −4.1, −4.2, −4.6; HRMS (CI) calculated C 39 H 70 O 6 Si 2 SN (M+H + ) 736.4462, found 736.4451.
Example 29
This example describes the synthesis of compound 94. To a stirred solution of 92 (195 mg, 0.32 mmol) in THF (1.5 mL) was added 2-(trimethylsilyl)ethanol (69 μL, 0.48 mmol) and triphenylphosphine (56.8 mg, 0.80 mmol). The solution was cooled to 0° C. and diethyl azodicarboxylate was added. After 1.5 hours, the reaction was quenched with saturated aqueous NH 4 Cl, and the solution was extracted with Et 2 O. The extract was concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 5-10% Et 2 O/petroleum ether, to give 94 (175 mg, 75%) as a colorless oil: [α] D 23 −27.0 (c 1.03, CHCl 3 ; IR (neat) 1741, 1690 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.23 (d, J=8.4 Hz, 2H), 6.85 (d, J=8.4 Hz, 2H), 4.39 (s, 2H), 4.3-4.4 (m, 1H), 3.83 (d, J=7.8 Hz, 1H), 3.80 (s, 3H), 3.58 (dd, J=5.7, 9.1 Hz, 1H), 3.31 (dq, J=7.2, 7.2 Hz, 1H), 3.18 (dd, J=7.3, 9.1 Hz, 1H), 2.46 (dd, J=3.1, 16.1 Hz, 1H), 2.26 (dd, J=7.0, 16.1 Hz, 1H), 1.7-1.85 (m, 1H), 1.14 (s, 3H), 1.06 (s, 3H), 1.01 (d, J=6.9 Hz, 3H), 0.95 (d, J=6.9 Hz, 3H), 0.88 (s, 9H,), 0.87 (s, 9H), 0.08 (s, 3H), 0.05 (s, 6H), 0.02 (s, 3H); 13 C NMR (CDCl 3 ) δ 218.5, 172.7, 159.3, 131.0, 129.5, 113.9, 74.1, 73.1, 71.8, 55.5, 53.6, 51.8, 46.3, 40.4, 38.9, 29.9, 26.5, 26.2, 24.0, 18.8, 18.7, 18.4, 17.0, 15.7, −3.3, −3.5, −4.3, −4.4; HRMS (CI) calculated for C 38 H7307Si (M+H + ) 725.4664, found 725.4666.
Example 30
This example describes the synthesis of compound 95. To a stirred solution of 94 (150 mg, 0.20 mmol) in EtOH (4.0 mL) was added palladium-on-carbon (55 mg, 10% Pd), and the mixture was stirred under an atmosphere of H2. After 1 hours, the H2 atmosphere was replaced by Ar, and the mixture was filtered through Celite (EtOH rinse). The filtrate was concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 10-30% Et 2 O/petroleum ether, to give 95 (108 mg, 89%) as a colorless oil: [α] D 23 −8.47 (c 1.18, CHCl 3 ); IR (neat) 3538, 1743, 1694 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 4.40 (dd, J=2.9, 6.9 Hz, 1H), 4.17-4.11 (m, 2H) 3.93 (dd, J=2.0, 7.8 Hz, 1H), 3.6-3.7 (m, 1H), 3.5-3.6 (m, 1H), 3.31 (dq, J=7.5, 7.5 Hz, 1H), 2.43 (dd, J=2.7, 16.3 Hz, 1H), 2.26 (1H, dd, J=6.9, 16.3 Hz), 1.55-1.65 (1H, m), 1.22 (3H, s), 1.13 (3H, s), 1.09 (d, J=7.0 Hz, 3H), 0.95 (d, J=7.1 Hz, 3H), 0.92 (s, 9H), 0.87 (s, 9H), 0.85 (m, 2H), 0.02 (s, 9H) 0.12 (s, 3H), 0.10 (s, 3H), 0.09 (s, 3H), 0.01 (s, 3H); 13 C NMR (CDCl 3 ) δ 218.4, 172.8, 78.2, 73.6, 64.9, 60.3, 53.9, 51.9, 47.0, 40.3, 39.8, 29.9, 26.4, 26.2, 24.1, 19.1, 18.6, 18.4, 17.2 16.1, −3.0, −3.4, −3.6, −4.3, −4.4.
Example 31
This example describes the synthesis of compound 96. To a stirred mixture of 95 (200 mg, 0.33 mmol) and powdered molecular sieves (300 mg) in CH 2 Cl 2 (6.0 mL) was added sequentially N-methylmorpholine-N-oxide (97 mg, 0.83 mmol) followed by tetra-n-propylammonium perruthenate (11.6 mg, 33 μmol). After 1.5 hours, the mixture was filtered through silica (Et 2 O rinse), and the filtrate was concentrated in vacuo to give the crude aldehyde as a colorless oil.
To a stirred solution of the crude aldehyde and K 2 CO 3 (91 mg, 0.66 mmol) in MeOH (5.0 mL) was added dimethyl 1-diazo-2-oxopropylphosphonate (74 mg, 0.46 mmol). The solution was stirred for 4 hours at room temperature, diluted with Et 2 O (30 mL), washed with aqueous NaHCO 3 (5%), and extracted with Et 2 O (3×30 mL). The dried (MgSO 4 ) extract was concentrated in vacuo, and the residue was purified by flash chromatography on silica gel, eluting with 2% Et 2 O/hexanes, to give 96 (155 mg, 78%) as a colorless oil: [α] D 23 −25.1 (c 2.50, CHCl 3 ); IR (neat) 2946, 2928, 2848, 1734, 1690, 1468; 1 H NMR (300 MHz, CDCl 3 ) δ 4.45 (dd, J=3.1, 7.5 Hz, 1H), 4.11-4.16 (m, 2H), 3.76 (dd, J=2.1, 6.4 Hz, 1H), 3.35 (dq, J=7.3, 7.3 Hz, 1H), 2.22-2.24 (m, 3H), 2.06 (s, 1H),1.25 (s, 3H), 1.18 (d, J=7.5 Hz, 3H), 1.17 (s, 3H), 1.07 (d, J=6.8 Hz, 3H), 0.95 (obscured m, 2H) 0.92 (s, 9H), 0.86 (s, 9H), 0.10 (s, 3H), 0.07 (s, 3H), 0.07 (s, 3H), 0.03 (s, 9H), 0.02 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.6, 172.1, 85.6, 75.7, 73.3, 70.8, 62.7, 53.8, 46.5, 40.6, 32.2, 26.1, 26.0, 18.7, 18.5, 18.2, 17.2, 15.9, −1.6, −3.3, −3.9, −4.4, −4.7; HRMS (FAB) calculated for C 51 H 63 O 5 Si 3 (M+H + ) 599.3983, found 599.3982.
Example 32
This example describes the synthesis of compound 98. To a stirred solution of 96(60.0 mg, 0.10 mmol) and bis(triphenylphosphine)palladium dichloride (1.4 mg, (0.002 mmol) in THF (0.5 mL) at room temperature was added slowly tri-n-butyltin hydride (32.3 μL, 0.12 mmol). After 10 minutes, the solution was concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 5% Et 2 O/hexanes, to give 98 (79 mg, 89%) as a colorless oil: [α] D 23 −9.6 (c 1.35, CHCl 3 ); IR (neat) 2955, 2928, 2856, 1736, 1472 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.12 (dd, J=7.5, 19.3 Hz, 1H), 5.89 (d, J=19.3 Hz, 1H), 4.43 (dd, J=3.2, 6.8 Hz, 1H), 4.15 (m, 2H), 3.85 (dd, J=1.5, 7.9 Hz, 1H), 3.07 (dq, J=7.1, 7.1 Hz, 1H), 2.40 (dd, J=3.2, 16.2 Hz, 1H), 2.23 (dd, J=6.8, 16.2 Hz, 1H), 1.45-1.53 (m, 6H), 1.23-1.37 (m, 12H), 1.19 (s, 3H), 1.09 (s, 3H), 1.03 (d, J=7.0, 3H), 1.03 (d, J=6.9, 3H), 0.93 (s, 9H), 0.87 (s, 9H), 0.85-0.93 (m, 12H), 0.10 (s, 3H), 0.09 (s, 3H), 0.08 (s, 3H), 0.04 (s, 9H), 0.03 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 218.8, 172.6, 150.7, 129.1, 74.0, 63.1, 53.9, 47.5, 47.1, 41.0, 29.6, 27.7, 26.6, 26.4, 24.5, 19.2, 18.9, 17.7, 15.9, 14.1, 9.9, −1.1, −2.9, −3.4, −4.0, −4.3.
Example 33
This example describes the synthesis of compound 102. To a stirred solution of 100 (1.00 g, 2.48 mmol) in CH 2 Cl 2 (25 mL) at −78° C. was added 2,6-lutidine (61 mg, 0.66 mL, 5.72 mmol). After 4 minutes, triethylsilyl triflate (1.19 g, 1.0 mL, 4.5 mmol) was added to the cold solution, and after 30 minutes the reaction was quenched with saturated aqueous NH 4 Cl (60 mL) and extracted with Et 2 O (3×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 30-50% Et 2 O/hexane, to give 102 (1.00 g, 78%) as a colorless oil: [α] D 23 +31.2 (c 1.63, CHCl 3 ); IR (neat) 1782, 1714 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.15-7.4 (m, 5H), 5.35-5.5 (m, 2H), 4.55-4.7 (m, 2H), 4.05-4.2 (m, 2H), 4.0-4.15 (m, 2H), 3.8-3.9 (m, 1H of a diastereomer), 3.4-3.5 (m, 1H of a diastereomer), 3.36 (d, J=13.1 Hz, 1H of a diastereomer), 2.7-2.8 (m, 1H of a diastereomer), 2.45-2.55 (m, 2H), 2.46 (q, J=7.3 Hz, 1H), 1.5-1.8 (m, 9H), 0.97 (t, J=7.8 Hz, 9H), 0.62 (q, J=7.6 Hz, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ 173.9, 173.7, 153.3, 135.5, 134.9, 129.6, 129.1, 127.5, 124.0, 97.6, 96.9, 71.1, 66.7, 65.5, 65.2, 62.3, 61.9, 55.8, 37.9, 34.2, 33.7, 30.8, 30.7, 26.0, 25.7, 22.0, 21.9, 19.7, 19.4, 18.5, 6.7, 5.1; HRMS (CI) calculated for C 28 H 44 NO 6 Si (M+H + ) 518.2938, found 518.2908.
Example 34
This example describes the synthesis of compound 104. To a stirred solution of ethanethiol (361 mg, 430 μL, 5.82 mmol) in THF (25 mL) at room temperature was added KH (55 mg, 0.48 mmol, 35% in mineral oil). After 30 minutes, the mixture was cooled to 0° C. and a solution of 102 (1.00 g, 1.94 mmol) in THF (10 mL) was added via cannula during 5 minutes. An additional amount of THF (5 mL) was added, and after 1 hour at room temperature the reaction was quenched with saturated aqueous NH 4 Cl (25 mL). Air was passed through the solution for 2 hours to remove excess ethanethiol, and the mixture was extracted with Et 2 O (3×100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was taken up in 10% Et 2 O/petroleum ether, from which 4 benzyloxazolidin-2-one crystallized as a colorless solid. The decanted solution was concentrated and the residue was purified by chromatography on silica gel, eluting with 30% Et 2 O/hexane, to give the thioester (730 mg, 97%) as a colorless oil: [α] D 23 −16.8 (c 2.73, CHCl 3 ); IR (neat) 1684 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 5.35-5.5 (m, 1H), 4.55 (bs, 1H), 3.9-4.2 (m, 3H), 3.8-3.9 (m, 1H), 3.45-3.6 (m, 1H), 3.36 (d, J=13.1 Hz, 1H), 2.75-2.9 (m, 2H), 2.4-2.6 (m, 2H), 1.4-1.9 (m, 6H), 1.21 (t, J=7.5 Hz, 3H), 0.97 (t, J=7.8 Hz, 9H), 0.62 (q, J=7.8 Hz, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ 205.1, 205.0, 135.24, 135.16, 97.9, 97.4, 78.6, 65.7, 65.5, 62.3, 62.2, 34.5, 30.8, 25.9, 25.7, 22.6, 22.1, 22.0, 19.7, 19.6, 18.4, 14.8, 6.7, 5.1; HRMS (CI) calculated for C 20 H 37 NO 4 SSi (M+H + ) 401.2182, found 401.2172
To a stirred solution of CuI (2.60 g, 13.67 mmol) in Et 2 O (120 mL) at 0° C. was added MeLi (17.8 mL, 24.9 mmol, 1.4M in Et 2 O). The mixture was cooled to −50° C. and a solution of the thioester (960 mg, 2.49 mmol) in Et 2 O (50 mL) was added via cannula. An additional amount of Et 2 O (5 mL) was added to rinse the flask. After 30 minutes, the reaction was quenched with saturated aqueous NH 4 Cl (200 mL), and the mixture was extracted with Et 2 O (3×120 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 15% Et 2 O/hexane, to give the methyl ketone (548 mg, 62%) as a colorless oil: [α] D 23-11.0 (c 3.26, CHCl 3 ); IR (neat) 1719 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 5.35-5.5 (m, 5H), 4.5-4.55 (m, 1H), 3.9-4.1 (m, 3H), 3.75-3.9 (m, 1H), 3.4-3.5 (m, 1H), 2.3-2.5 (m, 2H), 2.10 (s, 3H) 1.4-1.9 (m, 6H), 0.97 (t, J=7.8 Hz, 9H), 0.62 (q, J=7.8 Hz, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ 211.7, 135.2, 135.1, 123.8, 123.5, 97.7, 97.3, 79.0, 65.5, 65.2, 62.2, 62.1, 33.2, 30.7, 25.8, 25.6, 25.5, 22.0, 19.6, 19.5, 18.2, 6.7, 5.1; HRMS (CI) calculated for C 19 H 37 O 4 Si (M+H + ) 357.2461, found 357.2455.
To a stirred solution of 53 (1.26 g, 5.08 mmol) in THF (9 mL) at −78° C. was added n-BuLi (4.7 mL, 5.00 mmol, 1.2 M in hexanes), and after 20 minutes, a solution of the methyl ketone (520 mg, 1.45 mmol) in THF (6 mL) was added via cannula. An additional amount of THF (2 mL) was added to rinse the flask. After 30 minutes, the solution was allowed to warm slowly to room temperature during 1 hour, then was cooled at −78° C. for an additional 30 minutes before the reaction was quenched with saturated aqueous NH 4 Cl (50 mL). The mixture was extracted with Et 2 O (3×65 mL), and the dried (MgSO 4 ) extract was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with 20% Et 2 O/hexanes, to give the thiazole (627 mg, 96%) as a colorless oil: [α] D 23 −33.9 (c 2.56, CHCl 3 ); IR (neat) 2950, 1512, 1455 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.91 (s, 1H), 6.45, (s, 1H), 5.35-5.5 (m, 1H), 4.5-4.6 (m, 1H), 3.9-4.2 (m, 3H), 3.8-3.9 (m, 1H), 3.45-3.6 (m, 1H), 2.70 (s, 3H), 2.2-2.4 (m, 2H), 1.99 (d, J=1.0 Hz, 3H), 1.4-1.9 (m, 6H), 0.92 (t, J=7.9 Hz, 9H), 0.72 (q, J=7.9 Hz, 6H); 13 C NMR (75 MHz, CDCl 3 ,) δ 164.2, 153.1, 142.5, 142.2, 133.4, 125.6, 125.5, 118.7, 118.6, 114.9, 97.4, 97.2, 78.4, 77.3, 65.4, 65.3, 62.0, 61.9, 35.0, 34.9, 30.6, 25.4, 21.7, 19.4, 19.4, 19.1, 13.8, 6.7, 4.7; HRMS (CI) calculated for C 24 H 42 NO 3 SSi (M+H + ) 452.2655, found 452.2645.
To a stirred solution of freshly prepared MgBr 2 (631 mg, 26.2 mmol of Mg, and 2.38 mL, 27.7 mmol, of 1,2-dibromoethane) in Et 2 O (50 mL) at room temperature was added the thiazole (556 mg, 1.20 mmol) in Et 2 O (5 mL) followed by saturated aqueous NH 4 Cl (approximately 50 μL). After 3.5 hours, the mixture was cooled to 0° C. and carefully quenched with saturated aqueous NH 4 Cl (50 mL). The mixture was extracted with Et 2 O (3×100 mL), and the dried (MgSO 4 ) extract was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with 30% Et 2 O/hexanes, to give 104 (390 mg, 89%) as a colorless oil: [α] D 23-31.0 (c 2.74); IR (neat) 3374 cm 1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.92 (s, 1H), 6.44, (s, 1H), 5.31 (t, J=7.7 Hz, 1H), 4.14 (d, J=12.2 Hz, 1H), 4.1-4.2 (m, 1H), 4.00 (d, J=12.2 Hz, 1H), 2.71 (s, 3H), 2.4-2.5 (m, 1H), 2.2-2.3 (m, 2H), 2.00 (s, 3H), 1.80 (s, 3H), 0.92 (t, J=7.9 Hz, 9H), 0.72 (q, J=7.9 Hz, 6H); 13 C NMR (75 MHz, CDCl 3 ) δ 164.8, 153.0, 142.4, 137.7, 124.4, 119.0, 115.4, 78.4, 62.0, 61.9, 35.5, 29.9, 26.0, 22.2, 19.3, 18.5, 14.3, 6.7, 4.7; HRMS (CI) calculated for C 19 H 34 NO 2 SSi (M+H + ) 368.2080, found 368.2061.
Example 35
This example describes the synthesis of compound 106. To a stirred solution of 104 (35 mg, 95 μmol) in CH 2 Cl 2 (0.6 mL) at 0° C. was added Et 3 N (23 μL, 161 μmol) followed by methanesulfonic anhydride (21 mg, 119 μmol). After 10 minutes, acetone (0.6 mL) was added followed by LiCl (40 mg, 950 μmol). After 4 hours at room temperature, the solution was concentrated in vacuo to remove acetone, diluted with saturated aqueous NH 4 Cl, and extracted with Et 2 O. The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 10-20% Et 2 O/petroleum ether, to give 106 (36 mg, 97%) as a colorless oil: [α] D 23 +28.1 (c 1.11, CHCl 3 ); IR (neat) 2954, 2875, 1453, 1072 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.94 (s, 1H), 6.49 (s, 1H), 5.41 (dt, J=1.3, 7.5 Hz, 1H), 4.15 (m, 1H), 4.14 (d, J=10.8, 1H), 4.00 (d, J=10.8, 1H), 2.71 (s, 3H), 2.35 (m, 2H), 2.01 (d, J=1.2, 3H), 1.75 (d, J=1.2, 3H), 0.93 (t, J=7.69, 9H), 0.58 (q, J=7.39, 6H); 13 C NMR (75 MHz, CDCl 13 ) δ 164.5, 153.5, 142.3, 133.4, 127.8, 119.4, 115.6, 78.4, 44.2, 35.8, 22.1, 19.6, 14.4, 7.2, 5.2; HRMS (FAB) calculated for C 19 H 33 ClNOSSi (M+H + ) 386.1741, found 386.1737.
Example 36
This example describes the synthesis of compound 108. A solution of 106 (44 mg, 114 μmol), tris(dibenzylideneactone)dipalladium-chloroform (7.1 mg, 6.8 μmol) and triphenylarsine (8.4 mg, 27 μmol) in THF (0.4 mL) was stirred at room temperature for 10 minutes solution of 98 (107 mg, 120 μmol) in THF (1.0 mL) was added, and the flask was briefly opened to the atmosphere, resealed, and heated to 65° C. After 18 hours, mixture was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 5% Et 2 O/hexanes, to give 108 (82 mg, 76%) as a colorless oil: [α] D 23 −6.2 (c 1.23, CHCl 3 ); IR (neat) 2955, 2856, 1753, 1694, 1471 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.91(s, 1H), 6.47 (s, 1H), 5.52 (dd, J=7.9, 15.6 Hz, 1H), 5.32 (dt, J=6.7, 8.5 Hz, 1H), 5.17 (t, J=7.3, 1H), 4.40 (dd, J=3.1, 6.7 Hz, 1H), 4.15-4.18 (m, 2H), 3.82 (dd, J=1.8, 7.2, 1H), 3.02 (dq, J=7.1, 7.1 Hz, 1H), 2.72 (s, 3H), 2.66 (d, J=6.6 Hz, 2H), 2.20-2.44 (m, 3H), 2.00 (s, 3H), 1.26 (s, 3H), 1.07 (s, 3H), 1.01 (d, J=7.0 Hz, 3H), 1.00 (d, J=6.0 Hz, 3H), 0.93 (t, J=7.8 Hz, 9H), 0.91 (s, 9H), 0.87 (s, 9H), 0.58 (q, J=7.8 Hz, 6H), 0.10 (s, 3H), 0.06 (s, 3H), 0.03 (s, 3H), 0.03 (s, 9H), 0.02 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.5, 172.6, 164.7, 153.6, 143.0, 136.0, 133.1, 129.7, 121.9, 119.0, 115.3, 79.0, 76.8, 63.1, 53.8, 46.6, 43.8, 42.8, 40.9, 26.6, 26.4, 19.6, 18.9, 18.6, 17.7, 16.7, 14.4, 7.3, 5.5, −1.1, −3.1, −3.4, −4.0, −4.2; HRMS (FAB) calculated for C 50 H 96 NO 6 SSi 4 (M+H + ) 950.6036, found 950.6065.
Example 37
This example describes the synthesis of compound 110. To a stirred solution of 108 (20 mg, 21 μmol) and powdered molecular sieves (100 mg) in THF (8.0 mL) at 0° C. was added tetra-n-butylammonium fluoride (16.5 mg, 63 μmol). After 6 hours, the mixture was filtered through glass wool, and aqueous citric acid (pH 5, 8 mL) was added to the filtrate, which was extracted with Et 2 O. The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by flash chromatography on silica gel, eluting with 4% MeOH/CH 2 Cl 2 , to give 110 (12.8 mg, 83%) as a colorless oil: [α] D 23 −22.4 (c 2.15, CHCl 3 ); IR (neat) 3252, 2956, 2929, 2856, 1712 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.96 (s, 1H), 6.58, (s, 1H), 5.54 (dd, J=7.5, 15.2 Hz, 1H), 5.38 (dt, J=6.7, 15.2 Hz, 1H), 5.20 (t, J=7.8 Hz, 1H), 4.40 (dd, J=3.2, 6.4 Hz, 1H), 4.16-4.24 (m, 1H), 3.83-3.86 (m, 1H), 3.02-3.09 (m, 1H), 2.72 (s, 3H), 2.69-2.72 (m, 2H), 2.28-2.55 (m, 5H), 1.98-2.08 (m, 2H), 2.03 (s, 3H), 1.63 (s, 3H), 1.17 (s, 3H), 1.12 (s, 3H), 1.04 (d, J=6.9 Hz, 3H), 0.97 (d, J=6.9 Hz, 3H), 0.92 (s, 9H), 0.89 (s, 9H), 0.11 (s, 3H), 0.07 (s, 3H), 0.07 (s, 3H), 0.06 (s, 3H)); 13 C NMR (75 MHz, CDCl 3 ) δ 218.8, 175.9, 165.4, 153.0, 142.1, 138.2, 133.3, 129.5, 120.6, 119.4, 115.7, 76.9, 76.7, 73.7, 54.0, 46.8, 43.6, 42.8, 40.4, 34.6, 30.1, 26.6, 26.4, 24.2, 20.1, 19.3, 18.9, 18.6, 16.9, 14.7, −3.1, −3.5, −3.7, −4.2; HRMS (FAB) calculated for C 39 H 70 NO 6 SSi 2 (M+H + ) 736.4462, found 736.4466.
Example 38
This example describes the synthesis of compound 112. To a stirred solution of 110 (22.0 mg, 30.0 μmol) in THF (0.5 mL) at 0° C. was added Et 3 N (7.6 μL, 54 μmol) followed by 2,4,6-trichlorobenzoyl chloride (5.6 μL, 36 μmol). After 45 minutes, the mixture was diluted with THF (0.4 mL) and toluene (0.7 mL), and was added via syringe pump to a stirred solution of DMAP (6.5 mg, 53 μmol) in toluene (7.2 mL) at 75° C. during 3.5 h. After an additional 1 hour, the solution was allowed to cool to room temperature, diluted with EtOAc, washed with saturated aqueous NH 4 Cl (20 mL), and extracted with EtOAc (4×40 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 5% EtOAc/hexanes, to give 112 (19.4 mg, 71%) as a colorless oil: [α] D 23 −2.12 (c 1.13, CHCl 3 ); IR (neat) 2929, 2856, 1735, 1700 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.94 (s, 3H), 6.54 (s, 3H), 5.44-5.46 (m, 2H), 5.28 (m, 1H), 5.22 (dd, J=3.3, 9.7, 1H), 4.63 (dd, J=3.2, 8.7, 1H), 3.90 (m, 1H), 3.16 (dq, J=6.8, 6.8 Hz, 1H), 2.71 (s, 3H), 2.20-2.71 (m, 6H), 2.14 (s, 3H), 1.68 (s, 3H), 1.10 (d, J=6.8 Hz, 3H), 1.10 (s, 3H), 1.07 (s, 3H), 1.04 (d, J=7.0, 1H), 0.93 (s, 9H), 0.85 (s, 9H), 0.11 (s, 3H), 0.11 (s, 3H), 0.10 (s, 3H), 0.88 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 215.9, 170.7, 165.1, 153.1, 138.7, 137.8, 133.9, 128.3, 120.3, 119.8, 116.8, 80.8, 77.7, 73.3, 55.1, 44.1, 43.1, 42.3, 42.0, 32.8, 26.6, 26.4, 21.2, 19.7, 19.1, 18.9, 18.2, 18.0, 17.2, 15.2, −2.5, −3.4, −3.8, −3.8; HRMS (FAB) calculated for C 39 H 68 NO 5 SSi 2 (M+H + ) 718.4357, found 718.4345.
Example 39
This example describes the synthesis of compound 114 To a stirred solution of 112 (14.5 mg, 20 μmol) in CH 2 Cl 2 (125 μL) at 0° C. was added trifluoroacetic acid (112 μL). After 8 hours, the mixture was concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 20-50% EtOAc/hexanes, to give 114 (9.3 mg, 19 μmol, 95%) as a colorless waxy solid: [α] D 23-35.4 (c 0.50, CHCl 3 ); IR (neat) 2971, 2927, 1729, 1691 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.98 (s, 1H), 6.55 (s, 1H), 5.53-5.48 (m, 2H), 5.38 (dd, J=2.8, 9.4 Hz, 1H), 5.23 (m, 1H), 4.23 (dd, J=4.3, 8.2 Hz, 1H), 3.71 (m, 1H), 3.27 (dq, J=5.8, 6.7 Hz, 1H), 2.27-2.77 (m, 6H), 2.72 (s, 3H), 2.11 (s, 3H), 1.69 (s, 3H), 1.26 (s, 3H), 1.17 (d, J=6.8 Hz, 3H), 1.10 (d, J=7.0 Hz, 3H), 1.05 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 219.7, 171.0, 165.2, 152.7, 138.4, 137.8, 132.8, 129.6, 120.4, 120.2, 116.6, 79.2, 77.0, 76.4, 74.6, 72.3, 53.3, 44.7, 42.9, 40.3, 39.5, 32.6, 21.6, 20.0, 19.6, 17.8, 17.1, 15.9, 15.2; HRMS (FAB) calculated for C 27 H 40 NO 3 S (M+H + ) 490.2627, found 490.2634.
Example 40
This example describes the synthesis of compound 118. To a stirred solution of alkyne 96 (38.0 mg, 0.063 mmol) in Et 2 O (1.0 mL) and DMF (0.2 mL) at room temperature was added Et 3 N (8.8 μL, 0.063 mmol) and CuI (12.0 mg, 0.063 mmol). After the mixture became clear (approximately 5 minutes), a solution of chloride 59 (12.2 mg, 0.315 mmol) in Et 2 O (0.5 mL) was added. The solution was stirred for 18 hours, quenched with saturated aqueous Na 2 S 2 O 3 (5 mL), and extracted with Et 2 O (3×2 mL). The combined extracts were dried (MgSO 4 ) and concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 50-60% CH 2 Cl 2 /hexanes to give dienyne 118 (17.4 mg, 58%) as a colorless oil: [α] D 23 −12.1 (c 1.74); IR (neat) 1737, 1692 cm −1 ; 1 H NMR (CDCl 3 , 300 MHz) δ 6.91(s, 1H), 6.47 (s, 1H), 5.37 (t, J=6.7 Hz, 1H), 4.44 (dd, J=3.2, 6.64 Hz, 1H), 4.20-4.09 (m, 3H), 3.74 (dq, J=2.1, 11.5 Hz, 1H), 3.34 (dddd, J=2.7, 2.7, 7.6, 7.6 Hz, 1H), 2.71 (s, 3H), 2.41-2.25 (m, 5H), 2.02 (s, 3H), 1.68 (s, 3H) 1.25 (s, 3H), 1.16 (s, 3H), 1.13 (d, J=7.1 Hz, 3H), 1.06 (d, J=6.9 Hz, 3H), 0.98 (obscured m, 2H), 0.94 (t, J=8.1, 9H) 0.92 (s, 9H), 0.88 (s, 9H), 0.59 (q, J=7.9, 9H), 0.10 (s, 3H), 0.07 (s, 6H), 0.04 (s, 9H), 0.03 (s, 3H); 13 C NMR (CDCl 3 , 75 MHz) δ 219.2, 172.6, 164.7, 153.6, 142.9, 132.8, 122.4, 119.1, 115.4, 83.5, 80.6, 78.8, 76.4, 73.9, 63.9, 54.1, 41.1, 36.0, 33.0, 30.1, 26.4, 24.1, 19.6, 19.5, 19.4, 19.1, 18.9, 18.7, 18.6, 17.7, 16.1, 14.4, 7.3, 5.22, −1.1, −−2.9, −3.5, −4.0, −4.3; HRMS (FAB) calculated for C 50 H 94 NO 6 SSi 4 (M+H + ) 948.58790, found 948.59258.
Example 41
This example describes the synthesis of compound 120. To a stirred solution of dienyne 118 (8.0 mg, 8.4 μmol) and powdered molecular sieves (100 mg) in THF (1.5 mL) at 0° C. was added tetra-n-butylammonium fluoride (6.0 mg, 25 μmol). After 1 hour, the mixture was filtered through glass wool, and aqueous citric acid (pH 5, 3.0 mL) was added to the filtrate, which was extracted with Et 2 O. The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by flash chromatography on silica gel, eluting with 4% MeOH/CH 2 Cl 2 , to give 120 (8.2 mg, quantitative) as a colorless oil: [α] D 23 −0.17 (c 0.82, CHCl 3 ); IR (neat) 3338, 2954, 2929, 2856, 1713 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.96 (s, 1H), 6.58, (s, 1H), 5.50 (t, J=6.7 Hz, 1H), 4.46 (dd, J=2.1, 4.7 Hz, 1H), 4.20 (t, J=4.7H), 3.80 (dd, J=1.1, 5.6 Hz, 1H), 3.34 (dddd, J=5.5, 5.5, 5.5, 10.9 Hz, 1H), 2.9 (s, 1H), 2.73 (s, 3H), 2.58-2.25 (m, 5H), 2.05 (s, 3H), 1.72 (s, 3H) 1.24 (s, 3H), 1.20 (s, 3H), 1.15 (d, J=5.4 Hz, 3H), 1.10 (d, J=5.2 Hz, 3H), 0.93 (s, 9H), 0.90 (s, 9H), 0.11 (s, 3H), 0.09 (s, 9H); 13 C NMR (75 MHz, CDCl 3 ) δ 219.1, 175.4, 165.4, 153.0, 142.2, 134.6, 121.2, 119.3, 115.8, 84.1, 80.4, 76.4, 73.6, 54.4, 46.7, 40.4, 34.7, 33.0, 30.1, 29.6, 26.5, 26.4, 23.9, 19.2, 19.2, 18.9, 18.6, 16.9 16.4, 14.9, −2.94, −3.5, −3.6, −4.2; HRMS (FAB) calculated for C 39 H 68 NO 6 SSi 2 (M+H + ) 734.43082, found 734.42877.
Example 42
This example describes the synthesis of compound 122. To a stirred solution of seco acid 120 (8.8 mg, 12.0 μmol) in THF (0.2 mL) at 0° C. was added Et 3 N (2.9 μL, 21 μmol) followed by 2,4,6-trichlorobenzoyl chloride (2.2 μL, 14 μmol). After 45 minutes, the mixture was diluted with THF (0.16 mL) and toluene (0.26 mL), and was added via syringe pump to a stirred solution of DMAP (2.4 mg, 20 μmol) in toluene (2.8 mL) at 75° C. during 3.5 h. After an additional 1 h, the solution was allowed to cool to room temperature, diluted with EtOAc, washed with saturated aqueous NH 4 Cl (10 mL), and extracted with EtOAc (4×20 mL). The dried (Mg 2 SO 4 ) extract was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 5% EtOAc/hexanes, to give macrolactone 122(4.1 mg, 47%) as a colorless oil: [α] D 23 11.9 (c 0.41, CHCl 3 ); IR (neat) 2925, 2854, 1739, 1702, 1463 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.94 (s, 3H), 6.55 (s, 3H), 5.70 (t, J=6.2, 1H), 5.33 (dd, J=2.6, 11.3 1H), 4.64 (dd, J=2.5, 8.2, 1H), 3.94 (dd, J=2.5, 8.1 1H), 3.26 (dq, J=7.0, 14.9 Hz, 1H), 2.71 (s, 3H), 2.70-2.35 (m, 5H), 2.15 (s, 3H), 1.66 (s, 3H), 1.16 (d, J=7.1 Hz, 3H), 1.14 (s, 3H), 1.14 (s, 3H), 1.13 (obscured d, 1H), 0.91 (s, 9H), 0.86 (s, 9H), 0.13 (s, 3H), 0.10 (s, 3H), 0.08 (s, 3H), 0.07 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 215.7, 170.9, 165.1, 153.1, 139.0, 137.8, 132.9, 121.5, 120.1, 116.7, 85.5, 80.3, 79.8, 77.6, 76.4, 73.3, 55.2, 44.4, 42.5, 33.1, 32.5, 30.1, 29.0, 26.4, 26.4, 19.8, 19.7, 18.7, 18.5, 18.0, 17.4, 15.2, −2.9, −3.3, −3.8, −4.1; HRMS (FAB) calculated for C 39 H 66 NO 5 SSi 2 (M+H + ) 716.42003, found 716.42093.
Example 43
This example describes the synthesis of compound 124. To a stirred solution of 122 (4.1 mg, 5.7 μmol) in CH 2 Cl 2 (200 μL) at 0° C. was added trifluoroacetic acid (100 mL). After 10 hours, the mixture was concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 20-50% EtOAc/hexanes, to give 124 (2.4 mg, 19 μmol, 86%) as a colorless waxy solid: [α] D 23 −37.9 (c 0.24, CHCl 3 ); IR (neat) 3480, 2925, 1731, 1692 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.98 (s, 1H), 6.56 (s, 1H), 5.49 (t, J=7.9, 1H), 5.38 (dd, J=3.1, 9.9, 1H), 4.43 (dd, J=5.6, 5.6, 1H), 3.60 (dd, J=8.2, 8.2, 1H), 3.26 (dddd, J=6.7, 6.7, 6.8, 15.5 Hz, 1H), 2.71 (s, 3H), 2.65-2.35 (m, 5H), 2.11 (s, 3H), 1.74 (s, 3H), 1.27 (d, J=6.9, 3H), 1.25 (d, J=7.1, 3H) 1.21, (s, 3H), 1.09 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 218.5, 171.1, 165.3, 152.6, 137.8, 134.5, 121.3, 120.4, 116.8, 82.7, 82.3, 79.2, 77.6, 76.6, 72.1, 53.5, 47.4, 39.8, 32.7, 31.9, 29.5, 22.2, 19.6, 19.4, 18.9, 17.0, 16.8, 15.8; HRMS (FAB) calculated for C 27 H 38 NO 5 S (M+H + ) 488.24676, found 488.24707.
Example 44
This example describes the synthesis of compound 81. To a stirred solution of the crude aldehyde 79 in t-BuOH (0.88 mL) and H 2 O (0.83 mL) was added 2-methyl-2-butene (0.16 mL) followed sequentially by NaH 2 PO 4 (55.7 mg, 0.46 mmol) and NaClO 2 (27.1 mg, 0.30 mmol). After 1 hour, the reaction was quenched with saturated aqueous NaCl (1.5 mL), and the mixture was extracted with Et 2 O (4×5 mL). The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 20% EtOAc in hexanes to give acid 81 (38 mg 0.061 mmol, 93%) as a colorless oil: [α] D 23 −26.8 (c 1.20, CHCl 3 ); IR (neat) 2400-3400, 1735, 1722 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 4.40 (dd, J=3.6, 6.9 Hz, 1H), 4.15 (m, 3H), 4.03 (dd, J=2.2, 7.9 Hz, 1H), 3.36 (dq, J=7.3, 7.3 Hz, 1H), 2.45 (td, J=2.2, 7.4 Hz, 1H), 2.37 (d, J=3.4 Hz, 1H), 2.26 (dd, J=7.0, 16.1 Hz, 1H), 1.23 (d, J=7.1 Hz, 3H) 1.22 (s, 3H), 1.14 (s, 3H), 1.11 (d, J=6.9 Hz, 3H) 0.98 (m, 3H), 0.93 (s, 9H), 0.87 (s, 9H), 0.15 (s, 3H), 0.14 (s, 3H), 0.10 (s, 3H), 0.04 (s, 9H), 0.02 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.2, 177.4, 172.7, 76.6, 73.9, 63.2, 54.2, 46.8, 45.2, 40.9, 30.1, 26.4, 26.4, 24.1, 19.3, 18.7, 18.6, 17.6, 15.9, 15.6, −1.1, −3.2, −3.5, −4.0, −4.2; HRMS (CI) calculated for C 30 H 63 O 7 Si 3 619.38750; found 619.38817.
Example 45
This example describes the synthesis of compound 124. To a stirred solution of 81 (30.0 mg, 0.048 mmol) in THF (0.25 mL) was added 104 (20.6 mg, 0.073 mmol) and triphenylphosphine (31.4 mg, 0.12 mmol). The solution was cooled to 0° C. and diethyl azodicarboxylate (0.017 mL, 0.11 mmol) was added. After 4 hours, the reaction was quenched with saturated aqueous NH 14 Cl, and the solution was extracted with Et 2 O. The extract was concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 10% Et 2 O/petroleum ether, to give ester 124 (30 mg, 65%) as a colorless oil: [α] D 23 −20.7 (c 1.50, CHCl 3 ); IR (neat) 2954, 1735, 1251 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.92 (s, 1H), 6.46 (s, 1H), 5.42 (t, J=7.3 Hz, 1H), 4.61 (d, J=12.1 Hz, 1H), 4.51 (d, J=12.1 Hz, 1H), 4.41 (dd, J=3.0, 6.6 Hz, 1H), 4.13 (m, 3H), 3.47 (dq, J=7.1, 7.1 Hz, 1H), 2.71 (s, 3H), 2.47-2.13 (m, 5H) 1.99 (s, 3H), 1.75 (s, 3H), 1.24 (s, 3H), 1.15 (d, J=7.1 Hz, 3H), 1.12 (s, 3H), 1.04 (d, J=6.9 Hz, 3H), 0.98 (m, 3H), 0.92 (t, J=7.7, 9H), 0.85 (s, 18H), 0.57 (q, J=7.9 Hz, 6H), 0.09 (s, 3H), 0.07 (s, 3H), 0.04 (s, 3H), 0.03 (s, 9H), 0.02 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.2, 173.7, 172.6, 164.9, 153.2, 142.6, 131.9, 127.2, 119.1, 115.5, 78.5, 76.3, 74.2, 63.7, 63.1, 53.9, 45.6, 40.9, 35.5, 26.4, 24.2, 22.1, 17.7, 15.5, 15.1, 14.4, 7.2, 5.2, −1.1, −3.5, −4.0, −4.2; HRMS (CI) calculated for C 49 H 94 O 8 SSi 4 968.57773; found 968.57748.
Example 46
This example describes the synthesis of compound 130. To a stirred solution of 124 (30 mg, 31 μmol) and powdered molecular sieves (100 mg) in THF (5.0 mL) at 0° C. was added tetra-n-butylammonium fluoride (24.0 mg, 96 μmol). After 2 hours, the mixture was filtered through glass wool, and aqueous citric acid (pH 5, 5 mL) was added to the filtrate, which was extracted with Et 2 O. The dried (MgSO 4 ) extract was concentrated in vacuo and the residue was purified by flash chromatography on silica gel, eluting with 3% MeOH/CH 2 Cl 2 , to give seco acid 130(15.0 mg, 66%) as a colorless oil: [α] D 23 −26.9 (c 0.75, CHCl 3 ); IR (neat) 3107, 2929, 1716, 1422 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.96 (s, 1H), 6.64 (s, 1H), 5.46 (t, J=7.3 Hz, 1H), 4.69 (d, J=11.8 Hz, 1H), 4.47 (d, J=11.8 Hz, 1H), 4.42 (dd, J=3.6, 6.3 Hz, 1H), 4.17 (t, J=6.8 Hz, 1H), 4.09 (dd, J=2.5, 7.7 Hz, 1H), 3.42 (dq, J=7.4, 7.4 Hz, 1H), 2.72 (s, 3H), 2.56-2.19 (m, 5H) 2.00 (s, 3H), 1.80 (s, 3H), 1.23 (s, 3H), 1.17 (s, 3H), 1.16 (d, J=7.1 Hz, 3H), 1.08 (d, J=6.9 Hz, 3H), 0.88 (s, 9H), 0.87 (s, 9H), 0.10 (s, 3H), 0.10 (s, 3H), 0.08 (s, 3H), 0.05 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.4, 175.3, 173.8, 165.6, 152.8, 142.4, 133.5, 126.7, 118.9, 115.6, 76.1, 73.8, 63.8, 54.3, 45.9, 45.7, 40.6, 34.4, 26.4, 24.2, 22.2, 19.4, 19.2, 18.7, 16.1, 15.3, 13.8, −3.6, −3.7, −3.8, −4.2; HRMS (CI) calculated for C 38 H 68 O 8 NSSi 2 754.42042; found 754.42119.
Example 47
This example describes the synthesis of compound 132. To a stirred solution of 130 (15.0 mg, 20.0 μmol) in THF (0.4 mL) at 0° C. was added Et 3 N (4.9 μL, 35 μmol) followed by 2,4,6-trichlorobenzoyl chloride (3.6 μL, 23 μmol). After 45 minutes, the mixture was diluted with THF (0.3 mL) and toluene (0.4 mL), and was added via syringe pump to a stirred solution of DMAP (4.2 mg, 34 μmol) in toluene (4.6 mL) at 75° C. during 4 hours. After an additional 1 hour, the solution was allowed to cool to room temperature, diluted with EtOAc, washed with saturated aqueous NH 4 Cl (20 mL), and extracted with EtOAc (4×40 mL). The dried (Mg 2 SO 4 ) extract was concentrated in vacuo and the residue was purified by chromatography on silica gel, eluting with 5% EtOAc/hexanes, to give 132 (9.0 mg, 60%) as a colorless oil: [α] D 23 −36.6 (c 0.45, CHCl 3 ); IR (neat) 2927, 1741, 1471 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 6.96 (s, 1H), 6.57 (s, 1H), 5.44 (dd, J=5.7, 11.8 Hz, 1H), 5.34 (dd, J=3.3, 8.8 Hz, 1H) 4.83 (d, J=11.5 Hz, 1H), 4.46 (m, 2H), 4.02 (dd, J=1.6, 8.7 Hz, 1H), 3.34 (dq, J=7.4, 7.4 Hz, 1H), 2.82 (m, 1H), 2.71 (s, 3H), 2.56 (m, 3H), 2.28 (m, 1H) 2.15 (s, 3H), 1.74 (s, 3H), 1.23 (d, J=7.4 Hz, 3H), 1.20 (d, J=7.1 Hz, 3H), 1.16 (s, 3H), 1.09 (s, 3H), 0.90 (s, 9H), 0.85 (s, 9H), 0.15 (s, 3H), 0.07 (s, 3H), 0.06 (s, 3H), 0.02 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 217.0, 173.4, 170.8, 165.1, 152.8, 136.6, 133.7, 126.7, 121.3, 116.8, 79.2, 76.6, 73.7, 62.6, 54.2, 48.3, 45.6, 41.9, 33.3, 26.5, 25.1, 22.3, 20.4, 19.7, 18.7, 18.6, 17.4, 15.2, −3.4, −3.5, −3.7, −4.2; HRMS (CI) calculated for C 38 H 66 O 7 NSSi 2 736.40986; found 736.40850.
Example 48
This example describes the synthesis of compound 134. To a stirred solution of 78 (4.5 mg, 6 μmol) in CH 2 Cl 2 (200 μL) at 0° C. was added trifluoroacetic acid (100 μL). After 8 hours, the mixture was concentrated in vacuo, and the residue was purified by chromatography on silica gel, eluting with 20-2% MeOH/CH 2 Cl 2 , to give 79 (3 mg, 6 μmol, 99%) as a colorless oil: [α] D 23 40.0 (c 0.15, CHCl 3 ); IR (neat) 3503, 2924, 1732, 1458 cm −1 ; 1 H NMR (300 MHz, CDCl 3 ) δ 7.00 (s, 1H), 6.60 (s, 1H), 5.45 (dd, J=6.0, 11.0 Hz, 1H), 5.28 (d, J=9.6 Hz, 1H) 5.02 (d, J=11.2 Hz, 1H), 4.21 (d, J=12.3 Hz, 1H), 4.02 (m, 1H), 3.77 (m, 1H), 3.46 (m, 1H), 3.23 (dq, J=6.8, 6.8 Hz, 1H), 2.74 (s, 3H), 2.67 (m, 3H), 2.45 (m, 2H), 2.24 (m, 1H), 2.11 (s, 3H), 1.78 (s, 3H), 1.38 (d, J=7.1 Hz, 3H), 1.31 (s, 3H) 1.27 (d, J=6.8 Hz, 3H), 1.10 (s, 3H); 13 C NMR (75 MHz, CDCl 3 ) δ 218.9, 177.2, 170.9, 165.4, 152.8, 137.9, 133.6, 126.1, 120.7, 116.9, 78.9, 75.6, 73.3, 63.9, 52.7, 47.9, 41.7, 39.0, 32.7, 22.3, 21.9, 21.8, 19.6, 16.8, 16.5, 15.7; HRMS (CI) calculated for C 26 H 38 O 7 NS 508.23690; found 508.23641.
The present method has been described in accordance with working embodiments; however, it will be understood that certain modifications may be made thereto without departing from the method. We claim as our invention the disclosed embodiments and all such modifications and equivalents as come within the true spirit and scope of the following claims. | A method for making epothilones and epothilone analogs is described, as are novel compounds made by the method. Exemplary novel compounds include those according to the formula:
With respect the formula, G is selected from the group consisting of
R 2 substituents independently are selected from the group consisting of H and lower alkyl groups; Z is selected from the group consisting of the halogens and —CN; M is selected from the group consisting of O and NR 3 ; R 3 is selected from the group consisting of H, lower alkyl, R 4 CO, R 4 OCO, and R 4 SO 2 ; R 4 is selected from the group consisting of H, lower alkyl, and aryl; T is selected from the group consisting of CH 2 , CO, HCOH and protected derivatives thereof; W is H or OR; and X and Y independently are selected from the group consisting of O, NH, S, CO, and C. Embodiments of the method provide convenient access to analogs of the epothilones, such as those having alternate stereochemistry and those containing an ester, amide, thioester, or alkyne moieties in the macrocycle. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to the field of beds and particularly to a crib for newborns and infants that can be placed in close proximity to the parents' bed.
2. Background
It is common practice for newborns and infants to sleep in cribs. The crib may be located in the parents' bedroom or in a separate nursery. Child-care experts suggest that children should be trained at a very early age to sleep alone and, therefore, the child should be physically removed from the parents at night. However, many dispute this theory and believe that young children should sleep with their parents, at least until weaned. But, if the child is allowed to sleep in the parents' bed, there is a risk of physical injury or suffocation.
Conventional cribs, even if placed in the parents' bedroom keep the child physically separated from the parents. At best, the crib can only be brought adjacent to the bed, and even then the child will likely be separated from its parents by a panel of bars.
One solution has been a crib that physically attaches to the parents bed. Examples of this are shown in U.S. Pat. Nos. 134,847; 328,157; 413,107; 484,975; 884,509; 920,009; 1,138,451; 1,267,244; 1,495,988; 5,148,561 and 5,293,655. Each of these prior art cribs is more or less permanently attached to the parents' bed and cannot be easily relocated. Moreover, in each of these designs, the crib is not self-supporting, but instead depends upon at least partial support by the frame of the parents' bed.
SUMMARY OF THE INVENTION
The present invention overcomes the disadvantages of the prior art by providing a free-standing crib that can be brought into close proximity to the parents' bed and can extend at least partially thereover. The invention comprises an otherwise conventional crib mattress; a mattress retainer having an essentially flat-bottom surface and a peripheral wall at least partially surrounding the mattress; means for supporting the mattress retainer; a pair of generally upright supports coupled to the mattress retainer supporting means; a pair of generally horizontal base supports, each coupled to a respective one of the generally upright supports, said base supports extending transversely below the mattress retainer supporting means and having first and second ends; a pair of diagonal supports, each extending between an upper portion of a respective generally upright support and the first end of the respective base support; wherein the mattress retainer extends substantially beyond the generally upright supports in a transverse direction toward the second ends of the base supports.
In use, the base supports are positioned with the second ends extending under the parents' bed with the upright supports adjacent to the parents' mattress. This allows the mattress and mattress retainer to extend partially over the top surface of the parents' mattress.
When it is desired to relocate the crib, it can be simply drawn away from the parents' bed since it is entirely self-supporting. The mattress retainer may be in the form of a portable bassinet that can be readily removed from the mattress retainer supporting means.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is perspective view illustrating a crib constructed in accordance with the present invention positioned adjacent to the parents' bed.
FIG. 2 is an end elevation view of the crib of FIG. 1.
FIG. 3 is a top plan view of the crib of FIG. 1.
FIG. 4 is a side elevation view of the crib of FIG. 1.
FIG. 5 is a detailed view of a connector used in a preferred embodiment of the present invention.
FIG. 6 is a cross-sectional view along line 6--6 of FIG. 4 illustrating the height adjustment mechanism of the present invention.
FIG. 7 is a partial bottom plan view of the crib shelf of the present invention.
FIG. 8 is a partially cut away detailed side view of the crib shelf.
DETAILED DESCRIPTION OF THE INVENTION
In the following description, for purposes of explanation and not limitation, specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known methods and devices are omitted so as to not obscure the description of the present invention with unnecessary detail.
An infant bed or crib 10 constructed in accordance with the present invention is shown generally in FIG. 1. As can be seen, the infant sleeping in crib 10 is easily accessible from the parents' bed in the event that the infant awakens.
Referring now to FIG. 2, crib 10 comprises a frame 12, a shelf 14 and a mattress retainer 16. Frame 12 is preferably constructed of a plastic material, such as PVC pipe, although other suitable materials may be employed. As seen in FIG. 2, the principal components of frame 12 are upright member 20, base member 22 and diagonal support member 24. As will be apparent from the discussion that follows, frame 12 supports one side of crib 10, there being a substantially identical frame 12' on the opposite side.
To place crib 10 in its preferred position relative to the parents' bed, base member 22 is slid under the bed until upright member 20 is immediately adjacent to the edge of the bed. In this position, shelf 14 and mattress retainer 16 extend over the top surface of the parents' bed so that the child is in intimate proximity with its parents. Since there is no physical attachment between crib 10 and the parents' bed, the crib can be easily relocated when desired, such as when the child naps during the day.
A top plan view of crib 10 is shown in FIG. 3. Side frames 12 and 12' are joined by transverse interconnection members 26 and 27. Additional transverse interconnection members 28 and 29 are hidden from view in this figure. In a preferred embodiment, mattress retainer 16 is a generally rectangular, tub-like bassinet, which may be provided as a component part of the crib set or may be separately available. In either case, the bassinet is preferably removable from the crib. The bassinet preferably has a pair of folding handles 32, 34 with which the bassinet can be conveniently carried when removed from crib 10.
Bassinet 16 is surrounded by a peripheral wall 17 to retain mattress 18. If desired, this wall may be cut-out or partially eliminated on the side facing the parents' bed so that the child will be more easily accessible. Of course, suitable means must then be provided to prevent the child from falling out of the bassinet if it is removed from crib 10 or if crib 10 is relocated away from the parents' bed.
As best seen in FIG. 4, mattress retainer/bassinet 16 is normally supported in crib 10 by shelf 14. Shelf 14 is bonded or otherwise suitably attached to height adjustment members 36, 38. These adjustment members are generally cylindrical in shape and slide over upright supports 20 and 20', respectively. Alternative means for supporting mattress retainer/bassinet 16 may be employed. For example, the bassinet may be self-supporting across its bottom surface and may be secured at the head and foot ends to side frames 12 and 12' with suitable brackets. As another example, the bassinet may be suspended by handles 32, 34 or other means from the side frames 12 and 12'. This alternative would allow the bassinet to be rocked, if desired.
Shelf 14 is surrounded by a shallow lip 15 which serves to retain the bassinet 16 laterally. Clamps or other positive locking means may be provided to secure the bassinet to the tray so that it cannot be inadvertently dislodged.
Details of the attachment of transverse interconnection members 26-29 to side frames 12 and 12' are shown in FIG. 5. Side frames 12 and 12' have threaded nipples 40 bonded thereto at appropriate locations. Each end of the transverse interconnection members is fitted with a threaded collar 42, which is retained by a flange 44. The frame of crib 10 is easily assembled by threading each of collars 42 onto the corresponding nipples 40. This facilitates shipping and storage of crib 10.
FIG. 6 shows details of the height adjustment mechanism. Each of upright support members 20 and 20' is fitted with a push-button 50 which is loaded by spring 52. Adjustment members 36 and 38 each have a plurality of holes 54 which may be engaged by push-button 50. To adjust the height of shelf 14, push-buttons 50 are depressed and the adjustment members 36, 38 are moved to the desired vertical position at which push-button 50 engages one of holes 54. In order to more securely lock shelf 14 into position, adjustment members 36, 38 are notched and threaded at their lower ends. A threaded collar 56 is provided at the bottom of each of adjustment members 36, 38. Once shelf 14 has been placed in the desired vertical position, collars 56 are tightened to clamp the adjustment members to their respective vertical supports.
Referring to FIGS. 7 and 8, shelf 14 is reinforced with supporting rod 60, which may be formed of mild steel or other suitable material. Rod 60 may be either bonded to the underside of shelf 14 or may be molded in. In either case, ends 62 of rod 60 are bent upwardly and are bonded or molded into the fillet between shelf 14 and adjustment members 36, 38.
It will be recognized that the above described invention may be embodied in other specific forms without departing from the spirit or essential characteristics of the disclosure. Thus, it is understood that the invention is not to be limited by the foregoing illustrative details, but rather is to be defined by the appended claims. | A crib for newborns and infants is easily placed in close proximity to the parents' bed without being physically attached thereto. An otherwise conventional crib mattress is retained in a bassinet or similar structure. The bassinet is supported in a frame that partially slides under the parents' bed, thereby allowing the bassinet to extend partially over the top surface of the parents' mattress. | 0 |
BACKGROUND OF THE INVENTION
The present invention broadly relates to dispensing containers and, more specifically, pertains to a new and improved construction of a dispensing container for a highly viscous filler material or package component and to a new and improved construction of an expulsion device for such dispensing container.
Generally speaking, the dispensing container of the present invention comprises: a cartridge containing the highly viscous filler material, the cartridge having a forward end and a rear end and defining a longitudinal direction; the forward end being provided with a dispensing orifice for the highly viscous filler material or package component; the cartridge comprising a longitudinally translatable piston for expelling the highly viscous filler material or package component; an adapter for a conventional pressurized gas container sealingly fastenable to the rear end of the cartridge, the adapter sealingly closing the rear end of the cartridge and defining conjointly with the piston a pressure chamber devoid of the highly viscous filler material or package component; the dispensing container defining a forward direction and the adapter being structured to connect a conventional pressurized gas container with the pressure chamber for generating a pressure cushion or pressure charge active upon the piston for driving the piston in the forward direction.
The expulsion device of the present invention is intended for a dispensing container for a highly viscous filler material or package component. This dispensing container is in the form of a cartridge having a rear end and a piston moveably arranged therein and comprises: an adapter for a conventional pressurized gas container and sealingly fastened to the rear end of the cartridge; the adapter accommodating the conventional pressurized gas container, sealingly closing the rear end of the cartridge and defining conjointly with the piston a pressure chamber devoid of the highly viscous filler material or package component; the expulsion device defining a forward direction and the adapter being structured to connect the conventional pressurized gas container with the pressure chamber for generating a pressure cushion or pressure charge active upon the piston for driving the piston in the forward direction.
Numerous highly viscous or pasty products such as caulking compounds, putties, adhesives and the like are now packaged in cartridges. Standard cartridges are cylindrical containers provided with a usually conically convergent application orifice at their forward end and closed at their other end by a movable piston. For removing the product from the cartridge, the cartridge is inserted into an application device by means of which the piston is either manually or pneumatically pressed forward, thus expelling the product.
The manually operated application devices work in discrete portions and therefore do not permit a uniformly continuous bead or strand of product. Furthermore, the requisite piston rod can be disturbing and the manual pumping can often lead to rapid fatigue.
The pneumatic application devices do not exhibit these disadvantages but are relatively complicated in design and are dependent upon a compressor or the like, so that they remain practically exclusively reserved for professional usage.
A cartridge package is also known, for instance, from the U.S. Pat. No. 3,568,892, granted Mar. 9, 1971, in which the cartridge containing the filler material is clamped in a holder analogous to the situation in the above-mentioned manually operated packages. In contradistinction to the latter, an aerosol pressure container is provided in this package which generates a pressurized gas cushion between the cartridge piston and a support plate of the holder sealingly closing the end of the cartridge. This pressure cushion bears upon the piston and thereby drives out the filler material. The supply of pressure medium from the pressure container into the pressure chamber between the cartridge piston and the support plate is controlled by a trigger mechanism acting upon the pressurized container or its valve.
This known cartridge package is relatively complicated in design for a mass-produced product and furthermore does not permit stopping the dispensing of filler material as long as the pressure cushion is still strong enough to drive the piston forwards in the cartridge.
A further pressurized gas-actuated cartridge package is known, for instance from the U.S. Pat. No. 3,217,932, granted Nov. 16, 1965. In this package, the cartridge is not situated in a holder of its own, but the aerosol pressure container is fastened to the rear end of the cartridge by means of a special adapter. A threaded nipple is provided in the adapter upon which an appropriately formed valve component of the pressure container can be screwed, thereby sealingly connecting the pressurized container to the cartridge and fixing it thereupon, while a pressurized gas cushion simultaneously is formed in the rear end of the cartridge which acts upon the cartridge piston and drives the latter forward as long as a special application valve screwed onto the forward end of the cartridge is open.
In this known cartridge package the control of the dispensing of the product is therefore effected via the application valve and the cartridge is constantly under service pressure. The latter is disadvantageous for various reasons. Furthermore, this known cartridge package is still relatively complicated in design.
Other constructions of dispensing devices are exemplified by U.S. Pat. No. 3,250,443, granted May 10, 1966 and U.S. Pat. No. 3,367,545, granted Feb. 6, 1968.
SUMMARY OF THE INVENTION
Therefore, with the foregoing in mind, it is a primary object of the present invention to provide a new and improved construction of a dispensing container for a highly viscous filler material or package component which does not exhibit the aforementioned drawbacks and shortcomings of the prior art constructions.
Another and more specific object of the present invention aims at providing a new and improved construction of a dispensing container of the previously mentioned type as well as an expulsion device for such a dispensing container which both exhibit an extremely simple and correspondingly economical design, on the one hand, and with which, on the other hand, a manner of operation and function convenient in practice can be attained while avoiding the above-described faults or limitations of the known cartridge packages of this type.
Yet a further significant object of the present invention aims at providing a new and improved construction of a dispensing container and of an expulsion device of the character described which are relatively simple in construction and design, extremely economical to manufacture, highly reliable in operation, not readily subject to breakdown and malfunction and require a minimum of maintenance and servicing.
Now in order to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the dispensing container of the present invention is manifested by the features that: the conventional pressurized gas container is of the type equipped with a recloseable valve; the adapter comprises means for actuating the recloseable valve of the conventional pressurized gas container; a pressure exhaust or venting orifice is provided in the adapter and communicates with the pressure chamber and with ambient air; and the pressure exhaust or venting orifice is arranged such that the pressure exhaust or venting orifice is simply obturatable by a finger of an operator when the dispensing container is in service.
The expulsion device of the present invention is manifested by the features that: the conventional pressurized gas container is of the type equipped with a recloseable valve; the adapter comprises means for actuating the recloseable valve of the conventional pressurized gas container; a pressure exhaust or venting orifice is provided in the adapter and communicates with the pressure chamber and with ambient air; and the pressure exhaust or venting orifice is arranged such that the pressure exhaust or venting orifice is simply obturatable by a finger of an operator when the expulsion device is in service.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above, will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein throughout the various figures of the drawings there have been generally used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 schematically illustrates a longitudinal section through a first embodiment of the invention in a first phase of operation;
FIG. 2 schematically illustrates a longitudinal section through the first embodiment of the invention in a second phase of operation;
FIG. 3 schematically illustrates an analogous representation of a second embodiment in a first phase of operation;
FIG. 4 schematically illustrates an analogous representation of the second embodiment of the invention in a second phase of operation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that to simplify the showing thereof only enough of the structure of the dispensing container and of the expulsion device has been illustrated therein as is needed for one skilled in the art to readily understand the underlying principles and concepts of this invention. Turning now to FIG. 1 of the drawings, the apparatus illustrated therein by way of example and not limitation will be seen to comprise a plastic cartridge K having a dispensing orifice O and a screwed-on application tip S, a piston P moveably arranged and sealingly seated within the cartridge K and an adapter A for a standard aerosol pressure container D. The adapter A is sealingly fastened at the rear end 1 of the cartridge K to this cartridge K which would otherwise remain open. A highly viscous or pasty filler material or package component F to be dispensed is situated in a forward space 2 of the cartridge K between the piston P and the dispensing orifice O. The rear cartridge space situated between the piston P and the attached or inserted adapter A is devoid of filler material and is designated in the following as the pressure chamber 3.
The adapter A has the shape of an H in longitudinal section and comprises a bulkhead or body member 8 and two sleeves 11 and 70 extending therefrom. The sleeve 70 at the left in FIG. 1 surrounds the rear end 1 of the cartridge K. Additionally, an annular groove 18 is provided in the body member 8 for accommodating the outer edge of the cartridge end 1. In this manner the adapter A is firmly and sealingly fastened to the rear end 1 of the cartridge K.
A through conduit or open-ended passage 10 is provided in the body member 8 coaxial to the adapter A. The opening or bore 9 of this open-ended passage 10 remote from the cartridge K is enlarged for accommodating a dispensing tubelet 13 of a dispensing valve 12 of the pressurized gas container D. The latter is situated in the sleeve 11 of the adapter A and is retained in the adapter A only by its dispensing tubelet 13. Its dispensing valve 12 is here constructed as a standard tipping or canting valve, i.e. it can be opened by laterally tipping or canting the dispensing tubelet 13 in relation to the pressurized gas container D. An elastically inwardly pressable hand grip 73 is provided in the retainer sleeve 11 by means of which the pressurized gas container D can be laterally pivoted or rocked in the manner shown in FIG. 2 and its valve 12 thereby opened.
A pressure exhaust or venting conduit or passage 71 branches laterally from the open-ended passage 10 penetrating the body member 8. The pressure exhaust or venting conduit or passage 71 opens into ambient air laterally of the adapter A through a nipple or pressure exhaust or venting orifice 72.
In order to prepare the dispensing container for service, the pressurized gas container D is inserted into the adapter A in accordance with FIG. 1. Then the pressure exhaust or venting passage 71 is obturated with the thumb or another digit and the pressurized gas container D is laterally deflected by means of the hand grip 73 in accordance with FIG. 2. The canting or rocked dispensing valve 12 of the pressurized gas container D is thereby opened and the requisite pressure for driving out or expelling the highly viscous filler material or package component F builds up in the pressure chamber 3 in the cartridge end 1. As soon as this pressure is attained, the hand grip 73 can be released so that the pressurized gas container D returns to its original position visible in FIG. 1 and in which its canting dispensing valve 12 is closed. If the removal of filler material is to be interrupted, the pressure exhaust or venting passage 71, respectively its venting orifice 72, need only be released, i.e. opened to the ambient air. The gauge pressure in the pressure chamber 3 then immediately collapses, as will be evident from FIG. 1.
A particularly compact and extremely simple design and practical embodiment of the invention is shown in FIGS. 3 and 4.
In this embodiment of the invention, the adapter A comprises a relatively stable ring or annular body or annulus 80 and a diaphragm or floor component 81 formed elastically in the annulus 80. The annulus 80 comprises an annular gap 82 and is pressed over the rear end 1 of the cartridge K with a press fit, the cartridge rear end 1 seating in the annular gap 82.
The annulus 80 comprises retention members or tabs 83 protruding somewhat elastically inward or possibly an analogous retention ring or annular ledge in its interior. These retention tabs 83 engage a valve cover 84 of the pressurized gas container D and fasten the pressurized gas container D in the adapter A in this manner. The pressurized gas container D is, in contradistinction to all other embodiments, here inverted with its dispensing valve 12 facing in the direction of the rear end 1 of the cartridge K. Communicating channels 85 are also provided in the annulus 80 which establish a connection between the spaces situated before and behind the valve cover 84 retained by the retention tabs 83.
The diaphragm or floor component 81 is relatively stable in its central region but is relatively elastic and folded at its edge region, so that it is axially elastically inwardly movable. The center of the diaphragm 81 is constructed as a hollow nipple 86 which is provided with a through-pressure or open-ended exhaust or venting orifice 87 and support or bearing ribs 88 for the dispensing tubelet 13 of the dispensing valve 12 of the pressurized gas container D.
The diaphragm 81 is normally situated in the idle position shown in FIG. 4 and in which the support or bearing ribs 88 are lifted from the dispensing tubelet 13 of the dispensing valve 12 or at least exert no axial pressure upon the latter.
To establish the gauge pressure requisite for removing filler material, the pressure exhaust or venting orifice 87 is obturated by a finger and simultaneously the hollow nipple 86 is pressed axially inward according to FIG. 3. The support or bearing ribs 88 come into contact with the dispensing tubelet 13 and also press the latter axially inward until the dispensing valve 12 finally opens. Now the pressurized gas flows between the support or bearing ribs 88 and through the communication channels 85 into the pressure chamber 3 of the cartridge K situated behind the valve cover 84. When the desired operational pressure, which may be about 2.5 bar, is attained, the pressing force upon the hollow nipple 86 is removed but the pressure exhaust or venting orifice 87 is kept obturated. The removal of filler material then continues to proceed. For interrupting the removal of filler material, the finger is simply lifted from the hollow nipple 86, thus freeing the pressure exhaust or venting orifice 87 and depressurizing the pressure chamber 3, according to FIG. 4.
In both of the embodiments illustrated, the adapter A is fastened to the cartridge K by a press fit. Naturally other types of fastening are possible. For instance, the adapter A could also be welded to the cartridge K or connected thereto by a suitable flanging or flaring.
The adapter A forms conjointly with the pressurized gas container D an expulsion device for the filler material or package component F situated in the cartridge K. This expulsion device either can be fastened to the cartridge K during fabrication or can form an independent unit which can then be employed as an exchangeable expulsion device for many cartridges if provided with a suitable type of fastening.
The dispensing container of the invention and the expulsion device of the invention for a piston-type cartridge both unite all advantages of hitherto known devices of this type without simultaneously exhibiting their disadvantages. In particular, a uniform continuous application of the filler material or package component F is assured by this dispensing container and by this expulsion device with a minimum of structural complication. Manipulation is simple and fatigue-free and the dispensing container is always automatically pressure-relieved when not in operation.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. Accordingly, | A conventional pressurized gas container in the form of a standard aerosol container is fastened to a commercially available standard cartridge having a movable piston by means of an adapter. The adapter of the dispensing container contains an actuating member for the valve of the pressurized gas container and a pressure exhaust or venting orifice which is in flow communication with a pressure chamber situated between the piston and the adaptor and such pressure venting orifice is obturatable by the finger of an operator in service. The dispensing container is particularly simple in design and fulfills all practical requirements in service and manipulation. | 1 |
This application claims the benefit of Korean Patent Application No. 10-2005-0105980 filed on Nov. 7, 2005, which is hereby incorporated by reference as if fully set forth herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a red light-emitting phosphorescent compound (hereinafter, referred to simply to as a ‘red phosphorescent compound’) and an organic electroluminescent (EL) device using the same. More particularly, the present invention relates to a red phosphorescent compound, and an organic electroluminescent device comprising a laminate of an anode, a light-emitting layer and a cathode wherein the red phosphorescent compound is used as a dopant of the light-emitting layer.
2. Discussion of the Related Art
With recent trends toward large-area displays, there has been increased demand for flat display devices that take up little space. In particular, technology of organic electroluminescent (EL) devices (also termed ‘organic light emitting diodes (OLEDs)’) as flat display devices has been rapidly developed. A variety of prototypes of organic electroluminescent (EL) devices have been reported to date.
When charge carriers are injected into an organic film formed between an electron injecting electrode (cathode) and a hole injecting electrode (anode) of an organic electroluminescent device, electrons combine with holes to create electron-hole pairs, which then decay to emit light. Organic electroluminescent devices have advantages in that they can be fabricated on flexible transparent substrates (e.g., plastic substrates) and can be operated at a voltage (e.g., 10V or below) lower than voltages required to operate plasma display panels (PDPs) and inorganic electroluminescent devices. Other advantages of organic electroluminescent devices are relatively low power consumption and excellent color representation. Further, since organic electroluminescent (EL) devices can emit light of three colors (i.e., green, blue and red), they have been the focus of intense interest lately as next-generation display devices capable of producing images of various colors. A general method for fabricating organic EL devices will be briefly explained below.
(1) First, a transparent substrate is covered with an anode material. Indium tin oxide (ITO) is generally used as the anode material.
(2) A hole injecting layer (HIL) is formed to a thickness of 10 to 30 nm on the anode. Copper (II) phthalocyanine (CuPc) is mainly used as a material of the hole injecting layer.
(3) A hole transport layer (HTL) is introduced into the resulting structure. The hole transport layer is formed by depositing 4,4′-bis[N-(1-naphthyl)-N-phenylamino]-biphenyl (NPB) to a thickness of about 30 to about 60 nm on the hole injecting layer.
(4) An organic light-emitting layer is formed on the hole transport layer. If necessary, a dopant may be added to a material for the organic light-emitting layer. For green light emission, tris(8-hydroxyquinoline)aluminum (Alq 3 ) as a material for the organic light-emitting layer is deposited to a thickness of about 30 to about 60 nm on the hole transport layer, and N-methylquinacridone (MQD) is mainly used as the dopant.
(5) An electron transport layer (ETL) and an electron injecting layer (EIL) are sequentially formed on the organic light-emitting layer. Alternatively, an electron injecting/transport layer is formed on the organic light-emitting layer. In the case of green light emission, since Alq 3 has excellent electron-transport ability, the formation of the electron injecting/transport layer may be unnecessary.
(6) A cathode material is coated on the electron injecting layer, and finally a passivation film is covered thereon.
The type of the organic electroluminescent devices (i.e. blue, green and red light-emitting devices) will be determined depending on the kind of materials for the light-emitting layer.
In the light-emitting layer, holes injected from the anode are recombined with electrons injected from the cathode to form excitons. Singlet excitons and triplet excitons are involved in the fluorescence and phosphorescence processes, respectively. Fluorescent materials using triplet excitons, which are involved in the phosphorescence process, whose probability of formation is 75%, exhibit high luminescence efficiency, as compared to fluorescent materials using singlet excitons whose probability of formation is 25%. In particular, the luminescence efficiency of red phosphorescent materials is considerably high, compared to that of fluorescent materials. Accordingly, a number of studies associated with the use of red phosphorescent materials in organic electroluminescent devices are being made to enhance the luminescence efficiency of the organic electroluminescent devices.
Phosphorescent materials for use in organic EL devices must satisfy the requirements of high luminescence efficiency, high color purity and long luminescence lifetime. As shown in FIG. 1 , as the color purity of an organic EL device using a red phosphorescent material becomes higher (i.e. as the x-values on CIE chromaticity coordinates increase), the spectral luminous efficacy of the organic EL device decreases, making it difficult to achieve high luminescence efficiency of the organic EL device.
Thus, there is a demand to develop a red phosphorescent compound that exhibit desirable chromaticity coordinate characteristics (CIE color purity X≧0.65), high luminescence efficiency, and long luminescence lifetime.
SUMMARY OF THE INVENTION
Accordingly, the present invention is directed to a red phosphorescent compound and an organic electroluminescent (EL) device using the same that substantially obviate one or more problems due to limitations and disadvantages of the related art.
An object of the present invention is to provide a compound of Formula 1 that follows.
Another object of the present invention is to provide an organic electroluminescent (EL) device with high color purity, high luminance and long lifetime which uses one of the compounds as a dopant of a light-emitting layer.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
To achieve these objects and other advantages and in accordance with the purpose of the invention, as embodied and broadly described herein, there is provided a red phosphorescent compound of Formula 1:
wherein
is
R1 is a C 1 -C 4 alkoxy group; R2, R3, R4 and R5 are independently selected from hydrogen, C 1 -C 4 alkyl groups and C 1 -C 4 alkoxy groups; and
is selected from 2,4-pentanedione
2,2,6,6-tetramethylheptane-3,5-dione
1,3-propanedione
1,3-butanedione
3,5-heptanedione
1,1,1-trifluoro-2,4-pentanedione
1,1,1,5,5,5-hexafluoro-2,4-pentanedione
and 2,2-dimethyl-3,5-hexanedione
wherein
is
R1 is a C 1 -C 4 alkoxy group; R2, R3, R4 and R5 are independently selected from hydrogen, C 1 -C 4 alkyl groups and C 1 -C 4 alkoxy groups; and
is selected from 2,4-pentanedione
2,2,6,6-tetramethylheptane-3,5-dione
1,3-propanedione
1,3-butanedione
3,5-heptanedione
1,1,1-trifluoro-2,4-pentanedione
1,1,1,5,5,5-hexafluoro-2,4-pentanedione
and 2,2-dimethyl-3,5-hexanedione
Examples of preferred compounds that can be represented by Formula 1 include the following compounds:
In yet another aspect of the present invention, there is provided an organic electroluminescent (EL) device comprising an anode, a hole injecting layer (HIL), a hole transport layer (HTL), an light-emitting layer, an electron transport layer (ETL) and an electron injecting layer (EIL), and a cathode laminated in this order wherein the red phosphorescent compound of Formula 1 is used as a dopant of the light-emitting layer.
A host used in the light-emitting layer of the organic EL device according to the present invention may be selected from Al complexes, Zn complexes, and carbazole derivatives. The dopant may be preferably used in an amount of 0.5 to 20% by weight, based on the weight of the host. When the dopant is used within this range, the desired effects of the organic EL device can be achieved. The Al and Zn complexes may have at least one ligand selected from quinolyl, biphenyl, isoquinolyl, phenyl, naphthyl, methylquinolyl, dimethylquinolyl and dimethylisoquinolyl groups. The carbazole derivatives may be preferably 4,4′-N,N′ dicarbazole biphenyl (CBP).
It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the principle of the invention. In the drawings:
FIG. 1 shows a graph showing a phenomenon wherein the color purity of an organic EL device becomes higher (i.e. as the x-values on CIE chromaticity coordinates increase), the relative sensitivity of the organic EL device decreases; and
FIG. 2 shows the structural formulas of NPB, copper (II) phthalocyanine (CuPc), (btp) 2 Ir(acac), Alq 3 , BAlq and CBP used in Example Section according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Reference will now be made in detail to the preferred embodiments of the present invention associated with a red phosphorescent compound and an organic electroluminescent (EL) device using the red phosphorescent compound according to the present invention, examples of which are illustrated in the annexed drawings.
Hereinafter, a method for synthesizing iridium (III) (2-(3-methylphenyl)-6-methoxyquinolinato-N,C 2′ )(2,4-pentanedionate-O,O) (“A-2”), which is a red phosphorescent compound represented by Formula 1, for use in an organic electroluminescent device.
SYNTHESIS EXAMPLES
1. Synthesis of 2-(3-methylphenyl)-6-methoxyquinoline
3-Methylphenyl borate (1.3 mmol), 2-chloro-6-methoxyquinoline (1 mmol), tetrakis(triphenylphosphine) palladium(O) (0.05 mmol) and potassium carbonate (3 mmol) were dissolved in THF (30 mL) and H 2 O (10 mL). The resulting solution was stirred in a bath at 100° C. for 24 hours. After completion of the reaction, the solvents were removed. The reaction mixture was extracted with dichloromethane and water and distilled under reduced pressure. The resulting residue was purified by silica gel column chromatography. The eluate was distilled under reduced pressure. The residue was recrystallized from dichloromethane and petroleum ether, and filtered to yield 2-(3-methylphenyl)-6-methoxyquinoline as a solid.
2. Synthesis of Dichloro-Crosslinked Dimer Complex
Iridium (III) chloride hydrate (1 mmol), the 2-(3-methylphenyl)-6-methoxyquinoline (2.5 mmol) and a mixed solvent (30 mL) of 2-ethoxyethanol and distilled water (3:1 (v/v) were put in a dried two-neck round-bottom flask. After the mixture was refluxed for 24 hours, water was added thereto to obtain a solid. The solid was filtered and washed with methanol and petroleum ether to yield the dichloro-crosslinked dimer complex.
3. Synthesis of iridium (III) (2-(3-methylphenyl)-6-methoxyquinolinato-N,C 2′ )(2,4-pentanedionate-O,O)
The dichloro-crosslinked dimer complex (1 mmol), 2,4-pentanedione (3 mmol), sodium carbonate (Na 2 CO 3 ) (6 mmol) and 2-ethoxyethanol (30 mL) were put in a dried two-neck round-bottom flask. Then, the mixture was refluxed for 24 hours. The reaction mixture was allowed to cool to room temperature, and then distilled water was added thereto to obtain a solid. The solid was filtered and dissolved in dichloromethane. The solution was filtered through silica gel. The solvent was distilled off under reduced pressure and the resulting residue was washed with methanol and petroleum ether to yield iridium (III) (2-(3-methylphenyl)-6-methoxyquinolinato-N,C 2′ )(2,4-pentanedionate-O,O).
Hereinafter, a detailed description will be made of preferred examples of the present invention. The invention is not to be construed as being limited to the examples.
EXAMPLES
Example 1
An ITO-coated glass substrate was patterned to have a light-emitting area of 3 mm×3 mm, followed by cleaning. After the patterned substrate was disposed in a vacuum chamber, the standard pressure of the chamber was adjusted to 1×10 −6 torr. CuPc (200 Å), NPD (400 Å), BAlq+A-2 (7%) (200 Å), Alq 3 (300 Å), LiF (5 Å) and Al (1000 Å) were sequentially deposited on the ITO glass substrate to fabricate an organic EL device.
The luminance of the organic EL device was 1,052 cd/m 2 at an electric current of 0.9 mA and a voltage of 6.5 V. At this time, the CIE chromaticity coordinates were x=0.648 and y=0.349. The lifetime (defined as the time taken before the luminance of the organic EL device decreases to half its initial value) of the organic EL device was 4,300 hours at 2,000 cd/m 2 .
Example 2
An ITO-coated glass substrate was patterned to have a light-emitting area of 3 mm×3 mm, followed by cleaning. After the patterned substrate was disposed in a vacuum chamber, the standard pressure of the chamber was adjusted to 1×10 −6 torr. CuPc (200 Å), NPD (400 Å), BAlq+A-6 (7%) (200 Å), Alq 3 (300 Å), LiF (5 Å) and Al (1000 Å) were sequentially deposited on the ITO glass substrate to fabricate an organic EL device.
The luminance of the organic EL device was 1,095 cd/m 2 at an electric current of 0.9 mA and a voltage of 6.2 V. At this time, the CIE chromaticity coordinates were x=0.651 and y=0.337. The lifetime (defined as the time taken before the luminance of the organic EL device decreases to half its initial value) of the organic EL device was 4,500 hours at 2,000 cd/M 2 .
Example 3
An ITO-coated glass substrate was patterned to have a light-emitting area of 3 mm×3 mm, followed by cleaning. After the patterned substrate was disposed in a vacuum chamber, the standard pressure of the chamber was adjusted to 1×10 −6 torr. CuPc (200 Å), NPD (400 Å), BAlq+A-7 (7%) (200 Å), Alq 3 (300 Å), LiF (5 Å) and Al (1000 Å) were sequentially deposited on the ITO glass substrate to fabricate an organic EL device.
The luminance of the organic EL device was 938 cd/m 2 at an electric current of 0.9 mA and a voltage of 5.3 V. At this time, the CIE chromaticity coordinates were x=0.652 and y=0.344. The lifetime (defined as the time taken before the luminance of the organic EL device decreases to half its initial value) of the organic EL device was 4,200 hours at 2,000 cd/M 2 .
Comparative Example 1
An ITO-coated glass substrate was patterned to have a light-emitting area of 3 mm×3 mm, followed by cleaning. The patterned substrate was disposed in a vacuum chamber. Then, the standard pressure of the chamber was adjusted to 1×10 −6 torr. CuPc (200 Å), NPD (400 Å), BAlq+(btp) 2 Ir(acac) (7%) (200 Å), Alq 3 (300 Å), LiF (5 Å) and Al (1000 Å) were sequentially deposited on the ITO glass substrate to manufacture an organic EL device.
The luminance of the organic EL device was 780 cd/m 2 at an electric current of 0.9 mA and a voltage of 7.5 V. At this time, the CIE chromaticity coordinates were x=0.659 and y=0.329. The lifetime (defined as the time taken before the luminance of the organic EL device decreases to half its initial value) of the organic EL device was 2,500 hours at 2,000 cd/m 2 .
The organic EL devices fabricated in Examples 1 to 5 and Comparative Example 1 were evaluated for efficiency, CIE chromaticity coordinates, luminance and lifetime characteristics. The results are shown in Table 1.
TABLE 1
Electric
Current
Power
Life time (h)
Voltage
current
Luminance
efficiency
efficiency
CIE
CIE
(half the initial
Device
(V)
(mA)
(cd/m 2 )
(cd/A)
(lm/W)
(X)
(Y)
luminance)
Ex. 1
5.6
0.9
1,358
13.58
7.61
0.648
0.349
4,300
Ex. 2
5.7
0.9
1,423
14.23
7.84
0.651
0.337
4,500
Ex. 3
6.1
0.9
1,501
15.01
7.73
0.652
0.342
4,200
Comp.
7.5
0.9
780
7.8
3.3
0.659
0.329
2,500
Ex. 1 | Disclosed herein is a red phosphorescent compound of the following Formula 1:
wherein
is includes a phenyl part and a quinoline part, the quinoline part has one substituent selected from a C 1 -C 4 alkoxy group and the phenyl part has substituents independently selected from hydrogen, C 1 -C 4 alkyl groups and C 1 -C 4 alkoxy groups, and
is selected from 2,4-pentanedione, 2,2,6,6-tetramethylheptane-3,5-dione, 1,3-propanedione, 1,3-butanedione, 3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, and 2,2-dimethyl-3,5-hexanedione. | 2 |
FIELD
[0001] The present invention is related to the field of medical devices. More particularly, the present invention is related to catheters and other elongate medical devices incorporating guidewire lumens.
BACKGROUND
[0002] The use of catheters for minimally invasive medical procedures has become widespread. In many such procedures, a guidewire is used to help place the distal end of a catheter at a desired location. In practice, the use of a guidewire and an elongate medical device such as a catheter can create a number of difficulties.
[0003] If a guidewire or catheter proves unsuitable once inserted into a patient, it is removed and replaced. With early technologies, the catheter typically tracked over the guidewire along its entire length. When a catheter was removed, these early technologies required allowing the entire length of the catheter (typically 150 cm or longer) to pass over the guidewire without releasing the proximal end of the guidewire. This required a guidewire having a length of at least 300 cm, or a shorter guidewire used in combination with a guidewire extension. Such long guidewires required extra hands in the operating arena, increasing costs and creating a greater risk of loss of sterility, as well as making procedures last longer.
[0004] Rapid exchange catheters and single operator exchange catheters have been developed to make it easier and quicker to substitute one catheter or guidewire for another. An example single operator exchange catheter is the Autotome™ RX sphincterotome, marketed by Boston Scientific Corporation, Natick, Mass., which makes use of an elongated guidewire lumen in the form of a C-shaped channel.
[0005] The C-shaped channel allows lateral movement of a guidewire out of the guidewire lumen through the opening in the C-shaped channel over the longitudinal length of the channel. Such an opening, as well as openings or accesses created by the use of C-shaped, U-shaped, perforated or slit guidewire lumens, makes the longitudinally extending guidewire lumen a laterally accessible guidewire lumen. Lumens having a weakened, thin, or thinned wall through which a guidewire may tear for removal may also be considered as including a laterally accessible guidewire lumen.
SUMMARY
[0006] The present invention, in an illustrative embodiment, includes a guidewire exit ramp member that may be placed over a tubular member having a longitudinally extending guidewire lumen that is laterally accessible generally continuously over at least a portion of the length of the tubular member. The guidewire exit ramp member can be placed to force a guidewire passing into the guidewire lumen in a first direction to be forced out of the lumen via an opening, slit or channel. The guidewire exit ramp member, in an illustrative embodiment, takes the form of a ramp member having a proximal portion and a distally extending flap. The flap may be designed to enter and remain in a longitudinally extending laterally accessible guidewire lumen.
[0007] Another illustrative embodiment includes a method of providing a guidewire exit location for an elongate medical device. A guidewire exit ramp member is placed on an elongate member having a longitudinally extending guidewire lumen with a slit or opening therein over a certain length. The elongate member may include a skive or other opening into the guidewire lumen. The guidewire exit ramp member is placed near the skived portion or opening and slid in a direction such that a flap of the guidewire exit ramp member goes through the skive into the guidewire lumen. In some embodiments, the guidewire exit ramp member may be secured in place by heat bonding, adhesive, or the other attachment methods. When the method is complete, a guidewire passed through the guidewire lumen in a first direction is forced out of the guidewire lumen by the flap of the guidewire exit ramp member. In a further embodiment, the flap is flexible enough such that, when a guidewire is passed through the guidewire lumen in a second direction, the guidewire readily passes by the flap with little or no added resistance.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1A is a partial elevational view of a medical device shaft having a longitudinally extending laterally accessible guidewire lumen;
[0009] FIG. 1B is a cross-sectional view along line 1 B- 1 B of FIG. 1A ;
[0010] FIG. 2 is a plan view of a cannula including a longitudinally extending laterally accessible guidewire lumen;
[0011] FIG. 3 is a perspective view of a guidewire exit ramp member for use in conjunction with a medical device shaft having a longitudinally extending laterally accessible guidewire lumen;
[0012] FIG. 4 is an elevation view of the illustrative guidewire exit ramp member of FIG. 3 showing the flap;
[0013] FIG. 5 is a side view of the illustrative guidewire exit ramp member of FIG. 3 ;
[0014] FIG. 6 is an end view from a distal location of the illustrative guidewire exit ramp member of FIG. 3 ;
[0015] FIG. 7 is an elevation view of an alternative example guidewire exit ramp with a curved flap;
[0016] FIG. 8A is an elevation view of an illustrative guidewire exit ramp coupled with a medical device shaft having a longitudinally extending laterally accessible guidewire lumen;
[0017] FIG. 8B is a section view along line 8 B- 8 B of FIG. 8A ;
[0018] FIGS. 9A-9C are section views along lines 9 A- 9 A, 9 B- 9 B, and 9 C- 9 C of FIG. 8A ;
[0019] FIGS. 10A-10C , 11 A- 11 C, and 12 A- 12 C illustrate placement of a guidewire exit ramp on another medical device shaft having a closed longitudinally extending laterally accessible guidewire lumen;
[0020] FIGS. 13A-13C illustrate in elevation and section views an alternative embodiment using a relatively stiff plastic guidewire exit ramp member; and
[0021] FIGS. 14A-14C illustrate placement of the embodiment of FIGS. 13A-13B on an elongate medical device shaft.
DETAILED DESCRIPTION
[0022] The following detailed description should be read with reference to the drawings. The drawings, which are not necessarily to scale, depict illustrative embodiments and are not intended to limit the scope of the invention.
[0023] FIG. 1A is a partial elevational view of a medical device shaft having a longitudinally extending laterally accessible guidewire lumen. The shaft 10 includes a channel 12 for laterally accessing a guidewire lumen passing therethrough. FIG. 1B is a cross-sectional view along line 1 B- 1 B of FIG. 1A . As illustrated by FIG. 1B , the guidewire lumen 14 includes the channel 12 . Two auxiliary lumens 16 , 18 are also illustrated. While a triple lumen shaft 10 is illustrated, any number of lumens, from a single lumen up to 3, 4, or more lumens, may be provided in a shaft for use with the present invention.
[0024] The channel 12 is illustrated for providing access to a generally U-shaped guidewire lumen. Instead of a U-shape, a C-shaped opening may be provided, the C-shape helping to retain a guidewire in the lumen 14 . Additionally, a slit may be used. Alternatively, instead of an channel 12 creating an opening, a wall for the lumen 14 where the channel is shown may be thin or intentionally thinned to enable a guidewire to be torn therethrough. Perforations may also be provided to make the longitudinally extending guidewire lumen 14 laterally accessible. Laterally accessible, as used herein, refers to a guidewire lumen that can be accessed along a length thereof, where access can be had either through an existing opening or by tearing a guidewire disposed in the guidewire lumen laterally through a slit, thin, thinned, perforated, or otherwise relatively weak lumen wall section.
[0025] FIG. 2 is a plan view of a cannula including a longitudinally extending laterally accessible guidewire lumen. The cannula 20 may incorporate a shaft 10 as illustrated in FIGS. 1A and 1B having a distal end 22 and a proximal end 24 . A slit 26 extends along a length of the shaft toward the distal end 22 ; while not shown, the slit 26 may extend proximally to a guidewire entry adaptor 28 . The example also illustrates marker bands near the distal end. Proximal of the adaptor 28 is a manifold 30 including two fluid infusion ports. The cannula in FIG. 2 may have a similar cross section to that shown in FIG. 1B , except to the extent that a slit 26 is used instead of a U-shaped opening. The fluid infusion ports on the manifold 30 may be coupled to the auxiliary lumens of the cannula shaft for infusing fluids to a location at or near the distal end 22 .
[0026] The adaptor 28 shown functions by having a side-directed ramp/lumen with an opening allowing for lateral removal of a guidewire therefrom. The proximal end of the guidewire is controlled proximal of the adaptor 28 such that there is no need to force a backloaded guidewire from the guidewire lumen. The guidewire can be removed through the slit 26 once the exchange procedure starts. However, the exact location where the guidewire exits the slit 26 is not controlled. In particular, if a guidewire is backloaded into such a rapid exchange catheter, the adaptor 28 does not force the guidewire out of the catheter.
[0027] An example and description of such an adaptor 28 is given by Windheuser et al., in U.S. Pat. No. 6,606,515, the disclosure of which is incorporated herein by reference. The adaptor 28 has a relatively large profile in order to achieve ease of guidewire entry through a funnel-shaped portion, as further discussed by Windheuser et al., and is designed to prevent passage of the entire adaptor through a side port in an endoscope. Such sizing would also typically prevent passage through a guide catheter used in a vascular procedure.
[0028] During a catheter exchange procedure, with the guidewire already in place at a desired location in the patient (i.e., a vascular location, a location in the biliary tract, or any other cannulated location), the guidewire will extend through the guidewire lumen from the adaptor 28 to the distal end 22 . To exchange the cannula 20 , the guidewire is moved laterally out of the adaptor 28 and held in place as the cannula 20 is withdrawn. As the cannula 20 is withdrawn, the guidewire passes through the slit 26 , remaining in its internal location in the patient without requiring a guidewire extension. The slit 26 may extend to the distal end 22 , or may stop proximal of the distal end.
[0029] FIG. 3 is a perspective view of a guidewire exit ramp member for use in conjunction with a medical device shaft having a longitudinally extending laterally accessible guidewire lumen. The illustrative example guidewire exit ramp member includes a proximal portion 50 , a flap 52 , and a distal section 54 . The proximal portion 50 surrounds and/or tracks over an elongate medical device on which the guidewire exit ramp member is used. The shape is shown as cylindrical but may instead be oval, polygonal, or other shapes including polygons with one or more curved sides.
[0030] In other illustrative examples, the proximal portion 50 may only partly surround an elongate medical device, and may instead take the form of a partial cylinder, or may have one or more gaps. In several embodiments, the form illustrated in FIG. 3 is used for its low profile, allowing the guidewire exit ramp member to be readily placed and used even in situations where low profile is a concern.
[0031] FIG. 4 is an elevation view of the illustrative guidewire exit ramp member of FIG. 3 showing the flap 52 more clearly. As can be seen, the example flap 52 has rather angular distal ends, extending distally relative to, but shorter than, the distal section 54 . In other embodiments the flap 52 may be longer than the distal section 54 , and, in one embodiment, the distal section 54 may be entirely omitted. For some embodiments, the flap 52 will be inserted through a transversely cut opening in an elongate medical device, as further explained below. For such embodiments, the inclusion of the distal section 54 may help maintain the shape, pushability, and/or anti-kinking characteristics of the elongate medical device across the transverse cut since the transverse cut may weaken the elongate medical device.
[0032] FIG. 5 is a side view of the illustrative guidewire exit ramp member of FIG. 3 . The distal portion 54 has a reduced profile due to the flap 52 . FIG. 6 is an end view of the illustrative guidewire exit ramp member of FIG. 3 . The flap 52 is shown extending down into the lumen defined by the distal portion 54 , which is in line with the lumen formed in the proximal portion 50 . In an illustrative embodiment, the flap 52 is biased to bend down as illustrated by FIGS. 3 and 5 - 6 .
[0033] In one embodiment, the guidewire exit ramp member shown in FIGS. 3-6 is formed by a molding process. In other embodiments, the guidewire exit ramp member may be formed by cutting a tubular member. The ramp member may be sized to correspond to a given size of elongate medical device shaft. For example, given a 6-French elongate medical device shaft, the inner diameter defined by the proximal portion of the ramp member may be just large enough to slide over such a device shaft. The inner surface of the ramp member may include a lubricious coating to allow easy movement and placement over the device shaft. Alternatively, the material chosen for making the ramp member may be chosen for its lubricious properties.
[0034] The ramp member may be formed of a wide variety of materials. In some embodiments the ramp member is formed of a nylon material, which is inexpensive and easy to mold, as well as being a popular material for medical applications. Polycarbonate may also be used, as well as any of a wide variety of polymers, copolymers and metals or alloys known for use in medical devices, catheters, cannulas, endoscopes, and the like. Any other suitable biocompatible material may also be used and/or incorporated.
[0035] FIG. 7 is an elevation view of an alternative example guidewire exit ramp member with a curved flap. As illustrated, the guidewire exit ramp member includes a proximal portion 60 , a flap 62 , and a (optional) distal portion 64 . As shown at 66 , the flap 62 has curved ends, which may allow the flap 62 to extend into and generally match the contours of a guidewire lumen having curved interior contours. Rather than a simple curve as shown, the flap 62 may be designed to match a particular guidewire lumen shape/cross section.
[0036] FIG. 8A is an elevation view of an illustrative guidewire exit ramp coupled with a medical device shaft having a longitudinally extending laterally accessible guidewire lumen. A device shaft 100 is shown with a guidewire exit ramp member 102 placed thereover. The ramp member 102 includes a flap 104 that is aligned with and enters a channel 106 (shown as a U-shaped channel for the purposes of illustration). The longitudinal cross section of FIG. 8B illustrates that the ramp member 102 has a proximal portion that surrounds the device shaft 100 , with the flap 104 extending down into the channel 106 .
[0037] The transverse section views of FIGS. 9A-9C illustrate that the device shaft 100 is shown having the channel 106 as well as auxiliary lumens 108 and 110 . As shown in FIG. 9B , along line 9 B- 9 B in FIG. 8A , the flap 104 extends partly into the channel 106 , with the optional distal portion of the ramp member 102 extending around the device shaft 100 at that location. FIG. 9C is taken at a more distal location along the device shaft 100 and ramp member 102 , as shown by line 9 C- 9 C of FIG. 8A . By this point, the flap 104 extends down to the base of the channel 106 . If a guidewire is backloaded into the channel 106 , the flap 104 will force the guidewire out of the channel 106 . However, if a guidewire is passed distally from a more proximal location, as can be seen in FIG. 8B , the slant of the flap 104 will allow the flap 104 to deflect so that the guidewire may pass with little resistance generated by the flap 104 .
[0038] FIGS. 10A-10C , 11 A- 11 C, and 12 A- 12 C illustrate placement of a guidewire exit ramp on another medical device shaft having a closed longitudinally extending laterally accessible guidewire lumen. Referring to FIGS. 10A-10C , a guidewire exit ramp member 200 having a flap 202 is shown placed on a device shaft 204 , the device shaft 204 having an opening shown as skive 206 . The ramp member 200 is shown some distance proximal of the skive 206 on the device shaft 204 .
[0039] As highlighted in FIG. 10B , (a section view along line 10 B- 10 B of FIG. 10A ) the device shaft 204 includes a guidewire lumen 208 having a thinned wall 210 , as well as an additional auxiliary lumen 212 . The thinned wall 210 enables a guidewire to laterally exit the guidewire lumen 208 by tearing through the thinned wall 210 . To further weaken the wall, perforations may be provided. The thinned wall 210 may be provided during extrusion or by post-extrusion machining. The longitudinal cross section of FIG. 10C illustrates the skive opening into the guidewire lumen 208 .
[0040] Turning to FIGS. 11A-11C , FIG. 11A shows that the ramp member 200 has been advanced such that the flap 202 partly enters the skive 206 in the device shaft 204 . FIG. 11B shows in transverse cross section that the flap 202 reaches partly down into the guidewire lumen 208 through the skive 206 . As shown by FIG. 11C , the skive 206 enables easy entry of the flap 202 down into the guidewire lumen 208 through the thin wall 210 . In some embodiments, the flap 202 may be biased downward such that it readily extends through the skive 206 . It should be noted that the thinned wall 210 would not be necessary to use the guidewire ramp member 200 in the fashion shown, since the flap 202 simply enters through an opening into the guidewire lumen 208 .
[0041] Referring now to FIGS. 12A-12C , the ramp member 200 is moved distally along the device shaft 204 until the flap 202 completely enters the guidewire lumen 208 through the skive 206 . Once this location is reached, the flap 202 may rest against an interior wall of the guidewire lumen 208 . When so located, a guidewire proximal end passing in a proximal direction through the guidewire lumen 208 may be forced laterally out of the device shaft 204 by the flap 202 . Thus backloading of a guidewire into the device shaft 204 can be performed easily with an assurance that a guidewire will exit the device shaft 204 at a desired location defined by the skive 206 and the ramp member 200 . In various illustrative embodiments, the ramp member 200 may be moveable with respect to the shaft or secured (by adhesive or welding, for example) to the device shaft 204 once placed as shown in FIG. 12A .
[0042] FIGS. 13A-13C illustrate in elevation and section views of an alternative embodiment making use of a pinch or squeeze type of ramp. As can be seen, the ramp member 300 includes a proximal portion 302 and a pinching portion 304 . The pinching portion 304 may be sized to reduce the internal diameter or cross-sectional area of the ramp member sufficient to collapse a portion of a guidewire lumen. In one embodiment, the reduced diameter/area is sized to prevent pinching of any auxiliary lumens of an associated medical device, though some compression may be acceptable. It should be noted that the pinching portion need not be cylindrical and may take on a variety of shapes adapted for use with various catheter shafts. As shown in FIG. 13C , the transverse section of the pinching portion 304 is shaped to receive a catheter shaft without pinching any auxiliary lumens, instead being shaped to compress only the guidewire lumen. The dashed lines of FIG. 13C represent, in phantom, the locations of a guidewire lumen and two auxiliary lumens for a catheter shaft received and pinched by the ramp member 300 . It can be seen that two of the lumens (the auxiliary lumens) would not be significantly blocked.
[0043] FIGS. 14A-14C illustrate placement of the embodiment of FIGS. 13A-13B on an elongate medical device shaft. As shown in FIG. 14A , the elongate medical device shaft 310 is provided with a transverse cut 312 that may take the form of a skive or slit. If desired, the shaft 310 may include a guidewire lumen having a thinned or weakened wall. As shown in FIG. 14B , the ramp member 300 is slid onto the shaft 310 until the ramp member 300 engages the transverse cut 312 . At the location of the transverse cut 312 , the shaft 310 will be inherently weaker due to the transverse cut 312 across a portion of the wall of the guidewire lumen. Turning to FIG. 14C , it can be seen that the ramp 304 of the ramp member 300 collapses a portion of the wall of the guidewire lumen 314 , but the auxiliary lumen 316 is not significantly affected. The proximal portion 302 aids in letting the ramp 306 collapse the wall of the guidewire lumen 314 . A guidewire backloaded into the shaft 310 will now be forced out of the guidewire lumen 314 at the ramp 304 . Any suitable plastics may be used for the shaft 310 and the ramp member 300 . For the alternative embodiments of FIGS. 13A-13B and 14 A- 14 C, the ramp member 300 may be formed of a stiffer material than the material used to define the guidewire lumen 314 . To preserve the patency of the auxiliary lumen 316 , some embodiments may make use of a reinforcing member to support the auxiliary lumen 316 .
[0044] Those skilled in the art will recognize that the present invention may be manifested in a variety of forms other than the specific embodiments described and contemplated herein. Accordingly, departures in form and detail may be made without departing from the scope and spirit of the present invention as described in the appended claims. | Guidewire exit ramp members that may be placed over a tubular member having a guidewire lumen, which longitudinally extending and laterally accessible, and methods of use. The guidewire exit ramp member can be placed to force a guidewire loaded through the lumen in a first direction to be forced out of the lumen via an opening, slit or channel. The guidewire exit ramp member, in an illustrative embodiment, takes the form of a relatively short member having a proximal portion and a distally extending flap. The flap may be designed to enter and remain in a longitudinally accessible guidewire lumen. Combinations of such ramp members and device shafts having longitudinally extending laterally accessible guidewire lumens are also disclosed, as are methods for securing such combinations together. A method of backloading a guidewire into a catheter while causing lateral exit of the guidewire at a desired location is also shown. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the priority date of the provisional application entitled “Sailboat Rudder” filed by Joel F. Santarone on Nov. 3, 2006 with application Ser. No. 60/856,418.
FIELD OF THE INVENTION
The present invention relates generally to rudder and steering systems for water-born vessels and more particularly to rudder systems for sailboats, wherein the rudder is capable of being raised to a stowed position or lowered to a steering position as required. The preferred embodiment relates to transom-mounted (externally mounted), sailboat “kick-up” rudders that allow upward pivoting of a rudder upon grounding, to help protect the rudder and boat from damage.
BACKGROUND OF THE INVENTION
Sailing technology has existed for millennia and there are numerous variations on sailboat rudders. More specifically, there exist numerous sailboat rudders that are retractable in nature.
Retractable rudders are useful for passing a boat through shallow water in order to prevent the rudder from running aground and being damaged. Alternatively, if a rudder is retractable and it accidentally strikes a surface under water, the rudder may release upward from the downward position so that it is not damaged. Retractable rudders also enable the operator of the craft to lift the rudder from under the stern in order to place the boat on a trailer.
Often the design of such retractable rudders requires that the rudder be attached to a rope or other retraction means for manually retracting the rudder. In order to retract the rudder, the rope must be pulled and the rudder lifted from the water. This type of design is problematic for a number of reasons. The first reason being that the rudders are usually heavy and require significant strength and attention from the operator or crew of the sailboat to retract the rudder. Retracting the rudder may distract the operator or crew of the boat from other important duties or events occurring in the craft. A second reason that a conventional retractable rudder is problematic is that once the rudder is retracted it must be tied off or cleated so that it remains in the retracted position and does not drop back into the water. Cleating a retractable rudder takes additional time, effort, and attention of the operator or crew of the boat. Additionally, if a rudder is cleated and an urgent need for control of the craft arises, it takes a significant amount of time and effort to release the rudder back into the water. Due to the often rapid pace of events in a moving sailboat, any time saved may be crucial in preventing catastrophic errors.
Other retractable rudders that are known to the art are designed so if the sailboat runs into shallow water or the rudder strikes an underwater object, the rudder will kick up. However, this design may be problematic if the rudder is held by a friction mounting. A friction mounting allows a rudder that strikes an underwater object to yield to the underwater object, but the rudder will remain in a displaced or elevated position above or near the surface of the water. In order to move the rudder back into the water, an operator or crew member on the sailboat must manually push the rudder back into the water. This takes time and strength that may be needed in the craft. Additionally, if the rudder is stuck in an elevated position above or at the surface of the water the sailboat will have little or no control. A second problem may arise if the rudder is extended to the rearward from the transom or stern of the craft. In such a case, an increased amount of force is placed on the rudder mounting and the tiller arm when the rudder is in this position. If the rudder strikes an object or control of the boat is attempted with the rudder extended horizontally on the surface of the water, the force exerted on the rudder mounting may be great enough to tear the mounting from the transom of the sailboat or cause the tiller arm to fracture. Either of these events may cause catastrophic consequences because of loss of control of the sailboat.
SUMMARY OF THE INVENTION
The present invention relates generally to rudder systems used to steer water-born vessels, and more specifically, to rudder systems used on sailboats.
The preferred rudder system is designed to be pivotally mounted upon the transom of a vessel and provides a mechanism wherein the rudder may be raised to a secured position or lowered to an employed “steering” position as desired by the boater. The rudder may pivot greater than 90 degrees, and preferably approximately 180 degrees, between the steering position and secured position. The invented mechanism for raising and lowering the rudder may be called a “one-pull” system. A single pull of an uphaul line, such as a cord or cable, may be effective in raising the rudder to the secured position, and a single pull of the same uphaul line may be effective in lowering the rudder to the steering position. A pneumatic/gas cylinder or “strut” may be used to dampen the rudder movement between the steering and secured positions, may assist in raising and lowering the rudder, and may help retain the rudder in the desired position once the rudder has been raised or lowered.
The aforementioned rudder system is preferably constructed of suitably strong, lightweight, corrosion resistant, waterproof materials such as, but not limited to, plastics (polymers), stainless steel and aluminum. The preferred gas cylinder has a stainless steel housing.
The preferred embodiment is comprised of a generally vertical member, said member containing appropriate mounting bearings and fasteners for attachment to the vessel. Upon the lower end of the vertical member, a pivotal mounting structure is provided, wherein the rudder is installed. Protruding forwardly from and perpendicular to the upper end of the vertical member, a tiller bar is provided to rotate the vertical member and rudder to accomplish steering of the vessel. In alternative embodiments, the rudder system may be operatively connected to a steering wheel rather than a tiller bar.
To facilitate movement of the rudder from a secured, upright position to a lowered, “employed” or “steering” position, a cable and pulley system and gas cylinder are provided in the preferred embodiment wherein the boater may accomplish the desired movement using just one pull (for each of the lowering and the raising functions) and preferably just one hand. When the rudder is in the lowered, steering position, should the rudder inadvertently strike an underwater object, the aforementioned system allows rotational movement of the rudder sufficient to clear said underwater object, thereby preventing damage to the rudder, the preferred gas cylinder system provides a bias that returns the rudder to the employed position when the rudder is free from the underwater object.
The purpose of the foregoing Abstract is to enable the public, and especially the scientists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection, the nature and essence of the technical disclosure of the application. The Abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
Still other features and advantages of the present invention will become readily apparent to those skilled in this art from the following detailed description describing preferred embodiments of the invention, simply by way of illustration of the best mode contemplated by carrying out my invention. As will be realized, the invention is capable of modification in various obvious respects all without departing from the invention. Accordingly, the drawings and description of the preferred embodiments are to be regarded as illustrative in nature, and not as restrictive in nature.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation view of one embodiment of the invented rudder system installed on a sailboat, showing in dot-dash lines the rudder pivoting between the raised (“secured” or “up”) position and the lowered (“employed,” “steering,” or “down”) position, according to one embodiment of the present invention.
FIG. 2 is a partial top plan view of the embodiment of FIG. 1 , viewed along line 2 - 2 in FIG. 1 .
FIG. 3 is a partial side elevation view of the embodiment of FIGS. 1 and 2 , illustrating the rudder in the raised position and illustrating, in more detail, one embodiment of the invented “one-pull” system.
FIG. 4 is a partial side elevation view of the embodiment of FIGS. 1-3 , illustrating the position of the components of the preferred “one-pull” system upon fully-lowering the rudder.
FIG. 5 is a partial side elevation view according to a second embodiment of the present invention, which comprises a different location for the gas cylinder.
FIG. 6 is a partial side elevation view according to a third embodiment of the present invention, which does not comprise a gas cylinder as part of the raising and lowering system.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
While the invention is susceptible of various modifications and alternative constructions, certain illustrated embodiments thereof have been shown in the drawings and will be described below in detail. It should be understood, however, that there is no intention to limit the invention to the specific form disclosed, but, on the contrary, the invention is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the invention as defined in the claims.
Until now, the boat industry has seen a long and unresolved need for a retractable rudder system that allows the operator of a boat to raise and lower a rudder with minimal effort and ease, while also allowing the rudder to have a security mechanism that allows the rudder to yield to underwater obstructions.
The present invention is a retractable sailboat rudder that is moveable from the up or secured position to the down or employed position or from the down to the up position with minimal effort. This functionality is accomplished by an uphaul line and pulley system coupled with a gas filled cylinder (“compressible resistance member”). The uphaul line is pulled to initiate both the upward and the downward movement, thereby improving the ease and simplicity of use over prior designs. Additionally, the gas filled cylinder both assists in the raising and lowering of the rudder and allows the rudder to yield to underwater obstructions that the rudder might strike while the boat is in motion. This functionality allows the rudder to raise as it contacts the object and automatically return to the steering position once the boat has passed the object.
In the following description and in the figures, like elements are identified with like reference numerals. The use of “or” indicates a non-exclusive alternative without limitation unless otherwise noted. The use of “including” means “including, but not limited to,” unless otherwise noted.
Referring to the Figures, there are shown several, but not the only, embodiments of the invented rudder system used to steer a boat while underway upon water. The rudder system may be used on a boat during motor and/or sail and/or drifting, and may be adapted for use with a tiller arm and/or a steering wheel. Preferably, the invented rudder system is a transom-mounted system, but other mounting, construction, and installation systems may be used.
FIGS. 1-6 illustrate three embodiments being lowered from a generally vertical raised position (for storage, securement during travel on a trailer over the road, or other reasons when the rudder is not in use) to a fully-lowered employed (again generally vertical) position. In FIG. 1 , the uphaul line (“cable”) and handle are resting on top of the tiller arm. FIG. 1 also illustrates multiple rudder positions during “one-pull” raising or lowering of the rudder. FIG. 3 shows the rudder in a fully raised or up position. FIGS. 4-6 show the rudder in the fully-lowered or down position.
FIG. 5 illustrates another embodiment, wherein this embodiment have a cylinder/strut connected to the rear edge of the post and to the edge of the rudder. FIG. 5 shows the rudder in the fully-lowered position, and show the strut in an extended condition.
FIG. 6 illustrates yet another embodiment being raised, wherein this embodiment does not use a cylinder/strut, and the raising and lowering of the rudder is done entirely by the force of the cable and pulley system. This embodiment is very similar to that in FIG. 6 .
FIGS. 1-6 illustrate the “rudder head” (“one or more rudder brackets”), which may be extendible to different lengths by a telescoping or other system, and which may be mounted by simple, pivotal means to the transom.
Referring now to FIG. 1 , it will be observed that the preferred rudder mechanism 10 is comprised generally of rudder 12 , rudderpost 14 and tiller bar 16 . Rudderpost 14 has, preferably permanently affixed upon its forward, vertical surface, mounting bearings 18 and 20 and associated fasteners, these being used to mount and secure the rudder system 10 to the transom T of boat B. Mounting bearings 18 and 20 can also be bearings in the boat hull and deck, through which the rudderposts extends. When rudder system 10 is so installed, the mounting fasteners are adjusted so that rudderpost 14 may rotate to the right or left with respect to transom T. (See FIG. 2 ). Mounted at the upper end 22 of rudderpost 14 and extending forwardly from and generally perpendicular to rudderpost 14 is tiller bar 16 , used by the boater/sailor to rotate rudder system 10 to the right or left, thereby steering the boat to port or starboard while underway. Some boats may have a vertical transom, others may have an undercut or an overhanging transom, and the rudderpost generally is parallel to the transom of the boat. At the lower end 24 of rudderpost 14 are permanently mounted rudder brackets (“rudder head”) 28 and 30 , extending rearward from and perpendicular to rudderpost 14 . Brackets 28 and 30 contain pivot holes 32 to correspond with pivot hole 34 in rudder 12 , through which fastener 36 is inserted and secured, thereby pivotally mounting rudder 12 within rudder brackets 28 and 30 . Fastener 36 may be adapted to be allow removal of the rudder for repair or replacement, and may be adapted to be adjustable, for example, adjusting the compression of the rudder brackets 28 , 30 on the rudder 12 or otherwise adjusting the tightness of the pivotal mounting of the rudder. Thusly mounted, rudder 12 is free to pivot upwardly and downwardly through an arc of greater than 90 degrees, preferably 160 -200 degrees, and most preferably 180 degrees. Force exerted by the boater upon the uphaul line (“cable”) 38 , passing through pulley 40 affixed to rudder 12 with stud (“fastener”) 41 , is applied to raise or lower rudder 12 . Pulley 40 is free to pivot about the outer end of stud 41 . Cable 38 is fixed/immovable at its lower end 42 to rudderpost 14 . Rudder 12 , at its pivotal end (“first end”), contains within its edge portion, slot 13 to aid in maintaining alignment between cable 38 and rudder 12 . Cable 38 , at its upper end 44 , passes through aligning eye 46 , which is affixed to the upper end 22 of rudderpost 14 . Also at upper end 44 of cable 38 is affixed handle 48 , this being used by the boater to attain a firm grip upon cable 38 when it is desired that rudder 12 be pivoted.
Referring now to FIGS. 3 and 4 , it will be seen that, mounted parallel to the vertical center plane of rudderpost 14 is gas cylinder (“compressible resistance member”) 50 , secured pivotally at its upper end (“first end”) 52 to rudder post 14 , and at its lower end (“second end”) 54 within slot (“arched slot”) 56 in bracket 28 and pivotally secured to rudder 12 near the top end (“first end”) of rudder 12 and near a first edge of the rudder 12 (said first edge being the inner, front edge of the rudder when the rudder is in the raised position, as in FIG. 3 ). There gas cylinder 50 , therefore, is generally in a plane parallel to, but offset to one side of the plane of the rudder.
Operation of the rudder system 10 will now be discussed, beginning with the rudder 12 in the upright, secured position.
Referring now to FIG. 3 , it will be noted that the lower end 54 of gas cylinder 50 resides at end 56 A(“first lower slot position”) of slot 56 , specifically, with lower end 54 or, more typically, the fastener (“connection piece”) that connects the end 54 to the rudder, extending through the slot for connection to the rudder. Besides a gas cylinder, the compressible resistance member can be a gas filled cylinders, a piston, springs, compressible struts, or compressible elongate elastic material, or other compressible structures.
The force exerted downwardly by the pressure within gas cylinder 50 while in this position, indicated by arrow F 1 , tends to keep rudder 12 in the upright position. When the boater desires to lower the rudder 12 , cable 38 at handle 48 is grasped and pulled toward the forward end of the boat. When sufficient force through cable 38 is exerted by the boater, indicated by arrow F 2 (and which is applied by the cable 38 being pulled forward on the boat in view of the cable 38 changing directions via eye 46 ), the force F 1 exerted by gas cylinder 50 is overcome. Force F 2 acts upon pulley 40 affixed to rudder 12 with stud 41 , in view of end 42 of cable 38 being fixed to rudderpost 14 , to pivot the rudder outward.
As Force F 2 pivots the rudder outward, lower end 54 of gas cylinder 50 then begins to move upwardly and rearwardly, sliding within slot 56 , and rudder 12 rotates rearwardly and downwardly. Upon continued force F 2 , still exerted by the boater pulling forward on the handle 48 , lower end 54 of gas cylinder 50 rotates through approximately 90 degrees of arc in slot 56 , rudder 12 rotating a corresponding 90 degrees. Through this position, the gas cylinder 50 is being shortened, and Force F 1 is working against the boater pulling on the handle/cable, but Force F 2 overcomes F 1 with the assistance of the pulley. Note that pulley 40 , in FIGS. 3 and 4 , because of its attachment point on the rudder, is below the cable attachment point (at 42 ) on rudderpost 14 . Also, the rudderpost and cable may be adapted to adjust the attachment point for end 42 (raise or lower the attachment point on the post) to fit different rudders and to fit different users. Note also that the pulley is moveable during its use in the preferred system, and it moves generally upwards from its position in FIG. 3 as the cable 38 is pulled, or upwards from its position in FIG. 4 as the cable is pulled. Pulley 40 may be considered a moveable (Class 2) pulley, and offers a 2:1 force advantage; this has been found to be effective for raising many rudders, for example, those weighing about 20 pounds. Alternative pulley systems, including more than one pulley, may be used, but the simplicity of a single, moveable pulley is preferred.
Upon reaching the zenith (“intermediate zenith slot position”) of slot 56 at approximately 90 degrees of rotation, the lower end 54 of gas cylinder 50 begins to travel downwardly in slot 56 (lengthening as it travels through the left half of the slot 56 in FIGS. 3 and 4 ) and gas cylinder 50 once again is able to apply downward force, indicated by arrow F 3 , upon lower end 54 , whereupon lower end 54 is stopped at end (“second lower slot position”) 56 B of slot 56 . Rudder 12 has now rotated through 180 degrees of arc, coming to rest at the lowered, steering position. The force F 3 exerted by gas cylinder 50 tends to keep rudder 12 in the lowered position. It will be noted from FIG. 4 that a portion of cable 38 now resides in slot 13 , thereby tending to keep cable 38 aligned with rudder 12 .
While the boat is underway, should the rudder strike an underwater object such as rocks or a sand bar, the rudder 12 is free to rotate upwardly to clear said object, thereby preventing rudder damage. Upon clearing said object, the rudder 12 will automatically return to the fully lowered steering position, as it is biased into this position by the gas cylinder.
When the boater desires to return the rudder 12 to the upright, secured position, force is exerted by the boater forwardly through handle 48 and cable 38 , thereby overcoming force exerted by gas cylinder 50 at F 3 . Lower end 54 of gas cylinder 50 begins travel upwardly and forwardly in slot 56 and rudder 12 begins rotation upwardly and forwardly. Having traveled through 180 degrees of arc (generally in the reverse of the description above) rudder 12 now resides in the up position and lower end 54 of gas cylinder 50 comes to rest at end 56 A of slot 56 , as shown in FIG. 3 .
Thus, in both the lowering and raising of the rudder, the same cable 38 pulled the same direction is used to overcome the forces of the gas cylinder and/or the rudder weight, but once the gas cylinder lower end has moved over the “crest” of its rotation, it assists with the rudder movement into the desired position. Further, the gas cylinder provides a dampening effect, because of its bias (F 1 and F 3 ) so that the rudder movement is made smoother and does not tend to “slam” into either position. Alternative biasing means may be used, such as other cylinders or struts, springs, or elongated elastic members, but the gas cylinder is preferred because of its consistency of operation, its aesthetics, and its durability.
Referring now to FIG. 5 , a second embodiment of the invented rudder system is shown wherein compressible strut 58 may be used interchangeably with gas cylinder 50 and is mounted so that its centerline lies in the same plane as that of rudderpost 14 and rudder 12 . Bracket 60 is provided upon rudderpost 14 to pivotally mount upper end (“first end”) 52 of gas cylinder 50 . Lower end (“second end”) 54 is pivotally mounted upon stud (“fastener”) 41 utilizing the same fastener as that which mounts pulley 40 , so that the lower end 54 may be mounted to the edge of the rudder (“first edge periphery of the first end of the rudder”) (an outer, upper edge when the rudder is in the full-lowered position). It will be noted that in this embodiment, slot 56 has been removed from bracket 28 , or at least is considered optional, as it is no longer required for movement of the lower end 54 . Operating method and all other components remain substantially the same as those in the preferred embodiment, with the exception that, when the rudder is moving into the raised position, the lower end 54 moves close to the rudderpost 14 and, in effect, becomes hidden along with the pulley between the rudder edge and the post. This embodiment may be less preferred, because there may tend to some interference between the gas cylinder and the cable during raising or lowering of the rudder.
Referring now to FIG. 6 , a third embodiment of the invented rudder system is shown wherein a gas cylinder is not used and completely manual manipulation of cable 38 is used to raise and lower rudder 12 . This embodiment may certainly be effective, depending, for example, on the size and weight of the rudder and the characteristics of the mounting of the rudder in the rudder head (brackets 28 and 30 ). Operating method and all other components remain the same as those in the preferred embodiment, except that the gas cylinder is not available to assist as described above for the first and second embodiment.
Preferred embodiments of the invention, therefore, may be described as a system for raising a rudder more than 90 degrees from its employed position, and preferably approximately 180 degrees. The system for raising and lowered the rudder may be a one-pull, single line system, which does not require separate lines/cables for raising and for lowering the rudder. The preferred system utilizes a pulley and cable properly placed so that, when the rudder is already raised, pulling on the cable pivots the rudder outward and downward, and so that, when the rudder is already lowered, pulling on the same cable preferably in the same direction pivots the rudder upward and inward. This provides and comfortable, easy to operate, and one may even say elegant, apparatus and method of controlling the level and position of the rudder. Further, in transom-mounted embodiments, the post and its system for connection to the boat may be easily adapted for different sizes, styles, and types of boats.
The preferred embodiments may be described as a manually-raised and manually-lowered rudder system, which preferably includes a cylinder (piston) but most preferably only a self-contained cylinder/piston (rather than one that is powered or controlled by a separate fluid, gas, or other actuation system). The simple and effective one-pull cable/pulley system preferably utilizes a single cable and a single pulley, so that a single cable extends from a handle, around a single pulley, and then to an anchor point. This may be differentiated from a complex cable system, with multiple cables and multiple cable portions extending many different directions and/or having multiple handles.
Although this invention has been described above with reference to particular means, materials, and embodiments, it is to be understood that the invention is not limited to these disclosed particulars, but extends instead to all equivalents within the scope of the Description, Drawings, and Photographs.
The exemplary embodiments shown in the figures and described above illustrate but do not limit the invention. It should be understood that there is no intention to limit the invention to the specific form disclosed; rather, the invention is to cover all modifications, alternative constructions, and equivalents falling within the spirit and scope of the invention as defined in the claims. While there is shown and described the present preferred embodiment of the invention, it is to be distinctly understood that this invention is not limited thereto but may be variously embodied to practice within the scope of the following claims. From the foregoing description, it will be apparent that various changes may be made without departing from the spirit and scope of the invention as defined by the following claims. | A rudder mechanism for use upon a sailboat is capable of being raised or lowered at the discretion of the boater using a single connected cable operating system, so that the system may be called a “one-pull” system for both raising and for lowering the rudder. The rudder is preferably pivotal, using the cable operating system, greater than 90 degrees, and more preferably, about 180 degrees. A self-contained gas cylinder may aid in the raising and lowering operation and to dampen and smooth the vertical, pivotal movement of the rudder. The cylinder also may be utilized to retain the rudder in a raised or lowered position, once the boater/sailor has purposely placed the rudder in that position, and to return the rudder to the fully-lowered position after grounding has temporarily “kicked-up” the rudder. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
Embodiments of the present invention relate to a method and apparatus for cleaning a pad used in chemical mechanical polishing (CMP) or electrochemical mechanical polishing (ECMP).
2. Description of the Related Art
ECMP is one method of planarizing a surface of a substrate. ECMP removes conductive materials from a substrate surface by electrochemical dissolution while polishing the substrate with a reduced mechanical abrasion compared to conventional CMP processes, which may require a high relative down force on a substrate to remove materials, such as metals and metal containing layers, from the substrate.
The polishing pad is one of the most critical parts for CMP or ECMP. The success or failure of the polishing process largely depends upon the pad. The pad has taken on a greater importance in recent years in ECMP wherein the pad provides two equally important functions, providing electrical contact to the substrate and providing surface abrasion. The pad to substrate contact area is what determines the pad performance in a polishing process, so it is critical to have a pad cleaning process that provides the best possible pad surface properties.
The surface of the pad is periodically conditioned to restore polishing performance. Conditioning is typically an abrasive process that may leave particles or other contaminants on the pad surface. To remove these contaminants, the pad is cleaned during and/or after conditioning.
One method for cleaning a pad includes rinsing the pad with a high pressure jet of liquid. Although high pressure rinsing may be suitable for cleaning conventional dielectric pads, the cleaning efficiency of a simple high pressure rinse is insufficient for ECMP processes due to the nature of the conductive pads utilized for ECMP processes. For example, debris located deep inside perforations in the conductive pad may be moved to the pad's surface during high pressure rinsing. Once at the pad's surface, the contaminants may stay on the surface or within scratches that are present on the surface of the pad.
There is a need in the art to provide an effective method and apparatus for cleaning polishing pads.
SUMMARY OF THE INVENTION
The present invention comprises a method for cleaning a polishing pad. In one embodiment, the method for cleaning a polishing pad comprises spraying the polishing pad with a washing fluid, and directing the washing fluid off of the pad. The washing fluid may be applied to the pad with a high pressure water jet (HPWJ). The washing fluid may be directed off of the polishing pad with a downstream director. The downstream director may be at least one of a fluid stream or spray, a vacuum, wiper or other object or device suitable for directing the washing fluid from the pad.
In another embodiment, the method for cleaning a polishing pad comprises directing polishing fluid off of the pad to create a fluid free zone, and spraying the fluid free zone of the polishing pad with a washing fluid. The washing fluid may be applied to the pad with a HPWJ. Fluids, such as polishing fluid, may be directed off of the polishing pad with an upstream director so that the washing fluid from the HPWJ is delivered directly to the pad without energy loss due to residual polishing fluid being disposed on the pad. The upstream director may be at least one of a gas stream or spray, a vacuum, wiper or other object or device suitable for directing the polishing fluid from the pad.
In another embodiment, the method for cleaning a polishing pad comprises rotating the polishing pad, spraying water from a HPWJ onto the polishing pad, and directing the water away from the polishing pad with air. The HPWJ and the air source may be positioned over the polishing pad using separate arms.
In yet another embodiment, an apparatus for cleaning a polishing pad is disclosed. The apparatus comprises a rotatable platen, a polishing pad disposed on the platen, an air jet mounted on a first delivery arm pivotable over said polishing pad, and an HPWJ mounted on a second delivery arm positioned over said polishing pad.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
FIG. 1 is a side view of an ECMP station having one embodiment of the pad cleaning assembly of the invention.
FIG. 2 is a top view of the ECMP pad station of FIG. 1 .
FIG. 3 is a partial side view of a high pressure water jet assembly of the invention.
FIGS. 4A-B are partial side views of various embodiments of a downstream director of the invention.
FIG. 5 is a plan view of another ECMP station having another embodiment of the pad cleaning assembly of the invention.
FIG. 6 is a partial side view of the ECMP station of FIG. 5 taken along section lines 6 - 6 .
DETAILED DESCRIPTION
The present invention provides a method and apparatus for cleaning a polishing pad. While the invention will be described in the context of a conductive polishing pad, it should be understood that the method for cleaning a pad could be practiced on a dielectric polishing pad, and on a web polishing material, both conductive and dielectric. While the particular apparatus in which the present invention can be practiced is not limited, it is particularly beneficial to practice the invention in a REFLEXION LK ECMP™ system or MIRRA MESA® system sold by Applied Materials, Inc., Santa Clara, Calif. Additionally, apparatus described in U.S. patent application Ser. No. 10/941,060 filed Sep. 14, 2004, U.S. Pat. No. 5,738,574, and U.S. Pat. No. 6,244,935, which are hereby incorporated by reference in their entirety, can also be used to practice the invention.
FIG. 1 depicts a sectional view of an ECMP station 102 having a planarizing head assembly 152 positioned over a platen assembly 230 . The planarizing head assembly 152 comprises a drive system 202 coupled to a carrier head 204 held by an arm 138 . The drive system 202 provides at least rotational motion to the carrier head 204 . The carrier head 204 additionally may be actuated toward the platen assembly 230 such that the substrate 114 , retained in the carrier head 204 , may be disposed against a contact surface of the ECMP station 102 during processing. The head assembly 152 may also oscillate during processing.
In one embodiment, the carrier head 204 may be a TITAN HEAD™ or TITAN PROFILER™ wafer carrier manufactured by Applied Materials, Inc. The carrier head 204 comprises a housing 214 and a retaining ring 216 that defines a center recess in which the substrate 114 is retained. The retaining ring 216 may circumscribe the substrate 114 disposed within the carrier head 204 to prevent the substrate 114 from slipping out from under the carrier head 204 during processing. The retaining ring 216 can be made of plastic materials such as PPS, PEEK, and the like, or conductive materials such as stainless steel, Cu, Au, Pd, and the like, or some combination thereof. It is further contemplated that a conductive retaining ring may be electrically biased to control the electric field during the ECMP process or an electrochemical plating process. It is also contemplated that other planarizing or carrier heads may be utilized.
The ECMP station 102 includes a platen assembly 230 that is rotationally disposed on a base 108 . The platen assembly 230 is supported above the base 108 by a bearing 238 so that the platen assembly 230 may be rotated relative to the base 108 . The platen assembly 230 is coupled to a motor 232 that provides the rotational motion to the platen assembly 230 . The motor 232 is coupled to a controller that provides a signal for controlling for the rotational speed and direction of the platen assembly 230 . The motor received its power from a power source 244 , and a vacuum can be drawn from a vacuum source 246 . The platen assembly 230 is fabricated from a rigid material, such as aluminum, rigid plastic, or other suitable material.
An area of the base 108 circumscribed by the bearing 238 is open and provides a conduit for the electrical, mechanical, pneumatic, control signals and connections communicating with the platen assembly 230 . Conventional bearings, rotary unions and slip rings, collectively referred to as rotary coupler 276 , are provided such that electrical, mechanical, fluid, pneumatic, control signals and connections may be coupled between the base 108 and the rotating platen assembly 230 through a hollow drive shaft 212 .
A pad assembly 222 is disposed on an upper surface of the platen assembly 230 . The pad assembly 222 may be held to the surface of the platen assembly 230 by magnetic attraction, static attraction, vacuum, adhesives, or the like. The pad assembly 222 depicted in FIG. 1 includes a contact layer 208 defining an upper surface of the pad assembly 222 , a sub pad 215 , and an electrode 292 . The electrode 292 may be a single electrode, or may comprise multiple independently biasable electrode zones isolated from each other. Zoned electrodes are discussed in United States Patent Publication No. 2004/0082289, which is hereby incorporated by reference.
The upper surface of the contact layer 208 is adapted to contact a feature side 115 of the substrate 114 during processing. The contact layer 208 may be fabricated from polymeric materials compatible with the process chemistry. The polymeric materials may be dielectric or, alternatively, conductive. The contact layer 208 may be smooth or patterned to facilitate distribution of the polishing solution over the surface of the pad assembly 222 . The pad assembly 222 may further include perforations 218 which expose the electrode 292 to process (e.g., polishing) fluids disposed on the upper surface of the contact layer 208 during processing.
The plurality of perforations 218 may be formed uniformly distributed pattern and has a percent open area of from about 10% to about 90% (i.e., the area of the perforations 218 open to the electrode as a percentage of the total surface area of the polishing layer). The location and open area percentage of the perforations 218 in the pad assembly 222 controls the quantity and distribution of polishing fluid contacting the electrode 292 and substrate 114 during processing, thereby controlling the rate of removal of material from the feature side 115 of the substrate 114 in a polishing operation, or the rate of deposition in a plating operation.
In another embodiment, the pad assembly 222 may include conductive contact elements adapted to extend above the contact layer 208 . Examples of polishing pad assemblies having contact elements that may be utilized are described in United States Patent Publication No. 2002/0119286, United States Patent Publication No. 2004/0163946, and United States Patent Publication No. 2005/0000801, which are hereby incorporated by reference.
Polishing pad assemblies may be conditioned at three separate times. The first time that the polishing pad is conditioned is at break-in. Break-in is the procedure used to condition a new polishing pad before its first use. Polishing pads are broken-in to ensure uniform and predictable pad to pad processing results.
The second time that the polishing pad is conditioned is in-situ processing. In-situ conditioning occurs during processing of the substrate on the pad. In-situ maintains a substantially constant pad surface condition so that process variation is minimized between the beginning to end of a substrate polishing process.
The third time for polishing pad conditioning is ex-situ conditioning. Ex-situ conditioning occurs between polishing of substrates. Ex-situ conditioning may occur between each substrate processed, between batches of substrates, or on an as needed basis.
The method and apparatus for pad conditioning may be utilized with most conditioning processes. One conditioning process includes pressing a rotating disk against the pad assembly. The rotating disk is located at the end of an arm 420 that is supported on a support structure 415 . The arm 420 is rotated to sweep the rotating disk 413 across the pad surface. One example of a pad conditioning process can be found in U.S. patent application Ser. No. 11/209,167, filed Aug. 22, 2005, which is hereby incorporated by reference in its entirety.
During polishing, a polishing fluid is provided from a polishing fluid supply 248 to the polishing pad assembly 222 through a polishing fluid delivery nozzle 306 . The polishing fluid delivery nozzle 306 is located on a separate arm 304 from the arm 420 on which the conditioning pad assembly 413 is attached. The polishing fluid delivery nozzle 306 is positioned at the end of the arm 304 . The arm 304 is coupled to a support structure 315 which allows the arm 304 to selectively position the delivery nozzle 306 over desired locations above the polishing pad assembly 222 .
A washing fluid is provided to the polishing pad assembly 222 to remove debris that may collect on the surface of the polishing pad assembly 222 and within the perforations 218 . The washing fluid is removed from the surface of the pad assembly by a downstream director 120 to prevent debris removed from the perforations from settling out of the washing fluid on the surface of the pad assembly and rotated into contact with the substrate 114 being polished on the polishing pad assembly 222 . In one embodiment, the washing fluid is provided by a high pressure water jet (HPWJ). However it is to be understood that the washing fluid can be provided by other high pressure delivery devices and to the surface of polishing pad assembly 222 .
In the embodiment depicted in FIG. 1 , the downstream director 120 provides a second fluid to the polishing pad assembly 222 at an angle and velocity that moves the washing fluid out of an area of the polishing pad assembly 222 that will be swept under the substrate 114 during polishing. One suitable downstream director 120 is an air knife 320 . While the second fluid is described as being provided from an air knife 320 , it is to be understood that any fluid, gas or liquid that can be directed against the pad assembly to sweep the washing fluid wake and debris off of the polishing pad assembly 222 may be provided by other devices. Moreover, it is contemplate that the air knife 320 may be replaced by one or more fluid streams or sprays.
A washing fluid supply 405 provides the washing fluid that will be used to clean the polishing pad. The washing fluid is fed from the washing fluid supply 405 through a supply line 410 to one or more nozzles 412 that spray the washing fluid to the polishing pad 222 . The nozzles 412 may be positioned on the same arm 420 as the conditioning pad assembly 413 . In one embodiment, the washing fluid supply 405 is a HPWJ water supply, and the nozzle 412 is a HPWJ. In another embodiment, the washing fluid is water or deionized water. The nozzle 412 may be selectively positioned laterally along the arm 420 .
FIG. 3 depicts a side view of the nozzle 412 mounted to the arm 420 . The nozzle 412 is attached to a guide 403 that runs along a rail 401 mounted to the arm 420 . The nozzle 412 may be dynamically positioned along the rail 401 using an actuator (not shown) or be locked in place using a clamp, detent or set screw 402 .
To remove the washing fluid and any entrained debris prior to interfacing with the substrate, the downstream director 120 , shown in this embodiment as an air knife 320 , has a second nozzle that is provided to direct the second fluid against the pad assembly between the nozzle 412 and the carrier head 204 (as referenced by the pad rotation). The second fluid source is provided from a fluid source 305 and travels within the supply line 310 to the second nozzle, shown in FIG. 1 as an air knife 320 . The air knife 320 provides the fluid to the polishing pad assembly 222 in a sheet that is oriented substantially radially across the pad. Thus, as the washing fluid disposed on the pad assembly rotates towards the carrier head 204 , the sheet of second fluid creates a barrier that drives the washing fluid radially off the polishing pad assembly thereby substantially preventing the washing fluid from contacting the substrate. It is contemplated that the sheet may be alternatively formed by a plurality of nozzles. The air knife 320 may be coupled to the same arm 304 as the polishing fluid delivery nozzle 306 .
In one embodiment, the second fluid is air. It is to be understood that the second fluid may be any gas or fluid that does not adversely effect processing of the substrate. The second fluid is delivered from the air knife 320 with sufficient force to remove the washing fluid. In one embodiment, the second fluid is delivered from an air knife to impinge the pad assembly over a linear span of at least 200 mm, and in another embodiment, at least 300 mm.
FIGS. 4A-B depict alternative embodiments of downstream directors that may be utilized in the ECMP stations described therein. In the embodiment depicted in FIG. 4A , a downstream director 600 includes a body 602 having one or more suction ports 604 one a side of the body 602 facing the polishing pad assembly 222 . The suction port 604 is coupled to an exit port 606 formed in the body 602 . The exit port 606 is coupled to a vacuum source 610 . The vacuum source 610 pulls a vacuum though the suction port 604 that, when the body 602 is placed in close proximity to the polishing pad assembly 222 , the washing fluid is removed from the surface of the pad assembly 222 through the director 600 . The downstream director 600 may be coupled to the polishing fluid delivery arm 304 (not shown in FIG. 4B ), or supported by another suitable member.
In the embodiment depicted in FIG. 4B , a downstream director 700 includes a body 702 having lip 704 extending from a side of the body 702 facing the polishing pad assembly 222 . The lip 704 may be made from a material that does not damage the surface of the pad assembly 222 if placed in contact therewith. In one embodiment, the lip 704 is a polymer, such as an elastomer or plastic. The lip material is selected to be compatible with the fluids disposed on the pad assembly 222 . When the body 702 is placed in close proximity to, or in contact with, the polishing pad assembly 222 , the lip 704 of the director 700 wipes the washing fluid from the surface of the pad assembly 222 . The downstream director 700 may be coupled to the polishing fluid delivery arm 304 (not shown in FIG. 4B ), or supported by another suitable member.
FIG. 2 is a simplified top view of an ECMP station. The nozzle 412 is mounted on the arm 420 so that the nozzle 412 may be rotated relative to the pad 222 . Further, the height of the nozzle 412 relative to the upper surface of the pad 222 may also be adjustable. The arm 420 is shown with its center line 375 at an angle relative to a radial centerline 370 of the pad 222 for convenience. It is to be understood that the arm 420 can pivot about its axis P so that the nozzle 412 can reach any point between the center C of the polishing pad 222 and the periphery. Arrow 380 denotes the direction of rotation of the pad 222 .
The air knife 320 is mounted on the arm 304 so that the air knife 320 may be rotated relative to the pad 222 . Further, the height of the air knife 320 relative to the upper surface of the pad 222 may also be adjustable. The arm 304 is shown with its center line 475 at an angle relative to a radial centerline 370 of the pad 222 for convenience. It is to be understood that the arm 304 can pivot about its axis Q so that the air knife 320 oriented across the polishing pad 222 . Arrows 381 and 382 denote the path of the second fluid as it is directed off the polishing pad 222 by the air knife 320 .
In operation, the washing fluid is sprayed onto the polishing pad at high pressure during and/or after conditioning. The washing fluid wake, along with any debris loosened from the polishing pad surface, is directed away from the polishing pad by the second fluid delivered to the pad surface by the air knife. In one embodiment, the washing fluid is directed to the polishing pad at about 1500 psi to about 2000 psi. In one embodiment, the washing fluid is directed to the polishing pad at about 1650 to about 1900 psi. In yet another embodiment, the washing fluid is directed to the polishing pad at about 1800 to about 1850 psi. During the cleaning, the washing fluid is swept across the surface of the polishing pad by pivoting the arm 420 about its axis P. Optionally, the nozzle 412 may be moved along the arm.
The polishing pad is rotated during the cleaning so that all areas of the polishing pad will be sprayed with the washing fluid. The polishing pad may be rotated at about 10 to about 100 rpm during the cleaning process. In another embodiment, the polishing pad to rotate at about 30 to about 60 RPM during the cleaning process. In another embodiment, the polishing pad rotated at about 40 to about 50 RPM during the cleaning process.
The washing fluid will clean debris from substantially all surfaces of the polishing pad, including the perforations. The spray of washing fluid may be directed towards the edge of the polishing pad so that any debris collected within the wake of the washing fluid will be swept away. The second fluid provided by the air knife will sweep away the washing fluid wake, as well as any debris collected by the washing fluid wake. The arm 304 may be pivoted about its axis if desired.
The second fluid and the washing fluid can be provided to the polishing pad simultaneously. It is also contemplated by the present invention for the second fluid to be provided before the washing fluid so that loose debris can be removed from the polishing pad surface. Additionally, it is contemplated that the washing fluid can be provided to the polishing pad before the second fluid.
Rotating the polishing pad during the cleaning is beneficial to the cleaning process. If the polishing pad is not rotated, then the washing fluid will be provided at a high pressure to only the area that the arm 420 holding the nozzles 412 can cover when rotated about its axis. The other areas of the polishing pad would only receive the washing fluid wake.
FIG. 5 is a plan view of another ECMP station 800 having another embodiment of the pad cleaning assembly of the invention. The ECMP station 800 generally includes a rotating disk 413 for conditioning a pad assembly 222 , a polishing fluid delivery nozzle 306 and optionally, a downstream director 120 . The ECMP station 800 also includes an upstream director 802 for directing polishing fluid 806 (after passing by or polishing the substrate 114 ) off of the pad assembly 222 , as shown by arrows 820 to create a fluid free zone 804 . The fluid free zone 804 is generally defined between the upstream director 802 and the HPWJ nozzle 412 . The fluid free zone 804 has substantially no polishing fluid 806 disposed therein as compared to an area of the pad assembly 222 immediately upstream (via pad rotation) of the upstream director 802 , as illustrated in the partial side view of the ECMP station 800 depicted in FIG. 6 . Washing fluid 808 is sprayed the fluid free zone 804 of the polishing pad assembly 222 . As substantially all of the polishing fluid has been removed from the surface of the pad assembly by the upstream director 802 , the washing fluid may more energetically impinge upon the pad surface, thereby more effectively removing debris from the apertures of the pad assembly 222 . The upstream director 802 may be at least one of a gas stream or spray, a vacuum, wiper or other object or device suitable for directing the polishing fluid from the pad, and may be constructed similar to as described with reference to the downstream director 120 .
In embodiment wherein the downstream director 120 is present, the washing fluid 808 is moved off the pad assembly 222 , as shown by arrows 381 , 382 , prior to dispensing the polishing fluid 806 on the pad assembly 222 . Thus, the downstream director 120 substantially prevents intermixing of the washing and polishing fluids 806 , 808 directly in front of the substrate 114 .
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. | A method for cleaning a polishing pad is disclosed. In CMP and ECMP, a polishing pad must be conditioned to obtain good and predictable polishing results. During conditioning, debris is generated that must be removed to prevent processing defects. An effective method to clean a polishing pad is disclosed herein. In one embodiment, a washing fluid is directed at the pad to clean debris from the while a second fluid is utilized to remove the washing fluid. In another embodiment, the washing fluid is provided by a high pressure water jet while the second fluid is provided by an air knife. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of International Application No. PCT/GB2003/004570 filed Oct. 24, 2003, the disclosures of which are incorporated herein by reference, and which claimed priority to Great Britain Patent Application No. 0225192.4 filed Oct. 30, 2002, the disclosures of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention is concerned with stability control in road vehicles using a form of video based enhancement.
A so-called Active Torque Overlay (ATO) system has been developed recently which is based on the integration of EPS, (Electronic Power Steering) and ABS/VSC (Vehicle Stability Control) and is a method for injecting torque into the steering to adjust the steering feel or to assist the driver in limit/emergency manoeuvres. In this connection a “limit manoeuvre” is one which takes place at or near the vehicle handling limits.
The following scenarios that occur at or near the vehicle handling limits are benefited by ATO:
1. Oversteer.
In the early stages of oversteer, ATO acts to assist the driver to stabilise the vehicle. ATO demands an additional assist torque of the EPS. If oversteer develops past a defined threshold then VSC acts to stabilise the vehicle through brake intervention.
2. Understeer.
In the early stages of understeer, ATO acts to feedback information to the driver about the onset of understeer. ATO adjusts the assist torque of the EPS to exaggerate the reduction of rack force as felt by the driver via the steering wheel. This control is termed understeer haptic feedback. If understeer develops past a defined threshold then VSC acts, through brake intervention, to provide a yaw moment to maintain the perceived vehicle trajectory.
3. Split-μ Braking.
During a split-μ stop, a yaw moment due to the asymmetric longitudinal braking forces is generated on the vehicle. In passive vehicles the brake pressure build up is limited to allow the driver to apply the required steering correction to maintain a desired trajectory. The ATO control however assists the driver in balancing this yaw moment by applying a torque to the steering system to assist the driver achieve the required counter moment to stabilise the vehicle. Due to the improved stability, more aggressive braking and so reduced stopping distances can be achieved.
In all these scenarios, the control systems can restore or assist in the restoration of the stability of the vehicle and/or attempt to maintain a perceived trajectory. However they cannot guarantee that the vehicle is returned to the correct direction of travel as they have no means of detecting the direction of travel. Instead, the driver necessarily corrects the direction of travel.
Video lane detection systems are known to provide a means of detecting the direction of travel of a vehicle. Such lane detection systems have been used for several Driver Assistance Systems (DAS) functions, such as Lane Departure Warning, Lane Keeping and Autonomous Cruise Control (ACC) Target Selection.
BRIEF SUMMARY OF THE INVENTION
In accordance with one aspect, the present invention uses integration of the technologies of ATO and video lane detection to enhance vehicle control and to assist the driver in maintaining the correct direction of travel under limit handling conditions. The control strategies are termed herein “limit handling assistance” controllers.
The invention also provides a stability control system for road vehicles which is adapted to correct or compensate for lane or vehicle trajectory offsets, as would be imposed on a vehicle undergoing a dynamic state change, by means of offset detection using a video image processing system.
According to one embodiment of the present invention there is provided a stability control system for road vehicles comprising a limit handling assistance controller which uses video lane detection measurements in conjunction with vehicle dynamics information, including inertial, brakes and steering measurements, to control vehicle EPS and VSC systems to assist the driver stabilise the vehicle and/or correct for any lane offset prior to and/or during any of understeer, oversteer, split-μ and heavy braking conditions, and lane changes.
Preferably, in the case of an understeering vehicle condition detected by the vehicle VSC, an appropriate wheel is arranged to be braked to achieve a desired yaw rate in accordance with a driver's command expressed via the steering wheel, and in addition to decelerate the vehicle to reduce the understeer.
Advantageously, once the understeer has been reduced sufficiently for the front tyres to be no longer saturated, a torque is arranged to be demanded of the steering to assist the driver correct for any lane offsets detected by a video lane detection sensor providing said video lane detection measurements.
Preferably, for the purposes of preventative understeer or oversteer, the video lane detection measurements are used to obtain look-ahead information of a bend, the controller being arranged to demand brake intervention to decelerate the vehicle to an appropriate speed so that the bend can be safely negotiated without understeer or oversteer being provoked.
Preferably, in the case of an oversteering vehicle condition detected by the vehicle VSC, a torque is arranged to be applied to the steering to assist the driver stabilise the vehicle following which, if the oversteer progresses to a threshold, the VSC is arranged to brake an appropriate wheel to stabilise the vehicle and achieve a desired yaw rate in accordance with a driver command via the steering wheel.
Advantageously, during oversteer correction phases or oversteer control, an additional overlay torque is arranged to be demanded of the steering to assist the driver correct for lane offsets detected by a video lane detection sensor providing said video lane detection measurements.
Advantageously, during heavy braking while running in a lane, a torque can be demanded of the steering system using vehicle inertial, steering and video lane detection measurements to assist the driver stabilise the vehicle and keep the vehicle in that lane when undergoing said braking.
Preferably, in a split-μ stop, the driver is assisted to balance the yaw moment due to the asymmetric longitudinal braking force by demanding a torque to the steering system to assist the driver achieve the required counter moment.
Advantageously, an additional torque to assist the driver correct for lane offsets detected by the video lane detection sensors is used to augment the first mentioned torque.
Advantageously, when a lane change selected by the driver is detected by the video lane detection sensor in association with the steering and vehicle inertial sensors, a torque is arranged to be demanded of the steering system to assist the driver in making the lane change.
Other advantages of this invention will become apparent to those skilled in the art from the following detailed description of the preferred embodiment, when read in light of the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram representative of the control algorithm structure of a limit handling assistance controller which is generic to all of the aforegoing scenarios (a) to (e);
FIG. 2 is a block diagram of an in-lane position and yaw controller for use in the present invention;
FIG. 3 is a schematic diagram illustrating steering and braking demand allocation;
FIG. 4 is a schematic diagram of a steering demand controller; and
FIG. 5 is a schematic diagram of an application controller.
DETAILED DESCRIPTION OF THE INVENTION
An assistance system in accordance with the invention makes use of video detection measurements from a video lane detection sensor which may, although not necessarily, be part of a lane guide (or lane departure warning) system. The EPS and VSC are combined with the lane detection to give driver assistance in any or all of the following scenarios:
(a) Understeer
In this scenario the VSC detects understeer (typically in a bend) and brakes the appropriate wheel (typically but not necessarily the rear inner) to achieve the desired yaw rate (as commanded by the driver through the steering wheel). Braking the wheels also acts to decelerate the vehicle. Reducing the speed of the vehicle reduces/helps to reduce the understeer. Once the understeer is reduced so that the front tyre forces are no longer saturated then a torque is demanded of the steering to assist the driver correct for the lane offsets detected by the video lane detection sensor.
(b) Preventative Understeer/Oversteer
In this scenario the video lane detection is used to obtain look-ahead information of a bend. The controller demands brake intervention to decelerate the vehicle to an appropriate speed so that the bend can safely be negotiated without understeer or oversteer being provoked. This strategy can be further enhanced with preview information obtained from a map based GPS system.
(c) Oversteer
An oversteer scenario is detected by the VSC. In a vehicle with ATO functionality, the first means for controlling the oversteer is via the steering where a torque is applied to the steering to assist the driver stabilise the vehicle. If the oversteer progresses to a threshold then the VSC brakes the appropriate wheel (typically but not necessarily the front outer) to stabilise the vehicle and achieve the desired yaw rate (as commanded by the driver through the steering wheel). The braking also reduces the speed of the vehicle. During and/or subsequent to the oversteer correction phases of the oversteer control, an additional overlay torque is demanded of the steering to assist the driver correct for the lane offsets detected by the video lane detection sensor.
(d) Braking
In some instances during heavy braking, a vehicle can become unstable. This is due to load transfer along the vehicle causing a reduction of the vertical force on the rear tyres and an increase in vertical force on the front tyres. This results in the rear tyres having a reduced force generating capability with the front tyres having an increased lateral force generating capability. Utilising vehicle inertial, steering and video lane detection measurements a torque is demanded of the steering system to assist the driver stabilise the vehicle and keep the vehicle in lane when undergoing such braking. During a split-μ stop, the ATO controller assists the driver in balancing the yaw moment due to the asymmetric longitudinal braking forces by demanding a torque to the steering system to assist the driver achieve the required counter moment. An additional torque to assist the driver correct for lane offsets detected by the video lane detection sensor augments this torque.
(e) Lane Change Assistance
The video lane detection in association with the steering and vehicle inertial sensors detects a lane change. A torque is demanded of the steering system to assist the driver in making the lane change. A vehicle can be provoked to oversteer in, for example severe lane changes (such as an emergency lane change). In a severe lane change, the lane change assistance reduces the likelihood of the vehicle oversteering. In extreme cases where the vehicle does oversteer (maybe provoked by a surface transition during a lane change) then control as detailed in (c) is applied. In a lane change with braking, the brake force demanded is distributed in such a way as to provide a yaw moment to assist the driver in making the lane change.
Referring now to the control algorithm structure of FIG. 1 , the use of scenario flags to control gains within the algorithm allows the controller to respond differently to each handling scenario. Hence, the single structure is suitable for all five scenarios (a) to (e) described hereinbefore.
By way of example of the implementation of the present system, a simple design example is now described for the oversteer case (c).
The system of FIG. 1 has the following inputs:
Vehicle Measurement Data
1. Steering wheel angle and rotational rate measurements received from the vehicle steering system.
2. Wheel speed measurements and brake pressure estimates/measurements from the vehicle braking systems (including for example a VSC system).
3. Yaw rate received from a vehicle inertial sensor.
4. Vehicle longitudinal velocity received from for example processed wheel speed measurements.
Lane Detection Data (from a Video Sensor)
5. Lateral position error from the centre of the lane.
6. Heading angle error from the centre of the lane.
7. Lane curvature.
HMI and Automatic Inputs
8. Human Machine Interface (HMI) inputs, (for example, on/off switch, activate switch, indicators).
9. Automated switches (for example, a safety monitoring system to detect component failure).
The system also has the following outputs:
1. Steering column torque demand to the steering (e.g an EPS system) 2. Brake pressure demands to the braking systems (e.g a VSC system) 3. Outputs to the HMI (for example, mode light, buzzer)
The various blocks in FIG. 1 are now described.
Mode Control Block ( 10 )
The system mode (for example, “Active”, “Off” or “Standby”) may be set manually by the driver or automatically by another system (for example, a safety monitoring system to detect component failure). The mode flag is output to the Application Control Block.
Scenario Control Block ( 12 )
The Scenario Control Block 12 may, for example, be located in the vehicle VSC system. The vehicle measurements and certain HMI inputs (for example, indicators) are used to estimate the vehicle's dynamic state (for example, understeer/oversteer/heavy braking) and the driver's intentions (for example, lane change). The output is a series of scenario flags that inform the controller of what vehicle control action is available. The scenario flag signals are output to the Position & Yaw Control Block and the Steering & Braking Control Block described below.
Position & Yaw Control Block ( 14 )
The lane detection data and longitudinal velocity data are used to calculate the yaw rate required to return the vehicle to the centre of the lane. If the scenario flag indicates that a lane change is desired, then a suitable yaw rate is calculated for the lane transition.
Steering & Brake Control Block ( 16 )
The Steering & Brake Control Block 16 comprises three main subsystems.
(a) Steering & Braking Yaw Demand Allocation Block ( 18 )
The total yaw rate demanded by the Position & Yaw Rate Control Block 18 is proportioned to the steering and braking systems according to the scenario flags. The yaw rate demanded of the steering system is output to the Steering Demand Control Block 20 . The yaw rate demanded of the braking system is output to the Braking Demand Control Block 22 .
For example, if the scenario flag indicates that the vehicle is oversteering, then it may be more effective to brake a single wheel and steer than brake all four wheels and steer. Hence the yaw rate demand would be split in a certain proportion (determined from the scenario flags) between the braking system for the relevant wheel and the steering system.
(b) Steering Demand Control Block ( 20 )
The steering yaw rate demand is compared to feedback measurements of the current steering wheel angle and rotational rate. The output is an assisting steering column torque demand that is passed to the EPS system.
(c) Braking Demand Control Block ( 22 )
The braking yaw rate demand is compared to feedback estimates of the brake pressures. The outputs are brake pressure demands that are passed to the VSC system.
Application Control Block ( 24 )
The Application Controller 24 works as a mode switch for the system and can also operate as a safety shutdown system. If the mode flag from the Mode Control Block 10 indicates that the system is “Active”, then the steering and braking demands are transferred to the EPS and VSC systems. Otherwise, a zero output is given. HMI outputs are used to show the system's status to the driver.
There is now described a simple implementation of the algorithm structure shown in FIG. 1 . Further enhancements (such as safety checks, validity checks and robustness to errors) are required in a production version, which add significant complication to the details of the system. Hence this example is given as an example only to illustrate the system's basic functionality. For this example, a typical oversteer scenario is used.
Position & Yaw Controller
The Position & Yaw Controller, 14 shown in FIG. 2 is suitable for all in-lane and lane-change scenarios. For lane-change scenarios, an offset equal to one lane's width is added to the lateral position error until the lane detection system indicates that the vehicle has crossed the lane boundary.
The rate of road curvature is calculated at block 26 using the product of road curvature and longitudinal velocity. This gives the vehicle yaw rate required to match the road curvature. The lateral position error indicates what additional yaw rate is required to return the vehicle to the centre of the lane. The gain k 2 is tuned to the vehicle characteristics and speed to give the desired response. The product of longitudinal velocity and heading error at block 28 gives a measure of the lateral velocity in lane. This is fed via gain k 1 (tuned to the vehicle characteristics and scheduled with vehicle speed) to provide damping to the error response. The output yaw rate demand is the summation of the road curvature demand and the lateral position error demand.
Steering & Braking Yaw Demand Allocation
The most effective way of achieving the demanded yaw rate is estimated using a look-up table 30 , which acts as a series of gains that can be changed according to the scenario and vehicle speed. This divides the total input yaw rate demand into steering and braking yaw rate demands, as shown in FIG. 3 .
In this simple oversteer example, the scenario flags might indicate that braking would be ineffective so the steering alone is required to achieve the total yaw rate demand. The look-up table outputs zeros for the braking demands and passes the yaw rate demand to the Steering Demand Controller.
Steering Demand Controller
The Steering Demand Controller 20 operates regardless of the current scenario, as this has already been accounted for earlier in the algorithm. Hence this controller is suitable for all scenarios where steering is required.
Feedback from the steering column is used to design the desired response, as shown in FIG. 4 . Gains k 3 and k 4 are tuned according to the vehicle characteristics and speed. The yaw rate error is then scaled to a motor torque demand by gain k 5 (scheduled with vehicle speed).
The Braking Demand Controller 22 operates in a very similar way, using estimates of brake pressure feedback. A separate braking controller is used to control each wheel.
Application Controller
For this simple example, the Application Controller 24 works as an “ON/OFF” switch, as shown in FIG. 5 . The default setting for the switch is “OFF” where zero output is fed on the EPS and VSC systems. If the mode flag indicates that the system is “Active”, then the switch passes the steering and braking demands to the EPS and VSC systems.
As made clear above the current system has been described herein in its basic format. If, for example, better quality information about the surrounding environment is required, one approach can be to combine outputs from multiple sensors. For example, video requires a clear optical path. This is the primary limitation of the range of lane detection systems (˜80 m). Navigation systems can be used to significantly enhance this range, as well as providing other useful information such as road gradient, speed limits and road curvature.
The functionality of the basic algorithm structure described herein shows how it is designed to be generic to all five handling scenarios. A more complete design will include other supporting subsystems, such as:
Safety and failsafe systems Redundancy Robustness to errors Control refinements Data validity checks
However, the nature of these subsystems have not been described herein as they do not affect the functionality of the main controller system.
In accordance with the provisions of the patent statutes, the principle and mode of operation of this invention have been explained and illustrated in its preferred embodiments. However, it must be understood that this invention may be practiced otherwise than as specifically explained and illustrated without departing from its spirit or scope. | A stability control system for road vehicles comprising a limit handling assistance controller which uses video lane detection measurements in conjunction with vehicle dynamics information, including inertial brakes and steering measurements to control vehicle EPS and VSC systems to assist the driver stabilize the vehicle and correct for any lane offset prior to and/or during of understeer, oversteer, split-μ and heavy breaking conditions, and lane changes. | 1 |
This application is a division of application Ser. No. 07/537,509, filed Aug. 13, 1990.
FIELD OF THE INVENTION
This invention relates to an improved fluid driven pump apparatus and method for pumping a viscous product, such as condiments used in the food service industry. More particularly, the present invention relates to a pumping apparatus and method for providing a variable volume, low flow rate of highly viscous materials without mixing the driving fluid or other impurities into the product being pumped.
BACKGROUND OF THE INVENTION
As is well known, a variety of products typically marketed by fast-food retail establishments are provided to consumers after having been prepared with condiments such as ketchup, mustard, mayonnaise, or relish. In this regard, many such establishments currently utilize manual dispensing systems for such condiments which deliver a metered quantity of condiment therefrom.
The majority of prior art condiment dispensing systems have comprised a portable, hand-held manually activated dispensing devices which are used to supply a quantity of the condiment to a food product. Although such prior art dispensing systems have generally proven suitable for their intended purposes, they possess inherent deficiencies which have detracted from their overall effectiveness and use in the trade.
The foremost of these deficiencies has been the inability of the prior art dispensing system to dispense more than one variety of condiment, in that such devices are typically suited for dispensing only one condiment at a time. Moreover, the dispensing devices currently known are generally hand-held, mechanical devices, having a storage hopper for the condiment thereof. Due to the relatively small size of the hopper necessary to permit proper handling and manipulation by the user, such devices must be refilled frequently with the condiment. This repeated refilling operation decreases operational effectiveness and gives rise to a greater likelihood of condiment contamination whereby the device is more susceptible to having a foreign material introduced thereinto during a refilling operation.
Thus, there exists a substantial need in the art for a reliable, relatively inexpensive apparatus and method for dispensing a variety of condiments through a single dispensing unit in a metered quantity and at a low flow rate, which is adapted to be connected directly to corresponding modern, sanitary bag-in-box containers for such condiments, thereby eliminating repeated refillings of the dispensing system and reducing the possibility of condiment contamination.
SUMMARY OF THE INVENTION
The present invention specifically addresses and overcomes the deficiencies associated with prior art condiment dispensing devices. More particularly, the present invention provides a fluidic driven pump having a housing defining a first cavity and a second cavity. Disposed within the first cavity is a piston/diaphragm which is reciprocally movable through intake and exhaust strokes within the first cavity for pumping a condiment therefrom. The piston/diaphragm is attached to a piston/diaphragm support member which is slidably positioned within the second cavity. The first cavity further includes a product inlet and a product outlet which are in fluid communication therewith. During operation of the pump, the first cavity is in fluid communication with the inlet via a unidirectional check valve during an intake stroke of the piston and is in fluid communication with the outlet via a unidirectional check valve during an exhaust stroke of the piston. In this respect the first cavity alternately has a condiment inputted thereto and expelled therefrom as the piston/diaphragm reciprocates in the first cavity. A first biasing spring is also disposed within the first cavity and cooperates with the piston/diaphragm for biasing the piston/diaphragm toward the second cavity when the second cavity is being vented. The housing also includes an adjusting means comprising a cap member which is threadably received onto one end of the housing. This cap is configured such that if rotated in a clockwise direction, the piston/diaphragm stroke will be decreased while rotating the cap in a counter-clockwise direction will increase the piston/diaphragm stroke. In this regard, the increase or decrease of the piston/diaphragm stroke will regulate the quantity of condiment which is inputted into and subsequently discharged from the first cavity of the pump.
Disposed external of the pump housing is a hand-held, portable dispensing apparatus or nozzle having preferably plural valve assemblies disposed thereon, each of which is fluidly connected to a respective fluid driven pump to actuate pumping cycles for multiple condiments. Each valve assembly includes plural passages formed therein which are configured to alternatively supply and vent a pressurized fluid to the second cavity of a respective pump and deliver a quantity of desired product therefrom. The valve assembly additionally includes at least one reciprocable valve stem which is slidably mounted therein, i.e. movable between a first position and a second position to actuate the pumping cycle of a respective pump.
When in the first position, the valve stem is operable to apply a pressurized fluid into the second cavity of a respective pump through a port contained within the housing, thereby actuating the piston/diaphragm through an exhaust stroke and pushing the condiment from the first cavity through the product outlet. When in the second position, the valve stem is operable to allow the fluid contained within the second cavity to be vented to ambient atmosphere. In this regard, the intake stroke of the piston is facilitated by the action of the first biasing spring. During this intake stroke, a quantity of condiment is intaked into the first cavity by means of the product inlet which is attached to a bag-in-box containing a condiment. The product outlet is connected back to the dispensing apparatus whereby the condiment is disposed or output onto a food product through a dispensing aperture contained within the apparatus. Importantly, in the preferred embodiment of the present invention, the dispensing apparatus includes three valve stems sharing a common first pressurized fluid inlet passage. Additionally, multiple, i.e. three, pumps are included wherein each is connected to a different condiment source. Thus, the hand-held dispensing apparatus is configured to be able to independently dispense multiple, i.e. three, different types of condiments therefrom.
The present invention is economical, relatively mechanically simple, and is highly reliable in long-term continuous operation.
BRIEF DESCRIPTION OF THE DRAWINGS
These as well as other features of the present invention will become apparent upon reference to the drawings wherein:
FIG. 1 is a perspective representation of a condiment dispensing system;
FIG. 2 is a perspective view of the dispensing apparatus used in conjunction with the dispensing system;
FIG. 3 is an end view illustrating the input and output ports of the dispensing apparatus shown in FIG. 2;
FIG. 4 is a cross-sectional view of the pump according to the preferred embodiment, showing relative positions of the piston during operation thereof; and
FIG. 5 is a cross-sectional view of the dispensing apparatus taken along line 5--5 of FIG. 1, illustrating the valve assembly including the valve stems and flow passages.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings wherein the showings are for purposes of illustrating a preferred embodiment of the present invention only, and not for the purposes of limiting the same, FIG. 1 perspectively illustrates the condiment dispensing system according to the present invention. In the preferred embodiment of the present invention, the dispensing system generally comprises a dispensing apparatus 10 fluidly connected to plural pumps, for instance a first pump 12, a second pump 14, and a third pump 16. Also connected to dispensing apparatus 10 is a pressurized fluidic source, preferably carbon dioxide gas source 18. Pump 12 is also connected to a first condiment containing bag-in-box storage reservoir 20, while second pump 14 is connected to a second bag-in-box reservoir 22, and third pump 16 is connected to a third bag-in-box reservoir 24. In operation, actuation of the dispensing apparatus 10 causes a quantity of condiment to flow from a respective bag-in-box 20, 22, 24 through pumps 12, 14, 16 and into dispensing apparatus 10, as will be described in greater detail below.
PUMP CONFIGURATION
Referring now to FIG. 4, a cross-sectional view of pump 12 is illustrated. It should be noted that pumps 12, 14, 16 have identical configurations and that pump 12 was arbitrarily selected to be described with regard to FIG. 4. Pump 12, according to the present invention, includes a pump housing 26 generally consisting of a first housing section 26a and a second housing section 26b. Defined within first housing section 26a is a first cavity 28 and within second housing section 26b is a second cavity 30. First housing section 26a further includes a product inlet 12a and a product outlet 12b adjacent the closed end thereof. Pump housing 26 is formed of first section 26a and second section 26b for ease of manufacture and assembly of components, and further for convenience of inspection, cleaning, and maintenance.
Disposed within first housing section 26a is a piston 38 which is adapted to be reciprocally moveable therein. Piston 38 is positioned within first housing section 26a so as to be in axial alignment with first cavity 28. In FIG. 4, piston 38 is shown at the outer limit (i.e. full exhaust stroke) of its range of motion and also illustrated at the inner limit of its range of motion (shown in phantom lines). When piston 38 moves toward its inner limit, fluid enters the product inlet 12a and subsequently into first cavity 28. When piston 38 moves toward its outer position, the fluid is pushed by piston 38 through product outlet 12b.
The lower surface 37 of piston 38 is mounted to a piston support member 40. Piston support member 40 is generally comprised of a circular plate member 39 having an inner surface 39a and an outer surface 39b. Extending axially outwardly from inner surface 39a is a tubular member 41 which is attached thereto, and defines a pressurized air receiving cavity 42. Piston 38 is attached to piston support member 40 by means of a fastener 44 which is received into a threaded aperture disposed within lower surface 37 of piston 38. A gasket 46 is provided between fastener 44 and inner surface 39a of support member 40 to provide an air-tight seal therebetween. Additionally, a rolling diaphragm 48 is positioned between lower surface 37 of piston 38 and outer surface 39b of circular plate member 39. An outer edge 50 of rolling diaphragm 48 is further secured between first housing section 26a and second housing section 26b. Importantly, rolling diaphragm 48 moves with piston 38 and piston support member 40, as piston 38 reciprocates relative to pump housing 26.
Second cavity 30 of second housing section 26b is enclosed through the utilization of a seal assembly 52 which is threadably attached to the threaded portion of the outer surface of second housing section 26b. Seal assembly 52 generally comprises a sealing member 54 which defines a generally cylindrical recessed portion 56, a channel 58, and a circular outer flange 60. One end of channel 58 terminates into recessed portion 56, while the other end terminates into a carbon dioxide inlet/exhaust port 12c. Sealing member 54 is disposed within second housing section 26b such that the outer edge of outer flange 60 is in direct contact with the inner surface 26b' of second housing section 26b. Outer flange 60 includes an O-ring 62 disposed within a slot contained in the outer periphery thereof to facilitate the seal between sealing member 54 and inner surface 26b'. Sealing member 54 is attached to a cap member 64 through the utilization of a snap ring 66. The interior threaded portion of cap member 64 is sized and configured to threadably engage the outer threaded surface of second housing section 26b. Importantly, when cap member 64 is placed on second housing 26b, piston support member 40 and sealing member 54 are configured such that circular receiving cavity 42 and cylindrical recessed portion 56 as well as channel 58 are axially aligned whereby outer surface 41b of tubular member 41 is in sliding contact with inner surface 56a of recessed portion 56. As can be appreciated with this particular alignment, the intake stroke of piston 38 will be stopped when outer edge 43 of tubular member 41 is abutted against surface 57 of recessed portion 56. In this respect, the clockwise rotation of cap member 64 will cause sealing member 54 to move inwardly toward piston 38 thereby reducing the stroke of piston 38. Conversely, the counter-clockwise rotation of cap member 64 will cause sealing member 54 to move outwardly away from piston 38, thereby increasing the stroke of piston 38. By increasing or decreasing the stroke of piston 38, the volume of first cavity 28 is likewise increased or decreased. Thus, the quantity of condiment that is outputted by the dispensing system may be adjusted through the rotation of sealing assembly 52.
Piston 38 is actuated by pressurized fluid, preferably carbon dioxide, entering inlet/exhaust port 12c. After entering through port 12c, the fluid travels through channel 58 and enters receiving cavity 42 of piston support 40. It will be appreciated that initially only receiving cavity 42 is filled with fluid, since at the beginning of the exhaust stroke, lower edge 43 of tubular member 41 will be abutted against surface 57 of recessed portion 56. Fluid within receiving cavity 42 then presses against the exposed surface of fastener 44 thereby moving piston 38 through an exhaust stroke. The exhaust stroke of piston 38 is limited by a biasing spring 68, one end of which is abutted against a lip 70 contained within first housing section 26a and the other end of which is retained within a circular notch 72 disposed within the upper surface 35 of piston 38. As can be appreciated, after piston 38 has completed its exhaust stroke, the inlet stroke is facilitated by the action of biasing spring 68 returning to an extended position when the pressurized air then contained within receiving cavity 42, recessed portion 56, and channel 58 is exhausted through port 12c.
Condiment product entering first cavity 28 through product inlet 12a during an intake stroke of piston 38 first passes through an inlet check valve 74. Similarly, condiment product pushed by piston 38 through product outlet 12b during an exhaust stroke of piston 38 passes through outlet check valve 76. During operation of pump 12, during an intake stroke, inlet check valve 74 opens and outlet check valve 76 closes. Conversely, during an exhaust stroke, outlet check valve 76 opens while inlet check valve 74 closes.
DISPENSING APPARATUS CONFIGURATION
Referring now to FIGS. 1-3, dispensing apparatus 10 generally comprises a handle portion 78 and an outlet nozzle 80. Disposed within an end surface 82 of handle portion 78 are a plurality of apertures which are interfaced to pumps 12, 14, 16 and carbon dioxide source 18 as will be discussed in greater detail below. The control of condiment flow through dispensing device 10 is regulated by a valve configuration disposed within handle portion 78.
Referring now to FIG. 5, the valve configuration generally comprises a first valve stem assembly 84, a second valve stem assembly 86, and a third valve stem assembly 88. Each of the valve stem assemblies 84, 86, 88 have identical configurations and therefore the particular structures associated with each such assembly will be described with respect to valve stem assembly 84, though it will be appreciated that this particular assembly has been selected arbitrarily. Valve stem assembly 84 generally comprises an elongated valve stem 90 having a manual actuation button 92 disposed on one end thereof. Valve stem 90 further includes a first flange 94, a second flange 96, and a third flange 98 which extend radially outwardly about the periphery of various portions of valve stem 90. First flange 94 and second flange 96 define a first annular slot or recess 100 which extends about the periphery of valve stem 90 while second flange 96 and third flange 98 define a second annular slot or recess 102 which likewise extends about the periphery of valve stem 90. Disposed within first annul-ar slot 100 is a first O-ring 104 and disposed within second annular slot 102 is a second O-ring 106.
Valve stem assembly 84 is used in conjunction with a first air passage 108, a second air passage 110, a third air passage 112, and a fourth air passage 114. Contained within the upper region of second passage 110 is an O-ring 116 which creates a seal between the upper portion of valve stem 90 and an interior surface of handle portion 78. Also contained within second passage 110 is a first biasing spring 118, one end of which is abutted against third O-ring 116 and the other end of which is abutted against first flange 94 of valve stem 90. The lower region of second passage 110 includes a first annular lip 120 extending about the diameter thereof, which is adapted to form a sealing surface with first O-ring 104. Fourth air passage 114 is disposed within an exhaust member 122 inserted into handle portion 78, whereby fourth air passage 114 is axially aligned with second air passage 110. Exhaust member 122 is utilized so as to facilitate a less complicated manufacturing process with regard to the fabrication of the various air passage configurations utilized in conjunction with valve stem assembly 84. Exhaust member 122 includes a notch 124 extending about the periphery of the outer surface thereof into which is disposed a fourth O-ring 126. Fourth O-ring 126 is used to provide an air-tight seal between exhaust member 122 and an interior surface of handle portion 78. Disposed within the bottom wall 132 of exhaust member 122 is an exhaust port 128 which is used to vent pressurized fluid within the valve stem assembly 84 to the ambient environment, as will be explained in greater detail below. The exhaust ports of each of the valve stem assemblies 84, 86, 88 are covered by an exhaust cover 140, as best seen in FIGS. 2 and 5. Disposed within fourth passage 114 is a second biasing spring 130, the upper end of which is abutted against third flange 98 of valve stem 90 and the lower end of which is abutted against bottom wall 132 of exhaust member 122. Exhaust member 122 further includes a second annular lip or seat 134 disposed about the diameter of the upper end thereof which is adapted to form a sealing contact with second O-ring 106.
As can be seen in FIG. 5, valve stem assemblies 84, 86, 88 are each shown in various stages of actuation wherein valve stem assembly 84 is in a fully unactuated position, valve stem assembly 86 is in an intermediate stage of actuation, and valve stem assembly 88 is shown as being fully actuated. In the unactuated position, shown by valve stem assembly 84, button 92 is maintained in a fully upright position due to the action of second biasing spring 130 contained within fourth passage 114. Button 92 is contained within switch plate 142 attached to handle portion 78 through the utilization of a projection 136 contained on the lower end of button 92 which catches on a lip 138 disposed within the upper surface of switch plate 142.
When pressurized fluid is injected into dispensing apparatus 10, the fluid travels along first passage 108 whereby such pressurized air is injected into second passage 110 of valve stem assembly 84. As can be appreciated, such pressurized fluid will also be injected from first passage 108 into the passages of valve stem assemblies 86, 88 corresponding to second passage 110, though such second passage has only been specifically described with respect to valve stem assembly 84. As best seen with respect to valve stem assembly 84, when a valve stem is in a fully unactuated position, first O-ring 104 is sealed against first annular lip or seat 120 due to the action of second biasing spring 130, thereby confining, i.e. valving, the inputted fluid within first passage 108 and second passage 110. At the same time, fourth passage 114 is opened, i.e. O-ring 104 is raised above the seat 134, thus allowing the fluid to be vented from third passage 112 into the ambient air through exhaust port 128. As can be best seen with respect to the configuration shown by valve stem assembly 86, as button 92 is being depressed by the finger of an operator of the dispensing system, first O-ring 104 is slowly moved away from first annular lip or seat 120 second biasing spring 130 is being compressed. Importantly, as first O-ring 104 is being moved away from first annular lip 120, second O-ring 106 is simultaneously moved toward second annular lip or seat 134. As can be best seen with respect to the configuration shown by valve stem assembly 88, when button 92 is fully depressed, an open fluid passageway is formed between first passage 108, second passage 110, and third passage 112, thus pressurizing third passage 112. At the same time, fourth passage 114 will be valued, i.e. blocked, by the seal created by second O-ring 106 against second annular lip or seat 134.
DISPENSING SYSTEM OPERATION
Having thus described the structure of pumps 12, 14, 16, and dispensing apparatus 10, the flow patterns and operation of the dispensing system will now be described.
Referring now to FIGS. 1-4, pressurized fluid from the carbon dioxide gas source 18 is applied into dispensing apparatus 10 through aperture 18' contained in end face 82. To facilitate the exhaust stroke of piston 38, valve stem 90 is fully actuated as shown in valve stem assembly 88. As previously described with regard to the actuated position, fluid from carbon dioxide source 18 entering handle portion 78 through aperture 18' will enter and travel through first passage 108, second passage 110, and into third passage 112. From third passage 112 the fluid will exit through aperture 12c' and be injected into inlet/exhaust port 12c, thereby causing piston 38 to begin an exhaust stroke, i.e. pumping stroke, as previously described, thus pushing the condiment out of product outlet 12b. From outlet 12b the condiment is forced into dispensing apparatus 10 by way of aperture 12b' and will exit dispensing apparatus 10 through aperture 12b" contained within outlet nozzle 80. After the exhaust stroke has been completed, button 92 is returned to the unactuated position shown by valve stem assembly 84. Due to the configuration of the air passages with respect to the unactuated Position as previously described, the action of biasing spring 68 in first cavity 28 of pump 12 initiates the intake stroke of piston 38 thereby pushing the residual pressurized fluid within cavity 42, recessed portion 56, and channel 58 out through inlet/exhaust port 12c. From inlet/exhaust port 12c the fluid will enter handle portion 78 through aperture 12c', and travel into third passage 112, fourth passage 114, and through exhaust port 128, thus being vented into the ambient air. As this venting process is occurring, condiment from bag-in-box 20 will once again enter first cavity 28 through product inlet 12a during the intake stroke of piston 38. As can be appreciated, a procedure identical to the aforementioned occurs with respect to inlet/outlet ports 14a, 14b, 14c, of pump 14, and apertures 14b', 14c', and 14b" of dispensing apparatus 10, as well as inlet/outlet ports 16a, 16b, 16c of pump 16 and apertures 16b', 16c' and 16b" of dispensing apparatus 10. Thus, in the preferred embodiment of the present invention, three varieties of condiment may be dispensed from dispensing apparatus 10, though it will be appreciated that more or less pumps and valve stem assemblies may be utilized to dispense different numbers of condiments with respect to the present dispensing system.
Additional modifications and improvements of the invention may also be apparent to those skilled in the art, as, the particular combination of parts described and illustrated herein is intended to represent only one embodiment of the invention, and is not intended to serve as limitations of alternative devices within the spirit and scope of the invention. | An improved condiment dispensing system for delivering a measured quantity of condiment at a constant flow rate. The device comprises a pump which is fluidly connected to a condiment source and a dispensing apparatus. The dispensing apparatus includes a valve assembly which is connected to both a pressurized fluid source and to the pump whereby actuation of a valve assembly contained on the surface of the dispensing apparatus causes a measured quantity of condiment to be dispensed from an outlet nozzle contained thereon. | 1 |
RELATED APPLICATIONS
This is a continuation-in-part of commonly assigned co-pending application Ser. No. 08/153,712 entitled OPTICAL SENSING OF SAMPLE COLOR MARKINGS ON MEDIA IN A CARRIAGE-TYPE GRAPHICAL WRITING SYSTEM filed Nov. 16, 1993, now abandoned, in the names of Messrs. Beauchamp, Rosello, Tarradas, Halpenny & Boeller, which is a divisional of commonly assigned co-pending application Ser. No. 07/763,889 entitled MONITORING AND CONTROLLING QUALITY OF PEN MARKINGS ON PLOTTING MEDIA filed Sep. 20, 1991, now U.S. Pat. No. 5,262,797, in the names of Messrs. Boeller, Halpenny, Tarradas, Rosello & Beauchamp, which is a continuation-in-part of commonly assigned previously pending Ser. No. 07/504,437 entitled WRITING SYSTEM FOR AND METHOD OF PRODUCING VISIBLE MARKINGS ON A MEDIUM filed Apr. 4, 1990, now abandoned, in the names of Messrs. Boeller, Halpenny, Tarradas & Rosello, all of which applications are incorporated herein by reference.
This is also a continuation-in-part of commonly assigned co-pending application Ser. No. 08/540,908, entitled MULTIPLE INKJET PRINT CARTRIDGE ALIGNMENT BY SCANNING A REFERENCE PATTERN AND SAMPLING SAME WITH REFERENCE TO A POSITION ENCODER filed Oct. 11, 1995, now U.S. Pat. No. 5,600,350, in the names of Messrs. Cobbs, Beauchamp & Sorenson, which is a continuation of co-pending application Ser. No. 08/055,624 entitled MULTIPLE INKJET PRINT CARTRIDGE ALIGNMENT BY SCANNING A REFERENCE PATTERN AND SAMPLING SAME WITH REFERENCE TO A POSITION ENCODER filed Apr. 30, 1993, abandoned, in the names of Messrs. Cobbs, Beauchamp & Sorenson, which applications are incorporated herein by reference.
Two other related commonly assigned co-pending applications are Ser. No. 08/551,297 entitled COMPACT FLEX-CIRCUIT FOR MODULAR ASSEMBLY OF OPTICAL SENSOR COMPONENTS IN AN INKJET PRINTER filed Oct. 31, 1995 in the name of Robert W. Beauchamp, and Ser. No. 08/558,571 entitled UNITARY LIGHT TUBE FOR MOUNTING OPTICAL SENSOR COMPONENTS ON AN INKJET PRINTER CARRIAGE filed Oct. 31, 1995 in the name of Robert W. Beauchamp, which applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
This invention relates generally to plotters, and more specifically to monitoring and controlling the quality of markings on plotting media.
A typical plotter comprises a pen for producing markings on a medium in response to instructions from, for example, a computer. The medium such as paper is movable in a first direction along the X-axis and the pen on a main carriage is movable in a second direction along the Y-axis which is perpendicular to the first direction. Thus, by appropriate control of the drives for the pen and paper movement, any desired graphical representation can be produced on the medium. The writing system also typically comprises a plurality of pens, for example pens of different colors. A pen handling mechanism is provided which permits a pen to move into position on the carriage for plotting on the medium and replaces that pen by another one, for example when a different color is desired.
Writing systems such as the above-mentioned pen plotter are typically used for producing rather complex graphical representations, for example circuit layouts or construction diagrams, which are electronically stored in a computer on which they may also have been created by a user. Once the plotting of those electronically stored drawings has been initiated by a user, the plotting continues automatically and the user only has to take the completed drawing from the plotter. In practice, however, the completed drawings have not always been satisfactory. As a consequence thereof, the entire drawing generally had to be plotted again.
Thus, a considerable amount of time is wasted and the efficiency of the plotting is decreased. Usually these problems are resolved by perfecting the components of the plotter.
Despite such attempts for perfection of the writing components, writing failures may still occur.
More recently, the full color inkjet printer/plotters which have been developed comprise a plurality of inkjet pens of diverse colors. A typical color inkjet printer/plotter has four inkjet pens, one that stores black ink, and three that store colored inks, e.g., magenta, cyan and yellow. The colors from the three color pens are mixed to obtain any particular color.
The pens are typically mounted in stalls within an assembly which is mounted on the carriage of the printer/plotter. The carriage assembly positions the inkjet pens and typically holds the circuitry required for interface to the heater circuits in the inkjet pens.
Full color printing and plotting requires that the colors from the individual pens be precisely applied to the media. This requires precise alignment of the carriage assembly. Unfortunately, mechanical misalignment of the pens in conventional inkjet printer/plotters results in offsets in the X direction (in the media or paper axis) and in the Y direction (in the scan or carriage axis). This misalignment of the carriage assembly manifests as a misregistration of the print images applied by the individual pens. In addition, other misalignments may arise due to the speed of the carriage, the curvature of the platen and/or spray from the nozzles.
However, the integration of the optical and electronic components in the optical sensor, as well as positioning the optical sensor on the carriage have been complicated, expensive and to some extent imprecise in prior printers/plotters. The need for reliability and precision is even greater in recent inkjet printers/plotters which print high resolution color graphics and images, often on very large poster-size printouts.
SUMMARY OF THE INVENTION
It is an object of the invention to solve the aforementioned deficiencies of the prior art, and provide a method and apparatus for assuring that a high degree of reliability is achieved for nonattended plotting.
A related object is to provide a pen verification system that provides predictable performance for different color pens.
A further object is to provide adequate optical sensing of pen lines under varying ambient light conditions.
In accordance with the foregoing objects, the invention provides a method of monitoring and controlling the quality of pen markings on a plotting medium by optically sensing across a sample line drawn on an actual medium.
In another separate and important aspect of the invention, a customized optical sensor is provided for monitoring plotter pen performance by sensing the quality of lines drawn on a medium. An LED emitting a green light beam is angularly directed toward an underlying line so as to reflect into an optical sensor which measures the print contrast ratio of a point on the line. Circuit means amplifies and filters the signal generated by the optical sensor.
Thus, by appropriate selection of the wavelength of the light used for sensing the markings on the medium, it is easily possible to check multi-color drawings for correct quality and colors.
In a presently preferred embodiment of the invention implemented in a color inkjet printer/plotter, a green LED is used for sensing sample patterns printed by each of the black (K), cyan (C) and magenta (M) printheads, while a blue LED is used for sensing sample patterns printed by the yellow (Y) printhead.
Moreover, a light tube on a carriage-mounted optical sensor has inner walls which help direct light from an LED toward an area surrounding a point under the sensor, and outer walls which help block out undesirable external light from being reflected from the area surrounding a point under the sensor into the photocell.
Thus, the invention contemplates optical sensing of different color markings on media using different color lights, whether those markings are vector lines drawn by a pen plotter or raster "lines" (i. e. bars) printed on a pixel grid by an inkjet printer/plotter.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram of a first embodiment showing various circuit interconnections between a pen carriage and a microprocessor;
FIG. 2 is an exploded view of the main carriage of a first embodiment of the invention;
FIG. 3 is a bottom view of the Z-axis carriage showing a pen path which is offset from an optical sensor path;
FIG. 4 is a side view of the main carriage of FIG. 2 showing the Z-axis (darkly outlined) holding a pen in raised position;
FIG. 5 is a perspective view showing an optical sensor holder which is mountable on the Z-axis carriage;
FIG. 6 is a perspective view showing an LED holder which is attachable to the optical sensor holder;
FIG. 7 is a schematic circuit diagram showing an amplifier and filter circuit for processing a signal from the sensor;
FIGS. 8 and 9 are schematic diagrams showing exemplary locations for optically sensing the quality of a line by scanning across a point on the line;
FIG. 10 is a flow chart for qualifying pens and thereafter setting the print contrast ratio (PCR) threshold for that particular pen;
FIG. 11 is a perspective view of a second embodiment of a large format inkjet printer/plotter incorporating the features of the present invention;
FIG. 12 is close-up view of the carriage portion of the printer/plotter of FIG. 11 showing a carriage-mounted optical sensor of the present invention;
FIG. 13 is a close-up view of the platen portion of the printer/plotter of FIG. 11 showing the carriage portion in phantom lines;
FIG. 14 is a schematic representation of a top view of the carriage showing offsets between individual print-heads in the media advance axis and in the carriage scan axis;
FIG. 15A is an isometric view showing a fully assembled optical sensor unit incorporating a presently preferred embodiment of the invention;
FIG. 15B is a bottom view of the optical sensor unit taken along the line 15B--15B in FIG. 15A;
FIG. 16 is a front view of the optical components of the sensor unit of FIG. 15A;
FIGS. 17A, 17B, 17C and 17D are a sequential representation showing a presently preferred set of modular assembly steps for the optical sensor unit;
FIG. 18 is an isometric view looking down from the right front side of the carriage showing the optical sensor and one print cartridge mounted on the carriage;
FIG. 19 is an isometric view looking up from the right rear side of the carriage showing the optical sensor and one print cartridge mounted on the carriage;
FIG. 20 is an isometric view looking down from the right rear side of the carriage showing the optical sensor mounted on the carriage;
FIG. 21 is a top view of the entire flex-circuit showing the details of the co-planar junction portion at a first end of the flex-circuit;
FIG. 22 is a top view identifying an exemplary circuit arrangement at a second end of the flex circuit;
FIG. 23 is an enlarged sectional view showing an exemplary through-hole for the co-planar junction portion
FIG. 24 is a schematic representation showing the interconnection between the circuitry interconnections between the flex-circuit and the photocell;
FIG. 25A is a cross-sectional view showing the optical sensor unit with light rays from one of the two LEDs illuminating a portion of the platen;
FIG. 25B is a cross-section view like FIG. 25A, but which shows the optical sensor unit with light rays being reflected from a portion of the platen through a lens to the photocell;
FIG. 26 is a table showing typical data obtained by using the optical sensor unit of the present invention;
FIG. 27 is a schematic showing the test pattern used for determining relative printhead alighment in the Y-axis;
FIG. 28 is a schematic showing the test pattern used for determining relative printhead alignment in the X-axis; and
FIG. 29 is an exemplary curve of the type generated by the photocell.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Generally speaking, as exemplified in a first embodiment shown in FIGS. 1-10, the invention is incorporated in a pen plotter comprising a pen for producing markings such as graphical representations on a medium, for example on a sheet of paper. The pen is held on a main carriage by a Z-axis carriage which can be lowered such that the tip of the pen contacts the medium in order to produce markings thereon. The pen comprises an ink reservoir containing ink of a certain color. The pen is held on the Z-axis carriage in a way so that it can easily be replaced by another pen, for example if a different color for the graphical representation is desired or if the ink reservoir in the pen is empty. The replacement of the pen can be done manually by a user, but it is preferred to perform the replacement automatically under-computer control. Several replacement pens and additional pens of different colors can be arranged in a pen carousel (not shown) from which they can be transported to the Z-axis carriage and inserted there. For producing two-dimensional plots on a sheet of paper, the paper is moved in a first direction (X-direction) and the main carriage is moved in a second direction (Y-direction) orthogonal thereto. The driving of the paper can be accomplished by means of a grit wheel and pinch wheel assembly between which the paper is moved. By appropriate movement of the paper (either in the positive or negative X-direction) and coordinated related movement of the main carriage (either in the positive or negative Y-direction), any desired graphical representation can be made on the paper sheet. Of course, the invention is not limited to any particular type of plotter, but can be utilized in any plotter configuration where line vectors are drawn on media by pens. For example, another type of plotter which may utilized the invention holds the paper stationary while the main carriage is moveable in the X- and Y-directions so that the pen can be placed on any desired point of a media sheet.
A sensing system intermittently monitors the quality of the pen on the media by scanning across a point on a line, with the point illuminated by light emitted from a light source as an LED emitting a beam of green light.
The output signals of the sensing system are amplified filtered and converted into digital data. This digital data is then supplied to a microprocessor 79 for comparison with benchmark data.
Optical sensor circuits 78 provide input signals to a light source on the pen carriage 20 and then process output signals from the optical sensor on the pen carriage 20 back to the microprocessor 79.
Referring now to FIG. 1, the various interconnecting circuits for actuating the pen verification procedures are shown in a block diagram. Since a light source in the form of an LED 80 and a optical source sensor 82 are directly mounted on the pen carriage 20, a pen-lift drive circuit 83 is interconnected between the microprocessor 79 and the pen carriage 20 to move the carriage into the optimum focal distance above the media. Signals from the microprocessor 79 are passed through latch 84 to a digital/analog converter 86 which produces an output signal which passes through driver 88 to the LED 80. The LED transmits a wide beam of light (see outwardly flared arrows schematically extending below LED 80 in FIG. 4) having a color centered in the visual spectrum to a predetermined locale around a line vector on the medium, and the sensor 82 measures the intensity of the reflected light as the sensor scans across the line (i.e., from one side of the line through a point on the line to the other side of the line). Typical scans of actual plots are shown in FIGS. 8-9 at 96, 97, and 98, and a typical curve of the intensity for a satisfactory pen marking a shown in graph 100 of FIG. 10.
The structural details of the pen carriage 20 are shown in the exploded view of FIG. 2, and the front view of FIG. 4. A main carriage 120 carries variously positioned Y-direction tires 122 mounted on bearings 124, and a bumper 123, to facilitate the movement along the Y-axis. In order to provide movement of the Z-carriage and the pen between a raised position to a lowered position (see the double pointed arrows in FIG. 8), the main carriage also carries a magnetic cup 126 and a Z-direction tire 130 for engagement with a Z-axis carriage 128. An energized coil 132 mounted on an insert 133 in the Z-axis carriage is magnetically pushed away from its matching magnetic cup 126 to move the pen into the down position. The actual location of the pen (and sensor/LED assembly described in more detail below) relative to the underlying media is monitored by an encoder scale 134 which moves up and down adjacent to an optical encoder 136. A carriage PCB 138 carries the encoder 136 and also provides the circuit interconnections through wires 140 to the coil as well as the circuit interconnections to the LED 80 and the sensor 82. A stationary inner linear bearing 142 engages a matching moving outer bearing sleeve 143, and an expansion spring 144 holds the Z-carriage in a normally raised position.
When a pen is mounted on the carriage 20, a compression spring 146 forces a pawl 148 into locking engagement against the outer pen casing 150 (see FIG. 3).
It is preferable to calibrate each plotter before it is used in order to optimize the ability of the sensor to measure the light intensity of a plotted line. Accordingly, as best shown in FIG. 4, the pen is removed and a paper feeler 152 can then be used to determine the actual distance to a sheet of underlying media for this particular plotter. In addition, the paper feeler can scan the platen along the entire length of the Y-axis to determine variations in this actual distance measurement. Such actual distances measured during calibration are recorded in memory so that during normal operation the Z-axis carriage can be moved to achieve the optimum focal distances as shown in mm in the drawing of FIG. 4. It has been determined that the present invention nevertheless operates satisfactorily for a photodiode 156 spaced a distance "Si" of 17.2 mm from a lens 154 even though the distance "So" of 15.1 mm between the lens and the medium may vary plus or minus 1.5 mm.
The sensor 82 is shown in detail in FIGS. 5-6 and includes a casing 160, a chip assembly 162, a cap 164, and a sleeve 166 having a bracket 168 for holding the LED 80. The sleeve snaps into position at the bottom of the casing 160 and holds the lens in fixed position inside the sleeve at the lower end of the casing. The chip assembly includes a photodiode as well as a two-stage amplifier, and the lower portion 179 of the chip assembly is transparent (such as clear plastic) to allow reflected light to pass unimpeded to the photodiode. The cap 164 must fit snugly over the top of the chip assembly to nest into a casing receptacle to prevent any extraneous light: from passing through to the photodiode. Although both the sensor and the LED are shown at an angle with respect to the Z-direction, it is possible to have other angular positioning of the sensor, so long as the LED preferably emits light at an angle to avoid undue specular glare from the media.
Thus, the invention provides a method and apparatus for using a uniquely designed optical sensor that periodically senses the quality of plotted lines by scanning across selected points on the lines, and measuring the difference in contrast between the actual plotted line and a benchmark such as a default value or an actual value obtained when that particular pen was qualified. When the optical line sensor detects a pen failure or pen deficiency, the plotter corrects the problem.
FIG. 7 shows in more detail the processing of the output signal from the sensor through op-amp 180, resistors 182, 183, filter circuits 184, 185 and A/D converter 186.
In the flow chart of FIG. 10, it is important to first check the media such as paper at the actual spot where the sample vectors are to be drawn to be sure there are not a ready previous plots or other non-white interference. The first percentage measurement at 200 is based on the percentage drop in reflected signal intensity from total white to absolute dark (total light absorbance). Thus, if five of the proposed six points each show a print contrast ratio of less that 8%, the it is ok to proceed to the next stage of actually drawing the sample plot as shown at 202.
In order to establish the PCR threshold, various procedures can be used. In the preferred form of the invention, the average intensity of the PCRs for five points is computed, and then so long as the pen plots checked during the pen verification procedure have PCRs of not less than 40% of such average, then the plots actually tested are deemed satisfactory. If a user is using only black pens and does not need high quality plotting, it is possible to forego the actual pen qualification procedure and just accept that any pen having a print contrast ratio of more than the default of 8% on the scale of percentage signal drop form all white to total darkness will be deemed a "good" pen.
A second embodiment of the invention is exemplified in a large format color inkjet printer/plotter as shown in FIGS. 11-29. More specifically, FIG. 11 is a perspective view of an inkjet printer/plotter 210 having a housing 212 mounted on a stand 214. The housing has left and right drive mechanism enclosures 216 and 218. A control panel 220 is mounted on the right enclosure 218. A carriage assembly 300, illustrated in phantom under a cover 222, is adapted for reciprocal motion along a carriage bar 224, also shown in phantom. The position of the carriage assembly 300 in a horizontal or carriage scan axis is determined by a carriage positioning mechanism 310 with respect to an encoder strip 320 (see FIG. 12). A print medium 330 such as paper is positioned along a vertical or media axis by a media axis drive mechanism (not shown). As used herein, the media axis is called the X axis denoted as 201, and the scan axis is called the Y axis denoted as 301.
FIG. 12 is a perspective view of the carriage assembly 300, the carriage positioning mechanism 310 and the encoder strip 320. The carriage positioning mechanism 310 includes a carriage position motor 312 which has a shaft 314 which drives a belt 324 which is secured by idler 326 and which is attached to the carriage 300.
The position of the carriage assembly in the scan axis is determined precisely by the encoder strip 320. The encoder strip 320 is secured by a first stanchion 328 on one end and a second stanchion 329 on the other end. An optical reader (not shown) is disposed on the carriage assembly and provides carriage position signals which are utilized-by the invention to achieve optimal image registration in the manner described below.
FIG. 13 is perspective view of a simplified representation of a media positioning system 350 which can be utilized in the inventive printer. The media positioning system 350 includes a motor 352 which is normal to and drives a media roller 354. The position of the media roller 354 is determined by a media position encoder 356 on the motor. An optical reader 360 senses the position of the encoder 356 and provides a plurality of output pulses which indirectly determines the position of the roller 354 and, therefore, the position of the media 230 in the X axis.
The media and carriage position information is provided to a processor on a circuit board 370 disposed on the carriage assembly 100 for use in connection with printhead alignment techniques of the present invention.
The printer 210 has four inkjet print cartridges 302, 304, 306, and 308 that store ink of different colors, e.g., black, magenta, cyan and yellow ink, respectively. As the carriage assembly 300 translates relative to the medium 230 along the X and Y axes, selected nozzles in the inkjet print cartridges 302, 304, 306, and 308 are activated and ink is applies to the medium 230. The colors from the three color cartridges are mixed to obtain any other particular color. Sample lines 240 are typically printed on the media 230 prior to doing an actual printout in order to allow the optical sensor 400 to pass over and scan across the lines as part of the initial calibration.
The carriage assembly 300 positions the inkjet print cartridges and holds the circuitry required for interface to the ink firing circuits in the print cartridges. The carriage assembly 300 includes a carriage 301 adapted for reciprocal motion on front and rear slider rods 303, 305.
As mentioned above, full color printing and plotting requires that the colors from the individual print cartridges precisely applied to the media. This requires precise alignment of the carriage assembly as well as precise alignment of the print cartridges in the carriage. Unfortunately, paper slippage, paper skew, and mechanical misalignment of the print cartridges results in offsets in the X direction (in the media advance axis) and in the Y direction (in the carriage or axis) as well as angular theta offsets. This misalignment causes misregistration of the print images/graphics formed by the individual ink drops on the media. This is generally unacceptable as multi-color printing requires image registration accuracy from each of the printheads to within 1/1000 inch (1 mil).
FIG. 14 shows a presently preferred embodiment of printheads each having two groups of nozzles with a column offset 410. By comparing the relative positions of corresponding nozzles in different printheads along the Y axis, it is possible to determinine an actual horizontal offset 412 between two printheads, and by comparison with a nominal default offset 414 determine an actual offset 416 in the carriage scan axis. This is repeated for all of the different printheads while they remain on the carriage.
Similarly, by comparing the relative positions of corresponding nozzles in different printheads along the X axis, it is possible to determine an actual vertical offset 418 in the media advance axis. This is also repeated for all of the different printheads while they remain on the carriage.
In order to accurately scan across a test pattern line, the optical sensor 400 is designed for precise positioning of all of its optical components. Referring to FIGS. 15A, 15B and 16, the sensor unit includes a photocell 420, holder 422, cover 424, lens 426, and light source such as two LEDs 428, 430. A unitary light tube or cap 432 has a pair of notched slots 434 which engage matching tabs 436 on a lower end of the holder 422 upon insertion and relative rotation between the cap and the holder. The two LEDs are held in opposite apertures of two shoulders 438 which have a size slightly less than the outside diameter of the LEDs, to prevent the LEDs from protruding into a central passageway which passes through the holder to the photocell
A protective casing 440 which also acts as an ESD shield for the sensor components is provided for attachment to the carriage as well as for direct engagement with the shoulders of the light tube. In that regard, the top of the shoulders are sized and shaped to snugly fit inside downwardly tapered side walls 442 of the casing, with the top of the LEDs abutting against an upstanding flange 444 and with a lower portion of the shoulders held tightly by arms 446 which flex outwardly to an open position while the light tube is being pushed into a position of engagement with the casing. Upon completion of the engagement, the arms return to a closed latched position with a lip 448 on the end of each arm 446 preventing disengagement of the light tube (and its LEDs) during normal use.
FIGS. 17A-17E show a preferred sequence of steps for assembling the optical sensor. Firstly, a modular flex-circuit assembly is created with an elongated TAB circuit 450 having a junction portion 452 with soldered through-holes which (a) connect and support a first pair of wire leads 454 to one LED, (b) connect and support a second pair of wire leads 456 to another LED, and (c) connect and support a set of three wire leads 458 coming from the photocell (FIG. 17A). Secondly a U-shaped cover 424 holds the photocell in nested position at the upper end of the holder, while the LEDs and holder are positioned by the light tube (FIG. 17B-17C). Finally, the subassembly is inserted into the casing, with a free end 462 of the TAB circuit extending out through an access slot in the casing (FIGS. 17D and 17E).
It will be appreciated by those skilled in the art from the foregoing description that the invention provides a self-fixturing modular assembly whereby the light tube acts as a cap for holding both the two LEDs as well as the lens/holder/photocell/cover composite in fixed relative positions. Accordingly, if desirable the soldering of the interconnections at the co-planar junction portion of the flex-circuit can be done after assembly of the various component parts held by the cap.
The fully assembled optical sensor unit can then be placed inside of vertical rib 464 and against back plate 466 for self-attachment by rear tab 468, front notch 470, and lower front hook 472 to matching X/Y/Z datum-like surfaces on the carriage (see FIGS. 18-20).
It will be understood by those skilled in the art that by having the electronic components of the optical sensor all connected through a common co-planar junction portion of a flex-circuit allows the flex-circuit to be small and less costly. Also, it allows for the substitution of an even less expensive printed circuit board at the common junction if that is deemed necessary.
The specification details of the flex-circuit member and its co-planar junction are shown in FIGS. 21-23, and are self explanatory. It is noted that the co-planar junction 452 is wider than the rest of the TAB circuit to allow sufficient space for a pair of solder connections 480 for a blue light LED, a pair of solder connections 482 for a green light LED, and a set of three solder connections 484 for the photocell. A first activation line 486 connects the blue light LED and a second separate activation line 488 connects the green light LED to allow independent control over the LEDs depending on the media markings. It is noted that in this particular embodiment, the green light LED is used to sense media markings made by black, or cyan, or magenta ink, while the blue light LED is used to sense media markings made by yellow ink.
The details of the through-holes in the junction portion are shown in FIG. 23, with an enlarged diameter upper hole 490 through a polyimide coverlay 492 and an smaller diameter lower hole 493 through a polyimide base 494 and a copper conductor layer 495. Acrylic adhesive layers 496 provide the required lamination for the TAB circuit. A small bottom stiffener layer 498 provides support for exposed ends of the conductors to be connected to a carriage circuit board such as through a zif connector.
The circuitry for both the photocell 420 (with amplifier) as well as for the green light and blue light LEDs is shown schematically in FIG. 24.
FIG. 25A shows the path of light emitted from one LED as the light is transmitted through the inside passageway of the light tube to the platen. FIG. 25B shows the path of light reflected back from the platen through the lens to the optical sensor. The inner walls 500 of the light tube help to focus the transmitted light in an area surrounding a point centrally located under the optical sensor, while the outer walls 502 of the light tube help to block excessive external light from being reflected from the platen up to the photocell. The lower end 504 of the light tube (i.e., cap) is preferably positioned in close proximity to the platen.
One of the features of the invention is the unitary construction of the light tube which provides both optical and structural benefits. In that regard, although there may be other smooth plastic-like materials which are suitable, the light tube selected for use in the preferred embodiment was made from a poly-carbonate material.
There is an abrupt inner diameter change at the upper end of the passageway leading to the photocell, from approximately 3.5 mm to 1.5 mm, leaving a 1 mm ledge which defines a protective aperture 506 leading to the photocell, in order to screen out as much as possible as indirectly reflected light so that the photocell will primarily measure light directly reflected from the central platen point under the optical sensor.
FIG. 26 shows some exemplary data taken for various distances from the bottom of the cap to the platen, showing that the optical system of the present invention can operate to accurately measure the print contrast ratio (PCR) despite variations which increase or decrease the preferred 2 mm distance.
The formula for calculating the PCR from the data shown in FIG. 26 is: ##EQU1## Vwhite=sensor voltage output for white reflection Vmin=sensor voltage output for minimum reflection
Vdk=sensor voltage output for absolute darkness
FIG. 27 shows how a sample pattern is printed in order to provide a basis for determining Y axis printhead offsets between C, M, K and Y nozzle arrays. In the preferred form, the width of each bar is 14 pixels on a 600 dpi grid and the white space between bars is 18 pixels, while the preferred length of each bar is 170 pixels on a 600 dpi grid. The Y axis alignment patterns are scanned in a routine which obtains samples at 600 samples/inch from the centered half portion 510 of each different color C M K Y alignment pattern (i.e., the 13 central bars). The number of samples read across each vertical bar is 416.
Similarly, FIG. 28 shows how a sample pattern is printed in order to provide a basis for determining X axis printhead offsets between C, M, K and Y nozzle arrays. In the preferred form, the actual relative width of each bar and white space is the same as for the Y axis sample patterns. But the C, K, and Y sample patterns (shown as blank bars in FIG. 28 to distinguish them from the magenta bar pattern) are each preceded by a pattern of M bars, since in the preferred form all of the relative alignment spacings are measured from the position of the magenta printhead. The magenta bar pattern is repeated again after each separate C K Y pattern in order to provide a basis for determining paper advance error.
The X axis alignment patterns are scanned in a routine which obtains samples at 600 samples/inch from the centered two-thirds portion 512 of each different ink color alignment pattern (i.e., the 12 central bars). The number of samples read across each horizontal bar is 384.
It has been found satisfactory to print the sample bars at a resolution of 300 dpi and then scan the bars in a direction normal to the bar every 1/600th of an inch in order to generate data which will provide for correction in the Y axis in 1/600 inch increments.
The scanning speed is 6 inches/sec and uses the green LED for scanning the K, C and M patterns, and the blue LED for scanning the Y patterns.
Even though the sample bars are generated by raster printing, the technique of passing the sensor across the "line" to obtain the V-white and V-min readings is substantially the same technique used in the first pen plotter embodiment for obtaining the PCR date for vector lines drawn by a color pen.
It should be understood that the foregoing description is only illustrative of the invention. Various alternatives and modifications will be understood and developed by those skilled in the art without departing from the spirit of the invention. According, the present invention is intended to include all such alternatives, modifications and variations which fall within the scope of the following claims. | Light emitted from an obliquely angled LED source is directed by peripheral light tube walls which extend vertically toward media displaying printed indicia. The emitted light provides an illuminated area surrounding the printed indicia, while the light tube walls shield the printed indicia from excessive external light, so that a sensor measures the intensity of emitted light directly reflected from the media through a protective aperture. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel NAD synthetase, a process for production of said enzyme and an assay method using the same.
More particularly, the present invention relates to a novel NAD synthetase, which at least catalyzes the reaction (a) hereinbelow in the presence of Mg++ or Mn++ ion, and does not catalyze the reaction (b) hereinbelow in the presence of Mg++ ion, utilizes ammonia including ammonium ion as a substrate, and does not utilize at least glutamine and asparagine as a substrate, to a process for production of the same, and to an assay method of any one of ATP, deamide-NAD and ammonia including ammonium ion in a specimen by incubating the said specimen with the present NAD synthetase. ##STR3##
2. Description of the Prior Art
Heretofore, NAD synthetase has been known to exist in rat liver [J. Biol. Chem. 233, 493-500 (1958)], porcine liver [ibid., 236, 525-530 (1961)], yeast [ibid., 247, 4794-4802 (1972)] and E. Coli [ibid., 236, 1494-1497 (1961) and 242, 385-392 (1967)].
These NAD synthetases are classified as NAD synthetase (EC 6.3.1.5) which catalyzes the reaction: ##STR4## and NAD synthetase (EC 6.3.5.1.) which catalyzes the reaction: ##STR5##
These NAD synthetases utilize NH 3 and an amide of L-Gln as a substrate, and are differentiatd by the inhibitory action of azaserine.
Km-values of NAD synthetase (EC 6.3.1.5) are reported as 6.5×10 -5 M (NH 4 +) and 1.6×10 -2 M (L-Gln) [J. Biol. Chem., 1494-1497, (1961), ibid., 242, 385-392 (1967)] and Km-values of NAD synthetase (EC 6.3.5.1) are reported as 6.4×10 -8 M (NH 4 +) and 5×10 -8 M (L-Gln) [J. Biol. Chem., 247, 4794-4802 (1972), ibid. 233, 493-500 (1958)].
An assay method for NAD synthetase has been reported, in which the generated NAD is reduced by alcohol dehydrogenase (EC 1.1.1) and the absorbency of the generated reduced NAD (hereinafter designated NADH) is spectrophotometrically measured at 340 nm, or the generated NAD is measured by fluorometry.
The above method assays a component in a specimen, selected from ATP, deamide-NAD and an amide donor, and comprises, as a main reaction step, incubating the specimen containing ATP, deamide-NAD or an amide donor such as NH 3 , L-glutamine or L-asparagine, with known NAD synthetase (EC 6.3.1.5 and EC 6.3.5.1) in the presence of ATP, deamide-NAD, an amide donor and Mg++ to generate NAD, and further comprises, as a side reaction, performing coenzyme cycling reaction by combining the oxidation-reduction reaction system of coenzyme NAD with the oxidation-reduction reaction system of coenzyme reduced NAD, whereafter a consumed or generated component in the said cycling reaction is measured to effect the assay (Japan Unexam. Pat. Publ. No. 59-198995).
As explained, known NAD synthetases utilize an amide donor substrate of L-glutamine, whereas the present NAD synthetase, which catalyzes at least the reaction (a) hereinbelow in the presence of Mg++ or Mn++ ion, and does not catalyze the reaction (b) hereinbelow in the presence of Mg++ ion, utilizes ammonia including ammonium ion as a substrate and does not utilize at least glutamine and asparagine as a substrate, is heretofore unknown. ##STR6## Also, the known NAD synthetases have substrate specificity on L-glutamine, and so NH 3 cannot be measured using these enzymes in the presence of L-glutamine.
SUMMARY OF THE INVENTION
We have found that a strain of Bacillus, namely sp. H-804, isolated from a soil sample obtained from hot spring water at Tanoyu-machi, Beppu-shi, Oita-ken, Japan, produces the present NAD synthetase, which catalyzes at least the said reaction (a) hereinbelow in the presence of Mg++ or Mn++ ion, and does not catlayze the said reaction (b) hereinbelow in the presence of Mg++ ion, utilizes ammonia including ammonium ion as a substrate, and does not utilize at least glutamine and asparagine as a substrate. ##STR7##
OBJECTS OF THE INVENTION
A first object of the present invention is to provide the present NAD synthetase.
Another object of the present invention is to provide a process for production of the said enzyme.
A further object of the present invention is to provide an assay method for any one of ATP, deamide-NAD and ammonia including ammonium ion in a specimen by incubating the said specimen with the present NAD synthetase, and measuring a component consumed or generated in the ensuring reaction.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1: optimum pH curve of the present NAD synthetase;
FIG. 2: pH-stability curve of the present NAD synthetase;
FIG. 3: heat-stability curve of the present NAD synthetase;
FIG. 4: optimum temperature curve of the present NAD synthetase;
FIG. 5: assay curve of ATP;
FIG. 6: assay curve of ammonium;
FIG. 7: assay curve of creatinine;
FIG. 8: assay curve of ammonia measured at 340 nm;
FIG. 9: assay curve of ammonia measured with generated ATP;
FIG. 10: assay curve of deamide-NAD;
FIG. 11: optimum concentration curve of MgCl 2 ; and
FIG. 12: optimum concentration curve of MnCl 2 .
DETAILED DESCRIPTION OF THE INVENTION
Taxonomical properties of the strain which produces the present NAD synthetase are as follows:
A. Morphological properties:
Observed by microscope on nutrient agar slant medium at 50° C. for 1-3 days cultivation.
1. Form and arrangement: round edges, straight or slightly curved bacilli, single or binary chains.
2. Size: 0.5-1.0×1.6-5.5 μm.
3. Motility: motile by peritrichous flagella.
4. Spores: forms center or subterminal, 0.8-1.0×1.0-1.5 μm, swelling the sporangia.
B. Growth on various media (at 50° C.):
1. Nutrient agar plate: colonies grayish to pale yellowish white with semi-transparent, weak linear growth. No soluble pigment formation.
2. Nutrient agar slant: grayish to pale yellowish with semi-transparent, round plain colonies. No soluble pigment formation.
3. Bouillon agar: uniformly turbid, good growth. Precipitate forms in 2-3 days.
4. BCP milk: no change.
C. Physiological properties (+: positive, -: negative):
______________________________________Gram's stain +KOH reaction -acid-fast staining -capsulation -anaerobic growth -catalase production + (weak)oxidase production + (weak)urease formation(SSR medium) -(Chris. medium) -lecithinase production no growthgelatin hydrolysis +starch hydrolysis +casein hydrolysis +esculin hydrolysis +arginine hydrolysis -cellulose hydrolysis -indole production -H.sub.2 O production + (lead acetate paper)acetonin production -MR test -nitrate reduction -growth on NaCl addedmedium +growth on 0.1% NaCladded medium +growth on 0.25% NaCladded medium +growth at 65° C. +growth at 50° C. +growth at 37° C. -growth at pH 9.0 -growth at pH 8.0 +growth at pH 5.6 +growth at pH 4.8 -acid formation from sugar* (no gas formation):adonitol - D-mannose +L(+)arabinose + melezitose +cellobiose + melibiose +dulcitol - raffinose +meso-erylthritol - rhamnose -D-fructose - D-ribose +fucose - salicine -D-galactose + L-sorbose -D-glucose + sorbitol -glycerin + starch +inositol - saccharose +inilin - trehalose +lactose + D-xylosemaltose -D-mannitol +OF test (Hugh-Leifson medium) NT (no change)OF test (modified)** O (oxidation) *basal medium: (sugar added ammonium medium)(ASS)
(NH.sub.4).sub.2 HPO.sub.4 1.0 g KCl 0.2 gMgSO.sub.4.7H.sub.2 O 0.2 g Yeast ex 1.0 gAgarose 3.0 g BTB 0.02 gDistilled water 1000 ml pH 7.0 **modified medium: 10.0 g glucose added to basal medium.Utilization test: Simmons medium Christensen mediumcitrate - -malonate - -gluconate - +propionate - -maleinate - -succinate - +malate + +______________________________________
According to the above taxonomical properties, present strain H-804 is a bacterium having the characteristics of round edges, straight or slightly curved bacilli, Gram-positive, sporulating at 0.5-1.0×1.6-5.5 μm thermophilic bacterium, weak catalase and oxidase production, no motile and oxidative degradation of sugar (glucose). Comparing these taxonomical properties with Bergey's Manual, 8th Ed., 1974, Manual of Medicinal Bacteriology, 2nd Ed., 1974 and Agriculture Handbook, p. 427, "The genus Bacillus", the present strain is characterized by spore formation and aerobic growth and as so is referred to as genus Bacillus. Among the strains belonging to genus Bacillus that are thermophilic or thermotolerant, (a) Bacillus subtilis, (b) Bacillus coagulance, (c) Bacillus liqueniformis, (d) Bacillus brevis and (e) Bacillus stearothermophilus can be mentioned. The present strain can be grown at over 30° C., and hence (A) Bacillus stearothermophilus and (B) Bacillus brevis are suggested. A comparison of these strains with the present strain is as follows: (+: positive, -: negative, d: different in strain)
______________________________________Size (μm) H-804 (A) (B)______________________________________width 0.5-1.0 0.5-0.1 0.6-0.9length 1.6-5.5 2-3.5 1.5-4.0Gram's strain +(decolor) indefinite indefinitesporulation + + +swelling of spore + + +motility - + +catalase production (+) + +anaerobic growth - - -acetoin production - - -growth temperaturemax. (°C.) >65 65-75 40-60min. (°C.) >37 30-45 10-35growth at pH 5.7 + - dgrowth at 5% NaCl - d -added mediumacid formation from sugar:glucose + + +arabinose + d -xylose + d -mannitol + d dgas production from sugar - - -starch hydrolysis + + dcitrate utilization - - dnitrate reduction - d dindole production - - -caseine hydrolysis + d +______________________________________
The properties of the present strain are quite similar to those of Bacillus stearothermophilus, it is reported that the non-motile strain can easily be obtained, and a comparison of the other properties suggested the similarity of the present strain with Bacillus stearothermophilus. The present strain is thus named Bacillus sterothermophilus H-804. The strain has been deposited in the Fermentation Research Institute and assigned FERM BP-1408.
In the present invention, among the present NAD synthetase-producing microorganisms belonging to the genus Bacillus, the above strain is an example, but any strain which belong to the genus Bacillus and produces the present NAD-synthetase can be used.
Also, an artificial mutant can be prepared by isolating DNA bearing the genetic code of the present NAD synthetase, by recombinant DNA technology from the present NAD synthetase-producing microorganisms, cloning the said NAD into other microorganisms which do not produce the present NAD synthetase, and thus imparting to said other microorganisms the ability to produce the present NAD synthetase. The present enzyme produced by such mutants and an assay method using the same are included in the scope of the present invention.
An NAD-synthetase-producing microorganism belonging to the genus Bacillus is cultured in a conventional medium for enzyme production. Cultivation is carried out in liquid or solid culture, and submerged aeration culture is preferred for industrial production.
The nutrient sources of the medium can be conventional media for microorganism cultivation. Examples of carbon sources are assimilable carbon compounds such as glucose, sucrose, lactose, maltose, starch, dextrin, molasses or glycerin. Examples of nitrogen sources are assimilable nitrogen sources such as corn steep liquor, soybean powder, cotton seed powder, wheat gluten, peptone, meat extract, yeast extract or casein hydrolyzate. Salts such as magnesium, potassium, sodium, zinc, iron, manganese, phosphate or halogen, can be used.
The culturing temperature for Bacillus stearothermophilus H-804 is chosen with regard to the growth of NAD-synthetase-producing microorganisms and the production of the enzyme, and is 48°-70° C., preferably 55°-60° C. The culturing time can be varied depending on the culturing conditions, and is generally 10-20 hours. Naturally, cultivation should be stopped upon maximum production of enzyme. The aeration agitation speed is usually 200-400 r.p.m.
Since the enzyme is an endo-enzyme, the cultured cells are collected by means of filtration or centrifugation, and the collected cells are mechanically disrupted by ultrasonication. This is followed by French pressing or glass bead treatment, or enzymatic digestion by lysozyme, with the addition, if necessary, of surface active agents such as Triton X-100 (trade name) or Adekatol SO-120 (trade name).
The enzyme solution is, with or without concentration, subjected to slating-out by adding soluble salts such as ammonium sulfate, or treated by adding a water-miscible organic solvent such as methanol, ethanol, acetone or isopropanol to precipitate the enzyme. The precipitation is dissolved in water or a buffer solution, dialyzed if necessary, and chromatographed by an ion exchange resin such as DEAE-Sephadex, DEAE-Sepharose, carboxymethyl cellulose, carboxymethyl Sepharose or carboxymethyl Sephadex, or by gel-filtration using a molecular sieve such as Sephadex G-200, Sephadex CL-6B or Sephacryl S-200 (trade name). If required, stabilizing agents are added and lyophilized to prepare purified enzyme.
The biochemical properties of the above NAD synthetase are as follows:
(1) Molecular weight: approximately 50,000 [gel filtration with polyvinyl-gel (trade name GPC 3,000 SW: Toyo Soda Co.), using column (7.5 mm ID×60 cm). Standard proteins: aldorase (rabbit muscle, M.W. 150,000), bovine serum albumin (M.W. 67,000), avoalbumin (egg: M.W. 45,000) and cytochrome C (horse heart, M.W. 13,000)]
(2) Isoelectric point: approximately pH 4.6 (electrophoresis using carrier-Ampholite, using a column (24×30 cm LKB Co.), 700 V, 48 hrs. cutting each 2 cm, measured pH and activity)
Mg++ or +Mn++
(3) Activity: ATP+deamide-NAD+NH 3 →ATP+PPi+NAD
(4) Substrate specificity:
NH 3 including ammonium ion.
In an assay method for enzyme activity hereinafter described (NH 4 ) 2 SO 4 25 mM is replaced by L-valine, L-homoserine, L-serine, L-alanine, L-methionine, L-tyrosine, L-threonine, L-leucine, L-isoleucine, L-arginine, L-phenylalanine, L-histidine, L-asparagine and L-glutamine, and the enzymatic activity is measured. Relative activity of the present enzyme on these amino acids is 0.0 when that on (NH 4 ) 2 SO 4 is set at 100. Therefore the present enzyme can utilize only ammonia including ammonium ion as a substrate, but does not utilize at least the above-mentioned amino acids.
(5) Optimum pH:
Reaction medium I, identified hereinafter under the assay method for enzymatic activity, is mixed with dimethylglutarate-NaOH buffer (pH 5.0-7.0), Tris-HCl buffer (pH 6.5-9.0) and glycine-NaOH buffer (pH 8.5-10.0), and the enzymatic activity is measured after stopping the enzyme action by heating at 100° C. for 10 minutes. As shown in FIG. 1, the optimum pH is pH 8.5-10.0.
(6) pH stability:
The present enzyme is dissolved in 50 mM dimethyl-glutarate-NaOH buffer (pH 5.0-7.0), Tris-HCl buffer (pH 6.5-9.0), or glycine-NaOH buffer (pH 8.5-10.0), and the solution is incubated at 60° C. for 15 minutes. The remaining enzymatic activity is measured by means of an assay method for enzyme activity. The results are shown in FIG. 2, wherein the enzyme is stable at pH 7.5-9.0.
(7) Heat stability:
The present enzyme dissolved in 50 mM Tris-HCl buffer (pH 8.0) is held at various temperatures for 15 minutes each, and the remaining enzymatic activity is measured. The results are shown in FIG. 3, wherein the enzyme is stable at least below 60° C.
(8) Optimum temperature:
The present enzyme is mixed with the reaction medium I hereinafter identified under the assay method for enzymatic activity, and incubated at temperatures of 50° C., 55° C., 60° C., 65° C. and 70° C. for 10 minutes each, immediately whereafter the mixture is cooled, and reaction medium II (defined hereinafter under the assay method for enzymatic activity) is added thereto at 37° C., then the enzymatic activity is measured. Results are shown in FIG. 4, wherein the optimum temperature is approximately 60° C.
(9) Effect of enzyme activators and inhibitors:
In an assay for enzymatic activity, each metal ion (5 mM), EDTA (20 mM) or each surface active agent (0.1%) in Table 1 is added separately to the reaction medium I, and the enzymatic activity is measured. Results are shown in Table 1. The enzyme is inhibited by Ni ion (NiCl 2 , 5 mM) and no activity is observed in EDTA (20 mM).
Furthermore, MgCl 2 (5 mM) is replaced by MnCl 2 (3 mM) in the reagent identified in the enzymatic assay method hereinafter. Enzyme activity is increased 150% in the presence of MnCl 2 (3 mM) as compared with MgCl 2 (5 mM).
TABLE 1______________________________________ Concentration Relative activity______________________________________No addition* -- 100 (%)LiCl 5 mM 100KNO.sub.3 " 99.2KCN " 100NaCl " 102.4NaNO.sub.3 " 96.8NaN.sub.3 " 102.4CaCl.sub.2 " 48.4BaCl.sub.2 " 89.5MnCl.sub.2 " 54.0NiCl.sub.2 " 7.3CsCl " 100AlCl.sub.3 " 73.4FeCl.sub.3 " 88.4EDTA 20 mM 0Triton X-100 0.1% 109.6Nonidet P-40 " 103.9Adekatol PC-8 " 98.7Adekatol SO-120 " 99.1Deoxycholate " 104.7Brig 35 " 102.2______________________________________ *MgCl.sub.2 (5 mM) is added. The other reactons similarly contain Mg.sup.++ in addition to each specified additive.
(10) Assay method for enzymatic activity:
Reaction medium I:
50 mM Tris-HCl buffer pH 8.0
1 mM KCl
5 mM MgCl 2
0.05% bovine serum albumin
2 mM ATP
0.5 mM deamide-NAD
25 mM (NH 4 ) 2 SO 4
Reaction medium II:
50 mM Tris-HCl buffer pH 8.0
10 U diaphorase (Toyo Jozo Co. from genus Bacillus
3% ethanol
10 U alcohol dehydrogenase/ml (Toyo Jozo, yeast)
0.025% NTB (nitrotetrazolium blue)
0.1% Triton X-100
10 mM EDTA
Reaction medium I (0.3 ml) in a test tube is preincubated at 37° C., and the enzyme solution (5 μl) is added thereto, whereafter the mixture is incubated at 37° C. for exactly 10 minutes.
Reaction medium II (0.8 ml) is added thereto to stop the reaction and simultaneously to start the cycling reaction at 37° C. for exactly 5 minutes. After stopping the cycling reaction by adding 0.1 N-HCl (2.0 ml), the absorbency at 550 nm is measured to calculate the enzyme activity. The enzyme activity is calculated by the following equation:
NAD synthetase activity (mU/ml)= ##EQU1##
wherein
ΔA: absorbency of specimen,
ΔS: absorbency of standard solution (0.1 mM NAD),
0.005: specimen volume (ml),
10: reaction time,
f: dilution ratio.
The reaction system of the present invention is summarized as follows: ##STR8##
A specimen for an assay according to the present invention can be a specimen containing at least ATP, deamide-NAD or ammonia including ammonium ion, for example a specimen previously containing any one of these components or a specimen in which one of these components is consumed or generated.
A preferred example of the above enzyme reaction system is a reaction system which consumes or generates ATP, deamide-NAD or NH 3 including ammonium ion, without the coenzyme NAD and NADH, as in the following non-limiting examples.
1. Enzymatic reaction systems which generate ATP:
(1) creatine kinase (EC 2.7.3.2): reducing agent ##STR9## (2) pyruvate kinase (EC 2.7.1.40): ##STR10## (3) acetate kinase (EC 2.7.2.1): ##STR11## (4) carbamate kinase (EC 2.7.2.2): ##STR12## (5) aspartate kinase (EC 2.7.2.4): ##STR13## (6) phosphoglycerate kinase (EC 2.7.2.3.): ##STR14## (7) arginine kinase (EC 2.7.3.3): ##STR15##
2. Enzymatic reaction systems which utilize ammonium generating soluble ammonium salts or NH 3 :
(1) Examples of water-soluble ammonium salts are inorganic or organic ammonium salts which generate ammonium ions, such as ammonium chloride, aqueous ammonia, ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium citrate, etc.
(2) nicotine amidase (EC 3.5.1.19):
nicotine amide+H.sub.2 O→nicotinate+NH.sub.3 +H.sup.+
(3) glutamyl-peptide-glutaminase (EC 3.5.1.44):
L-glutaminyl-peptide+H.sub.2 O→L-glutamyl-peptide+NH.sub.3
(4) arginine deaminase (EC 3.5.3.6):
L-arginine+H.sub.2 O→citrulline+NH.sub.3 +H.sup.+
(5) guanine deaminase (EC 3.5.4.3):
guanine+H.sub.2 O→xanthine+NH.sub.3 +H.sup.+
(6) adenosine deaminase (EC 3.5.4.4):
adenosine+H.sub.2 O→inosine+NH.sub.3 +H.sup.+
(7) creatinine deaminase (EC 3.5.4.21):
creatinine+H.sub.2 O→N-methylhydantoin+NH.sub.3 +H.sup.+
(8) threonine dehydratase (EC 4.2.1.16):
L-threonine+H.sub.2 O→2-oxobutyrate+CO.sub.2 +NH.sub.3 +H.sup.+
(9) aspartate ammonium-lyase (EC 4.3.1.1):
L-aspartate→fumarate+NH.sub.3 +H.sup.+
(10) L-methionine-γ-lyase (EC 4.4.41.11):
L-methionine+H.sub.2 O→2- oxobutyrate+methanethiol+NH.sub.3 +H.sup.+
(11) methylaminoglutamatemethyl transferase (EC 2.1.1.21):
N-methylglutamate+NH.sub.3 +H.sup.+ ⃡glutamate+methylamine
3. Enzymatic reaction system utilizing AMP for assaying deamide-NAD or NH 3 including ammonium ion in a specimen: Adenylate kinase (EC 2.7.4.3):
AMP+ATP⃡ADP+ADP
pyruvate kinase (EC 2.7.1.40):
ADP+phosphoenol pyruvate⃡ATP+pyruvate
(1) pyruvate oxidase (EC 1.2.3.3):
pyruvate+Pi+O.sub.2 +H.sub.2 O⃡acetyl phosphate+CO.sub.2 +H.sub.2 O.sub.2
Thus-generated H 2 O 2 is measured in the presence of peroxidase, and NH 3 including ammonium ion or deamide-NAD in a specimen is measured.
(2) lactate dehydrogenase (EC 1.1.1.27):
pyruvate+NADH+H.sup.+ →L-lactate+NAD
Decrease of A 340 according to an oxidation of NADH is measured in the presence of excess lactate dehydrogenase and NADH.
As illustrated hereinabove, in the present invention, not only reaction mixtures containing ATP or NH 3 that is consumed or generated in the illustrated enzymatic reaction system, but also reaction mixtures for measuring enzymatic activity that are used in the enzymatic reaction system, consumed substrate or generated product, can be used as a specimen to be assayed.
In these enzymatic reaction systems, ATP or NH 3 is assayed for the purpose of determining the enzymatic activity in the said enzymatic reaction or measuring any one of the components thereof. A substance other than the component to be assayed is added at a constant rate as a reagent. The amount of the specimen or reagent can be varied depending on the objects and conditions.
Examples of oxidation-reduction systems with coenzyme NAD are reaction systems constituting dehydrogenase (E 1 ) that consumes NAD to generate NADH and its substrate (S 1 ), or dehydrogenase (E 1 ) with coenzyme NAD or NADP and its substrate (S 1 ). The source of the dehydrogenase is not limited and at least this enzyme reacts with specific substrates and consumes coenzyme NAD to form NADH.
Examples of these enzymes and substrates are mentioned in Enzyme Handbook. Examples are as follows:
lactate dehydrogenase (EC 1.1.1.27) and L-lactate,
glycerol dehydrogenase (EC 1.1.1.6) and glycerol,
glycerol-3-phosphate dehydrogenase (EC 1.1.1.8) and glycerol-3-phosphate,
glucose dehydrogenase (EC1.1.47) and glucose,
malate dehydrogenase (EC 1.1.1.37) and L-malate,
glutamate dehydrogenase (EC 1.4.1.2) and L-glutamate,
3-α-hydroxysteroid dehydrogenase (EC 1.1.1.50) and 3-α-hydroxysteroid.
The amount of enzyme used in these oxidation-reduction reactions varies depending on the enzyme activity, the kind of substrate and the ration of coenzyme cycling. The substrate should be in molar excess as compared with the cycling coenzyme, because one mole of substrate is consumed per cycle, and so the amount of substrate is determined by the number of cycles per hour and the reaction time. The concentration of the substrate is preferably selected to attain a maximum reaction rate of oxido-reductase, and is 0.1 mM-100 mM.
The reaction system for coenzyme NADH is a reaction system of functional substances (E 2 ), which at least consumes NADH and generates NAD, and its substrate (S 2 ). Examples thereof are a reaction system with oxidoreductase, which at least consumes NADH and generates NAD, and its substrate, and a reaction system consisting of an electron-transfer agent and a tetrazolium salt.
Coenzyme cycling reaction system:
(a) oxidation-reduction reaction system with coenzyme NAD; ##STR16##
(b) transfer reaction system with coenzyme NADH; ##STR17## wherein;
NH 3 : compound containing monovalent ammonium ion,
E 1 : dehydrogenase which catalyzes a reaction consuming the substrates NAD and S 1 , and generating NADH and P 1 .
E 2 : active substance which catalyzes a reaction consuming NADH and S 2 , and generating NAD and P 2 ,
S 1 : reduced substrate in E 1 ,
S 2 : oxidized substrate in E 2 ,
P 1 : oxidation product of S 1 ,
P 2 : reduction product of S 2 .
A reaction utilizing NH 3 is illustrated as follows: ##STR18##
Examples of oxidoreductase hereinabove are a dehydrogenase which catalyzes, with at least coenzyme NADH, a reaction or an excess amount of specific substrate (S 2 ) to form NAD and reduced substrate (P 2 ) of S 2 ; or NADH: (acceptor) oxidoreductase wherein at least NADH is the coenzyme and the acceptor is cytochrome, a disulfide compound, quinone and its analogues, but the origin is not limited. These enzymes, substrates and acceptors are mentioned in Enzyme Handbook.
Examples of dehydrogenase and its substrate are lactate dehydrogenase (EC 1.1.1.27) and pyruvate, alcohol dehydrogenase (EC 1.1.1) and acetaldehyde, glycerol dehydrogenase (EC 1.1.1.6) and dihydroxyacetone.
Examples of NADH: (acceptor) oxidoreductase are cytochrome b 5 reductase (EC 1.6.2.2) and diaphorase.
Examples of acceptors are methylene blue, flavins, quinones and 2,6-dichlorophenol indophenol.
The combination of NADH: (acceptor) oxidoreductase and acceptor is not limited to an enzyme with coenzyme NADH and an electron acceptor, and is preferably diaphorase (EC 1.6.4.3) and tetrazolium salt, and methylene blue, NAD dehydrogenase (EC 1.6.99.3) and cytochrome c. The concentration thereof is usually 0.05-100 U/ml. The concentration of the tetrazolium salt depends upon solubility of the tetrazolium salt and the ultimately generated formazan, and is generally 1-100 ug per one ml of reagent.
Examples of electron transfer agents are substances which have an activity for oxidizing NADH to NAD without detrimental effect on coenzyme cycling, for example phenazine methosulfate, meldola blue or pyrocyanine. The concentration thereof depends on the cycling ratio and is 5 ug-0.5 mg per ml of reaction mixture.
The above cycling reaction is carried out usually at room temperature to 37° C., preferably at 30°-37° C. The reaction time is not limited but is usually at least one minute, preferably at least 5 minutes. The reaction can be terminated by adding an acid such as hydrochloric acid or phosphoric acid.
After terminating the cycling reaction, the consumed or generated substance in the cycling reaction is measured. Examples thereof are the reduction product (P 1 ) from the reduced substrate (S 1 ) of E 1 , or the reduced product (P 2 ) from the oxidized substrate (S 2 ) of E 2 as a generated component, and the reduced substrate (S 1 ) of E 1 or the oxidized substrate (S 2 ) of E 2 as a consumed component. One of the components P 1 , P 2 , S 1 or S 2 is measured. Most preferably, the product which is colorless as substrate and is colored or fluorescent as product, is colorimetrically measured by absorbency changes. For example, formazan generated from substrate (S 2 ) tetrazolium is reduced to form a reduced product (P 2 ) which is measured colorimetrically. Furthermore, when flavins or quinones are used as substrate (S 2 ), the consumed amount of the substrate (S 2 ) is preferably measured by colorimetry.
In the above reaction, a surface active agent is preferably added for preventing the precipitation of formazan from tetrazolium salt. Examples of surface active agents are non-ionic surface active agents such as Triton X-100 (iso-octyl phenoxy polyethyoxy ethanol, Rohm & Haas Co., USA) or Adekatol SO-120 (ethoxylate or secondary alcohol, Asahidenka Kogyo Co., Japan). The concentration thereof is 0.01-3% for a reagent. Adding a surface active agent provides an increased sensitivity of measurement and stability of formazan pigment.
The colorimetric assay of the generated formazan pigment can be performed by measuring the optical density (OD) at its specific adsorption wavelength such as at 500-550 nm.
In the method of the present invention, an assay method such as an end-point method, a rate assay method or a dry-chemical method (film method, immobilized solid) can advantageously be used.
The method of the present invention is useful for assaying any one of ATP, deamide-NAD, ammonia or ammonium ion, and especially ammonia including ammonium ion can be assayed without affecting amino acid in a specimen. Furthermore, the NAD synthetase enzyme of the present invention is a heat stable enzyme and is preferred for use in an assay method according to the present invention.
The following examples illustrate the present invention but are not to be construed as limiting:
EXAMPLE 1
A liquid medium (pH 7.6, 40 lit.) consisting of peptone 1%, glucose 0.5%, NaCl 0.05% and MgSO 4 .7H 2 O 0.05% a 50 l. jar fermenter was sterilized at 120° C. for 20 mins. A previously cultured Bacillus stearothermophilus H-804 seed-culture medium of the same composition (200 ml) was inoculated therein an the mixture was cultured at 60° C. for 10 hours with aeration of 40 l/min. and agitation of 150 r.p.m. After cultivation, the cells were collected by centrifugation, and were suspended in 10 mM Tris-HCl (pH 8.0 500 ml) containing 0.1% lysozyme, and the medium was incubatd at 37° C. for 30 mins. to lyse the cells. The lysed solution was centrifuged at 5,000 r.p.m. for 10 mins. to obtain a supernatant solution (450 ml). Ammonium sulfate was added thereto to fractionate the solution (0.5-0.71 saturation) and the resultant precipitate, dissolved in 10 mM Tris-HCl buffer (50 ml, 21 U), was dialyzed against the same buffer (5 lit.) The precipitated insolubles were removed by centrifugation (15,000 r.p.m., 10 mins.) The supernatant solution (20 U) was charged on a column (2.5×5 cm) of DEAE-Sepharose CL-6B buffered with 10 mM Tris-HCl buffer (pH 8.0) and eluted with gradient of 0-0.5 M NaCl. The fractions eluting with 0.25-0.3 M NaCl were collected (80 ml, 16.5 U), concentrated by ultra-filtration using a CF-25 membrane (Amicon Co. centriflow membrane cone), chromatographed with Sephadex G-100 (3.6×80 cm) and the active fractions collected to obtain the purified solution (5 ml, 14 U).
EXAMPLE 2
Assay of ATP in a specimen:
Reaction medium III:
50 mM Tris-HCl buffer pH 8.0
20 mM KCl
5 mM MgCl 2
0.05% bovine serum albumin
1 mM deamide-NAD
50 mM (NH 4 ) 2 SO 4
100 mU/ml the present NAD synthetase
Reaction medium IV:
50 mM Tris-HCl buffer pH 8.0
10 U dia-phorase/ml (Toyo Jozo, Bacillus)
3% ethanol
10 U alcohol dehydrogenase/ml (Toyobo, yeast)
0.025% NTB
0.1% Triton X-100
15 mM EDTA
Reaction medium III (0.3 ml) in test tubes was pre-incubated at 37° C., and 0, 10, 20, 30 and 40 μM ATP solutions (5 μl each) were added thereto, respectively; then each was incubated at 37° C. for 10 minutes. Reaction medium IV (0.7 ml) was added thereto, and each was incubated at 37° C. for exactly 5 minutes, whereupon the reaction was stopped by adding 0.1 N HCl (2.0 ml) and the absorbency was measured at 550 nm. The results are shown in FIG. 5. As shown in that figure, good linearity was obtained.
EXAMPLE 3
Measurement of ammonium ion:
50 mM (NH 4 ) 2 SO 4 in reaction medium III in Example 2 was replaced by 5 mM ATP to prepare the present reaction medium. Various concentrations of ammonium sulfate (0, 5, 10, 15 and 20 μM, 5 μl), were added thereto and treated the same way as in Example 2. As shown in FIG. 6, good linearity was obtained.
EXAMPLE 4
Assay of creatinine:
Reaction medium V:
50 mM Tris-HCl buffer pH 8.0
10 mM KCl
5 mM MgCl 2
1 mM ATP
0.05% bovine serum albumin
1 mM deamide-NAD
20 U/ml creatinine deaminase (KODAK)
100 mU/ml the present NAD synthetase
Reaction medium V (0.3 ml) in teest tubes was preincubated at 37° C., and 1, 2, 3 and 4 mg/dl creatinine solutions (10 μl each) were added thereto, respectively; whereafter the resulting series of mixtures were treated the same way as in Example 2. As shown in FIG. 7, good linearity was obtained.
EXAMPLE 5
Assay of ammonium ion:
Reaction medium VI:
50 mM Tris-HCl buffer pH 8.0
10 mM KCl
5 mM MgCl 2
1 mM ATP
0.05% bovine serum albumin
1 mM deamide-NAD
100 mU/ml the present NAD synthetase
Reaction medium VI (0.1 ml) in test tubes was preincubated at 37° C., and 0, 2.5, 5.0, 7.5 and 10.0 μM (NH 4 ) 2 SO 4 solutions (10 μl each) were added thereto, respectively; then each resulting mixture was incubated at 37° C. for 20 minutes and the absorbency was measured at 340 nm. The results are shown in FIG. 8. As shown in that figure, good linearity was obtained.
EXAMPLE 6
Assay of generated ATP:
Reaction medium VII:
50 mM Tris-HCl buffer pH 8.0
10 mM KCl
5 mM MgCl 2
1 mM ATP
0.05% bovine serum albumin
0.05% Triton X-100
1 mM deamide-NAD
10 U/ml myokinase kinase (Sigma, Bacillus)
10 U/ml pyruvate kinase (Sigma, Bacillus)
10 mM phosphoenol pyruvate
100 mU/ml the present NAD synthetase
Reaction medium VIII:
50 mM phosphate buffer pH 8.0
100 mU/ml pyruvate oxidase (Sigma, Pediococcus)
100 mU/ml peroxidase (Sigma)
0.2% phenol
0.3% 4-aminoantipyrine
Reaction medium VII (1 ml) in test tubes was preincubated at 37° C., and 0, 0.5, 1.5 and 2.0 mM (NH 4 ) 2 SO 4 solutions (10 μl each) were added thereto, respectively; then each resulting mixture was incubated at 37° C. for 30 minutes. Reaction medium VIII (0.1 ml) was added thereto, and each resulting mixture was incubated at 37° C. for 30 minutes and the absorbency was measured at 550 nm. The results are shown in FIG. 9. As shown in that figure, good linearity was obtained.
EXAMPLE 7
Assay of deamide-NAD:
Reaction medium IX:
50 mM Tris-HCl buffer pH 8.0
10 mM KCl
5 mM MgCl 2
0.05% bovine serum albumin
50 mM (NH 4 ) 2 SO 4
1 mM ATP
100 mU/ml the present NAD synthetase
3% ethanol
10 U alcohol dehydrogenase
0.1% Triton X-100
Reaction medium IX (1 ml) in test tubes was pre-incubated at 37° C., and 0, 2.5, 5 and 10 mM deamide-NAD solutions (10 μl each) were added thereto, respectively; then each resulting mixture was incubated at 37° C. for 30 minutes and the absorbency was measured at 340 nm. The results are shown in FIG. 10. As shown in that figure, good linearity was obtained.
EXAMPLE 8
Optimum concentration of metal ion:
Reaction medium X:
50 mM Tris-HCl buffer pH 8.0
10 mM KCl
2 mM ATP
0.05% bovine serum albumin
0.5 mM deamide-NAD
25 mM (NH 4 ) 2 SO 4
Reaction medium XI:
50 mM Tris-HCl buffr pH 8.0
10 U diaphorase/ml (Toyo Jozo Co., Bacillus)
3% ethanol
10 U alcohol dehydrogenase/ml (Toyobo Co., yeast)
0.025% NTB
0.1% Triton X-100
10 mM EDTA
To reaction medium X in test tubes were added 0.25, 0.50, 0.75, 1, 2, 3 and 4 mM MgCl 2 and 0.25, 0.50, 0.75, 1, 2, 3 and 4 mM MnCl 2 , respectively; then each resulting mixture was treated, after adding the present NAD synthetase solution, according to the previously described enzymatic assay method.
The results are shown in FIG. 11 (MgCl 2 added group) and FIG. 12 (MnCl 2 added group). As shown in that figure, optimum concentration of MnCl 2 is at 3 mM. | A novel NAD synthetase is produced by culturing a broth of Bacillus stearothermophilus H-804 FERM BP-1408. This new enzyme selectively catalyzes the reaction ##STR1## without catalyzing the reaction ##STR2## The enzyme uses ammonia or ammonium ion as a substrate, but does not use either glutamine or asparagine. Also disclosed is an assay method using the enzyme, for any one of ATP, deamide-NAD, ammonia or ammonium ion in a specimen to be assayed. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 10/987,415, filed on Nov. 12, 2004, which is a divisional of U.S. application Ser. No. 10/171,376, filed Jun. 13, 2002, now U.S. Pat. No. 6,881,229, which claims priority to U.S. Provisional Appln. 60/298,669, filed Jun. 14, 2001, all of which are hereby incorporated by reference herein in their entireties.
BACKGROUND OF THE INVENTION
[0002] This invention relates generally to improvements in articulating joint prostheses, particularly such as an improved prosthetic hip joint or the like. More specifically, this invention relates to a combination of an improved ceramic material articulating against a well known and established metal for use in a metal-ceramic composite articulation which exhibits long wear characteristics with substantial elimination of wear debris, and which further exhibits reduced in-vivo fracture risk. Additionally, this invention is also related to the ability to use metal femoral heads with ceramic acetabular liners. The specific clinical benefits of this feature stem from the ability to use fracture resistant heads with low wear and substantial wear debris elimination, the use of large head diameters, which greatly facilitates minimizing risk of dislocation of the head from the prosthetic joint, and providing surgeons and patients with the choice of using this combination for revision of failed joint prostheses.
[0003] Typical articulating joints, which consist of a metal surface articulating with a ultra-high molecular weight polyethylene (PE) are inadequate. Clinical studies have shown that the principal cause of implant failure is osteolysis secondary to wear of the implant bearing-surfaces. The primary cause appears to be particulate debris in the form of ultra-high molecular weight polyethylene (PE) released, for example, from the PE acetabular liner bearing of a hip prosthesis 1 . Such PE wear debris when released into the peri-implant tissues appears to elicit a deleterious biologic reaction, incorporating foreign-body giant cell and macrophage cell responses leading to bone resorption, and eventual loosening of the prosthetic implant. As a consequence, alternative rigid-on-rigid bearing materials such as ceramic-on-ceramic (C-C) (such as alumina), metal-on-metal (M-M), and the recent cobalt chrome alloy (CoCr)—heavily cross linked PE (XPE) are being introduced.
[0004] Clinical experience from 1983 to the present has encompassed over two million alumina ceramic femoral-head implants. 2,3 Total hip replacement studies incorporating both CoCr and alumina ceramic heads have established the superiority of ceramic-PE couples over metal-PE couples, with alumina-alumina couples demonstrating 2-3 orders lower wear volume than the best ceramic-PE couples. 4 Even so, the major limitation to use of alumina ceramics today is the likelihood of brittle fracture, even in just a low incidence of 2% or less. From the limited series of clinical studies available in the United States, the failure incidence of alumina heads was found to be surprisingly high and of quite short follow-up periods, anywhere from 9 months to 10 years.” 6,5 Thus the fracture incidence in ceramics is still of clinical concern. Typical ceramic materials have low toughness and are prone to failure by brittle fracture. As history has indicated, there is an urgent need to find an improvement to alumina, particularly with ceramic-ceramic couples which have higher bearing contact stresses. 6
[0005] Low wear of articulating components occurs when the mating surfaces have comparable and high hardness, good surface finish, conformal surface geometry, compatible mechanical properties and a low coefficient of friction. It is because of the first three conditions that ceramic-ceramic couples have demonstrated very low wear. Contact damage results in the weaker material when the moduli and hardness of the articulating surfaces are very different, as is the case for CoCr-PE or even zirconia or alumina ceramic-PE. An ideal articulating low wear couple will have closely matching properties and high toughness. Traditional ceramics such as alumina are prone to brittle fracture owing to their low toughness. Such brittle failure in ceramic materials results from propagation of microcracks initiated at and just below the surface. Other ceramic materials such as zirconia, zirconia toughened alumina or Si 3 N 4 that have higher toughness have significantly higher reliability than alumina, owing to the ability to avoid catastrophic failure. Specifically, using such ceramics can allow significant improvements in wear properties along with improved reliability. The specific advantages can be illustrated by considering the articulating hip joint. If the articulating hip joint can be made with a metal femoral head and a ceramic acetabular cup, additional significant clinical benefits can be obtained as listed below:
The metal femoral head does not fail catastrophically as ceramic heads can, assuring patient safety; The metal head can be made of a larger size, up to 44 mm diameter, than ceramic heads can typically be made, providing the surgeon greater flexibility in implant size selection; and The metal head can be used as both a primary hip prosthesis or a revision hip prosthesis.
[0009] This invention describes a Si 3 N 4 acetabular cup-CoCr femoral head couple. This couple is superior to other ceramic-metal couples such as alumina-metal, 7,8,9 owing to compatible properties such as hardness, tensile strength, elastic modulus, high fracture toughness, and lubricity. Si 3 N 4 also has an optimal combination of toughness and strength properties that gives superior damage resistance: the ability to retain strength following contact damage. Friction property studies of Si 3 N 4 ceramics show that Si 3 N 4 -(M-50) steel hybrid bearings and Si 3 N 4 —Si 3 N 4 bearings had the lowest friction coefficients under both lubricated and dry conditions of the materials tested. In contrast, alumina ceramic-ceramic and alumina-steel bearings had approximately three times the friction coefficient when tested under similar conditions.
[0010] It is therefore an object of this invention to provide a new set of bio-compatible articulating surface materials for use in prosthetic joints which will have:
Ultra-low wear with volumetric wear rates of less than 1 mm 3 /10 million cycles; Long in-vivo life; Wide range of sizes maximizing surgeon choice and optimizing fit to patient anatomy; Wide bio-mechanical margin of safety for all sizes, minimizing risk of in-vivo fracture; Preserving modularity of prosthetic articulating joint designs; and Allowing both primary and revision prosthetic articulating joint designs.
SUMMARY OF THE INVENTION
[0017] In accordance with the invention, an improved joint prosthesis such as a hip, knee or shoulder joint or the like is provided with articulation between a first component and a second component, wherein at least one of these joint components is formed from a selected ceramic material designed for high fracture toughness or resistance, and further wherein the assembled joint components are designed for long-term articulation with minimal wear and resultant minimal production of undesired wear debris. The first component has an articulation surface formed from a bio-compatible ceramic with enhanced flexural strength and toughness properties, and wear properties compatible with the second component which has an articulation surface formed from a bio-compatible ceramic with enhanced flexural strength and toughness properties, or from a metallic alloy.
[0018] For example, in one embodiment, an implantable articulating bone prosthesis (e.g., hip or joint prosthesis) is provided, which includes a pair of articulation components respectively defining a pair of articulation surfaces movably engageable with each other. In some embodiments, each of the articulation surfaces is formed from a biocompatible ceramic (e.g., doped silicon nitride ceramic) having a flexural strength greater than about 700 Mega-Pascal (MPa) and a toughness greater than about 7 Mega-Pascal root meter (MPam 0.5 ).
[0019] In a preferred form, the first component of the articulatory prosthesis is formed from a silicon nitride ceramic material doped with other oxides such as yttrium oxide and alumina. Other dopants can include magnesium oxide, or strontium oxide.
[0020] Other features and advantages of the invention will become more apparent from the following detailed description taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] The accompanying drawings illustrate the invention. In such drawings;
[0022] FIG. 1 is a graph illustrating the results of three point bend testing for Si 3 N 4 ceramic test samples;
[0023] FIG. 2 is a graph illustrating the fracture toughness of the Si 3 N 4 ceramic test samples depicted in FIG. 1 ;
[0024] FIG. 3 is a graph showing wear test results for simulated hip prostheses using Si 3 N 4 ceramic acetabular cup and femoral heads (Si 3 N 4 ceramic-Si 3 N 4 ceramic, Stations 1 and 2), and a Si 3 N 4 ceramic acetabular cup and CoCr metal femoral head (Si 3 N 4 ceramic-metal, Station 3); and
[0025] FIG. 4 is a graph showing wear performance of Si 3 N 4 ceramic acetabular cup and ceramic femoral head components (Si 3 N 4 ceramic-Si 3 N 4 ceramic), and Si 3 N 4 ceramic cup and metal (Si 3 N 4 ceramic-metal) head hip prostheses through an extended wear cycle, in comparison with metal-to-metal and traditional ceramic-to-ceramic in-vitro wear data.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] Powders of Si 3 N 4 and dopants such as alumina, yttria, magnesium oxide, and strontium oxide were conventionally processed to form a doped composition of silicon nitride. The dopant amount was optimized to achieve the highest density and mechanical properties. The homogeneous powders were then cold isostatic pressed at 300 Mega-Pascal (MPa) followed by sintering in a controlled atmosphere. Some cold isostatically pressed bars were hot isostatically pressed. A sintering temperature of 1875° C. was found optimal to achieve high density, absence of pores and other flaws and a uniform fine-grained microstructure. The best combination of density and mechanical properties was achieved with Si 3 N 4 doped with 6 weight % Y 2 O 3 +4 weight % Al 2 O 3 .
[0027] Flexural strength was measured on standard 3-point bend specimens per American Society for Testing of Metals (ASTM) protocol method C-1161 and fracture toughness measured using single edge notched beam specimens per ASTM protocol method E399. Bend tests were conducted using test fixtures designed to minimize spurious stresses, with a nominal span of 40 mm. The bending load was applied using a universal testing machine at a cross-head displacement speed of 0.5 mm/min. At least 6 bars were tested to get a measure of the distributions and the Weibull modulus. The composition/process that gave the highest fracture toughness, Weibull modulus and damage resistance was selected for fabricating 28 mm hip prosthesis implant articular femoral head and acetabular cup components. 28 mm CoCr metal femoral heads were obtained from Biomet, Inc. of Warsaw, Ind.
[0028] Wear performance tests of up to 1 million cycle duration were conducted. Wear detection was primarily done gravimetrically with some inspection of the surfaces for wear track analysis and wear debris analysis using scanning electron microscopy. In the hip prosthesis simulator test, the rotating cams (uni-directional) carrying the specimen chambers were driven at 1 Hz frequency through +23° arcs on orthogonal axes. Each vertical load column had a self alignment device and friction torque sensors. In addition, both the anti-rotation peg and the friction sensor pegs were guide mounted on rollers to provide continuous constraint. For this study, the cam rotation was synchronized with the hip-joint loading. The “Paul” physiologic load profile was used. 10,11 All tests were run at 2 KiloNewton (kN) peak load/0.2 kN minimum load. The test cups were arranged in an anatomically inverted position in the hip prosthesis simulator. A solution of 90% bovine serum was used as the lubricant with 10% standard additives of sodium azide and ethylene diamine tetra-acetic acid (EDTA). The specimen chambers were replenished with distilled water during the tests. Lubricant temperature was monitored but not controlled since the lubricant's bulk temperatures run in the range 36-40° C., close to body temperature. The ceramic cups were not sterilized prior to test. Soak control cups were not used for the ceramic-ceramic and ceramic-metal wear tests. The diametral clearance, surface finish and sphericity tolerance was noted. Component wear was determined using a gravimetric method. Wear components were cleaned and dehydrated and each set weighed four times in order with a 32 mm CoCr head as a calibration standard. The overall volumetric wear rate was determined by the slope of the linear regression line. A consistent wear rate, i.e. gradient of the linear regression trend was deemed more significant than the actual magnitude of the wear at any point in time.
[0029] Microstructural features such as grain size, pore size, porosity and defects were observed on sintered Si 3 N 4 specimens after etching with carbon tetra-fluoride plasma. The specimens were found to be dense, with no detectable porosity, and had substantially uniform grain size consistent with high quality ceramics.
[0030] For fracture toughness testing, 2.5 mm×5 mm×25 mm bar specimens with varying notch depth, a, were prepared. The prepared specimens were tested in three-point bending with a span length of 20 mm. The resultant fracture loads were converted to fracture toughness values using ASTM protocol method E399. The fracture strength and toughness values are given in Table 1, and are plotted in FIGS. 1 and 2 . As expected, hot iso-statically pressed specimens labeled as SNH and SNH-1 exhibited high strength, toughness and Weibull moduli. Hence hot iso-static pressed components were fabricated into acetabular and femoral components. The relevant mechanical characterization data obtained are tabulated in Table 1.
[0000]
TABLE 1
Weibull Modulus and Characteristic Fracture Strength of Si 3 N 4 .
Characteristic
Strength
Fracture Toughness
Material
Weibull Modulus M
σ f (MPa)
K lc (MPam 0.5 )
SNH
34.9
853
9.10 (0.66)
SNH-1
19.1
952
9.61 (0.95)
[0031] The results indicate that SNH and SNH-1 have a substantially optimized high flexural strength, greater than about 900 MPa, and fracture toughness, greater than about 9 MPam 0.5 .
[0032] A trial wear test using a hip simulator was conducted using Si 3 N 4 acetabular cups articulating against Biomet's standard 28 mm CoCr metal femoral heads (previously identified). Three Biomet 28 mm heads were used. The mating Si 3 N 4 acetabular ceramic cups were ground without lapping. The surface roughness value (R a ) value was ˜0.5 μm. High wear of the metal femoral heads was observed, attributed to the higher surface roughness, which resulted in scouring the surface of the CoCr metal femoral heads. The wear behavior was found to be linear and typical of 3-body wear, dominated by unstable characteristics. The lubricant solution exhibited the concomitant amount of CoCr metal debris. Further, the wear tracks showed non-polar contact rather than polar contact as anticipated from the low diametral clearance. Fine scratch marks and wear tracks were observed midway between the pole and equator, while the pole had a shiny sheen, indicative of equatorial contact.
[0033] For subsequent wear tests, the Si 3 N 4 acetabular and femoral components were ground and lapped to obtain an R a <0.05 μm. The diametral clearance and sphericity was also varied. The CoCr metal femoral heads were made from a wrought high carbon CoCr alloy containing about 64 weight % cobalt, about 28% weight chromium, about 6% weight molybdenum, about 0.5% weight manganese, about 0.25% weight iron, about 0.2% weight nickel, about 0.2% weight nitrogen and about 0.23% weight carbon. The conventional low carbon CoCr alloy had a similar elemental weight composition with a carbon content of about 0.06% by weight. Such CoCr alloys used for joint prostheses are wrought alloys conforming to ASTM Specification 1537. This high carbon alloy had an elastic modulus greater than 210 giga Pascal (GPa), which had a closer modulus match to the doped Si 3 N 4 ceramic (elastic modulus ˜300 GPa) compared to the low carbon CoCr alloy used in the trial run. The Vickers hardness of these alloys is in the range of 4-5 GPa compared to between 14-16 GPa Si 3 N 4 . The elastic modulus and hardness of the articulating surfaces of the doped Si 3 N 4 ceramic-Si 3 N 4 ceramic or the doped Si 3 N 4 ceramic-CoCr alloy pair are better matched compared to either CoCr-PE, or CoCr-XPE articulations. This was expected to result in better wear performance.
[0034] Relevant design data pertaining to the articulating femoral head and acetabular cup pairs chosen for the wear study are tabulated in Table 2. Stations 1 and 2 had Si 3 N 4 ceramic acetabular cup-Si 3 N 4 ceramic femoral head bearings, and Station 3 had a Si 3 N 4 ceramic acetabular cup-CoCr metal femoral head bearing. For the Si 3 N 4 ceramic-Si 3 N 4 ceramic bearings in Stations 1 and 2, a 70 and 100 μm diametral clearance was chosen to test the effect of run-in wear. The sphericity tolerance of the ceramic acetabular cups was between 1-1.5 μm in all cases and was less than 0.5 μm for both the ceramic femoral heads. For the Si 3 N 4 acetabular cup-CoCr femoral head bearing, a diametral clearance of about 200 μm was selected.
[0000]
TABLE 2
Design Tolerances for the Second Wear Performance Test.
Surface Roughness,
Components
Diameter (mm)
R a (μm)
Sphericity (μm)
Station 1
Ceramic Cup
28.0734
0.0390
1.486
Ceramic Head #4
27.9704
0.0440
0.419
Diametral Clearance
103
μm
Station 2
Ceramic Cup
28.0552
0.0074
1.448
Ceramic Head #2
27.9856
0.0447
0.851
Diametral Clearance
69.6
μm
Station 3
Ceramic Cup
28.0252
0.0091
1.041
CoCr Head 743650 C
27.7986
0.0149
3.785
Diametral Clearance
226.6
μm
[0035] The results from the wear test are plotted in FIG. 3 . Stations 1 and 3 with diametral clearance of about 100 and 225 μm showed ultra low wear, with no observable run-in wear. In contrast, Station 2 with a low diametral clearance of about 70 μm showed classic biphasic behavior as is typical for metal-metal and ceramic-ceramic bearings. This biphasic behavior is attributed to the lower diametral clearance which, owing to inadequate film lubrication between the articulating surfaces, results in run-in wear.
[0036] Comparing the wear performance of the silicon nitride ceramic-ceramic bearings in Stations 1 and 2, it was noted that the bearing in Station 2 exhibited a “grinding” noise along with an increase in lubricant temperature during the run-in period. Following the run-in period, both Stations 1 and 2 behaved normally, with very low steady state wear rates. This was attributed to the lower diametral clearance used in Station 2, which may have resulted in an inadequate lubricant film to be developed between the femoral head and acetabular cup. The wear performance of the Si 3 N 4 acetabular ceramic cup-CoCr metal femoral head bearing was characterized by an absence of run-in wear, similar to that of Station 1, and very low steady state wear rates. This result was as anticipated where, with better modulus matching, a ceramic-metal articulation couple could provide a ultra-low wear alternative for total hip arthroplasty.
[0037] The wear performance of these bearings was obtained over a 4 million cycle period. The weight loss data obtained were converted to volumetric wear rates and extrapolated to 10 million cycles to enable a comparison to literature values. The data, plotted in FIG. 4 , indicate that the Si 3 N 4 femoral head-Si 3 N 4 acetabular cup bearings and the Si 3 N 4 acetabular cup-CoCr metal femoral head show ultra-low wear of 0.65 mm 3 /10 million cycles and 3.4 mm 3 /10 million cycles respectively. In comparison, wear rates of 62 mm 3 /10 million cycles for CoCr-PE (clinical data), 6.5 mm 3 /10 million cycles for metal-metal (in-vitro) wear and 0.35-0.6 mm 3 /10 million cycles for alumina ceramic-alumina ceramic (in-vitro) have been reported.
[0038] Observation of the articulating components after 1 million cycles of wear testing, validated the ultra-low wear behavior by exhibiting a complete absence of wear tracks or other wear patterns. The articulating surfaces retained their high shine, consistent with the negligible weight loss observed for the components.
[0039] The above-described optimized material properties of Si 3 N 4 have demonstrated a 100% increase of fracture toughness over alumina, and a 50% increase in fracture strength over alumina ceramics, which typically have a fracture toughness of about 5 MPam 0.5 and a flexural strength of about 600 MPa. These properties of Si 3 N 4 can allow the manufacture of total hip arthroplasty implants and other prosthetic joint implants such as knee and shoulder joints with significantly higher safety and reliability. Wear performance of Si 3 N 4 femoral head-Si 3 N 4 acetabular cup components and Si 3 N 4 acetabular cup-CoCr femoral head components indicates that these bearings are better than metal-metal bearings and comparable to ceramic-ceramic bearings, with a volumetric wear rate of 2 orders of magnitude lower than CoCr-PE and 20 times lower than CoCr-XPE bearings.
[0040] The combination of the metal femoral head and a ceramic acetabular cup described above offers unprecedented benefits owing to inherent fracture resistance and excellent wear performance. The fracture resistance is derived from the use of metal femoral heads instead of ceramic femoral heads. It is well known from finite element analyses of the stresses in hip prosthetic joints that the femoral head component is subjected to high tensile stresses. Historically, such tensile stresses have been implicated in ceramic head fracture. Metal femoral heads do not fracture owing to the ductile nature of metals. Hence use of metal heads avoids fracture risk. In contrast, the acetabular cup component is typically subjected mainly to compressive stresses, which ceramics are designed to withstand. Furthermore, the combination of high toughness and flexural strength provides improved capability to withstand loads. Thus, as a general design principle for articulating prosthetic joints, the articulating component subjected to the higher tensile stresses can be made from a metal and the mating articulating component subjected to the higher compressive stresses can be made from the high strength high toughness ceramic with favorable tribiological properties. To illustrate this by way of example, in the hip joint, the femoral head can be made of metal and the mating acetabular cup can be made of the ceramic. In the case of knee joints, the condylar component which is subjected to higher tensile stresses, can be made from metal while the mating tibial component can be made from the ceramic. Similarly, the concept can be extended to other articulating prosthetic joints such as the shoulder joint.
[0041] The use of Si 3 N 4 femoral head-Si 3 N 4 acetabular cup components and Si 3 N 4 acetabular cup-CoCr femoral head components in the instant invention to demonstrate the concept of using a fracture resistant metal alloy articulating with optimized ceramics to obtain an ultra low wear joint are illustrative of the general concept. Alternate metal alloys suitable for medical implants such as zirconium based alloys, titanium based alloys or stainless steel alloys may be used for the femoral head of a hip joint (or the component subjected to higher tensile stresses). Alternate enhanced toughness ceramic materials such as doped zirconia or zirconia toughened alumina could also be used for the acetabular component of a hip joint (or the component subjected to higher compressive stresses). This concept can also be applied to other orthopedic joints such as the shoulder or knee joint.
[0042] A variety of further modifications and improvements in and to the invention will be apparent to those persons skilled in the art. Accordingly, no limitation on the invention is intended by way of the foregoing description and accompanying drawings, except as set forth in the appended claims.
LITERATURE CITED
[0000]
1. Callaway G. H., Flynn W., Ranawat C. S., and Sculco T. P., J. Arthroplasty, 10, No. 6:855-859, 1995.
2. Willman G., Pfaff H. G., and Richter H. G., Sonder. aus BioMed. Technik, 40, 12, pp. 342-346, 1995.
3. Clarke I. C. and Gustafson A., 6 th Biomat. Symp. Implant Matls. In Orthop. Surg., ed. H. Willert and G. Buchorn, Gottingen University, Germany, in press, 1995.
4. Clarke I. C. and Gustafson A., In Press, Intl. Ceramics Congress, Otsu City, Japan, November 1997.
5. Mangione, P. Pascarel, X., Vinciguerra B, and Honton J. L., Intl, Orthop., 18, pp. 359-362, 1994.
6. Holmer P. and Nielsen P. T., J. Arthrop., 8, 567, 1993.
7. B. Bhushan and L. B. Sibley, “Silicon Nitride Rolling Bearings for Extreme Operating Conditions”, ASME Trans. 25, 4, pp. 417-428, 1981.
8. D. L. Allen, “Effect of Composition and Physical Properties of Silicon Nitride on Rolling Wear and Fatigue Performance”, Tribology trans., Vol. 37, 2, pp. 410-414, 1994.
9. J. W. Lucek, “Rolling Wear of Silicon Nitride Bearing Materials”, ASME Gas Turbine and Aeroengine Congress and Expo., Brussels, Belgium, 1990.
10. Clarke I C, McKellop H A, Okuda R, McGuire P, Young R, and Hull D, “Materials and prosthesis design criteria—hip simulator studies”, Trans. 28th Ann. ORS, New Orleans, pp. 292, 1982.
11. McKellop H and Clarke I. C., “Degradation and wear of Ultra-High Molecular-Weight Polyethylene” In American Society for Testing & Materials, ASTM STP 859:351-368, 1985. | A prosthesis for articulation (e.g., hip or joint prosthesis) is provided, which includes a pair of articulation components respectively defining a pair of articulation surfaces movably engageable with each other. In some embodiments, each of the articulation surfaces is formed from a biocompatible ceramic (e.g., doped silicon nitride ceramic) having a flexural strength greater than about 700 Mega-Pascal (MPa) and a toughness greater than about 7 Mega-Pascal root meter (MPam 0.5 ). | 0 |
This is a Divisional of application Ser. No. 09/011,600 filed Mar. 10, 1998 (U.S. National Stage of PCT/IL96/00077, filed Aug. 8, 1996), now U.S. Pat. No. 6,183,954. The entire disclosure of the prior application is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention concerns a method for evaluating the metastatic tendency of tumor cells, and a kit for use in said method.
BACKGROUND OF THE INVENTION
Metastasis is a multifactorial process by which tumor cells escape from the primary tumor, disseminate through blood and lymph vessels, evade host immune defence, and home to specific target organs where they extravasate and re-colonize. Metastatic cells must encounter and cross the basement membrane during the extravasation of the blood vessels. The metastatic process is usually described as a three-step model, wherein metastatic cells must first adhere to the basement membrane, then digest via proteolytic enzymes the basal lamina, and finally migrate through the vessel wall.
Evaluating the metastatic potential of a specific tumor is essential for diagnostic and prognostic purposes, for determining optimal course of treatment, as well as for various research purposes such as developing therapeutical methods. and medicaments for the treatment of metastasis.
Correlation between various biomolecules and the metastatic tendency of tumor cells has been previously described. There has been a disclosure of association of increased basement membrane invasiveness, which is the first step in the process of metastasis, with the absence of estrogen receptor and expression of vimentin in a human breast cancer cell line (Thompson et al, J. of Cellular Physiol., 150:534-544 (1992)). A correlation between the invasive potential of various human breast cancer cell lines and binding and degradation of hyaluronan has also been described (Cultry et al., J. of Cellular Physiol., 160:275-286 (1994)). Metastatic potential of various tumor cell lines has also been associated with amplification in the expression of various proto-oncogenes, such as the HER-2/neu proto-oncogene which is amplified in 25% of human primary breast cancer and its amplification is associated with shorter time to relapse and shorter overall survival (Slamon et al., Science 244:707-712 (1989)).
Although currently change in the level of some of the above biomolecules, especially amplification of the HER-2/neu proto-oncogenes, is used for prognostic purposes, the prognostic use of expression or amplification of this gene has been quite controversial (Press, M. F. et al., Cancer Res, 53.4960-4970 (1993)). The prognostic factors currently used to assess the breast tumor state are: tumor size, histological grade, steroid hormone receptor status, DNA ploidity, proliferative index, cathepsin D and analysis of growth factor receptors such as epidermal growth factor receptor.
There is a great need today for additional, accurate prognostic factors for tumor cells which will be easy to identify and which are in good correlation to the metastatic tendency of those cells.
The thrombin receptor (ThR) has been cloned and identified as a member of the seven trans-membrane domain super-family of G-protein coupled receptors. It is activated by cleavage of the Arg 41 -Ser 42 residues of the extracellular N-terminus part of the receptor by the protease thrombin. This cleavage exposes the ligand of the thrombin receptor which is an integral part of the receptor itself. Thus, the ThR serves as a classical substrate for protease, rather than the traditional ligand-receptor complex, during the course of cellular activation (Vu, et al., Cell, 64:1057-1068, (1991)). Recently, there has been a report that W256 carcinoma and mouse melanoma tumor cells contain functional thrombin receptors (Wojtukiewicz, et al., Cancer Res., 55:698-704 (1995)), however, only the existence and function of the thrombin receptor has been assessed in this publication and there has been no determination of the level of its expression, nor its connection to the malignancy of the tumor.
SUMMARY OF THE INVENTION
The present invention is based on the surprising finding that there exists a direct correlation between the level of ThR expression in tumor cells and their metastatic tendencies, so that high levels of ThR expression are evident in aggressive metastatic tumor cells, low to moderate levels of expression can be detected in medium metastatic tumor cells and essentially no detectable expression of ThR is evident in non-metastatic tumor cells.
The above surprising finding enables to evaluate the metastatic tendency of tumor cells by determining the level of ThR expression therein.
Thus, the present invention provides a method for evaluating the metastatic tendency of tumor cells comprising:
(a) determining a test level of a cellular parameter in said cells said level of parameter being:
(aa) the level of thrombin receptor (ThR), or
(ab) the level of expression of a gene coding for ThR;
(b) comparing said test level with a control level, being a level of a corresponding parameter obtained from a cell having a known metastatic tendency, a high or low test level indicating a high or low metastatic tendency, respectively.
The term “metastatic tendency” refers to the expressed metastatic capacity of tumors which have already begun their metastatic spread and begun recolonization in target organs, as well as to the future metastatic potential of tumors which are still in the initial pre-metastatic stage and which may metastasize in the future. A high metastatic tendency refers to a situation where the tumor cells metastasize rapidly and colonialize in many target sites. Moderate metastatic tendency refers to tumor cells which metastasize slowly, and colonialize only at a few target sites, and low metastatic tendency refers to tumor cells which virtually do not metastasize and are confined to their original site.
The tumor cells which metastatic tendency is evaluated can be any type of tumor cells, especially those types which feature varying levels of metastatic tendencies such as breast cancer, testicle cancer, melanoma, epithelial carcinoma, colon carcinoma, ovarian carcinoma, cervical carcinoma, as well as various types of sarcoma.
The level of ThR can be determined either by assaying the level expression of the gene coding for the thrombin receptor, i.e. by determining the mRNA level, or by determining directly the level of the thrombin receptor present either on the membranes of the cells or within the cytoplasm.
The levels of the mRNA can be determined. for example, by separating the mRNA molecules, obtained from the assayed cells on an electrophoretogram (Northern blot) and then identifying the separated thrombin mRNA by hybridization with suitable probes which carry detectable labels; by in situ hybridization to the mRNA, present in the isolated tumor cell or present in isolated tissue obtained from the tumor, with suitable probes carrying detectable labels; or by RT-PCR amplification using suitable primers.
The ThR level may be determined for receptors present on the membrane of the tumor cells and/or present within the cell. The determination can be carried out, for example, by using antibodies capable of recognizing the thrombin receptor (either in its membranal or cytoplasmal forms, or in both forms) in one of the state-of-the-art immunoassays, or by determining the level of binding of a labeled ligand to the thrombin receptor.
Once the level of the thrombin receptor is determined, either through mRNA or through protein determination, it should be compared to the corresponding level of either mRNA or thrombin receptor of other cells which metastatic tendency is a priori known, which cells may also be non-tumor normal cells, or tumor cells from established cell lines known to have a high, low, or moderate metastatic tendency.
In practice and during clinical use there will be no need to calibrate de novo each ThR level obtained since it will already be known by the practitioner, due to prior experience. which specific color pattern of an in situ hybridization, unique pattern of band formation in Western or Northern blot, or specific amount of mRNA amplified using RT-PCR, indicates that the ThR level is high and thus that the tumor cell features a high metastatic tendency. It is also possible to compare the levels obtained from the tested tumor cells to two corresponding control levels: one obtained from highly metastatic cell lines, and the other obtained from low metastatic cell lines to determine more precisely whether the tested level is high, low or intermediate.
Cells, which after being compared as specified above show a high level of ThR, are those which feature a high metastatic tendency; cells which show a low or almost no level of ThR are those which have low metastatic tendency; and cells which show intermediate levels are those which are usually moderately metastatic.
The present invention also concerns a kit for use in the above method.
Where the determination of the level of ThR is carried out by determining the level of mRNA, the kit may comprise labeled probes and reagents suitable for in situ hybridization, labeled probes and reagents for carrying out Northern blot, or reagents and primers necessary for RT-PCR.
Where the determination of the ThR is carried out by determining the level of the thrombin receptor, the kit may comprise antibodies capable of specifically binding to the ThR, either when present on the membranal surfaces of the tumor cells or when present within the cells, together with reagents for carrying out a suitable immunoassay. Alternatively, the kit for determining the ThR protein level may be based on a ligand-binding assay and in that case the kit should comprise a labeled ligand, which can be for example the synthetic peptide corresponding to residues Ser 42 -Lys 51 of the native thrombin receptor (the so called “inner ligand”).
The invention will now be further illustrated with reference to some specific non-limiting drawings and embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 —a DNA electrophoretogram, lane A: 250 base pair fragment of human ThR DNA obtained by using RT-PCR human umbilical endothelial cells as a source; lanes B, C: same reaction of lane A with no DNA; lane D: molecular weight markers;
FIG. 2 —pGEM-vector restriction map, the human ThR 250 base pair fragment inserted into the pGEM-vector at sites BamH1 and ECOR1 restriction enzymes; (the size of the pGEM-3 vector is 2867 b.p., sequence reference points: 1—SP6 RNA polymerase transcription; 72—T7 RNA polymerase transcription initiation site; 2851-2868—SP6 RNA polymerase promotor; 73.89—T7 RNA polymerase promotor; 7.63—multiple cloning sites; 100.158 lac operon sequences; 1100-1960—β-lactomase coding region).
FIG. 3 —electrophoretogram of ThR mRNA obtained from various human breast cell lines; lanes A, B: MDA 435; lanes C.D,E: MDA 231; lanes F, G: MCF-7;
FIG. 4 —in situ hybridization of antisense (A,C) or sense (B,D) mRNA probes to human breast cancer cell lines having no metastatic potential MCF-7 (C,D) or high metastatic potential MDA 231 (A,B);
FIG. 5 —binding of anti-ThR antibodies to the N-terminal residue Ser 42 -Lys 51 of human ThR, determined by ELISA (SIH AB-antibodies against human ThR; SIH WR-white rabbit; pre-SIH pre-immune serum of white rabbit; BR black rabbit);
FIG. 6 —Western blot of cell lines expressing ThR (lanes A-D), and cell lines which do not express ThR (lanes E and F); lane G Molecular Weight Markers; and
FIG. 7 —SDS-PAGE of 125 I-thrombin receptor agonist peptide to SMC: (lanes 1,2: untreated cells; lanes 3,4: cells pre-treated with heparinase; lanes 5,6: cells treated with chondrotirase ABC; lanes 2,4,5: cells in the presence of labeled ligand; lanes 1,3,6: cells in the absence of labeled ligand).
FIG. 8 —the level of ThR as determined by RT-PCR;
DETAILED DESCRIPTION OF THE INVENTION
I. Preparation of Probes Used in Northern Blot and in situ Hybridization
(a) Method
A 250 base pair fragment of thrombin receptor was obtained by PCR using as primer the following sequences derived from the human thrombin receptors:
Primer 1: (SEQ ID NO:1); 5′ ATGGAAITCTGCCACCIIAGATCC
Primer 2: (SEQ ID NO:2); 5′ ATGGGATGCGGAGGCTGACTACAA
The 250 b.p. fragments were shown by nucleotide sequence analysis to be the internal part of the cloned thrombin-receptor (ThR), nucleotides: 329-575 (according to Vu et al., Cell 64:1057-1068), including the internal ligand region peptide and sequences beyond (i.e. SEQ ID NO: 3: SFLLRNPNDKYEPFWEDEEKNESGLTEYRLVSINKSSPLQKQLPAFIS EDASGYLTSSWLTLFVPSVYTGVFVVSLP). The length of the fragment was determined by electrophoresis on 1% agarose gel in TAE (0.04M Tris-acetate, 0.001M EDTA) buffer.
The 250 b.p. fragments were inserted into a pGEM vector at sites of BamH1 and ECOR1 restriction enzymes, and the pGEM restriction map is shown in FIG. 2 .
Bacteria ( E.coli strain DH5) were transformed with said vector and grown in large quantities. The plasmid was isolated by the Wizard™ Maxi prep (DNA Purification System, USA). The 250 b.p. fragment was isolated from the plasmid by digestion with the restriction enzymes: ECOR1 and BamH1 (Boehringer Mannheim, Mannheim Germany). The purified fragment, purified either by ethanol precipitation of Geneclean procedure, using Geneclean II kit, B10, (101 Joshua Way, Vista Calif. 92083), was labeled (according to Feinberg, A. P. and Vogelstein, B., Anal Biochem., 137:266, 1984) by using the random prime labeling of [α- 32 P]-dCTP (kit from Boehringer-Mannheim, Cat. 1004760. Mannheim Germany).
Riboprobes were prepared by using the RNA Color Kit for non-radioactive in situ hybridization (RNP3300; Amersham. Buckinghamshire. England). For this, the plasmid (pGEM-3) was linearized by digestion with ECOR1 for the source of RNA polymerase (using the SP6 promoter present in pGEM-3). In parallel, digestion with BamH1 was performed. and linearized DNA was used as a source for the T7 RNA polymerase (present in the pGEM-3 plasmid). Both linearized DNA were incubated, according to the manufacturer's instructions, with their appropriate RNA polymerase (either SP6 or T7) and with nucleotides and transcription reaction (Wilkinson, D. G., in “In-situ Hybridization: A practical approach”, Ed. D. G. Wilkinson, IRL Press, Oxford pp. 1-14, 1992; Brunnings, S. et al, “In-Situ Hybridization: A Guide to radioactive and Non-radioactive In-Situ Hybridization Systems”, Amersham International Amersham, 1993). Fluorescein-11-UTP incorporation during the transcription reaction determined the extent of synthesis.
Riboprobes at both directions: antisense, prepared using T7 SP6 promoter, and sense prepared using the T7 promoter which was used as a control, were added to paraffin embedded slides following appropriate deparaffinization step. Detection of the specifically hybridized mRNA was evaluated following appropriate blocking and addition of alkaline phosphatase conjugated antibody for 1 h at room temperature, developed in the presence of NBT and BCIP as substrates, in appropriate detection buffer.
(b) Results
The ThR DNA obtained by PCR amplification was separated on a 1% gel agarose electrophoresis in TAE (0.04M Tris-acetate, 0.001M EDTA) buffer and the separation results are shown in FIG. 1, wherein lane A is the above 250 b.p. fragment; lanes B, C are the same reaction as described above with no DNA present; and lane D is Molecular Weight Markers which verified the size of the PCR obtained probe.
II. Level of ThR Expression in Three Epithelial Carcinoma Cell-lines of Differential Metastatic Potential:
1. RNA Determination
(a) Method
Three epithelial carcinoma cell lines were used: MCF-7, characterized as an epithelial carcinoma with minimal aggressive properties which grows in nude mice without Matrigel but does not metastasize even in the presence of Matrigel; MDA 231 which is a moderately aggressive carcinoma which does not grow without Matrigel in nude mice but grows with moderate amounts of Matrigel; MDA 435 which is a very aggressive carcinoma which grows with wide-spread metastasis in nude mice even in the absence of Matrigel.
20 μg/lane of RNA were obtained from the above three carcinoma lines and were separated on a 1.5% agarose/formaldehyde gel. The 250 b.p. ThR DNA label with [α- 32 P] dCTP obtained as described in Example I above was used as the hybridization probe for the separated mRNA.
(b) Results
The results are shown in FIG. 3, wherein lanes A and B are the results with the highly metastatic cell line MDA 435; lanes C,D and E are results with the moderately metastatic cell line MDA 231 and lanes F and G are the results with the low metastatic cell line MCF-7.
As can be seen, the highly metastatic cell line expressed large amounts of ThR mRNA, the moderately metastatic cell line expressed intermediate amounts of ThR mRNA and the non-metastatic cell lines expressed essentially no ThR mRNA.
In order to ensure that the total amounts of mRNA in all three cell lines were essentially the same, the amounts of β-actin mRNA was also determined and was found to be about the same in all three cells lines (Data not shown).
2. Protein Determination
(a) Method
The highly metastatic MDA 435 cell line and the non-metastatic MCF-7 cell line were used. Lysates of cells were prepared and either 200 μg/lanes (lanes A,C,E) or 100 μg/lanes (lanes B,D,F) were applied for separation on SDS-Phase together with molecular weight markers.
(b) Results
The results are shown in FIG. 6 . As can be seen, lanes of cell lines which are highly metastatic (lanes A-D) show a high level of ThR protein while lanes which are not metastatic show essentially no expression of ThR (lanes E,F).
III. ThR Expression Detected by in situ Hybridization with Metastatic and Non-metastatic Epithelial Carcinoma Cell Lines
(a) Method
The data obtained in Example II above concerning the amounts of mRNA ThR in various carcinoma cell lines determined by Northern blot was confirmed by in situ hybridization analysis of the MDA 435 and MCF-7 cell lines monolayers using both sense and antisense riboprobes of ThR obtained as described in Example I.
The cell monolayers were fixed for 10 min in ethanol, hydrated sequentially by 5 min incubations in 70% ethanol, 50% ethanol and 30% ethanol. Then, 10 min incubation in 5 mM MgCl 2 followed by treatment of the cells with 0.02N HCl for 10 min, and washes in 5 mM EDTA in 2×SSC (50′C., 30 min). No proteinase K treatment was performed on the cell monolayers. Finally, cells were treated with 4% formaldehyde (25 min) followed by 2 washes in 5 mM MgCl 2 , Linearized plasmid with the relevant enzyme (estimated˜600 ng) were used for riboprobe synthesis (estimated˜20 ng/well) incubated overnight at 55° C. with the cell monolayers.
(b) Results
The results are shown in FIG. 4 were the antisense direction of the riboprobes is depicted in pictures A and C and sense riboprobes in pictures B and D. The cell lines used were either the non-metastatic MCF-7 (pictures C and D) or the highly metastatic MDA 435 cells (pictures A and B).
As can be seen, no hybridization was detected in MCF-7 cells, while strong and abundant distribution of the probe was present in the aggressive metastatic cells.
IV. In situ Hybridization of Paraffin-embedded Breast Tumors
In situ hybridization with the above riboprobes was also carried out for paraffin-embedded breast tumors of patients with highly invasive metastasis and patients with a primary tumor with no seemingly metastatic spread. For this, hybridization using digoxigenin (fluorescein-11)-UTP RNA color kit (Amersham, RPN 3300) was employed. Preliminary data show specific staining of the carcinoma cells of patients with metastasis, i.e. positive staining with the antisense riboprobe obtained by the SP6 promotor and no staining with the sense riboprobe obtained by the T7 promotor, as well as positive staining around vessel walls throughout the breast section. Patients with no metastasis, exhibited no detectable staining.
V. Anti-human ThR Antibodies
(a) Method of preparation
A synthetic peptide corresponding to residues Ser 42 -Lys 51 of the native thrombin (SEQ ID NO:4: S-F-L-L-R-N-P-N-D-K) was used to immunize a rabbit by a subcutaneous co-injection with Complete Freund's Adjuvant (1:1 ratio) for the first injection, then 2-3 weeks later another injection of the peptide, conjugated to KLH with incomplete Freund's Adjuvant (according to Antibodies. A Laboratory Manual by Ed Harlow and David Lane, Cold Spring Harbor Laboratory, 1988). The immune serum thus obtained was affinity purified for antibodies using the above synthetic peptide.
5 μg/lane of the above synthetic peptide were used to coat ELISA plates and the serum obtained from the rabbit as described above was analyzed for specificity by adding serial dilutions of antibody (2-16 h, 4° C.), followed by 3 washes and sequential incubation at 24° C. for 1 h with alkaline phosphatase conjugated anti-rabbit antibodies (Promega; Hollow Road, Madison, Wis., USA) added at a dilution of 1:5000. The wells were then washed three times and the substrate nitrophenyl phosphate (PNPP) in diethanolamine buffer was added. Positive reaction was evaluated by the color development at O.D. 405 nm.
(b) Results
As can be seen in FIG. 5, serum of immunized animal SIH UR 2318 (⋄) and SH BR 2318 () was able to specifically bind to the synthetic peptide as compared to serum of unimmunized animal SIH PR pre (▭) and SIH BR pre (▴) which showed no specific binding.
VI. Identifying the Level of ThR Protein Using a Ligand-binding Assay
(a) Method of preparation of labeled ligands
A synthetic 14 amino acid polypeptide which corresponds to the internal thrombin receptor ligand was radiolabeled. Radiolabeling of the 14 amino acid peptide (SEQ ID NO:5: S-F-L-L-R-N-P-N-D-K-Y-E-P-F) was performed using chloramine T. as previously described (McConahay, P. J. et al., Method Enzymol., 70:210 (1980)). Briefly, 10 μg of the peptide was added to 60 μl of 0.2 M sodium phosphate, pH 7.2, containing 1 μCi Na 125 I. Chloramine T (10 μl of 1 mg/ml) was added for 45 seconds at room temperature and the reaction was stopped by the addition of 50 μl 0.05% sodium metabisulfite and 50 μl of 10 mM KI. The reaction mixture was then applied on to a Sephadex G-10 column. Fractions were collected in phosphate buffer (0.1M, pH 7.2). The specific activity was 0.8-1.1×10 5 cpm/ng peptide and the labeled material was kept for up to 4 weeks at −70° C.
(b) Method of binding and crosslinking of the labeled peptides to Smooth Muscle Cells (SMC)
SMC cells were used as a model of cells carrying the ThR which can be detected by binding a labeled ligand prepared as described in (VIa) above.
5×10 5 Cells/well were grown to confluence in 60 mm culture wells. Confluent cultures were transferred to 4° C., washed once with PBS and incubated for 2 h with various concentrations of 125 I-peptide in the absence or presence of 1000 fold excess unlabeled peptide. The cultures were washed three times with PBS, followed by incubation for 30 min at 24° C. with the bifunctional cross-linker disuccinimidyl suberate (DSS; 4 mM) in DMEM containing 0.2% BSA. At the end of this incubation, cells were washed and dissolved in SDS-PAGE sample buffer for analysis by SDS-PAGE.
(c) Results
As can be seen in FIG. 7, the complex of the ThR and the labeled ligand (lanes 2,4,5) having a molecular weight of about 70 kDa could be detected as compared to ThR with no ligands (lanes 1,3,6) showing that the ligand-binding assay is valid for detecting ThR.
VII. The Level of ThR as Determined by RT-PCR
(a) Method
Different amounts of RNA (2.5, 5 and 10, μg/reaction) of the three cell lines: MCF-7, MDA-231 and MDA-435, respectively, were used to prepare cDNA. One-tenth (5 μl out of 50 μl total reaction mixture) of the cDNA formed was further used for PCR amplification in the presence of the ThR-primers. The PCR products were separated on 1% agarose gel in TAE buffer.
(b) Results
As can be seen in FIG. 8 at none of the concentrations used a distinct band product of ThR could be observed for the non-metastatic MCF-7 cells. The highly metastatic MDA-231 cells showed a high level of ThR at all concentrations used, while the moderately metastatic MDA-435 showed a distinct band but only at the high concentrations of 5 and 10 μg/reaction. | The present invention concerns a method for evaluating the metastatic tendency of tumor cells by determining the level of expression (mRNA level) of the gene coding for the thrombin receptor (ThR) or by determining the level of the thrombin receptor present on the membranes or within the tumor cells. A high level of either of the above indicates a high metastatic tendency, a low level indicates a low metastatic tendency and an intermediate level indicates a moderate metastatic tendency. The present invention further concerns a kit for use in the above method. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 11/272,042, filed Nov. 14, 2005, which is a non-provisional application of U.S. Provisional Application No.: 60/627,110, filed Nov. 12, 2004, both of which are hereby incorporated by reference in their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to method and devices for the photodynamic regulation of cell proliferation and gene expression of normal, engineered, autologous, donated, transplanted, apoptotic, necrotic, and other cells which have properties that may be beneficially or detrimentally affected. The cells might include damaged, suboptimally functioning, tumorous, cancerous, mutated or other altered cells existing in or out of the host body, in a laboratory, etc. In particular, the invention relates to photovitalization, photomodulation, photoregulation, and other light-based treatments for cells. In all illustrative embodiment, the invention may be configured to alter normal cell activity, revitalize apoptotic cells, and restore activity to necrotic cells. The light sources may include wideband, narrowband, and other sources of electromagnetic radiation in both the visible and non-visible portions of the spectrum, including electrical stimulation.
[0003] The invention further relates to methods and systems for photoregulating and photomodulating the energy production, electron transport, function, and behavior of non gene-based cells such as mitochondria. Such systems employ direct photonic interaction.
BACKGROUND OF THE INVENTION
[0004] Traditionally, light-based therapies have employed high-intensity, monochromatic sources for performing various treatments on mammalian tissue. More recently, low-intensity, narrowband light sources have been found to have therapeutic effects at the cellular level. For example, it has been found that non-coherent sources of near infrared radiation may protect human dermal fibroblasts from solar ultraviolet toxicity. Further, it has been found that real time RT-PCR indicates a correlation between retinoid-induced apoptosis and NGF-R mRNA levels in cells.
[0005] It would be desirable, therefore to be able to influence normal, apoptotic, and even necrotic cells using light sources, to affect the activity of such cells for the purpose of transporting organs (by maintaining cellular activity during transport), photorevitalizaing aging cells, and photorejuventating injured, dying, or dead cells. As well, of particular interest is the photovitalization of apoptotic cells—those which are undergoing pre-programmed cell death. Apoptosis denotes the complex contortions of the membrane and organelles of a cell as it undergoes the process of programmed cell death. During said process, the cell activates an intrinsic suicide program and systematically destroys itself in a controlled manner or by a self-regulated process. The following series of events can be observed:
[0006] The cell surface begins to bleb and expresses pro-phagocytic signals. The whole apoptotic cell than fragments into membrane-bound vesicles that are rapidly and neatly disposed of by phagocytosis, so that there is minimal damage to the surrounding tissue. The cell then separates from its neighbors. The nucleus also goes through a characteristic pattern of morphological changes as it commits genetic suicide. The chromatin condenses and is specifically cleaved to fragments of DNA.
[0007] Further, U.S. Pat. No. 6,723,798 teaches therapeutic treatment methods and compositions and devices for maintaining neural pathways in a mammal, including enhancing survival of neurons at risk of dying, inducing cellular repair of damaged neurons and neural pathways, and stimulating neurons to maintain their differentiated phenotype. In one embodiment, the invention provides means for stimulating CAM expression in neurons. The invention also provides means for evaluating the status of nerve tissue, including means for detecting and monitoring neuropathies in a mammal. The methods, devices and compositions disclosed therein include a morphogen or morphogen-stimulating agent provided to the mammal in a therapeutically effective concentration. Preferably, however, carrying out a similar function using light-therapy would advantageous due to the reduced cost and less-invasive nature of the treatment.
[0008] It would be particularly advantageous to employ light-based means for the photomodulation of apoptoltic cells, thereby restoring them to their normal activity state prior to necrosis.
DESCRIPTION OF THE INVENTION
[0009] The invention may be characterized as a system and method for photomodulating cells. The attached pages and charts illustrate the means by which low-intensity light sources, such as light emitting diodes, may cause the rejuvenation of apoptotic and necrotic cells or alter the state of normal cells. For example, the system may provide for the revitalization of skin tissue, hair growth, allow for the preservation of human organs during transport, treating sunburn, thermal and chemical burns and blistering (including those inflicted by chemical warfare agents), scar reduction, hair removal, wrinkle reduction, and the treatment of a wide variety of internal disorders where light may be used to stimulate a desired gene expression. Of particular value are treatments according to the present invention for stem cell disorders, bruising, acute spinal cord trauma, brain stokes, retinal injuries, and heart muscle vitalization and rejuvenation. Such treatments made be used prescriptively, prophylactically, intraoperatively, during post-operative recovery, and other times when it is desirable to affect cell health or behavior.
[0010] For application to dermatological disorders, the invention may be applied to a variety of approaches. Although historically, most methods utilize some form of triggering the body's own wound healing mechanism. The more destructive and traumatic methods use chemicals to peel off the stratum cornium epidermis and often a portion of the dermis or they mechanically abraded by sand papering or dermabrating or more recently high-energy thermal lasers have been used to vaporize or coagulate the skin. These methods have a prolonged and painful wounding period and require wound care and patients typically must limit theft daily social and business activities during the wound-healing phase. Subsequently the skin undergoes of months or years an on going wound healing and wound remodeling process whereby damage is repaired and new structural proteins in skin are generated. These treatments typically amount to trying to produce a controlled entry to the skin and proving the wound care environment that minimizes the risk of scarring. These methods are notoriously known for producing many problems and sometimes even disfiguring scarring or catastrophic pigment changes in the skin. However, properly performed and with good wound care, many people achieved significant and sometimes dramatic anti-aging effects. Other gentler methods have become more popular in recent years which involve the classic plastic surgery lifting procedures and newer procedures termed non-ablative where the outer stratum cornium and epidermis are not removed or blated from the skin, but are by various means and methods protected and left in tact. Non-ablative methods have typically been thermal in nature and through various means of laser light, intense pulsed light, radio frequency or microwave energy delivery then produced a thermal injury to the dermis. The theory behind these therapies is that this injury will result in a net increase in the desirable structural proteins, while not triggering, worsening, scarring or other complications. Results are occasionally traumatic but have been extremely variable with this therapy. The variability in individuals wound healing repair mechanism and the overall health of their body and skin and many other factors contribute to this variability.
[0011] There are various topical agents that have been developed for anti-aging purposes such as Retinoic acid, topical Vitamin C, topical Vitamin E and other antioxidant and other anti-wrinkle creams and lotions. Many of these are well defined. Additional topical compositions, cosmeceuticals, etc. are disclosed in applicant's copending application Ser. No. U.S. 09/899,894, entitled “Method and Apparatus for the Photomodulation of Living Cells”, filed Jun. 29, 2001, which is hereby incorporated by reference in its entirety. Further, methods for enhancing the penetration of such composition into the skin using ultrasound radiation are described in U.S. Pat. No. 6,030,374, and U.S. Pat. No. 6,398,753, each of which is hereby incorporated by reference in its entirety. Use of such compositions for wound treatment, acne reduction, and other dermatological conditions is described in applicant's copending application Ser. No. 09/933,870, filed Aug. 22, 2001, which is also incorporated by reference herein in its entirety. Additional discussion of the related art is described in applications copending application Ser. Nos. 10/119,772, filed Apr. 11, 2002, and 60/461,512, filed Apr. 10, 2003, which are also incorporated by reference herein in their entirety.
[0012] The present system contemplates the use of light-based therapy to stimulate gene expression within cells and direct photon stimulation of cells, as described generally in the attached figures. Methods to modulate cell growth or proliferation and gene expression include exposure to electromagnetic radiation in an amount or dose that is sufficient to stimulate the desired effect (e.g. see U.S. Pat. Nos. 6,398,753, 5,837,224, and 6,130,254; and U.S. Patent Application Nos. 2002/0028185, 2001/0053347, 2003/0004556, 2003/0004499, and 2002/0123746, all of which are specifically and entirely incorporated by reference). For example, exposure of skin to LED can stimulate or inhibit the expression of various gene products. These same methods can be used to cause stimulation or inhibition of cell proliferation or differentiation and cell cycle modulation in these cell populations. Further, photomodulation can be used in combination with certain oral agents (for systemic affects) or topical agents (for localized affects) (e.g. vitamin A, retin A, retinol), for a desired effect unachievable with either stimulant used individually.
[0013] The types of cells that can be affected include, but are not limited to skin cells (reversal of photoaging), nerve cells (disease prevention and treatment), stem cells (tissue reconstruction), cells of hair follicles (hair growth or inhibition), cells of the immune system including cells intimately involved with the process of inflammation (due to disease, infection, or congenital disorder), wound repair, eye/retina cells, heart cells, brain cells, entire organs, and combinations thereof. Modulation can be achieved by exposing cells to electromagnetic radiation (e.g. photomodulation) such as, preferably, visible light, (e.g. purple, blue, green, yellow, orange, red), infrared radiation, ultraviolet light (UVA, UVB, UVA1, UVA2, or combinations thereof), or combinations of any. Preferred exposure strengths and exposure times are as set forth in the attachments hereto, but may include pulsed exposures, continuous and periodic exposures.
[0014] Regulation of gene expression by light in living cells. Photomodulation of gene expression occurs in both nucleus and mitochondria. The following mechanisms are relevant to the use of light to regulate gene expression. 1) Light Capture—photons captured by antennae molecules or receptors; 2) Light Energy Transfer—photon energy is transduced into a signal; 3) Signal Coupling—the signal transduction couples to gene expression; and 4) Gene Expression—cellular activities and cell products regulated by gene expression.
[0015] Types of Regulation include: PhotoRegulation, PhotoRejuvenation, PhotoRevitalization, PhotoRegeneration, and PhotoReregulation. Photomodulation is determined by a set of parameters which may be termed the ‘cellular photomodulation code: light intensity (irradiance); spectral quality (spectral wavelength, spectral bandwidth, spectral ratio (ratio of different wavelengths), and polarization.
[0016] Factors which may be varied to achieve different levels of expression in particular genes or to cause expression in other genes include: light exposure (duration), frequency (if pulsed), time (pulse duration), off time (dark time), total number of pulses, interval between exposures (single/multiple wavelengths), synchrony (simultaneous or sequential).
[0017] Inhibition, modulation, quenching my occur by ‘interfering’ light or electromagenetic radiation or other factors which disrupt or modulate normal cell signal transduction. Competing endogenous or exogenous chromophores in living cells or tissue may alter spectral quality or photomodulation process. Photodamage may also occur (which is different than photoinhibition) and may be due to ‘excess’ photon flux or excess total number of photons.
[0018] Photophosphorylation is significant in cell transduction process. Reactive center/antenna molecule is the ‘Portal’ connecting the world of physical ‘light’ energy and biological life—this is central concept in the photomodulation of living cells and life processes. Redox state of primary electron acceptor ‘controls’ photomodulation (and photodamage). Maximum effect on gene expression may require photomodulation of more than one receptor (i.e., upstream or downstream reactive center/receptor photomodulation in addition to ‘primary’ receptor). | A method for stimulating, inhibiting, or regulating gene expression including exposing a living cell with at least one gene to an administered source of narrowband, multichromatic electromagnetic radiation. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a container or the like, which container is provided with a body having stiffening corrugations or beads, respectively, formed therein.
2. Description of the Prior Art
Containers are commonly provided with a body, a bottom and a cover. The bottom and the cover of such containers have various design and structure, are fixedly or releasably mounted to the body of the container, and may or may not be provided with a discharge opening such to meet prevailing requirements.
The load resistance, specifically the circumferential load resistance and the axial load resistance as well as the impact resistance, the latter being determined by dropping tests or radially directed impact tests, are mainly determined by the shape of the container body, i.e. the side walls thereof. It is desirable to manufacture containers which have a high axial load resistance and a high impact resistance and which are specifically stable under internal vacuum conditions.
Known containers are respectively provided with sheet metal or metal plate bodies. During manufacture, such bodies are initially formed by soldering or welding cylindrical sheet metal plates. Thereafter, the final shape is formed by means of shaping tools. The prior art is also cognizant of impressing aligned corrugations or beads, respectively, during the shaping of the body, which corrugations extend either vertically and/or horizontally and/or spirally in the circumferential surface of the body. Furthermore, the application of arbor supports for an improved impressing of the corrugations is also known.
However, the improvement of the load resistance of containers manufactured in accordance with the above outlined procedures is rather limited.
In the Belgian Pat. No. 411,724 horizontally extending corrugations are given priority. Because the vertically extending corrugations have a smaller depth than the horizontally extending corrugations, the effect thereof, relating to the axial load resistance, is eliminated at the intersections between the horizontal and the vertical corrugations, and, if subject to an axially directed load, the container is prone to fold or cave in at this area. Furthermore, the shape, i.e. the depth of the horizontally extending corrugations is strongly pronounced. Such shape is extremely disadvantageous regarding the axial pressure load resistance.
The same proves true for the containers disclosed in the U.S. Pat. Nos. 3,357,593 and 3,335,902, according to which nodal areas are formed at the intersections, thus reducing the axial pressure load resistance. In the mentioned areas the vertically extending corrugations are reduced to a line.
SUMMARY OF THE INVENTION
Hence, it is a general object of the present invention to provide an improved container having a higher load resistance and which, at the same time is simpler to manufacture.
A further object is to provide an improved container which allows the use of a thinner material for forming the body yet without suffering a reduction of its load resistance.
Yet a further object of the invention is to provide an improved method of manufacturing a container allowing the use of a thinner raw material yet achieving a higher load resistance.
Now, in order to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the improved container of this development is manifested by the features that the body is provided with corrugations or beads, respectively, or groups of corrugations or beads, respectively, consisting of individual vertically extending corrugations arranged side by side and staggered vertically relative to each other, which corrugations extend at least over the larger part of the height of the body, which vertically extending corrugations or individual corrugations intersect the area of the circumferential corrugations or the circumferential corrugations without disrupting same.
According to the invention, the vertically extending corrugations are given priority over the circumferentially extending corrugations. It has been recognized that a disruption of the circumferentially extending corrugations by vertically extending corrugations has practically no detrimental effect regarding the radial load resistance of the container, whereby however a disruption of the vertically extending corrugations produces an extremely harmful effect on the axial load resistance. According to a preferred embodiment the impressed depth of the vertically extending corrugations is larger than such of the relatively shallow horizontally extending corrugations.
Preferably, the vertically extending corrugations are arranged in groups which in turn are arranged circumferentially at a distance from each other. In case of a noncircular cross-sectional shape of the body, the mentioned groups are preferably foreseen in the corner areas thereof.
The invention ignores the fears of the prior art, according to which the superimposing of parallel extending corrugations with differently extending corrugations shall abolish at least partly the stiffening effect of the former corrugations and cause furthermore an unacceptable stressing or weakening of the material of the body. Surprisingly, the contrary has been proven, namely that the corrugations which are vertically superimposed over the horizontally extending corrugations lead not only to an improved axial load resistance of the body in a vertical, i.e. axial direction but also do not reduce the strength in circumferential direction and can rather possibly increase such strength if the vertically extending corrugations are arranged specifically skillfully such as e.g. in groups of which each vertical row of corrugations comprises individual corrugations arranged at a vertical distance from each other, whereby the individual corrugations of adjoining rows can be arranged staggered relative to each other.
An arrangement which has been proven as especially useful is such including two outer rows of corrugations having individual corrugations arranged at the same height and a center row of corrugations having thereto vertically staggered individual corrugations.
An especially surprising result is that an arrangement of such groups with vertically extending corrugations has proven to be advantageous if arranged at the corner areas of the cross section of the body. Commonly such bodies have been formed by an expansion shaping followed by the impressing of the corrugations. Accordingly, the person skilled in the art had to expect a specifically high load concentration in the material of the body.
The considerable increase of the load resistance of the container and specifically of the axial load resistance thereof allows a smaller wall thickness of the body material.
A further object of the invention is to provide a simpler manufacture of a container. An inventive method is manifested by the steps of expanding the body from within by an application of a deforming force and by an application of an outer counter holding and by a shaping into the desired form and impressing in the body circumference at least approximately in themselves closed horizontally or slightly inclined extending corrugations as well as vertically extending corrugations, whereby at least the horizontally and slightly inclined corrugations are impressed whilst maintaining the counter holding force and the shaping force.
In case of containers made of a plastics material obviously a thermoplastic shaping method can be applied.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is a perspective view of an embodiment of the inventive container;
FIGS. 2 to 4 show schematic side views of alternate embodiments of the body;
FIGS. 5 and 6 schematical top views of steps of manufacture of an inventive container;
FIGS. 7 to 9 vertical partial sections along the line A--A of FIG. 6, whereby for sake of clearness the parts of the tools taking part in the manufacture of the body to be shaped are shown retracted from the body; and
FIG. 10 is a sectional view taken along line B--B of FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings and considering initially the exemplary embodiment of the container in FIG. 1, it will be understood that same comprises a sheet metal body 1. A cover 2 and a bottom 3 are connected to the body means of jointed flange connections. The material used may be tin plate, black iron sheet, chrome-plated sheet metal, aluminium, nonferrous metal and the like.
It is also foreseeable to fabricate the container by a plastics-foil material.
The body 1 which as shown can taper against its top end is joined along a vertically extending seam 7 and comprises circumferentially extending horizontal first corrugations or beads 8 and comprises further at its four corner areas a group 9 of vertically extending second corrugations or beads each extending approximately or preferably along the entire height of the body 1. Every group of vertically extending corrugations comprises three rows of individual corrugations 10, 11, whereby the individual corrugations 10 of the outer rows are arranged at the same level and the individual corrugations 11 of the center row are arranged staggered thereto and thus overlap the individual corrugations 10 of the outer rows.
FIGS. 2 to 6 disclose various configurations of the arrangement of the corrugations whereby the arrangement of FIG. 3 corresponds to the arrangement shown in FIG. 1.
For sake of ease the various parts of the embodiments described below are provided with the same reference numerals as used above.
The embodiment of FIG. 2 differs from such of FIG. 3 in that the horizontally extending corrugations 8 are interrupted in the general area of the group 9 occupying the vertical corrugations 10, 11, whilst according to the embodiment of FIGS. 1 and 3 the horizontally extending corrugations 8 penetrate into the general area of the vertical corrugations 10, 11 that is, extend between the individual vertical corrugations of the group.
The embodiment of FIG. 4 comprises an arrangement of the corrugations 10, 11 which is basically similar to the embodiment of FIG. 2. The difference is here that the horizontal corrugations 8 extend slightly slanted or inclined, respectively, to the true horizontal direction. In order to maintain a sufficient stability the largest inclination retlative to the circumferential direction or radial direction, respectively, should amount to not more than 15°.
A practical embodiment made in accordance with FIG. 1, however, for a container with a circular cross section, has the following measurements:
Height of body: 380 mm (1 ft. 3 in.)
Diameter of body: 320 mm (1 ft. 19/32 in.)
Volume: 25 liters (6.6 US gals.)
Thickness of sheet metal: 0.25 mm (1/100 in.)
Axial loading capability: ca. 1000 kp (2200 lbs.)
In comparison with a prior art container having comparable dimensions the axial loading capability could be increased by about 400 kp (880 lbs.).
The steps of manufacturing a container shown in the above described figures are in the following explained with reference to FIGS. 5 to 9.
During a first stretching operation a sheet or foil material is expanded cylindrically by application of a shaping force (arrows a) and of outer counter holdings (arrows b). If the body 1 is to remain round or oval, the horizontally or slightly inclined, respectively, and the vertical corrugations 10, 11 are impressed simultaneously.
Should the final shape of the body feature a cornered cross section a further stretching operation in the direction of the arrows c is carried out such as shown in FIG. 6 by utilization of bar-like stretching tools 13 whereby also a counter holding in the direction of the arrows d acting from the outside is maintained. Following, the shaping force is reduced somewhat such that the body material is relieved partly, however not completely, from the tension loading applied in circumferential direction by the stretching bars. In this condition, whereby the body is still subject to a residual stretching tension the vertical corrugations are impressed.
It is of importance that the horizontal or inclined, respectively, corrugations which were impressed in the circular form condition of the body are maintained during the further stretching operation in accordance with FIG. 6 and that during this further stretching operation the vertical corrugations can be impressed. FIGS. 7 and 9 show schematically the thereto necessary profiles of the stretching bars 13 and counter holers 14, respectively.
In FIG. 7 there is shown the profile applied for the vertical corrugations. In FIGS. 8 and 9 there are shown possible profiles applied for the horizontal or inclined corrugations which in accordance with the impressed form sought for latter corrugations are superimposed over the stretching bar 13 or counter holder 14, respectively, or both in accordance with FIG. 7.
For shaping the forms of the corrugations shown in FIGS. 2 and 4 the stretching bars are profiled relative to the vertical corrugations such as shown in FIG. 7, whereby the stretching bars are additionally profiled relative to the horizontal or inclined corrugations in order to achieve the shapes of the corrugations in accordance with FIGS. 2 and 4 as shown in FIG. 8 and for the shapes in accordance with FIG. 3 as shown in FIG. 9.
During manufacture, the inventive combinations of corrugations can be realized with known machines and acceptable expenses regarding tools and with relative small forming forces which are lower than those needed for impressing the corrugations into sheet metals used for the bodies which are still in their flat condition.
The manufacturing can proceed automatically and in series whereby also thin sheets with relatively high rigidity can be processed. The increase in strength and rigidity thereby achieved by the cold shaping can be utilized to the desired extent.
The invention may be used for any size of containers, such as e.g. cans, tins or petrol cans or tins, large containers, barrels, drums, etc. Obviously the shaping in accordance with the invention can proceed from the inside towards the outside or from the outside towards the inside or both.
The inventive shaping of the container material can be made prior to, during or after the manufacture of the container and by means of various shaping methods.
The embodiment shown in FIG. 2 is specifically advantageous for cornered containers having rounded corners and the embodiment shown in FIG. 3 is specifically advantageous for the fabrication of circular containers.
The vertical corrugations 10, 11 are provided specifically in an embodiment of FIGS. 1 and 3, of which the horizontal corrugations 8 penetrate the general area of the vertical corrugations 10, 11 and have a deeper profile than the horizontal corrugations. Every individual vertical corrugation is uninterrupted along its complete extent including the areas of intersecting the horizontal corrugations and, therefore, is not weakened. Furthermore, the profile of the vertical corrugations 10, 11 remains unaltered at the intersections and are thereby at least substantially and preferably completely preserved.
The relatively flat or shallow, respectively, circumferential corrugations 8 surround preferably the circumference of the container in a tin themselves closed form. In the embodiment in accordance with FIGS. 1 and 3 they are interrupted only at the intersections with the vertical corrugations to an extent of the width of the vertical corrugations.
Usually the impressing of the corrugations is carried out in two steps. A first step involves an expanding of the body of the container from the inside, whereby a shaping force is applied and an outer counter holding maintained, whereby the body is brought into its desired shape and whereby the circumferential corrugations 8 are impressed simultaneously. Thereafter, during a second step the vertical corrugations 10, 11 are impressed either from the inside or from the outside while maintaining again a counter holding at the outside or inside, respectively. Prior to impressing the vertical corrugations the shaping force is relieved either completely or partially.
However, the circumferential corrugations 8 and the vertical corrugations 10, 11 can be embossed simultaneously in one step from the inside by maintaining mentioned shaping force and counter holding.
It is also possible to arrange the vertical corrugations of one group in more than three adjoining rows.
The groups of vertical corrugations 10, 11 could also be arranged closely following one another in circumferential direction such that no pronounced distance prevails between any group.
While there are shown and described preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. | An improved container in form of a barrel, drum can or the like, specifically a sheet metal container. The circumferential wall of the container is provided with horizontally extending corrugations or beads, respectively, and vertically extending corrugations. The vertically extending corrugations are ordered in groupwise spaced arrangements. Such container has improved loading characteristics in the axial and circumferential direction thereof and has an improved impact resistance. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to trampolines, and improvements in the performance of trampolines.
DESCRIPTION OF THE RELATED ART
[0002] As is well known, trampolines are recreational and sometimes sporting and entertainment apparatuses designed to both enhance a trampolinist's jump height and greatly cushion his or her return bounce. Nominally, a trampoline consists of a sturdy frame often in a circular or rectangular shape (although others are possible) with frame legs that raise the trampoline above the ground, a flexible mat upon which a trampolinist can bounce or jump, and several springs attached between the mat and the frame.
[0003] The mat deflection is directly proportional to the impulse forces transmitted by the trampolinist during a bouncing or jumping session. The mat deflection is inversely proportional to the spring constants of the trampoline spring members. If the spring constants are too high, the mat may not undergo the proper deflection needed for comfort or tumbling by a typical user. If the spring constant is lower, an appropriate amount of mat deflection may be achieved for a normal weight user. However, heavier users may cause excessive mat deflections and elevated spring fatigue.
[0004] The prior art approach to keeping mat deflections from being excessive is to use lower spring constants, but restrict the weights of trampolinists (sometimes to relatively low weights). Even so, there may still be very large variations in mat deflections.
[0005] What is therefore desirable but non-existent in the prior art, is an effective scheme for limiting variations in trampoline mat deflections. What is also desirable is a trampoline that can safely and effectively accommodate a larger range of trampolinist weights.
SUMMARY OF THE INVENTION
[0006] The present invention has been developed in response to the present state of the art, and in particular, in response to the problems and needs in the art that have not yet been fully solved by currently available trampolines. Accordingly, the present invention has been developed to provide a novel trampoline that at least includes: a trampoline frame; a trampoline mat operatively surrounded by the trampoline frame; and a plurality of trampoline spring members operatively coupled between the trampoline frame and the trampoline mat. Each trampoline spring member at least includes: a first spring coupler located at a first end of the spring member; a second spring coupler located at a second end of the spring member; a first spring member section coupled to the first spring coupler; a second spring member section coupled to the second spring coupler; at least a third spring member section coupled between the first spring member section and the second spring member section, the third spring member section having a spring constant greater than the spring constants of the first and second spring member sections. The effective spring constant of the spring members increases stepwise with increases in the forces transmitted by trampoline users, and overall spring member deflections are dampened with increases in the forces transmitted by trampoline users.
[0007] The present invention has also been developed to provide a trampoline that at least includes: a trampoline frame; a trampoline mat operatively surrounded by the trampoline frame; and a plurality of trampoline spring members operatively coupled between the trampoline frame and the trampoline mat. Each trampoline spring member at least includes: a first spring coupler located at a first end of the spring member; a second spring coupler located at a second end of the spring member; a first spring member section coupled between the first and second spring couplers; a second spring member section located within the first spring member section; a first deflection delayer coupled to a first end of the first spring member section and coupled to a first end of the second spring member section, the first deflection delayer adapted to delay the deflection of the first end of the second spring member section; and a second deflection delayer coupled to a second end of the first spring member section and coupled to a second end of the second spring member section, the second deflection delayer adapted to delay the deflection of the second end of the second spring member section.
[0008] The present invention has been further developed to provide a trampoline that at least includes: a trampoline frame; a trampoline mat operatively surrounded by the trampoline frame; and a plurality of trampoline spring members operatively coupled between the trampoline frame and the trampoline mat. Each trampoline spring member at least includes: a first spring coupler located at a first end of the spring member; a second spring coupler located at a second end of the spring member; a first spring member section coupled to the first spring coupler; a second spring member section coupled to the second spring coupler; at least a third spring member section coupled between the first spring member section and the second spring member section, the third spring member section having a spring constant lower than the spring constants of the first and second spring member sections. The wire cross-section area of the spring member sections is substantially identical, and the projected longitudinal area of the third spring member section is larger than the projected longitudinal areas of the first and second spring member sections. The effective spring constant of the spring members increases stepwise with increases in the forces transmitted by trampoline users, and the overall spring member deflections are dampened with increases in the forces transmitted by trampoline users.
[0009] Reference throughout this specification to features, advantages, or similar language does not imply that all of the features and advantages that may be realized with the present invention should be or are in any single embodiment of the invention. Rather, language referring to the features and advantages is understood to mean that a specific feature, advantage, or characteristic described in connection with an embodiment is included in at least one embodiment of the present invention. Thus, discussion of the features and advantages, and similar language, throughout this specification may, but do not necessarily, refer to the same embodiment.
[0010] Furthermore, the described features, advantages, and characteristics of the invention may be combined in any suitable manner in one or more embodiments. One skilled in the relevant art will recognize that the invention can be practiced without one or more of the specific features or advantages of a particular embodiment. In other instances, additional features and advantages may be recognized in certain embodiments that may not be present in all embodiments of the invention.
[0011] These features and advantages of the present invention will become more fully apparent from the following description and appended claims, or may be learned by the practice of the invention as set forth hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] In order for the advantages of the invention to be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments that are illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered to be limiting of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings, in which:
[0013] FIG. 1 is a top view of a version of the present-inventive trampoline;
[0014] FIG. 2 shows graphs of deflection versus force for prior art single spring constant spring members, and of a present-inventive spring member having a hybrid spring constant;
[0015] FIG. 3 is a side view of a first version of the present-inventive spring member in a contracted state;
[0016] FIG. 4 is a side view of spring member of FIG. 3 in an expanded state;
[0017] FIG. 5 shows oblique and side views of the deflection limiter of the present-inventive spring member,
[0018] FIG. 6 is a side view of a second version of the spring member of the present-inventive trampoline;
[0019] FIG. 7 is a cutaway side view of a third version of the spring member of the present-inventive spring member;
[0020] FIG. 8 is a cutaway longitudinal view (as seen from the middle to an end) of the spring member of FIG. 7 ;
[0021] FIG. 9 is a cutaway longitudinal view (as seen from the middle to an end) of a fourth version of the spring member of the present-inventive trampoline;
[0022] FIG. 10 is a side view of a fifth version of the spring member of the present-inventive trampoline; and
[0023] FIG. 10 is a side view of a sixth version of the spring member of the present-inventive trampoline
DETAILED DESCRIPTION OF THE INVENTION
[0024] For the purposes of promoting an understanding of the principles of the invention, reference will now be made to the exemplary embodiments illustrated in the drawings, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the invention is thereby intended. Any alterations and further modifications of the inventive features illustrated herein, and any additional applications of the principles of the invention as illustrated herein, which would occur to those skilled in the relevant art and having possession of this disclosure, are to be considered within the scope of the invention.
[0025] Reference throughout this specification to “one embodiment,” “an embodiment,” or similar language means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrases “one embodiment,” “an embodiment,” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment, different embodiments, or component parts of the same or different illustrated invention. Additionally, reference to the wording “an embodiment,” or the like, for two or more features, elements, etc. does not mean that the features are related, dissimilar, the same, etc. The use of the term “an embodiment,” or similar wording, is merely a convenient phrase to indicate optional features, which may or may not be part of the invention as claimed.
[0026] Each statement of an embodiment is to be considered independent of any other statement of an embodiment despite any use of similar or identical language characterizing each embodiment. Therefore, where one embodiment is identified as “another embodiment,” the identified embodiment is independent of any other embodiments characterized by the language “another embodiment.” The independent embodiments are considered to be able to be combined in whole or in part one with another as the claims and/or art may direct, either directly or indirectly, implicitly or explicitly.
[0027] Finally, the fact that the wording “an embodiment,” or the like, does not appear at the beginning of every sentence in the specification, such as is the practice of some practitioners, is merely a convenience for the reader's clarity. However, it is the intention of this application to incorporate by reference the phrasing “an embodiment,” and the like, at the beginning of every sentence herein where logically possible and appropriate.
[0028] The present-inventive trampoline is shown from the top in FIG. 1 . The trampoline 100 includes a trampoline frame 110 with frame legs (not shown), a trampoline mat 120 , several novel trampoline spring members 130 , and a pad (not shown) which covers the spring members for safety.
[0029] The spring members function to provide a hybrid spring constant as will be further described below. The graph labeled K 1 in FIG. 2 is that of deflection versus force for a prior art spring member. Also in FIG. 2 , the graph labeled K 2 is the response of a prior art spring member with a higher spring constant than for the K 1 spring member. It can be readily seen that for a given force exerted by a trampolinist, the deflection is higher in the spring member with the lower spring constant K. The deflection axis in FIG. 2 also shows a range of mat deflections from up to the maximum desired deflection d maxideal , and down to a minimum desired deflection d minideal for an average weight trampolinist.
[0030] The third graph in FIG. 2 is that of the response of a present-inventive spring member with a hybrid effective spring constant. The latter graph shows that up to a point, the response is similar to that of a lower spring constant spring member. When the mat impulse force reaches a certain level (consistent with heavier trampolinists or high jumping heights) the response begins to resemble that of the higher spring constant spring member with a lower slope. As a result, the deflection at the maximum force is lower than would be for the K 1 spring member, and the deflection at the minimum force (for average jumping by an average weight trampolinist) is higher than would be for the K 2 spring member. Thus, the present-inventive spring members create a restricted range of deflection for a larger weight range of trampolinists.
[0031] A first version of the present-inventive spring member 130 is shown in FIG. 3 . The spring member 130 includes two spring member coupling ends 432 and 434 for coupling the spring member between the trampoline frame and the trampoline mat. First and second spring member sections 436 and 438 connect to a middle spring member section 440 . The spring constant K for the middle spring member section 440 is distinctly higher than the spring constants of the outside spring member sections 436 and 438 . All of the spring member sections can be molded as one piece. Alternatively, the different sections can be joined by welds or mechanical means.
[0032] In operation, the outside sections deflect first when the spring member is placed in tension. The middle section deflects little in the beginning. When the deflections of the outside sections reach a predetermined level, deflection limiters 450 cause the outside sections to stop further deflection. At that point, additional deflection of the spring member occurs through the middle section. The deflection limiter serves to protect the outside spring member sections from inelastic deflections and excessive fatiguing. The spring member is shown in an expanded state in FIG. 4 .
[0033] One version of a suitable deflection limiter is shown in FIG. 5 . A plate 454 with a void 456 is fixed to the end of the middle spring member section. The void 456 receives a rod 452 with a stop 458 at its end. The rod 452 is fixed to the end of the outer spring member sections (or alternatively to the end couplers 432 and 434 ). When the outside spring members expand, the rods 452 continue to move axially with the spring sections until the stop 458 reaches the plate 454 . At this point, no further expansion of the outside spring member sections is allowed. Further expansion of spring members is via the middle spring member section.
[0034] The present-inventive spring member is not limited to three spring member section versions. For example, a five section spring member 630 is illustrated in FIG. 6 . The embodiment 630 , which operates similar to the embodiment 130 , may also contain several deflection limiters.
[0035] Yet another version of the spring member for the present-inventive trampoline is shown in the cutaway view of FIG. 7 . In this dual spring version of a spring member 730 , a lower spring constant member section 736 surrounds a higher spring constant member section 740 . The lower spring constant section 736 is directly connected to spring member coupler ends 732 and 734 . The higher member section 740 is slidably connected to the spring member ends 732 and 734 via deflection limiters 750 . A minor role of the deflection limiters is to constrict the expansion of the spring member section 736 near its ends. The primary role of the deflection limiters is to engage the spring member section 740 when the tension force in the spring member causes the spring member section 736 to reach a threshold deflection. The deflection limiters 750 are connected to the spring member consistent with the approach with respect to the spring member 130 , supra.
[0036] FIG. 8 illustrates the spring member 730 viewed longitudinally.
[0037] Given the above description, a layered spring member may include more than two concentric spring member sections. For example, a spring member 930 with three concentric spring member sections is shown (viewed longitudinally from the middle outward) in FIG. 9 .
[0038] Yet another version of the spring member used in conjunction with the present-inventive trampoline is shown in FIG. 10 . The spring member section 1030 has its lowest spring constant in its middle spring member section 1040 . All of the spring wires in each spring member section have the same wire diameter and wire shape, and the spring member is a single long wire, albeit wound into several distinct sections. Additionally, the outside diameter of the middle spring member section 1040 continually tapers until it reaches the beginning of adjacent spring member sections 1037 and 1039 . At the beginning of section 1037 (at the juncture with section 1040 ), the outside diameter of section 1037 is distinctly smaller than the diameter of section 1040 . The same is true of the juncture between sections 1037 and 1036 , where the outside diameter of section 1036 is distinctly smaller than the diameter of section 1037 .
[0039] The diameters at the junctures of sections 1040 and 1039 , as well as the diameters at the junctures of sections 1039 and 1038 are identically dimensioned as described above at the aforementioned junctures (between sections 1040 and 1037 , and between sections 1037 and 1036 , respectively). The spring member 1030 also includes spring member couplers 1032 and 1034 . Those skilled in the art will appreciate that for the identical spring wire used in the spring member sections, the outside diameters of the spring member sections are inversely proportional to their spring constants. Further, in the preferred embodiment, the diameter discontinuities between the spring member sections measure no more than twice the spring wire diameter. This need not be the case for other embodiments.
[0040] In operation, the middle spring member section 1040 deflects first when the spring member 1030 is placed under tension. The spring member sections 1037 and 1039 then begin to deflect, followed by the deflection of spring member sections 1036 and 1038 with increasing tension. Additionally, the overall effective spring constant of the spring member 1030 increases as the tension force on the spring member increases.
[0041] The spring member 1130 in FIG. 11 is very similar to the spring member 1030 described above. The principal difference between the two spring members is that the diameter tapering in the spring member sections of the spring member 1030 is linear, whereas the diameter tapering in the spring member sections of the spring member 1130 is non-linear. Otherwise, the elements 1132 1134 , 1136 , 1137 , 1138 , 1139 , and 1140 in FIG. 11 are identical to the elements 1032 1034 , 1036 , 1037 , 1038 , 1039 , and 1040 in FIG. 10 , respectively.
[0042] It is understood that the above-described preferred embodiments are only illustrative of the application of the principles of the present invention. The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiment is to be considered in all respects only as illustrative and not restrictive. The scope of the invention is, therefore, indicated by the appended claim rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
[0043] It is expected that there could be numerous variations of the design of this invention. For example, in one embodiment there may be a spring including different materials imparting varying strengths and therefore varying spring constants. There may be an embodiment including any combination of materials, portions, spring dimensions (including wire diameter, wire configuration, coil diameter, coil shape, spring length, etc;) that imparts an increasing spring constant whether gradual and/or stepped. Finally, it is envisioned that the components of the device may be constructed of a variety of materials.
[0044] Thus, while the present invention has been fully described above with particularity and detail in connection with what is presently deemed to be the most practical and preferred embodiment of the invention, it will be apparent to those of ordinary skill in the art that numerous modifications, including, but not limited to, variations in size, materials, shape, form, function and manner of operation, assembly and use may be made, without departing from the principles and concepts of the invention as set forth in the claims. | A novel trampoline at least includes: a trampoline frame; a trampoline mat operatively surrounded by the trampoline frame; and a plurality of trampoline spring members operatively coupled between the trampoline frame and the trampoline mat. Each trampoline spring member at least includes: a first spring coupler located at a first end of the spring member; a second spring coupler located at a second end of the spring member; a first spring member section coupled to the first spring coupler; a second spring member section coupled to the second spring coupler; at least a third spring member section coupled between the first spring member section and the second spring member section, the third spring member section having a spring constant greater than the spring constants of the first and second spring member sections. The effective spring constant of the spring members increases stepwise with increases in the forces transmitted by trampoline users, and overall spring member deflections are dampened with increases in the forces transmitted by trampoline users. | 0 |
BACKGROUND OF THE INVENTION
[0001] In recent years, consumer electronic devices such as digital cameras, Personal Digital Assistants (PDAs), smart phones, and digital audio and video recorders have driven a strong market demand for removable data storage components. The electronics industry has responded to this demand with products known generically as “memory cards.” A memory card usually contains one or more semiconductor memory chips within an industry-standard housing with dimensions that allow it to be used in conjunction with different devices from various manufacturers. Memory cards typically also have connectors on an external surface that allow electrical connections to the circuitry of consumer electronic devices. Examples of types of memory cards include PC Cards, MultiMedia Cards, CompactFlash Cards, and Secure Digital Cards. These devices are made in accordance with standards promulgated by trade associations such as the Personal Computer Memory Card International Association (“PCMCIA”) and the MultiMedia Card Association (“MMCA”).
[0002] An exemplary memory card, namely, a MultiMedia Card (“MMC”) 10 , is illustrated in top view, cross-sectional side view, and bottom view in FIGS. 1-3 , respectively. The MMC illustrated has standardized dimensions of 32 mm long, 24 mm wide, 1.4 mm thick, and typically includes a memory capacity of between 2 and 256 megabytes (“MB”) of memory, which is accessed through seven contacts 11 located on the bottom surface of the MMC using, e.g., a standard serial port interface (“SPI”) interface. A simple chamfer 12 on one corner of the MMC prevents incorrect insertion of the MMC into a connector in a host device.
[0003] The exemplary prior art MMC shown in FIGS. 1-3 comprises a rectangular substrate 13 , such as a printed circuit board (“PCB”), and one or more semiconductor memory dies 14 or “chips” mounted on and electrically connected thereto using, e.g., a layer of adhesive 15 and conventional wire bonds 16 , respectively. Surface mounted passive components, e.g., resistors, may also be mounted on and connected to substrate 13 . Contacts 11 are connected through substrate 13 to memory circuits defined by foregoing components and serve as input-output terminals of card 10 .
[0004] When the components have been mounted on and connected to the substrate 13 , prior art methods included a step in which chip 14 is protectively encapsulated by a “glob-topping” process. This step was necessary due to the high-pressure, high-temperature injection of thermoplastic material that would occur at a later stage. The high-pressure injection and high temperature can damage a microchip and other small electronic components, particularly wire bonds. In the glob-topping step a glob of a viscous encapsulant is dispensed onto the top surface of the chip and is allowed to flow over the chip's sides to the surface of the substrate. The encapsulant is cured to form a protective envelope 18 over the chip. An external cover or housing 19 (shown by the dotted outline in FIG. 1 ) of thin sheet metal or plastic is installed over the substrate 13 assembly by embedding the top surface of the assembly in a bed of adhesive contained in the housing 19 .
[0005] Prior art methods for making memory cards are, to a large degree, concerned with properly positioning and fixing electronic components, modules or assemblies inside the memory card. This concern is due to the fact that if the electronic components are not properly affixed they will be moved to random positions during injection of the thermoplastic material into a card-forming cavity. This is a particular problem in the prior art processes because the injection occurs under the influence of rather high pressures. Prior methods for making memory cards included the use of relatively large, mechanical holding devices having hard, sharply defined bodies for holding the electronic components in place during injection of thermoplastic materials. The use of such holding devices can limit the positioning options for the electronic components in the memory card. The positioning limitation also may cut down on the size and number of electronic components that can be placed in such memory cards. This limitation in turn limits the amount of memory that can be put into an MMC.
[0006] Additionally, due to differences in the coefficients of expansion of the materials used to make these relatively large holding devices—relative to the coefficient of expansion of the other elements of such cards—deformations often appear on the external surfaces of finished cards that contain such electronic component holding devices. That is to say that surface deformations can result from the mere presence of such holding members in the body of the card as it experiences different temperatures and pressures during its manufacture. Such deformations are, at best, unsightly; at worst, they may prevent the card from lying completely flat in the card-receiving receptacles in certain card reading machines.
[0007] Some memory card manufacturers have dealt with this problem by reducing the size of such holding devices or by using glues to securely position their electronic components in card-forming cavities during the thermoplastic injection process. The use of glues to secure electronic components has, however, resulted in another set of problems. These problems are due to the fact that most commercially available, fast-curing glues that are used to fix such electronic components in place are often characterized by their high degree of shrinkage. Moreover, relatively large volumes of glue are needed to fix the electronic components. Use of relatively large volumes of high-shrinkage glue tend to wrinkle and otherwise deform the region of the plastic sheet or layer to which such glues are applied. This wrinkling can transmit through the thin body of the memory card and cause the outer surface of the card to take on a local wave-like character. Beyond certain tolerances, these wave-like bends are unacceptable in the memory card industry because a deformed memory card will be inoperable in certain devices.
[0008] One additional limitation, which was touched on above, in the manufacture of prior art memory cards is that they are typically produced with prior art processes that involve the injection of filled epoxy resin or high-temperature, high-pressure thermoplastic injection into molded forms. In addition to the fact that a high-pressure, high-temperature injected material may stress or damage the electronic components of the card, it also takes a relatively long time to set and cool in the mold. Epoxy resins undergo a chemical reaction following injection, which can damage the electronic components of the memory card. What is needed is a method for producing memory cards that does not require providing a “glob-top” for memory die assemblies, with a rapid cure time and rapid manufacturing cycle time, and without the use of internal holding measures that could damage the memory card electronics.
SUMMARY OF THE INVENTION
[0009] It is therefore an object of this invention to provide a Memory Card or similar device with a thickness ranging from approximately 0.76 mm (the thickness of a conventional credit card) to approximately 5.0 mm that contains securely encapsulated Integrated Circuits and/or other electronics (e.g. a resistor) and with high quality exterior surfaces on which sophisticated graphics may be printed. The bottom surface of the Memory Card must include external contacts for electronic communication with other devices. It is additionally an object of this invention to securely encapsulate the electronics in a memory card using a low-pressure, low-temperature process in order to obviate the need for “glob-topping” the electronics. Removing the glob-topping process will save time in the processing of memory cards and will additionally provide valuable space inside of the memory card for additional memory or other electronic components. It is additionally an object of this invention to reduce manufacturing cycle time with a low-temperature process that improves production efficiency. A low-temperature process allows memory cards to be produced with less energy and enables production cycle time to be greatly reduced, thus improving manufacturing output.
[0010] This and other objects of the invention are achieved by providing a multi-layer Memory Card with an outer layer of material such as Teslin™ or other synthetic paper or suitable material (e.g. PVC, PC), with a core layer of injected polymeric material that securely encapsulates an Integrated Circuit (e.g. Multimedia card die assembly), and securely bonds to the outer layer of Teslin™ or other suitable material.
[0011] The use of low shrinkage glue to pedestal the electronic components above the bottom layer of the device facilitates an even flow and a complete encapsulation of the electronics by injected polymeric material. The mounds of low shrinkage glue positioned on the bottom layer of the device create and maintain a void space of approximately 0.1 to 0.15 mm to allow injected polymer to fill said void space and cover the top surface of the bottom layer and the bottom surface of the top layer, with no voids or pockets and with even and complete distribution of the polymer material in the void space below and above the electronics. Alternatively, the electronic components may be placed directly on a bottom mold without use of a bottom layer. In this way, the bottom of the electronic components comprises the bottom surface of the device.
[0012] The object of the Teslin™, PVC, or other suitable material inlay sheet design is to enable the production of inlays, which are the electronic components, with multiple inlays per sheet. For example, FIG. 6 illustrates a 16×10 array of inlays (a total of 160 Memory Cards).
[0013] The inlays are produced on a single continuous sheet, which is then cut by a machine tool in a form that allows the Memory Card perimeter to be covered by the injected polymer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIGS. 1-3 depict a prior art memory card in a top view cross-section, side view cross section, and bottom view, respectively.
[0015] FIG. 4 is a cut-away side view of a layer or sheet of a synthetic paper (e.g. Teslin™) or plastic material (e.g., PVC) as used to make prior art Memory Cards. This view is shown before ( FIG. 4 ( a )) and after ( FIG. 4 ( b )) a drop of a prior art, “high shrinkage” glue is allowed to cure on that layer of synthetic paper or plastic material.
[0016] FIG. 5 is a cut-away side view of a Memory Card made according to the teachings of this patent disclosure.
[0017] FIGS. 6 and 7 are cut-away side views of a mold tool set up for making a first preferred embodiment of an Memory Card of this patent disclosure wherein certain Memory Card components (e.g. Multimedia card die assembly) are shown before a liquid polymeric material is injected between the Memory Card's top and bottom layers (see FIG. 6 and after (see FIG. 7 ) the polymeric material is injected into a void space between the top and bottom layers and thereby filling said void space with a polymeric material and cold forming the top layer of the Memory Card to the contour of the top mold's Memory Card-forming cavity.
[0018] FIG. 8 is a cut-away view showing a mold tool being removed from a precursor Memory Card body formed by the system generally depicted in FIG. 7 .
[0019] FIG. 9 depicts a mold tool system that is capable of making 160 Memory Cards (with dimensions of approximately 24 mm×32 mm) simultaneously.
[0020] FIG. 10 is a cut-away side view of a finished Memory Card made without a separate bottom layer.
[0021] FIGS. 11 and 12 are cut-away side views of a mold tool set up for making a first preferred embodiment of an Memory Card of this patent disclosure wherein certain Memory Card components (e.g. Multimedia card die assembly) are shown before a liquid polymeric material is injected between the Memory Card's top layer and the electronic component. The polymeric material is injected into a void space between the top layer and the electronic components thereby filling the void space with a polymeric material and cold forming the top layer of the Memory Card to the contour of the top mold's Memory Card-forming cavity.
[0022] FIG. 13 is a cut-away view showing a mold tool being removed from a precursor Memory Card body formed by the system generally depicted in FIG. 12 .
DETAILED DESCRIPTION OF THE INVENTION
[0023] FIGS. 4 ( a ) and 4 ( b ) illustrate a problem involved with the prior art methods of making Memory Cards. FIG. 4 ( a ) depicts, in cut-away cross section, a sheet or layer of a plastic material 40 (e.g., a sheet or layer of polyvinyl chloride, polyurethane, etc.) having a top surface 41 and a bottom surface 42 . Such sheets will generally have a thickness 43 ranging from about 0.075 mm to about 0.25 mm. A mound, drop, or dollop of a liquid or semi-liquid, high shrinkage, glue 44 is depicted as being recently dispensed on the top surface 41 of the plastic sheet 40 shown in FIG. 4 ( a ). The mound of recently dispensed glue 44 depicted in FIG. 4 ( a ) is shown having an initial width W 1 . FIG. 4 ( b ) shows (in exaggerated form) the results of curing the mound of glue 44 shown in FIG. 4 ( b ) to a smaller mound of cured glue 44 ′. The width W 2 of the mound of cured glue 44 ′ depicted in FIG. 4 ( b ) is considerably less than the width W 1 of the mound of the newly laid liquid or semi-liquid glue 44 in FIG. 4 ( b ). For the sake of simplicity, the decrease or shrinkage from the original width W 1 to W 2 (i.e., ΔW) of the mound of newly dispensed, high shrinkage glue is represented in FIG. 4 (B) by the dimensions “½ ΔW,” on the left side of the mound of and a comparable “½ ΔW” on the right side of said mound of cured glue 44 ′. Such curing is also depicted by a decrease in the volume of the original mound of glue 44 . For example, this decrease in volume may be as much as 20 to 30 percent in many high shrinkage glues.
[0024] As previously noted the concept of a “high shrinkage” glue versus a “low shrinkage” glue also can be addressed in terms of the decrease in volume of a cured glue relative to the volume of that glue in its newly laid state.
[0025] The curing process associated with high shrinkage glues causes the mound of glue 44 depicted in FIG. 4 ( a ) to shrink from an initial size which can be thought of as having an initial width W 1 (wherein the mound of glue is in a semi-liquid or tacky state) to a final width W 2 (wherein the cured glue 44 ′ is in a substantially solid state) and that this high degree of shrinkage (e.g., greater than about 15 percent—and often as much as 20-30 percent) causes the top surface 41 of the layer or sheet of plastic material to “wrinkle up” or otherwise deform, e.g., form wrinkles 45 in FIG. 4 ( b ). Such deforming actions create forces in the relatively thin layer (e.g., 0.075 to 0.25 mm thick) of plastic material 40 . These forces are transmitted to the bottom surface 42 of that layer of plastic material 40 . These transmitted forces, in turn, cause deformations 46 , (curves, bends, waves, ripples, wrinkles, etc.), in the bottom surface 42 of the plastic layer 40 . Any such deviations from a flat, smooth surface are regarded as highly undesirable deformities by the Memory Card industry and, hence, must be minimized to the fullest extent possible. Achievement of Memory Card surfaces having no such waves, bends, wrinkles, or other imperfections is one of the primary objects of the processes of this patent disclosure.
[0026] FIG. 5 depicts a cut-away side view of a Memory Card 50 made according to the teachings of this patent disclosure. In its finished form, such a Memory Card 50 will be comprised of a top layer 51 , a bottom layer 52 , and a center or core layer 53 in which the Memory Card's electronic components (e.g. Multimedia die assembly 54 that includes a substrate 55 and contact pads 56 , etc.) are embedded in a thermosetting polymeric material 57 (e.g., an initially liquid or semi-liquid thermosetting resin) that, upon curing, constitutes the center or core layer 53 of finished Memory Card 50 . The thermosetting material 57 that eventually becomes the core layer 53 of Memory Card 50 is injected into the void space between the top layer 51 and bottom layer 52 .
[0027] The void space is of height 58 and extends from one side of the card to the other. As described herein above, prior art methods of making memory cards involved injection of epoxy resins that chemically reacted to solidify and form the body of a memory card. These reactions are potentially dangerous to sensitive electronic components such as a microprocessor. Alternatively, prior art methods involved high-pressure injection of a high-temperature thermoplastic material. The high-pressure and temperature of prior art methods of injection is also dangerous for electronic components, which is why “glob-topping” to protect the electronic components is common practice when using the prior art methods. The configuration of the electronic components shown in FIG. 5 , which does not include a protective “glob-top,” would not be usable with either epoxy resins or high-pressure injected high-temperature thermoplastic materials. Lastly, both epoxy resins and high-temperature thermoplastics when injected into a mold take a considerable amount of time to cure. The lengthy curing and cooling times required when using high-temperature thermoplastics and high-pressure injection greatly slows the process of producing devices.
[0028] For these reasons the injected polymeric material 57 provides significant advantages by being injected under the relatively cold, low pressure forming conditions employed in applicant's process.
[0029] In any case, such thermosetting polymeric materials will be injected into, and fill, the void space 58 defined between the inside surface 59 of the top layer 51 and the inside surface 60 of the bottom layer 52 . Upon curing, the polymeric material 57 of the core layer 53 should bond or otherwise adhere to both the inside surface 59 of the top layer 51 and the inside surface 60 of the bottom layer 52 to produce a unified Memory Card body. Such adherence can be aided by treating the inside surfaces 59 and 60 of the top and bottom layers in any one of several ways. For example, bonding agents known to this art (e.g. chloro-polyolefins) may be employed to enhance bonding between the core layer-forming thermoset material and the material(s) from which the top and bottom layers are made (e.g., Teslin, PVC). By way of example only, Minnesota Mining and Manufacturing's base primer product 4475 RTM can be used for this bond enhancing purpose, especially when the top or bottom layer material is PVC. Other treatments that can be applied to the inside surfaces of the top and/or bottom layers could include plasma corona treatments and acid etching.
[0030] The Memory Card's thickness 61 is defined by placement of the mold faces (not shown in FIG. 5 ) as the thermoset material is injected into the void space 58 as part of the cold, low pressure forming process of this patent disclosure. In effect, the injection of the thermoset material into the void space 58 between the top and bottom layers fills any portion of that void space 58 that is not otherwise occupied by the electronic components or by the mound(s) of low shrinkage glue 62 upon which the electronic components are placed.
[0031] Next, it should be noted that the Memory Card's electronic components (e.g., Multimedia die assembly substrate 55 , Memory chip 54 , etc.) are preferably positioned above the inside surface 60 of the bottom layer 52 through use of one or more drops or dollops of applicant's low shrinkage glue 62 . As described herein above, prior art methods of making memory cards did not employ glue to pedestal the electronic components of the memory card. This is due to the fact that the prior art methods involve injection of epoxy resins or high-pressure, high-temperature thermoplastic materials, both of which would damage the glue. Also, and more importantly, because the prior art methods involve injection of epoxy resins or high-pressure high temperature thermoplastic materials, the electronic components have to be “glob-topped” and it is therefore unnecessary to pedestal the electronics.
[0032] In applicant's method, the electronic components are most preferably placed on top of two or more mound(s) of glue 62 , etc. in the manner generally suggested in FIG. 5 so that the incoming liquid or semi-liquid polymeric material will flow under such electronic components as well as immerse these components from above and from their sides. In other words, in the more preferred embodiments of this invention the mound(s) of glue 62 will serve as one or more “pedestal(s)” upon which the electronic components are placed so that the underside of the electronic components do not come into direct contact with the top surface 60 of the bottom layer 52 , but rather are immersed in the incoming thermoplastic material 57 . This design enables these electronic components to better resist any flexion and/or torsion forces the Memory Card may encounter upon either of its major outside surfaces or on any of its four outside edge surfaces. In some of the more preferred embodiments of this invention these electronic components (e.g., Memory chip 54 ) will be positioned by the glue at a distance 63 of from about 0.075 mm to about 0.13 mm above the inside surface 60 of the bottom layer 52 .
[0033] FIGS. 6 and 7 are contrasted to illustrate a first preferred embodiment of applicant's methods for making Memory Cards and similar devices. That is to say that FIG. 6 depicts a particularly preferred embodiment of this invention wherein the flat, top layer or sheet 51 of synthetic paper such as Teslin™ or plastic material 51 such as PVC is shown before it is cold, low pressure formed according to the teachings of this patent disclosure. In other words, FIG. 6 depicts the mold tool set-up just prior to the injection of the polymeric material and wherein a flat, top layer 51 (e.g., a flat sheet of PVC) is shown as it is initially placed under a Memory Card-forming cavity of the top mold 64 and a bottom layer 52 (e.g., another flat sheet of PVC) is shown as it is placed over a bottom mold 65 . Again, however, in some less-preferred, but still viable, embodiments of applicant's processes the top layer 51 may be pre-molded or at least partially pre-molded, preferably, to the general contour of the Memory Card-forming cavity in the top mold 64 .
[0034] By way of comparison, the bottom mold 65 has no cavity comparable to the cavity in the top mold 64 . FIG. 7 depicts the effects of injecting the thermoset polymeric material 57 into the void space between the top and bottom layers 51 and 52 . Thus, FIG. 7 shows the top layer 51 after it has been molded into a Memory Card-forming cavity 66 in the top mold 64 .
[0035] Referring to FIG. 6 , a nozzle 67 for injecting a liquid or semi-liquid, thermoplastic or thermosetting polymeric material 57 is shown being inserted into an orifice 68 that leads to the void space that is defined between the inside surface 59 of the top layer 51 and the inside surface 60 of the bottom layer 52 . The distance between the top surface 69 of the top layer 51 and the bottom surface 70 of the bottom layer 52 is depicted by distance 78 . The void space is shown extending from orifice 68 to the opposite end of the juxtaposed top layer 51 and bottom layer 52 . In other words, in FIG. 6 a portion of the outside surface 69 of the top layer 51 is not yet in contact with the inside surface 72 of the Memory Card-forming cavity 66 of the top mold 64 . By way of contrast, the outside surface 70 of the bottom layer 52 is shown in substantially flat, abutting contact with the inside surface 74 of the bottom mold 65 .
[0036] In both FIGS. 6 and 7 the electronic components of the Memory Card (e.g., its substrate 55 , memory chip 54 , etc.) are shown positioned above the inside surface 60 of the bottom layer 52 . By way of example only, such electrical components are shown pedestaled on two dabs or dollops 62 of applicant's low shrinkage glue. These glue pedestals hold the electronic components far enough above the inside surface 60 of the bottom layer 52 (e.g., from about 0.075 mm to about 0.13 mm) that the incoming thermoset polymeric material 57 can flow in to the region 75 under the electrical components as well as the regions above these electronic components. Again, such glue pedestal arrangements are preferred because the presence of the thermoset polymeric material under the electronic components tends to augment the protection of such electronic components against any forces or shocks that may be received by the outside surfaces (i.e., the outside of the bottom layer and/or the outside of the top surface) of the Memory Card.
[0037] In FIG. 6 the top mold 64 is shown having a cavity 66 which defines the surface contour of the top of the Memory Card to be formed during the injection process. To this end, the injection of the liquid or semi-liquid thermoset polymeric material 57 should be under pressure and temperature conditions such that the top layer 51 is cold, low pressure, formed into the cavity 66 of the top mold 64 . FIG. 7 shows how the cold, low pressure forming process of this patent disclosure has in fact conformed the top surface 69 of the top layer 51 to the configuration of the Memory Card-forming cavity in the top mold 64 . Again, the bottom surface 70 of the bottom layer 52 is shown in FIG. 7 molded against a substantially flat inside surface 74 of the bottom mold 65 . This is a particularly preferred arrangement for making the Memory Cards of this patent disclosure.
[0038] In FIGS. 6 and 7 , a front lip region 76 of the top mold 64 and a front lip region 77 of the bottom mold 65 are shown spaced apart from each other by a distance 78 ′ that (taking into consideration the thickness of the top and bottom layers 51 and 52 ), in effect, defines the distance the width of the void space between top layer 51 and the bottom layer 52 at lip regions 76 and 77 of molds 64 and 65 , respectively. This distance should be such that the thermoset polymeric material 57 can be injected into the void space over the entire length of the Memory Card. The counterpart distance 58 of the mold device setting on the right side of the system shown in FIG. 6 may differ from that of distance 78 ′ on the left side. In any case the distance 58 should be such that the distance 58 ′ defined between the inside surface 59 of the top layer 51 that passes through the rear lip 79 of the top mold 64 and the inside surface 60 of the bottom layer 52 that passes through the rear lip 80 of the bottom mold 65 is very small—but still finite. That is to say that this very small distance 58 ′ should be large enough to allow gases 81 (e.g., air, polymeric ingredient reaction product gases, etc.) in the void space that originally existed between the top and bottom layers 51 and 52 , respectively (see again, FIG. 6 ), and excess polymeric material to be exhausted from said void space, but still be small enough to hold the injection pressures used to inject the thermoset polymeric material 57 . The distance 58 ′ is preferably sized large enough to allow even thin layers of the liquid polymeric material 57 itself to be “squirted” or “flashed” out of the void space—and thus allowing all gases residing in, or created in, the void space to be expunged out of said void space and, indeed, out of the mold system itself. Thus, all such gases 81 are completely replaced by the incoming liquid thermoset material 57 . This gas exhaust technique serves to prevent gas bubbles from forming in the body of the thermoset material 57 that eventually (i.e., upon curing of the thermoset material) comprises core layer 53 as shown in FIG. 7 .
[0039] FIG. 8 shows a semi-finished or precursor Memory Card of the type shown in FIG. 7 being removed from a mold system. Section lines 84 and 86 respectively show where the left end and right end of the precursor Memory Card can be cut or trimmed away to create the sharp edges and precise dimensions of a finished Memory Card. In this case the distance 82 is about 32 millimeters.
[0040] FIG. 9 illustrates a molding procedure being carried out according to some of the preferred embodiments of this patent disclosure wherein 160 Memory Cards 50 with dimensions of approximately 24 mm×32 mm are being molded simultaneously.
[0041] FIG. 10 illustrates a finished Memory Card 122 made using an alternate embodiment of the present invention in which an electronic component (in FIG. 10 , the memory die assembly is comprised of substrate 126 , memory die 134 , external electrical contacts 133 , and additional components) is used as the bottom layer, and no additional bottom layer is necessary.
[0042] FIGS. 11 and 12 illustrate this second embodiment of applicant's methods for making Memory Cards and similar devices. That is to say that FIG. 11 depicts a particularly preferred embodiment of this invention wherein a flat, top layer or sheet 124 of synthetic paper such as Teslin™ or plastic material 124 such as PVC is shown before it is cold, low pressure formed according to the teachings of this patent disclosure. In other words, FIG. 11 depicts the mold tool set-up just prior to the injection of the polymeric material and wherein a flat, top layer 124 (e.g., a flat sheet of PVC) is shown as it is initially placed under an Memory Card-forming cavity of the top mold 144 and an electronic component comprised, for example, of a substrate 126 , memory die 134 , and external contacts 133 , is shown as it is placed over a bottom mold 146 . Again, however, in some less-preferred, but still viable, embodiments of applicant's processes the top layer 124 may be pre-molded or at least partially pre-molded, preferably, to the general contour of the Memory Card-forming cavity 164 in top mold 144 .
[0043] By way of comparison, the bottom mold 146 has no cavity comparable to the cavity in the top mold 144 . FIG. 12 depicts the effects of injecting the thermoset polymeric material into the void space 136 between the top layer 124 and the electronic component. FIG. 12 shows the top layer 124 after it has been molded into a Memory Card-forming cavity 164 in the top mold 144 .
[0044] A nozzle 148 for injecting a liquid or semi-liquid, thermoplastic or thermosetting polymeric material 134 is shown being inserted into an orifice 149 that leads to the void space 136 that is defined between the inside surface 138 of the top layer 124 and the inside surface of the electronic component. The distance between the top surface 155 of the top layer 124 and the bottom surface 158 of the Memory Card is depicted by distance 125 . The void space 136 is shown extending from the left end to the right end of the juxtaposed top layer 124 and the electronic component. In other words, in FIG. 1 the outside surface 155 of the top layer 124 is not yet in contact with the inside surface 156 of the Memory Card-forming cavity 164 of the top mold 144 . By way of contrast, the outside surface 158 of the electronic component is shown in substantially flat, abutting contact with the inside surface 160 of the bottom mold 146 .
[0045] In FIG. 11 the top mold 144 is shown having a cavity 164 , which defines the surface contour of the top of the Memory Card to be formed during the injection process. To this end, the injection of the liquid or semi-liquid thermoset polymeric material 134 should be under pressure and temperature conditions such that the top layer 124 is cold, low pressure, formed into the cavity 164 of the top mold 144 . FIG. 12 shows how the cold, low pressure forming process of this patent disclosure has in fact conformed the top surface 155 of the top layer 124 to the configuration of the Memory Card-forming cavity 164 in the top mold 144 . Again, the bottom surface 158 of the electronic component is shown in FIG. 7 molded against a substantially flat inside surface 160 of the bottom mold 146 .
[0046] In FIGS. 11 and 12 a front lip region 166 of the top mold 144 and a front lip region 168 of the bottom mold 146 are shown spaced apart from each other by a distance 170 that (taking into consideration the thickness of the top layer 124 and electronic component), in effect, defines the distance the width of the void space between the top layer 124 and the electronic component at these lip regions of the two molds 144 and 146 . This distance 170 should be such that the thermoset polymeric material 134 can be injected into the void space 136 over the entire length of the Memory Card. The counterpart distance 170 ′ of the mold device setting on the right side of the mold system may differ from that of distance 170 on the left side. In any case the distance 170 ′ should be such that the distance 137 defined between the inside surface 138 of the top layer 124 that passes through the rear lip 167 of the top mold 144 and the inside surface of the electronic component that passes through the rear lip 169 of the bottom mold 146 is very small—but still finite. That is to say that this very small distance 137 should be large enough to allow gases 172 (e.g., air, polymeric ingredient reaction product gases, etc.) in the void space 136 that originally existed between the top layer 124 and the electronic component (see again, FIG. 11 ) and excess polymeric material to be exhausted from said void space 136 , but still be small enough to hold the injection pressures used to inject the thermoset polymeric material. The distance 137 is preferably sized large enough to allow even thin layers of the liquid polymeric material 134 itself to be “squirted” or “flashed” out of the void space 136 —and thus allowing all gases residing in, or created in, the void space 136 to be expunged out of said void space and, indeed, out of the mold system itself. Thus, all such gases 172 are completely replaced by the incoming liquid thermoset material 134 . This gas exhaust technique serves to prevent gas bubbles from forming in the body of the thermoset material 134 that eventually (i.e., upon curing of the thermoset material) comprises the core layer 128 ( FIG. 10 ).
[0047] FIG. 13 shows a semi-finished or precursor Memory Card of the type shown in FIG. 12 being removed from a mold system. Section lines 284 and 286 respectively show how the left end and right end of the precursor Memory Card can be cut or trimmed away to create the sharp edges and precise dimensions of a finished Memory Card. In this case the distance 274 is about 32 millimeters.
[0048] While this invention has been described with respect to various specific examples and a spirit that is committed to the concept of the use of special glues and gluing procedures, it is to be understood that the herein described invention should be limited in scope only by the following claims. | Memory Cards containing Integrated Circuits and other electronic components (e.g. resistors) in a variety of form factors having high quality external surfaces of polycarbonate, synthetic paper (e.g. Teslin), or other suitable material (e.g. PVC) can be made through use of injection molded thermoplastic material or thermosetting material that becomes the core layer of said Memory Cards and similar devices. The object of the invention is to provide the following properties to Memory Cards: rapid production cycle, high volume manufacturing throughput, security, electronics protection, better tamper resistance, durability, and highly reliable complex electronics encapsulation, achieved through a process utilizing low temperature and low pressure. | 1 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates, generally, to an injection molding machine, and more particularly, but not exclusively, the invention relates to three level stack mold injection molding machine.
[0003] 2. Background Information
[0004] The state of the art includes U.S. Pat. No. 5,707,666 that provides a four level mold having linkage for moving the molds that is capable of moving the molds simultaneously and in unison so that the molds open and close together. The linkage would not permit the use of a side entry robot nor does it show open and easy access through the top of the machine.
[0005] U.S. Pat. No. 5,518,387 describes a swing arm device for removing parts from a mold. The motion of the swing arm device is synchronized with the opening and closing of the mold to speed up part retrieval.
[0006] U.S. Pat. No. 5,185,119 shows a stack mold in Tandem configuration with cores aligned the same way. In this machine the mold is operated on alternate cycles so each side opens sequentially rather than simultaneously.
[0007] U.S. Pat. Nos. 6,027,681 and 6,099,784 describe a stack mold that has unequal strokes so that different parts can be molded in the adjacent molds.
[0008] U.S. Pat. No. 6,155,811 describes a two level mold that is mounted on linear bearings. This is the type of machine that has been modified by the present invention to provide a three level stack mold in the space occupied by the two level stack mold described in this patent.
[0009] U.S. Pat. Nos. 5,908,597 and 6,036,472 describe multiple stack mold machines that use rack and pinion devices to open and close the mold and includes part ejection means that is operated independently of the rack and pinion devices.
[0010] An article on page 14 of the September, 1991 issue of Plastics World describes a mold change system that includes self-locating/leveling mold guide slots.
[0011] An article by P. Glorio of Incoe Corp. published in ANTEC '88, pages 255 to 258 describes the development of quick mold change systems including systems that use hydraulically actuated wedge-lock clamps.
[0012] U.S. Pat. No. 4,473,346 describes a single level molding system where the molding dies are insertable and removable in either the horizontal or vertical direction.
[0013] U.S. Pat. No. 4,500,274 describes a quick-change mold system that includes adapter plates provided with service fittings that interconnect and disconnect upon insertion and removal of the molds together with the adapter plates.
[0014] U.S. Pat. No. 4,500,275 describes a quick-change mold system that includes a locator clamp for facilitating the insertion and removal of a mold from a molding machine
[0015] U.S. Pat. No. 4,568,263 describes the use of locator wedge clamp assemblies mounted on and extending from the platens
[0016] U.S. Pat. No. 5,096,404 describes the use of rollers and guide rails for aligning a mold press in a vertical plane above the injection molding machine.
[0017] U.S. Pat. No. 5,096,405 describes a mounting plate attachable to a molding machine platen. The mounting plate has a plurality of retention slots with hydraulically actuated clamps in the slots. Actuation of the clamps presses a mold part toward the platen in an adjusted position.
[0018] With the cost of injection molding machines and the competitive pricing of products made thereon, it is essential that the machine be as productive as possible. In the case where the machine must be capable of making a number of different parts, this requires that mold changes be quick and inexpensive. It is also cost effective to minimize the space requirements of the machine. In addition, it is essential that parts be removed from the molds as quickly as possible so the cycle time of the machine can be as short as possible. It is also advantageous to provide a machine that requires only a single set of hot runner plates for all moldsets usable on the machine.
[0019] The present invention provides an injection molding machine that enables mold changes to be made quickly and easily, provides robot accessibility to the parts that may be of a variety of heights without modifying the space requirements of the mold and allows a three level stack mold for high profile parts to be placed in space that was previously fully occupied by a two level stack mold.
[0020] The invention is achieved by creating a three level stack mold that provides open access to the molds from all sides when the molds are open. Side access is provided by designing a linkage for the stack mold that surrounds the mold opening but does not cross it when the molds are open. Moving all physical connections such as water and electrical lines to the side edges of the mold provides access through the top and bottom. To avoid any electrical faults caused by water leaks from occurring, the electrical connections are made at the top of the mold and the water connections at the lower point of the mold. Air connections are also provided at the top of the machine to avoid or minimize contamination of the air lines by a failure in the water supply system.
[0021] When the molds need to be changed, the mold is closed and each cavity plate is latched to its respective core plate. The mold is then opened and each moldset of a cavity plate and a core plate is removed from the machine as a single unit along guides. When the cavity and core plate moldset is fully removed, a new moldset of a cavity plate and a core plate is inserted into the mold and guided by the same grooves. The grooves guide the core plate so that it is slightly separated from the platen until it is very near its home position. When it reaches this position a wedge surface forces the core plate against the platen and automatically locks it into position on the platen. At the same time the air and water connections automatically connect to the core plate by automatic docking mechanisms. When the core plate is in position, the mold is closed and the cavity plate is disconnected from the core plate and firmly attached to the hot runner plate.
[0022] The invention also provides a machine in which all three moldsets in the three level stack mold are oriented in the same direction. This enables uniform robot actuation for all three moldsets without the need to reorientate molded parts. This further simplifies the retrieval of molded parts.
[0023] With this configuration, the robot can be located in the same position for all parts and enter between the cavity and core faces without interference with either face. The linkage assembly surrounds the mold opening when the mold is open and eliminates the need for robot adjustment when the molds are changed. This also provides weight distribution and manufacturing benefits.
SUMMARY OF THE INVENTION
[0024] The present invention provides a linkage assembly for a multiple level stack mold molding machine having a fixed platen, a movable platen, a plurality of carriage assemblies. The linkage assembly includes an arm on each carriage assembly pivotally connected to a central pivot point on one of the carriage assemblies. An arm also extends between the fixed platen and an end of one of the arms on a carriage assembly. Another arm extends between the movable platen and an end of another of the arms on another of the carriage assemblies. A pair of arms extend between each adjacent carriage assembly, each one of the pair of arms extends from an end of an arm of one carriage assembly to a central pivot point on an adjacent carriage assembly. Each arm of the pair of arms is shaped to extend around a periphery portion of a mold opening.
[0025] The invention more particularly provides a pair of linkage assemblies for a three level stack mold molding machine having a fixed platen, a movable platen and two carriage assemblies. Each linkage assembly includes a first arm pivotally connected to a first central pivot point on one of the carriage assemblies, a second arm pivotally connected to a second central pivot point on another of the carriage assemblies, a third arm pivotally connected to the fixed platen at one end and to a first end of the first arm at another end, a fourth arm pivotally connected to the movable platen at one end and to a first end of the second arm at another end and a pair of arms extending between the first and second arms. One of the third or fourth arms is connected to an upper end of one of the platens and the other of the third or fourth arm is connected to a lower end of the other of the platens. One of the the pair of arms extends between a second end of the first arm and the second central pivot point and the other of the pair of arms extends between a second end of the second arm and the first central pivot point. The pair of arms and the first and second arm surround an opening between mold faces of a central moldset when the mold is open and the third arm and fourth arm extend across a moldset in a position below or above mold faces of moldsets on either side of the central moldset to facilitate access to the mold faces when the mold is open.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Exemplary embodiments of the present invention will now be described with reference to the accompanying drawings, in which:
[0027] FIG. 1 is a rear perspective view of the injection-molding machine with the mold closed.
[0028] FIG. 2 is a rear perspective view of the injection-molding machine with the mold open.
[0029] FIG. 3 is a rear perspective view of the injection-molding machine having the three hot runners ready to be loaded into the machine.
[0030] FIG. 4 is a rear perspective view of the injection-molding machine with the three hot runners mounted in the machine and the moldsets in position to be loaded into the machine.
[0031] FIG. 5 is a second rear perspective view of the machine with the moldsets in position to be loaded into the machine.
[0032] FIG. 6 is a rear side view of a three level stack mold injection-molding machine with the mold open.
[0033] FIG. 7 is a rear perspective view of a three level stack mold machine with the mold open.
[0034] FIG. 8 is a schematic side view of a linkage assembly for the front of a three level stack mold showing the assembly when the mold is open.
[0035] FIG. 9 is a schematic side view of the linkage assembly for the front of the machine showing the linkage when the mold is open and when the mold is closed.
[0036] FIG. 10 is a perspective view of the mold for a three level stack-molding machine in a partially assembled condition.
[0037] FIG. 11 is a perspective view of a portion of the guide assembly for the core plate.
[0038] FIG. 12 is a perspective view of the guide assembly with a core plate entering the guide assembly.
[0039] FIG. 13 is a bottom perspective view of the guide assembly and core plate.
[0040] FIG. 14 is a perspective view of the movable platen with core plate guides.
[0041] FIG. 15 is a partial perspective view of a movable platen with a core plate fully engaged with the platen.
[0042] FIG. 16 is a bottom perspective view of the molding machine.
[0043] FIG. 17 is a perspective view of a moldset partially loaded into a machine.
[0044] FIG. 18 is a perspective view of a core plate with guides and a core plate separation block.
[0045] FIG. 19 is an enlarged view of a part of the core plate and the core plate separation block.
[0046] FIG. 20 is side view of the core plate and core plate separation block.
[0047] FIG. 21 is a perspective view of the core plate and core plate separation block.
[0048] FIG. 22 is a perspective view of a dial indicator device for indicating proper positioning of the core plate.
[0049] FIG. 23 is a partially cut-away view of a guide with the dial indicator.
[0050] FIG. 24 is a perspective view of the water manifold mounted on a carrier.
[0051] FIG. 25 is a perspective view of the two carrier assemblies with manifolds and hot runners.
DETAILED DESCRIPTION
[0052] As shown in FIGS. 1 and 2 , the injection-molding machine 10 includes a machine frame 12 and a stationary platen 14 supporting a fixed hot runner 30 . Column housing 20 is connected to the molding machine 10 at clamp block 16 . Clamp column 22 clamps the moldsets 24 , 26 and 28 closed during an injection cycle of the molding machine 10 . Moldsets 26 and 28 with their associated hot runners 33 and 34 are mounted on carriers 70 . Movable platen 32 and carriers 70 have rollers 128 that travel on frame 12 . A stroke cylinder is fixed inside the column housing 20 and drives the clamp column 22 to stroke the movable platen 32 . Stroking of the platen 32 drives the linkage assembly 38 to open and close the moldsets 24 , 26 and 28 . The four tiebars 18 are tensioned by the operation of the clamp piston inside clamp block 16 .
[0053] Mold cavity plates 40 , 42 and 44 are mounted on fixed hot runner 30 and movable hot runners 33 and 34 , respectively. Mold core plate 52 is mounted on movable platen 32 and core plates 48 and 50 are mounted on movable hot runners 33 and 34 . With this configuration, all the mold cores face in the same direction. This enables any take out robots to be orientated in a single direction so the ejection and removal of molded parts is simplified. This also allows each of the two central moving sections of the three level stack mold machine to be identical to one another. This provides manufacturing benefits as only a single design is required. Furthermore, as each section is identical, a more balanced weight distribution is maintained within the machine.
[0054] Water service lines 62 to the machine 10 are arranged inside of the legs of the machine 10 . The electrical lines 54 and 56 are shown connected to movable hot runners 33 and 34 over flexible cables joined to brackets 58 and 60 . Flexible water lines 62 are similarly connected to the underside of water manifolds 120 . The service connections will be fully described hereinafter.
[0055] FIG. 3 shows the unassembled machine with the fixed hot runner 30 and the movable hot runners 33 and 34 poised above the machine ready to be loaded onto the machine. Of course, in actual operation, only one of the hot runners at a time would be in position to be loaded onto the machine.
[0056] Fixed hot runner 30 is lowered onto the machine and bolted by bolts 64 to stationary platen 14 . The fixed hot runner 30 is supplied with water connection hoses from the machine to cool hot runner 30 and also provide a water circuit to the cavity plate 40 . However, movable hot runners 33 and 34 need to be guided onto the machine frame. Key slots 65 and 66 engage keys 68 on carriers 70 . The water connections or nipples 118 protruding from the service manifolds 120 engage female fittings on the base of hot runners 33 and 34 to provide a secure water supply to the hot runners 33 and 34 .
[0057] FIGS. 4 and 5 show the machine 10 with the movable platen 32 , movable hot runners 33 and 34 and fixed hot runner 30 installed and the moldsets 24 , 26 and 28 positioned over the machine ready to be loaded into the machine 10 . Each core plate in each moldset 24 , 26 and 28 has a guide slot 74 . Each guide slot 74 engages a guide bar 75 on the movable platen 32 or one of the movable hot runners 33 or 34 .
[0058] In the embodiment shown in the Figures, a central sprue bar 76 extends through the moldset 24 . To enable the moldset 24 to be loaded into the machine 10 , slots 78 and 80 are provided in the core plate 48 and cavity plate 40 of moldset 24 .
[0059] The guide slots 74 on each side of the core plate include core plate separation blocks 140 and 142 . The operation of these separation blocks 140 and 142 will be more fully described hereinafter.
[0060] FIGS. 6 to 9 illustrate the construction and operation of the linkage assembly for moving the mold between the open and closed positions. There are two assemblies 38 on the machine. The first assembly 38 shown on the back of the machine 10 in FIGS. 6 and 7 has an anchor point 84 at the base of stationary platen 14 for the short pivoting arm 86 . A second short pivoting arm 88 is connected to anchor point 90 near the top of movable platen 32 . Extending arms 92 and 94 are pivotably connected to carriers 70 at the mid-point of the carriers 70 . The lower end of arm 92 is pivotably connected to arm 86 and the upper end of arm 94 is pivotably connected to arm 88 . Two curved or L-shaped arms 96 and 98 connect the arms 92 and 94 together.
[0061] The lengths of the linking arms 86 , 88 , 92 , 94 , 96 and 98 are adjusted so that the moldsets 24 , 26 and 28 open and close simultaneously and the linking arms 86 , 88 , 92 , 94 , 96 and 98 do not interfere with side access to the open mold. In the present embodiment, the lower portion 92 a of arm 92 is longer than the upper portion 92 b. For arm 94 , the upper portion 94 b is longer than the lower portion 94 a. The arms 96 and 98 are curved to ensure that they do not extend across the access to the cores and cavities when the mold is open.
[0062] The linkage assembly 38 at the front of the machine is the reverse of the assembly 38 on the back of the machine. To emphasize the similarities between the two assemblies, similar elements have been designated with a prime. As shown in FIGS. 8 and 9 , arm 86 ′ is connected to an upper anchor point 84 ′ on stationary platen 14 and arm 88 ′ is connected to a lower anchor point 92 ′ on movable platen 32 . Extending arms 92 ′ and 94 ′ are pivotably connected to carriers (not shown) on the machine in the same manner as arms 92 and 94 . However, the longer portion 92 a′ of arm 92 ′ is the upper portion of the arm and the longer portion 94 b′ is the lower portion of arm 94 ′. By reversing the two assemblies 38 , the forces driving the molds between the open and closed positions are balanced and the molds close uniformly.
[0063] The linking arms 86 ′, 88 ′, 92 ′, 94 ′, 96 ′ and 98 ′ are also dimensioned so that they do not interfere with access to the cores and cavities when the mold is open. Thus, the molding machine provides ready access to the open molds from above, below and both sides. As will become apparent hereinafter, this enables the rapid and simple ejection of molded parts and easy and rapid replacement of moldsets.
[0064] FIG. 10 shows the cavity plates 40 , 42 , and 44 , core plates 48 , 50 and 52 and the fixed hot runner 30 and movable hot runners 33 and 34 separate from the injection-molding machine. Cavity plate 40 is attached to core plate 48 by latches 100 (only one shown). Each hot runner includes four hot runner leader pins 102 to align the respective cavity plate with the hot runner. Hot runner nozzles 104 extend out of each hot runner and into the associated cavity plate. Four straight interlocks 101 at the midsection of each cavity plate 42 and 44 interface with matching slots 103 on the respective hot runners. Cavity plate 40 only has three interlocks 101 because a slot 80 is formed in the plate 40 to permit the plate 40 to slide over the sprue bar 76 . The leader pins 102 ensure reasonable alignment of the cavity plates with the associated hot runner and the precise shape of the interlocks 101 and slots 103 tightly align the nozzles 104 with the gates of the cavities in the cavity plates. The outermost ends of the interlocks 101 are slightly tapered to ensure that the interlocks 101 enter into the slots 103 and do not have sharp corners that can impact on one another and cause damage. This ensures that the moldsets can be changed often without the creation of alignment concerns over time.
[0065] One embodiment of the guide slots for guiding the core plates onto the hot runners 33 and 34 is shown schematically in FIG. 11 . At the top of each hot runner 33 and 34 and movable platen 32 is a guide plate 106 . The guide plate 106 has a tapered surface 108 for receiving and guiding the core plate into the receiving slot 110 . A slightly raised surface 112 on the outer surface of each guide plate 106 forces the core plate away from the hot runner or movable platen so that the core plate does not scuff against the hot runner plate or the movable platen as it is being guided and loaded onto the machine.
[0066] FIG. 12 shows a core plate 114 being guided into a slot 110 and being pushed slightly away from the surface of the movable platen 32 by the raised surface 112 . A cavity plate 116 is attached to the core plate 114 . Water connections or nipples 118 extend from the water manifold 120 and will engage in connectors on the base of the core plate 114 when the core plate is placed in molding position. Guide pin 119 guides the core plate 114 onto the water manifold 120 to ensure a secure connection of the connectors 118 to the female connectors on the core plate 114 .
[0067] FIG. 13 is a partial assembly showing the guide slot 74 on core plate 52 just entering the guide plate 106 . The tapered surface 115 at the front edge of slot 74 permits the core plate 52 to align with the guide plate 106 . The raised surface 112 on the guide plate 106 moves the core plate 52 away from the surface of the movable platen 32 SO the core plate 52 does not scuff against the surface of the platen 32 as it is being loaded into the machine. The female connectors 121 on the underside of core plate 52 engage connectors 118 when the core plate is fully loaded into the movable platen 32 .
[0068] FIG. 14 is a perspective view of the movable platen 32 with the guide plates 106 and 122 installed. The guide plates 106 are mounted on an upper portion of the platen 32 and lower guide plates 122 are mounted on a lower portion of the platen 32 . Wedge plates 124 are mounted on water manifold 120 . A wedging surface 126 is formed on the upper end of plates 124 and engage the front face of the core plate when it is nearing its fully mounted position. The wedging surfaces 126 force the core plate into firm contact with the platen 32 . It is noted that each core plate is loaded in this same manner so it is unnecessary to describe the loading operation for the other two core plates onto the movable hot runners 33 and 34 .
[0069] FIG. 15 shows the core plate 52 fully installed on platen 32 and wedged tightly against platen 32 by wedge surface 126 on wedge plate 124 and a wedging surface on the separation block 140 . The separation block 140 is more fully described hereinafter.
[0070] FIG. 16 shows the flexible water lines 62 extending to the manifolds 120 on each hot runner. One set of lines 62 extends under tiebars 18 on one side of the machine and the other set of lines 62 extends along the underside of the other lower tiebar 18 . Lines 62 are out of the way of the mold opening so parts can be dropped downwardly without encountering interference from any components of the machine.
[0071] FIG. 17 shows a core plate 50 secured to movable hot runner 33 . Cavity plate 42 is secured to core plate 50 by latches 100 (only one shown) and is ready to be secured to the hot runner plate.
[0072] With this new design, the replacement of molds and servicing of the machine are much simplified over earlier designs
[0073] First, the mold guides 106 and 122 are installed on the movable platen 32 and movable hot runners 33 and 34 . The water manifolds 120 and wedge plates 124 are also installed on the movable platen 32 and movable hot runners 33 and 34 . The water manifolds 120 are installed on carriers 70 and the flexible water lines 62 attached from below. As shown in FIG. 3 , the movable hot runners 33 and 34 are each installed on carriers 70 and the hot runner 30 is bolted to the fixed platen 14 . Next, as shown in FIG. 5 , the moldsets 24 , 26 and 28 are lowered onto the hot runners 33 and 34 and the movable platen 32 , one at a time. A dial indicator, to be described hereinafter, is provided to indicate when the moldset is properly seated and the air and water connections are secure. When the moldset is in place it is bolted to its associated platen or hot runner and the crane hook is removed. After all three moldsets have been bolted, the machine is slowly closed to permit the cavity plates 40 , 42 and 44 to engage hot runner leader pins 102 , straight interlocks 101 and hot runner nozzles 104 . Clamp tonnage is then applied and each cavity plate is partially bolted to the hot runner associated with it. The bolts are sufficient in number to ensure that the cavity plate is secure when separated from the core plate. The stack mold carrier to hot runner bolts are now tightened. At this point, the latches 100 and the moldset lift bars are removed. The molds can now be slowly opened with the core plates separating from the cavity plates. When the molds are open the remaining cavity plate bolts can be tightened and the electrical cables attached to the top of the hot runners. The machine is now ready to mold parts.
[0074] When replacement of the moldsets is required, the procedure is reversed. The mold is opened and latches 100 are slid onto the cavity plates. Most of the bolts securing the cavity plate to the hot runner are removed. The remaining bolts need only hold the cavity plate in position. The mold is closed and the latches 100 are attached to the core plate. The remaining bolts securing the cavity plate to the hot runner are removed and the mold is opened. Now the crane hook can be attached to the moldset and the moldset removed from the machine.
[0075] The injection molding machine provides pre-assembled moldsets for each family of parts to be molded so that the moldsets can be changed quickly and efficiently. The guided moldset loading ensures that the moldsets install with minimal operator intervention. The hose-less coupling of the services ensures quick, sure and easy coupling of services to the machine and moldsets. The open linkage assembly ensures that parts can be readily retrieved by a robot from either side of the machine or simply freely dropped through the bottom of the machine. The robot could even enter from atop the machine.
[0076] FIGS. 18 to 21 illustrate apparatus for automatically connecting air supplies to the core plate. The apparatus also provides guide surfaces to keep the core plate away from the hot runner or platen faces during loading of the core plate and positively moving the core plate toward the platen or hot runner face when the core plate is near the end of travel. During removal, the apparatus moves the core plate away from the platen or hot runner face at the start of travel. The apparatus also provides means for indicating the positive loading of the core plate. In this embodiment, the core plate 148 has guide slots 174 for guiding the core plate 148 onto guide plate 206 in the same manner as previously described with reference to core plate 48 . Core plate 148 includes core plate separation blocks 140 and 142 . Each separation block 140 and 142 includes an air channel or channels to provide air to the core plate to enable ejection of parts from the cores on the core plate. This creates a separation of the air supply from the water supply at the base of the core plate thus reducing the possibility of contamination of the air supply in the event that the water supply remains pressurized when a core plate is not in position on the mold. Each guide plate 206 includes an air channel with a discharge outlet 144 . As the core plate 148 slides into position, an air opening 138 in the undersurface of each core plate separation block 140 and 142 engages a discharge outlet 144 . To ensure that the opening 138 makes an airtight seal with the outlets 144 , each outlet 144 has a compressible and pliable exit surface. In some instances, it may be desirable to provide the openings 138 with a similar compressible and pliable surface. A preferred material for the discharge outlets 144 is Ultra High Molecular Weight Polyethylene (UHMWPE).
[0077] The angular surface 146 , shown in FIG. 20 , on the separation blocks 140 and 142 engages a camming surface (not shown) on the guide plate 206 . The camming surface forces the separation blocks 140 and 142 and joined core plate 148 towards the platen or hot runner when the core plate is nearing its end of travel. A distance of approximately 50 mm from the end of travel is considered a reasonable place for this camming action to start. At the same time as this camming action is initiated, the wedge surfaces 126 on the wedge plates 124 are forcing the lower portion of the core plate 148 toward the face of the hot runner or platen. Thus, the core plate is forced toward the platen or hot runner in an upright manner so that it engages the platen or hot runner face evenly. This camming action also causes the opening 138 to positively engage with the discharge outlet 144 .
[0078] The angular surface 150 , shown in FIG. 21 , on the core plate separation blocks 140 and 142 acts with corresponding sloped surfaces (not shown) on the guide plates 206 to cam the core plate away from the platen or hot runner face upon initial movement of the core plate during extraction of the core plate from the mold.
[0079] Another feature of the machine is the provision of a dial indicator 130 shown in FIGS. 22 and 23 . Compression of the extended rod 132 by the downward movement of the core plate separation blocks 140 and 142 indicate directly whether the blocks 140 and 142 and the core plate 148 to which they are attached have been properly secured in the machine. The dial indicators 130 are situated under an overhang of the guide plate 206 so that they are protected from incidental contact. The use of two indicators provides an operator with the choice of standing on either side of the machine while the core plates are being installed. In operation, the dial indicators would be set during the initial or first installation of a moldset in the machine. This setting would be used to measure the proper insertion of subsequent moldsets.
[0080] As shown in FIGS. 24 and 25 , the water manifolds 120 are bolted to the carriers 70 and provide nipple connections 118 to the hot runners 33 and 34 and the core plates (not shown). When the hot runners and core and cavity plates are guided onto the carriers 70 , the nipple connectors 18 automatically engage corresponding openings in the hot runners and core and cavity plates. The guide pins 152 on the top of the water manifold 120 serve to guide a core plate 48 or 148 onto the manifold 120 and ensure that the tapered female connectors 121 on a core plate 48 or 148 are aligned with the nipples 118 along the front edge of the manifold 120 .
[0081] It will, of course, be understood that the above description has been given by way of example only and that modifications in detail may be made within the scope of the present invention. | A linkage assembly for a multiple level stack mold molding machine having a fixed platen, a movable platen, a plurality of carriage assemblies. The linkage assembly includes an arm on each carriage assembly pivotally connected to a central pivot point on one of the carriage assemblies. An arm also extends between the fixed platen and an end of one of the arms on a carriage assembly. Another arm extends between the movable platen and an end of another of the arms on another of the carriage assemblies. A pair of arms extend between each adjacent carriage assembly, each one of the pair of arms extends from an end of an arm of one carriage assembly to a central pivot point on an adjacent carriage assembly. Each arm of the pair of arms is shaped to extend around a periphery portion of a mold opening to enable full access to the core and cavity plates | 1 |
BACKGROUND OF THE NEW VARIETY
The present invention relates to a new and distinct variety of grapevine, which will hereinafter be denominated varietally as "3-14-71", and more particularly to a grapevine of the vinifera species characterized by large seedless berries of dark red to black color; which is mature for commercial harvesting approximately September 28th in McFarland, Calif.; and which has an exceptional ability to retain its freshness and palatability long after harvest during shipping, handling and in cold storage.
The "Thompson Seedless" grapevine is a variety which has been one of the most commercially successful producing large, green seedless berries of good flavor, ripening for harvest beginning in August and extending to mid September in the San Joaquin Valley of central California. Because of these attributes and because of the exceptional shipping and handling characteristics of the fruit as well as other factors, the "Thompson Seedless" grapevine has been one of the most extensively planted grapevine varieties in the San Joaquin Valley over many decades to whose climate it is uniquely well suited. Furthermore, the fruit of the "Thompson Seedless" grapevine has been well received in the marketplace.
In the marketing of grapes, which may generally be classified as to coloration as being either "green" or "colored", it is known that for any given segment of the season it is desirable to have fruit of both color types available for sale. The green class of grape varieties may vary in color form yellow-white to relatively deep green. The colored class of grape varieties may vary in color from red to black. During some portions of the season for grapes, there are varieties of both general color types available which have more or less compatible characteristics, in that they are seedless, flavorful and durable through harvesting, shipping and in cold storage. It has been found that during any such segment of the season, purchasers may exhibit a predilection for either color or both color types.
During the segment of the season occupied by the "Thompson Seedless" grapevine, there has not heretofore been a colored grape variety available having truly comparable attributes to those of the grapes of the "Thompson Seedless" grapevine. As a consequence, the development of a new colored grape variety having characteristics much more closely approaching those of the "Thompson Seedless" grapevine has been an objective long sought, but not heretofore achieved.
the "3-14-71" grapevine of the present invention is the result of an extensive breeding project directed toward the development of just such a new grapevine variety and which has been found substantially to achieve the objectives of that project in providing a grapevine producing a colored seedless grape ripening for harvest substantially later than the fruit of the "Thompson Seedless" grapevine and otherwise having attributes compatible therewith. The new variety is distinctly different from the "Thompson Seedless" grapevine. It fills a niche in the marketing season by offering a large seedless berry that is colored, maturing after the main harvest of "Thompson Seedless" grapevine.
ORIGIN AND ASEXUAL REPRODUCTION OF THE NEW VARIETY
The present variety of grapevine hereof resulted from a breeding project in which the selections were of complicated parentage, involving a number of progenitors. The parentage of the new variety is Hunisa, O.P. by Q25-6. A large berried selection of Hunisa grown for open-pollinated (O.P.) seed was used as a female parent. The pollen parent, the seedless variety Q25-6, was developed after several generations of crossing "Emperor" grapevines with a series of unnamed seedless selections. The cross which produced the parent grapevine of the new variety was made by the inventor in 1982 at Davis, Calif. The seedling of the new variety was planted near Richgrove, Calif. and bore its first fruit in 1985. The new variety was selected for asexual reproduction for all of the attributes hereinafter set forth. Cuttings were taken from the parent grapevine of the new variety in January 1986 and used asexually to reproduce the new variety in a planting at McFarland, Calif. The clonal progeny of the new variety were observed through several growing seasons and bore their first fruit in 1988. The inventor has confirmed through such observation that the clonal progeny of the new variety precisely retained those distinctive attributes which caused the parent of the new variety to be selected for asexual reproduction as hereinafter set forth.
SUMMARY OF THE NEW VARIETY
The grapevine is characterized as to novelty by producing large seedless grapes of a dark red to black coloration, having excellent durability during harvesting, handling and while in cold storage retaining its original fresh and flavorable character long after harvest. The grapevine of the subject invention has a high and uniform fruitfulness of basal buds, permitting short pruning and more economic production. The fruit produced by the "3-14-71" grapevine is ripe for commercial harvesting and shipment about two weeks later than the "Thompson Seedless" grapevine.
BRIEF DESCRIPTION OF THE DRAWING
The accompanying drawing is a color photograph of representative portions of the new grapevine of the present invention including bunches of grapes and sectioned portions of individual berries thereof, those on the left of center being in their natural form as described herein and those on the right of center being in the form resulting from treatments with gibberellic acid; and typical foliage and canes of the new variety.
DETAILED DESCRIPTION
Referring more specifically to the viticultural details of this new and distinct variety of grapevine, the following has been observed under the ecological conditions prevailing at a vineyard located in McFarland, Calif. All major color code designations are by reference to the Nickerson Color Fan published by Munsell Color Co. Incorporated. Common color names are also occasionally employed.
VINE
Generally:
Size.--Large.
Form.--Upright in growth habit, shoots slender and straight with long internodes. Bud burst in mid season.
Vigor.--Vigorous.
Shoot tip.--Open vinifera type. Internodes striped red on dorsal side with very sparse hairiness. No or feeble hairiness on nodes. Shoot tip reddish overall. Tendrils -- thin, trifid and very long and coiling readily on support.
Productivity: This new variety is highly fruitful, even the basal buds produce fruit clusters of commercial value. Thus, short spur pruning can be utilized, providing a more economic system that the long canes necessary for most seedless varieties.
Canes: Erect, ellipsoidal in cross section.
Surface.--Very smooth and glabrous.
Color.--Dark orange yellow (10 Y 6/8).
Color -- nodes and faint striations.--Moderate yellowish-brown (10 YR 4/4).
Nodes.--Generally -- Not prominent.
Internode length.--Long straight.
Dormant buds.--Conical, pointed and well-sealed.
Flowers.--Generally -- Hermaphrodite, stamens with erect and long filaments. Uniform in opening and shedding of pollen and calyptra.
Date of Bloom.--In McFarland, Calif. -- May 5th. In Richgrove, Calif. -- May 6th.
Berries.--Seedless, although there are often two collapsed and soft rudiments 3 mm (0.118 inches) to 5 mm (0.196 inches) in length that do not become gritty.
LEAVES
Size:
Generally.--Large. Three lobed, central lobe of blade cupped inward, often resulting in the superior sinuses, which are narrow and deep, being closed by the overlapping lobes.
Average length.--22.8 cm (8.976 inches).
Average width.--21.8 cm (8.582 inches).
Form: Outline -- wedge-shaped.
Color -- leaf blade: Dark green, dull aspect when fully expanded, glabrous except for few sparse arachnoid tufts between larger lateral veins.
Teeth: Very large, acute, rectilinear. Apical teeth on lateral lobes are often more prominent than the terminal one of the central lobe. This is a good mark of identification.
Teeth -- Number: Few.
Color -- Leaf: Veins on underside whitish in contrast.
Petiolar sinus: Narrow, V-shaped to lyre, closed.
Petiole:
Length.--Equal to that of the midrib.
Thickness.--Medium.
Color.--Pink at juncture with leaf blade.
Stipules: Not distinctive.
FRUIT
Maturity when described: Ripe for commercial harvesting and shipment in McFarland in the San Joaquin Valley of central California, on September 28th and in Richgrove, Calif., on October 1st. The fruit description refers to natural clusters arising from the first basal buds of medium canes borne on mature vines trained as bilateral cordons. The very high fruitfulness of basal buds permits very short spur pruning in the dormant period and later regulation and selection of the best clusters by deshooting.
Cluster:
Generally.--Conical and borne on nodes two and three, well filled, with peduncle offset from the cane.
Measuring from point of attachment.--Approximately 2.1 cm (0.826 inches) to first tendril branch, thence 3.7 cm (1.456 inches) to first fruiting branch, plus 24.8 cm (9.763 inches) of fruiting area to tip of the cluster.
Width.--12.7 cm (5 inches). Overall weight of the cluster is 446 g, (15.928 ounces) of which the stem structure (rachis) accounts for about 1.8 percent of the fresh weight. The mean number of berries per cluster is about 175, with less than one percent small (shot) berries. If longer spurs or canes are left at pruning time, the clusters are much larger in size, in which case, a winged or double cluster can arise.
Peduncle.--Medium width, woody only at point of attachment, rachis retains a bright green color for a very long time post-harvest. The berries retain their freshness and flavor after long periods of cold storage.
Berry: Ellipsoidal, flattened at point of attachment, 19 mm (0.748 inches)×22 mm (0.866 inches); mean weight of 10 largest berries per cluster 35.5 g (1.267 ounces); berry size increased substantially by girdling.
Berry color.--Varies from dark red to black depending on relative maturity.
Flesh:
Generally.--Meaty and firm.
Texture.--Skin is thin.
Juice.--Uncolored.
Flavor.--Neutral.
Aroma.--Not distinctive.
Ripening.--Late September to mid October at McFarland, Calif.
Eating quality.--Very good.
Seeds: Seedless, occasionally small rudiments that remain soft and unobjectionable.
use: Table grapes.
Shipping, handling and storage qualities: Excellent.
Although the new variety of grapevine possesses the described characteristics noted above as a result of the growing conditions prevailing in McFarland in the San Joaquin Valley of central California, it is to be understood that variations of the usual magnitude and characteristics incident to changes in growing conditions, fertilization, pruning, chemical treatment, irrigation and pest control are to be expected. | A new and distinct variety of grapevine producing fruit of dark red to black coloration which is mature for harvesting and shipment approximately two weeks after the "Thompson Seedless" grapevine and is of large size and possessing an exceptional ability to retain its freshness and flavor long after harvest and in cold storage. | 0 |
CROSS REFERENCE
This application is a continuation-in-part of U.S. patent application Ser. No. 884,190, filed July 10, 1986 now, U.S. Pat. No. 4,725,266 which is a continuation-in-part of U.S. patent application Ser. No. 715,928, filed March 25, 1985 for "LEFT VENTRICLE VACUUM CONTROL AND PRESSURE RELIEF VALVE," now U.S. Pat. No. 4,642,097.
BACKGROUND OF THE INVENTION
This invention is directed to a valve which limits the vacuum applied to the left ventricle during open-heart operation, prevents reverse flow to the heart, and vents the downstream line of gas or blood should pressure rise above atmosphere.
During some open-heart procedures, even though the heart is bypassed with the open-heart tubing, some blood finds its way into the left ventricle of the heart. Unless the blood is drained from the left ventricle, the blood causes the heart to distend. Such distension makes it difficult or impossible to resuscitate the heart at the end of the procedure. For this reason, some surgeons attach a slender tubing to the left ventricle to drain the blood from it. A suction pump may be used to provide the vacuum to remove the blood. Several problems may be caused by such a method. One problem arises if the opening of the drain line tube attaches itself to the inside of the heart chamber. This causes suction to be stopped, and the tubing must be wrenched away from the tissue. This causes trauma to the chamber tissue. The present valve limits the suction intensity to a reasonable level so that it is easier to pull the tube away from tissue.
Another problem which may occur during left heart venting arises from the fact that the amount of suction through the left ventricle drain line to the heart is regulated by the speed of the vacuum pump. The vacuum pump is controlled by the heart-lung machine technician who is not close to the surgical field, so the amount of suction intensity must be limited to prevent collapse of the tubing or tissue trauma when the distal end of the line is occluded.
Another problem which may occur is the buildup of pressure in the left ventricle drain line. This would drive air into the heart and cause an air embolism and even possible death of the patient. Such inadvertent pressure in the left ventricle drain line could be caused by any one of several means. For example, the vacuum pump switch could accidentally be positioned to run the pump in reverse so that, instead of suction, pressure would be produced in the drain line. Another possible cause of such pressure would occur when the suction pump is connected to discharge into a closed reservoir in which the pump causes a pressure buildup. In such a case, there is a chance that when the pump is stopped, the pressure may leak back through the drain line into the heart. Another cause of pressure buildup in the drain line is in the structure of the roller pump. In a roller pump, the tubing may be accidentally inserted in a backward orientation into the pump housing so that, even if the pump switch is in the "Forward" position, the pump is working backward.
In order to prevent such problems from causing dangers to the patient, the present left ventricle vacuum control and pressure relief valve was created. This valve prevents flow toward the heart and allows flow only away from the heart, whether the flow be blood or air. A vacuum vent in the valve body is covered on the interior by a resilient umbrella so that the vacuum drawn downstream and upstream of the check valve is limited. Furthermore, the valve of this invention permits any above atmospheric pressure in the downstream line to be vented to the atmosphere instead of being transmitted to the heart. When the venting is accompanied by the escape of blood from the valve, the surgeon is immediately notified that something is wrong (for example, there is inadequate suction to remove the blood) and can take corrective measures.
SUMMARY OF THE INVENTION
In order to aid in the understanding of this invention, it can be stated in essentially summary form that it is directed to a suction control valve for left ventricle venting which includes a body having a passage therethrough and a check valve therein which permits flow only from the inlet toward the outlet. Downstream of the check valve is a pressure vent valve and an umbrella vacuum vent valve which allows air to bleed into the passage when vacuum is applied.
It is, thus, an object and advantage of this invention to provide a valve for the left ventricle drain line which permits flow only away from the heart.
It is another purpose and advantage of this invention to provide a valve for the left ventricle drain line which does not allow full vacuum to be applied to the heart.
It is a further object and advantage of this invention to provide a valve for the left ventricle drain line which automatically vents pressure in excess of atmospheric pressure to prevent pressure buildup toward the heart, and to vent air if pressure builds up in the outlet end of the drain line.
It is a further object and advantage of this invention to provide a valve for the left ventricle drain line which is simple, small, and can be accurately mass-produced and pre-sterilized so that it can be easily and safely inserted in the left ventricle drain.
Other objects and advantages of this invention will become apparent from a study of the following portion of this specification, the claims and the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side-elevational view of the valve in accordance with this invention.
FIG. 2 is an enlarged section taken generally along the line 2--2 of FIG. 1.
FIG. 3 is a further enlarged transverse section taken generally along the line 3--3 of FIG. 2.
FIG. 4 is an enlarged section taken generally along the line 4--4 of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The left ventricle vacuum limit and pressure relief valve of this invention is generally indicated at 10 in FIGS. 1, 2, 3 and 4. Valve 10 is shown in longitudinal section in FIG. 2 and is shown in transverse section in FIGS. 3 and 4. Valve 10 has a body 12 and an inlet fitting 14. Body 12 has an outlet barbed nipple 16 on its outlet end with the nipple sized to be received in the left ventricle drain line. Passage 18 in the body adjoins passage 20 in the nipple, with the passages extending end-to-end through the body, defining a central axis there through.
Body 12 has an external surface 22 which is cylindrical about the axis, except for nipples 24 and 26 respectively at the outlet ends of pressure relief passages 28 and 30. Shoulder 33 extends radially outward at the right end of the body. Relief passages 28 and 30 are radial passages of circular cross section which extend from the internal passage 18 to the external surface 22. Vacuum vent passage 32 also is a radially oriented passage of circular cross section extending from the internal passage 18 outward through the body.
Cap 14 has a barbed inlet nipple 34 thereon sized the same as nipple 16 so that the left ventricle drain line can be cut at an appropriate location and the valve 10 inserted therein, with the valve connected to both ends of the line. Body 12 has a circular flange 36 extending to the left therefrom, as seen in FIG. 2, which embraces around a rightward extending circular extension 38 of the cap 14. These interengaging portions provide alignment for the cap on the body and provide for securement of the cap on the body, as by adhesive means, heat sealing, or preferably by ultrasonic bonding.
Inlet nipple 34 and cap 14 also have passage 42 therein which is in alignment with passages 18 and 20. Duckbill valve 44 is structured so that it permits flow from left to right through valve 10, as seen in FIG. 2, in the inlet nipple 34 and out of outlet nipple 16. The valve 44 is an elastomeric molding of generally cylindrical configuration, but, as seen in FIG. 4, has a pair of flat lips 46 and 48 which lie together. These are conventionally molded in one piece and slit afterwards. The result is a valve which opens to flow in the left-to-right direction with very low differential pressure and lies closed essentially without a differential pressure. If the pressure is higher on the right side, as seen in FIG. 2, the valve lips are forced closed to inhibit flow. Such valves are often called "duckbill" valves from their physical resemblance. Thus, valve 44 is a check valve which permits flow only in the left-to-right direction through valve 10. Passage 42 aligns with the interior opening within valve 44, while passage 18 embraces the main body 50 of valve 44. An outwardly directed flange 52 is captured between the body 12 and extension 38 on cap 14.
The cylindrical body 50 of duckbill valve 44 preferably does not occlude vacuum passage 32, as seen in FIGS. 2 and 3. However, should it cover the inside of passage 32, the valve 44 pulls away from passage 32 when vacuum exists inside the valve. Tubular boss 54 is secured on the side of body 12 over the vacuum passage 32, as is seen in FIGS. 2 and 3. Flange 56 extends across the open interior of tubular boss 54. Flange 56 has vent openings 58 therethrough arranged in a circular pattern around central opening 60, see FIG. 1. Umbrella valve 62 has its umbrella positioned on the inside of flange 56 and covering the vent openings 58. The stem 64 of the umbrella valve is barbed and extends upward through the central opening 60 to retain the umbrella valve in place. The umbrella valve is made of synthetic elastomeric material and can be molded to be very precise in its opening characteristic. The stress in the umbrella when installed keeps the vent openings 58 closed until the vacuum in outlet passage 20 goes too far below atmospheric pressure (approximately 125 mm Hg). Thereupon, the atmospheric pressure overcomes the resilient stress of the umbrella and the atmospheric pressure causes the umbrella to bend downward to admit atmospheric air. In this way, the lower limit of pressure downstream of the check valve 44 is controlled. It is to be noted that the entry of air in through the umbrella valve is downstream of the check valve so that it is isolated from the left ventricle.
Elastic ring 66 is engaged around external surface 22 and lies against shoulder 33. Elastic ring 66 is a cylindrical tube which gently engages upon surface 22 and on nipples 24 and 26. When the pressure rises in the central chamber of valve 10, in passage 18, the pressure in relief passages 28 and 30 lifts elastic ring 66 to permit venting of the pressure. However, when there is vacuum in passage 18, elastic ring 66 overlies the openings of relief passages 28 and 30 to prevent inflow from atmosphere. Thus, elastic ring 66 serves as a one-way valve and as the active member in the pressure relief function of valve 10.
As an economic and satisfactory method of manufacture, the body 12, cap 14 and sleeve 54 can be injection-molded of fairly rigid thermoplastic synthetic polymer composition bicompatible material such as polycarbonate or ABS. Almost all surfaces of the valve are surfaces of revolution about the axial centerline through the valve. This design reduces molding costs so as to provide an economic valve. Valve 48 is injection-molded of an elastomer, and after the molding, the valve opening is cut with a razor or the like. Elastic ring 66 can be sliced from an extruded tube or can be molded from thermoplastic elastomer. (As illustrated, the elastic ring 66 is of two external diameters and thus must be molded.) The larger diameter over the nipples 24 and 26 is to permit a heavier elastic force of the ring onto the closure of the pressure relief passages. The level of pressure relief can be controlled by the diameter, hardness, and thickness of the ring. After the assembly of the parts into the organization shown in FIG. 2, the structure is permanently assembled by attachment between flange 36 and extension 38. All of the parts must be of suitable characteristics for sterilization.
In the preferred utilization, the valve 10 is placed in the left ventricle vent line about 2 feet from and level with the heart so that the valve is positioned near the patient's groin on the sterile drape so that it may be observed by the surgeon. Alternatively, the valve can be placed in the line closer to the perfusionist's pump. The amount of suction desired in most cases is about 100-125 mm Hg. The pump speed is adjusted so that this level of vacuum is reached. Should the suction pump not be operating or should the suction pump be operating too slowly and the heart is putting blood into the left ventricle drain line, blood in the valve will leak out of the valve through relief passages 28 and 30. This presence of blood will immediately warn the surgical team of an undesirable condition. Efforts can be made to increase suction to withdraw the blood from the left ventricle drain line. In this manner, the blood is safely drained from the left ventricle, with the level of vacuum being limited by umbrella valve 62 to a proper level. The valve 10 incorporates structure which permits the relief of pressure and incorporates structure which prevents the reverse flow of fluid through the left ventricle drain line and, accordingly, the requirements of the application are satisfied.
This invention has been described in its presently contemplated best mode, and it is clear that it is susceptible to numerous modifications, modes and embodiments within the ability of those skilled in the art and without the exercise of the inventive faculty. Accordingly, the scope of this invention is defined by the scope of the following claims. | The valve is positioned in the left ventricle drain line and includes a check valve which permits flow only away from the heart. A vent valve is located downstream of the check valve to prevent buildup of pressure. In addition, the valve includes an inwardly directed umbrella valve to limit left ventricle drain line vacuum intensity applied to the heart. | 0 |
RELATED U.S. APPLICATION DATA
[0001] Not applicable.
SUMMARY
[0002] The embodiments of the device and method relate to the physical separation of solids of substantially different densities by introducing the solids into a rotating barrel through which a stream of forced air is introduced. For purposes of explanation, and not meant to be limiting, the various embodiments are described as facilitating the separation of coal from rock by forced air. Additional embodiments of the device and method also permit the recovered solids to be separated into size based lots.
[0003] A first embodiment of the device consists generally of at least one barrel, at least one helical blade on the interior surface of the barrel, and at least one blower.
[0004] A further embodiment utilizes at least one barrel, at least one helical blade on the interior surface of a barrel, at least one blower, a hopper, a conveyer system, pop-ups (i.e. barriers) placed between the gaps in the helical barrel blade that runs along the interior of the barrel, a blower placed at one end of the barrel, and a collection area at the end of the barrel opposite the blower.
[0005] A mixture of solids, e.g. coal and rock, also known as “run-of-mine coal”, is fed into various embodiments of the device from a hopper. The hopper is integrated into the device or it is a separate device apart from the separator itself. In an additional embodiment the hopper is affixed with a flow regulator to control the amount of coal exiting the hopper and entering the separator. An additional embodiment allows the hopper and/or the hopper contents to be mechanically agitated to facilitate the emptying of the hopper, e.g. mixing the ore or inducing a vibration in the hopper.
[0006] The contents of the hopper are dispensed onto a conveyer belt as part of a conveyor system. In an embodiment, the conveyer is configured so that the edges rise higher than the center, so as to act as a trough and prevent spillage over the sides as the mixture is being conveyed away from the hopper. In yet another embodiment, a traditional flat conveyor system may also be utilized. The conveyer carries the coal and rock into the separation barrel. At the end of the conveyer the coal and rock fall into the barrel of the device. In an additional embodiment, a wind barrier or shield is incorporated into the conveyor system and around the conveyer belt to prevent the coal and rock from being blown off the conveyer belt.
[0007] As the run-of-mine coal, or other mixture of solids of substantially differing densities empties into the barrel, the barrel turns in a manner so as to allow rock to be directed out of the rotating barrel by the helical blade to an exit point below the blower. In an embodiment of the device, the interior surface of the barrel also possesses barriers or ramps that run along the width of the barrel, in between turns of the spiral blade and roughly perpendicular to the blade. This forces the barrel contents up and over the barrier as the barrel rotates and makes them susceptible to the flow of high velocity air from the blower. The velocity of the air is regulated so as to be of insufficient force to blow rock out of the end of the barrel opposite the blower, thus allowing the rock to fall to the floor of the barrel to be removed by the turning helical blade and emptied out beneath the blower on the high density solids exit end of the barrel, but of sufficient force to blow coal out the low density solids exit end, i.e. opposite the blower. The blower size is proportional to the size of the barrel and the severity of the treatment is further refined based upon the density and size of the rock accompanying the coal.
[0008] In an embodiment, as coal is blown out of the rear of the barrel it is directed to collection bins which may or may not possess screens for further filtering. In another embodiment, the bins are collection hoppers. In a still further embodiment, the collection hoppers may empty onto conveyor systems to remove the segregated coal for remote storage or further separation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a perspective view of the separation system.
[0010] FIG. 2 is a cross-sectional view of the conveyor belt.
[0011] FIG. 3 is a cutaway view of the barrel exposing the helical blade and barriers.
[0012] FIG. 4 is an illustration of the movement of coal and rock across the blade and barrier system at the base of the interior barrel surface.
[0013] FIG. 5 is a perspective view of the collection bins relative to the separation system.
DETAILED DESCRIPTION
[0014] The following are non-exclusive descriptions of multiple embodiments of the solids separation system. In one embodiment of the device, as depicted in FIG. 1 , a mixture receptacle 21 (e.g. a hopper), is positioned above a conveyor belt system 23 outside of a long barrel 10 acting as the separator barrel 10 . In one embodiment, a separator 100 is equipped with a flow regulator to control the rate at which a mixture enters the barrel 10 . In yet another embodiment, a flow regulator is integrated into the mixture receptacle 21 . A non-limiting example of one type of flow regulator is a sliding plate that is used to increase or decrease the size of the exit of the mixture receptacle 21 . In an additional embodiment, the mixture receptacle 21 contents are affected by an agitator 25 to facilitate the flow or movement of the mixture out of the mixture receptacle 21 . The agitator 25 may operate within the hopper 21 to mechanically agitate the contents, e.g. mixing or stirring. Alternatively, an agitator induces a vibration in the walls of the mixture receptacle 21 . In yet another embodiment, the mixture receptacle 21 is shaken by way of a percussion type agitator 25 .
[0015] In one embodiment, the mixture receptacle 21 sides are sloped inward from top to bottom so as to utilize gravity to facilitate the movement of the mixture toward the mixture receptacle exit, the hopper exit port, situated above the conveyor belt system 23 . The mixture, e.g. run-of-mine coal, is transported into the barrel 10 by the conveyor belt system 23 . In yet another embodiment, the mixture receptacle 21 sides are vertically configured. In yet another embodiment, no hopper is positioned above the conveyor belt system 23 and coal is fed directly onto the conveyor belt 27 . In a further embodiment, a chute or slide delivers the run-of-mine coal to the conveyor belt system 23 . Alternatively, a chute or slide may deliver coal directly into the barrel 10 .
[0016] In embodiments utilizing a conveyor belt system 23 , the conveyor belt system 23 possesses a conveyor belt 27 driven by a conveyor belt motor 29 . The conveyor belt 27 is preferably wrapped around two conveyor belt end rollers 24 . One or both of the conveyor belt end rollers 24 is a powered roller and is driven by the conveyor belt motor 29 . Conveyor belt support rollers 26 are arranged within the circumference of the conveyor belt 27 and between the two conveyor belt end rollers 24 . Both the conveyor belt end rollers 24 and the conveyor belt support rollers 26 are preferably affixed to the conveyor belt frame 22 .
[0017] The profile of the conveyor belt 27 in previously described embodiments is concave across the conveyor belt 27 or alternatively is substantially flat in a further conveyor system embodiment. Conveyor guides 28 are affixed laterally to the conveyor belt 27 along the conveyor belt frame 22 . The conveyor belt 27 inverts around a conveyor belt end roller 24 , at which point the mixture, e.g. run-of-mine coal, is dumped into the barrel 10 .
[0018] A conveyor system frame 29 supports the conveyor belt frame 22 and consists primarily of a plate extending lengthwise into the barrel 10 from the hopper 21 at the rock exit end 12 of the barrel 10 and substantially across the width of the barrel 10 . A substantially vertical shield 18 is affixed on the conveyor system frame 30 past the conveyor belt end roller 24 at a sufficient distance to permit the run-of-mine coal to drop through the gap created between the conveyor belt end roller 24 and the shield 13 . In one embodiment, the shield 13 is positionable and is adjusted to accommodate the size of the available mixture, e.g. run-of-mine coal. The conveyor system frame 30 may extend from the shield 18 to the low density solids, e.g. coal, exit end 14 of the barrel 10 . This inhibits the flow of air across the mixture, e.g. run-of-mine coal, on the conveyor belt 27 and minimizes the opportunity for forced air from the blower 41 to dislodge the low density solids, e.g. coal, on the conveyor belt 27 thereby causing it to prematurely spill over the sides of the conveyor belt 27 into the barrel 10 of the separator 100 .
[0019] A blower 41 is stationed at the high density solids, e.g. rock from run-of-mine coal, exit end 12 of the barrel 10 . Air is used as a fluid media and forced through the barrel 10 at a volumetric rate sufficient to drive low density solids, e.g. coal out of the low density solids exit end 14 of the barrel 10 , but small enough to have a minimal effect on high density solids, e.g. rock from run-of-mine coal, which tends to fall to the floor of the barrel 10 because of its significantly greater density than coal. The barrel 10 is lined with at least one helical blade 15 which turns either clockwise or counter-clockwise through the barrel 10 along the interior barrel surface 17 from the high density exit end 12 of the barrel 10 to the low density solids exit end 14 of the barrel 10 . The helical blade 15 is preferably continuous and is a single unit one helical blade embodiment and comprised of multiple units connected together to functionally form a single blade in yet another helical blade embodiment. In an embodiment, gaps exist at various positions along the helical blade 15 so as to permit heavier pieces of the low density solids, e.g. coal, to be blown back across the barrel 10 from the high density solids exit end 12 of the barrel 10 to the low density solids exit end 14 of the barrel 10 . The barrel 10 rotates on barrel rollers 53 mounted on the carriage frame 51 . The direction of the rotation of the barrel 10 is matched to the turns of the helical blade 15 through the barrel 10 so that solids are guided by the turning helical blade 15 toward the high density solids exit end 12 of the barrel 10 . In an embodiment, the barrel 10 is rotated by a barrel belt 33 that is configured to engage the teeth a gear ring 35 around the circumference of the barrel 10 along the exterior barrel surface 16 . A barrel drive motor 31 engages the barrel belt 33 and drives the rotation of the barrel 10 .
[0020] Low density solids, e.g. coal, will sometimes fall between the blades of the barrel 10 and will need to be placed back in the stream of forced air to ensure its collection at the rock exit end 12 of the barrel 10 . Barriers 19 that run somewhat perpendicular to the run of the helical blade 15 on the interior barrel surface 17 will catch material resting between the turns of the helical blade 15 and force it back into the stream of forced air. The high density solids, e.g. rock from run-of-mine coal, mostly resist the flow of air and continue to move toward the high density solids exit end 12 of the barrel 10 by following the turns of the helical blade 15 . The barrel 10 is elevated at the low density solids exit end 14 of the barrel 10 relative to the high density solids exit end 12 of the barrel 10 which provides a gravity assist to the movement of high density solids, e.g. rock from run-of-mine coal, along the turns of the helical blade 15 , toward the blower and out the high density solids exit end 12 of the barrel 10 .
[0021] The low density solids, e.g. coal, exit the low density solids exit end 14 of the barrel 10 as it is susceptible to the fluid stream of air. The greater the mass of an individual piece of low density solid, the shorter the distance it travels after exiting the barrel 10 . The barrel 10 is cylindrical and formed as the hollow frustum of a cylinder, and acts as a wind tunnel within the confines of the barrel interior surface 17 . As the forced air exits the low density solids exit end 14 of the barrel 10 , it is no longer confined and the velocity decreases as the distance it travels from the low density solids exit end 14 of the barrel 10 increases and the high velocity air expands into the environment and loses velocity. As the air velocity decreases it increasingly loses the ability to fluidize the low density solids, e.g. coal, being ejected from the low density solids exit end 14 of the barrel 10 . The loss of air velocity over distance from the low density solids exit end 14 of the barrel 10 results in the heavier pieces of low density solids dropping out of the air stream first and the dust and fines traveling the farthest from the low density solids exit end 14 of the barrel 10 . The physical segregation of low density solids, e.g. coal, pieces by mass, and thus size, allows the low density solids, e.g. coal, to be recovered according to size.
[0022] In some embodiments, a single low density solids receptacle 80 is utilized at the low density solids exit end 14 . In additional embodiments, a compartmentalized low density solids receptacle 80 or a plurality of low density solids receptacles 80 are arranged at the low density solids exit end 14 of the barrel 10 . In yet other embodiments, the compartments of a receptacle 80 or the plurality of low density solids receptacles 80 are arranged linearly at increasingly further distances from the low density solids exit end 14 of the barrel 10 allows to allow low density solids, e.g. coal, of different sizes to be captured in a segregated manner as shown in FIG. 5 .
[0023] In an embodiment, screens are used as a filter atop a low density solids receptacle 80 . In a further embodiment, the separated low density solids, e.g. coal, captured in each low density solids receptacle 80 could under go further processing as the low density solids, e.g. coal, could be removed from the low density solids receptacle 80 and introduced into another separator 100 . Subsequent treatment of separated low density solids, e.g. coal, could utilize separation systems 100 which are optimized for the size of low density solids being introduced into that particular system 100 . | A solids separation system and methods for use; the system having a barrel rotatably mounted in a substantially horizontal arrangement, a carriage on which the barrel is mounted and inclined so as to elevate the coal exit end of the barrel in relation to the rock exit end, a motor to rotate the barrel, a blower, a blower motor, a blade affixed to and helically wound along the interior surface of said barrel, and barriers between the turns of the blades to force the contents up into a stream of air supplied by a blower. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to nozzles for use with vacuum cleaners and, more specifically, to a powered nozzle advantageously applied to bare floors, carpets and the like by the use of a wand like handle normally present on the hose end of a canister cleaner.
2. Description of the Prior Art
Although counter-balance springs are broadly old in the cleaner art, the showings of such consisting of tension, compression and torsion springs arranged in a variety of ways, it appears that the use of a torsion spring disposed so that its actual reaction points are against the bottom of a cleaner handle or member serving this purpose and the bottom side of a nozzle to thereby prevent lifting of the rear of the nozzle during cleaning has not heretofore been contemplated. More specifically, the use of such a spring arrangement in an independent, remote, free standing nozzle appears to be devoid in the prior art. At the same time, the use of a torsion spring so arranged provides very effective control of nozzle lift during rearward movement of the nozzle during cleaning and also permits ease in manufacturing because of the simplified mounting necessary.
The use of a resiliently mounted and height adjustable brush in such a nozzle is also old in the prior art and does advantageously permit flexibility in the cleaning surfaces for which the nozzle is effective. However, previous mounting arrangements for brushes of this sort are generally fairly costly in that they use specially shaped parts requiring special molds, complex stampings or the like or are not as direct acting or as flexible in positioning or as readily accessible to the user as the instant height adjustable brush arragement. Further, ease in coupling of the adjustable brush arrangement to an indicator means easily seen by the user is desirable.
Accordingly, it is an object of this invention to provide a torsion spring counterbalance arrangement for a nozzle in which the reaction points of the torsion spring are between the bottom of the handle and the bottom of the nozzle so as to counterbalance the nozzle and prevent lifting of the same during backstroke movement of the nozzle as cleaning occurs.
It is a further object of the invention to provide a simplified resilient, height adjustable brush for a nozzle in which the mounting and adjusting structure lends itself easily to accessibility for operator manipulation and permits easy attachment to a view-accessible indicator arrangement.
It is a still further object of the invention to combine the anti-lift feature provided by the described torsion spring and the resiliently mounted height adjustable brush in a single nozzle so as to obtain an improved easily operated nozzle readily adaptable to perform the remote cleaning function so common in today's canister cleaners.
SUMMARY OF THE INVENTION
In a preferred embodiment of the invention a nozzle for use with a wand or like member includes a torsion spring disposed about an axle for a pair of rear wheels providing transport for the nozzle. This spring has its reaction points at the bottom side of the wand and the bottom side of the nozzle forward of the wheel axle. It thereby provides a counterbalance force tending to maintain rearward portions of the nozzle in contact with a floor or rug being cleaned during rearward movement of the nozzle towards the user.
Additionally, in order to provide for flexibility of use, the nozzle also includes a brush member that is resiliently biased downwardly by a pair of leaf springs attached to the top side of a bottom plate for the nozzle. Between the top of the bottom plate and a bottom side of the leaf spring a camming bar is disposed. This bar includes a pair of spaced, tear shaped upwardly extending, projections formed therein by a conventional stamping operation. The tear shaped projections are the actual camming means for the brush and are arranged, as the camming bar reciprocates from side to side, to, in effect, engage against the leaf springs and cam the same upwardly. Because of these height adjustment cams, different brush settings are available for nozzle use. Thus, bare floors, short shags, regular pile and heavy shags, for example, are accommodated by the instant nozzle.
This bar is guided in its reciprocating movements by a pair of slots contained therein which carry tabs struck from the bottom plate. A lever, pivoted to the bottom plate and extending rearwardly therefrom, is provided to manually actuate the camming bar, the lever being attached to this bar by a tab and slot connection to accommodate the swinging motion of the lever. An indicator projects upwardly from the lever so as to extend through an aperture in an upper shell of the nozzle to be easily viewed by the user.
The upper shell of the nozzle also includes a series of compartments for housing the agitator motor, belt drive and rotating agitator. The compartment within which the rotating agitator is disposed connects with suction (through the wand) by means of a flexible conduit extending, in effect, through the rearward wall of the agitator compartment and attached, at its other end, to a wand coupling member that include bosses utilized for mounting it to a rear axle of the nozzle.
The bottom plate has an elongated opening in its forward portion through which the rotating agitator extends and through which suction is applied to the rug or floor being cleaned. A narrower elongated opening behind the rotating agitator opening permits resilient extension of the leaf spring mounted fixed brush. Outwardly (sidewardly) of the fixed brush aperture are a pair of wheel openings that permit small forward wheels mounted on the upper shell to extend downwardly into contact with the floor or rug.
The nozzle is completed, generally, by the addition of a wand lock arrangement including a locking pawl mounted with the wand connecting piece. This locking pawl engages a spring biased latch on the upper shell to provide a locked storage position for the wand connector.
DESCRIPTION OF THE DRAWINGS
Reference may now be had to the accompanying drawings for a better understanding of the invention, both as to its organization and function, with the illustration being only exemplary, and in which:
FIG. 1 is a perspective view of a nozzle incorporating the invention;
FIG. 2 is a top plan view of the same nozzle;
FIG. 3 is a bottom plan view, partly broken away to better illustrate the invention;
FIG. 4 is a cross sectional elevational view of the invention taken looking from the right half side of FIG. 3;
FIG. 5 is a top plan view of the bottom plate and attached structure;
FIG. 6 is a partial, sectional elevational view taken on line 6--6 of FIG. 5 with the adjustable brush fully extended; and
FIG. 7 is a view similar to that of FIG. 6 but showing the adjustable brush fully retracted.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As is shown most clearly in FIGS. 1 - 2, a powered nozzle 10 includes a downwardly opening upper shell 12 having rearward bosses 14, 14 that support a pair of large rear wheels 16, 16. Attached to the powered nozzle 10 is a hose coupling or wand member 18 that may confluently communicate with a wand 20 (only partially shown) or the like, the same to be utilizable as a propelling handle for the nozzle 10. An electric cord 19 provides power to the nozzle 10.
The upper shell 12 includes a series of vents 22, 22 disposed on opposite sides of the hose coupling member 18 for ventilation of the motor contained therein. A furniture guard 24 extends around nearly the whole periphery of a lower portion of the upper shell 12 so as to provide protection for both the nozzle 10 and furniture in the area where cleaning occurs. Also found in FIGS. 1 and 2 are a foot actuated pedal 26 for locking adjustment of the wand and a foot or hand actuated pedal 28 for brush height adjustment. The mechanism connected with foot actuated pedal 28 for brush height adjustment also includes an indicating means 30.
Turning now to the remaining Figures of the Drawings, the upper shell 12 is seen as including a wall 32 (FIG. 3) extending outwardly from its underside and from side to side relative to the width of the nozzle 10. This wall provides a compartment 34 within the upper shell 12 bounded by it, the outer walls of the upper shell 12 and another wall 33 extending rearwardly from the wall 32 and in which a motor 36 and suction conduit means 38 are mounted.
Motor 36 drives a belt 40 which extends around and is in driving contact with a rotating agitator 42 journalled in the upper shell 12 and extending through a pair of elongated apertures 44, 44 in a bottom pan or plate 46 (FIG. 5) that completes the peripheral outline of the powered nozzle 10. Suction conduit means 38 includes at its front a mounting flange 48 that is captured by a pair of flanges 50, 52 formed as integral extensions of the walls 32 and 33, respectively, so that the suction conduit means 38, at its front end, confluently communicates with another chamber 54 formed forwardly of the wall 32 in power nozzle 10. The rotating agitator 42 is also disposed within this chamber so that it is housed in the suction area of the power nozzle 10, with the elongated apertures 44, 44 in bottom plate 46 thereby providing a means to impose a vacuum on the surface being cleaned to pick up dirt and dust from this surface.
The upper shell 12 also journably mounts a pair of small forward rollers 56, 56 on formed ribs or the like (not shown) with the same extending through apertures 58, 58 in bottom pan 46, outwardly of the apertures 44, 44 so that these rollers provide stability in their floor contacting position. An elongated single aperture 60, substantially coextensive in length to the combined lengths of apertures 44, 44, is also disposed rearwardly of apertures 44, 44 for the rotating agitator 42. The aperture 60 has disposed in extending fashion within it, an elongated resiliently mounted brush means 62 utilized to provide an anti-kickback function to the power nozzle 10.
Insofar as related the power nozzle 10 is substantially conventional, the novelty residing therein relating to the manner of adjusting resiliently mounted brush means 62 and the manner of counterbalancing the powered nozzle 10.
Resiliently mounted brush means 62 includes a pair of plastic holders 64, 64 each having an elongated finger 66 and a brush holding extension 68. The brush holding extension 68 includes integrally laterally extending and depending hook portions 70, 70 that latchingly and clampingly hold a brush 72 therebetween to fixedly mount the brush into each of the plastic holders 64. The plastic holders 64, 64 are each attached to bottom pan 46 by a rivet 74 that mounts the same to a raised boss 76, formed in the bottom pan and, because of the depth of the bosses and the relative depth of brush 72, the plastic holders 64, 64 tend to extend the brush 72 almost completely through aperture 60 of bottom pan.
Although the plastic holders 64, 64 are somewhat resilient, in order to insure that sufficient resilient bias is imposed on the brush 72, a separate leaf spring 78 is provided for each of the plastic brush holders 64. Each of these springs overlies the major portion of one of the brush holder extensions 68 to urge the same downwardly to insure proper brush contact with the floor or rug. Leaf spring 78, in turn, is also connected to bottom pan 46 by rivet 74 and held by it tightly against brush holder extension 68. The brush 72 is thereby, positively resiliently urged downwardly.
In order to adjust resiliently mounted brush means 62 in or out a height adjustment means 80 is provided. This means includes a reciprocating bar 82 mounted for guidance on bottom pan 46 and being made of flat steel stock and disposed flat against the top side of the bottom plate. A pair of bent tabs, 84, 84 are struck from the bottom pan, so as to extend perpendicular from it so that these tabs are received in a pair of longitudinally extending grooves 86, 86 formed in reciprocating bar 82, to thus form the guidance arrangement for it. The reciprocating bar 82 also includes cam means 88 formed by two tear shaped cams 90, 90 spaced outwardly of the grooves 86, 86. These tear shaped cams are embossed in the reciprocating bar 82 by a conventional pressing operation and provide a pair of elongated bumps which gradually increase in height from a minimum 92 to a maximum 94 at substantially this widest point (i.e., laterally of the nozzle 10) so as to provide an incremental plurality of series of adjustments (if desired) when interposed between the bottom pan 46 and plastic brush holder means 64. The brush 72 can be seen in its maximum extension in FIGS. 5 and 6 when the cams are disengaged, while FIG. 7 illustrates the brush at its minimum extension. These are normally the two positions at which the powered nozzle 10 is operated.
As can be seen, then, height adjustment for the brush 72 is obtained by selective inter position of the tear shaped cams 90, 92 between the bottom surface of plastic brush holders 64, 64 and the top surface of the bottom pan. This provides a positive, direct height adjustment action and, at the same time, provides a structure in which the reciprocating bar 82 is automatically captured against the bottom plate by the resilient and resiliently biased plastic brush holding extensions 68, 68 and leaf springs 78, 78 without the use of additional structural elements. The elongated fingers 66, 66 may also be utilized to perform a portion of this "capture" function but they may also be dispensed with entirely.
A pair of downwardly formed bosslike tabs 85, 85 (only one shown) may also be desirably formed on the bottom surface of flat, reciprocating bar 82 to limit its sliding area engagement with the top surface of bottom pan 46 and to provide for proper spacing of the plastic brush holders 64, 64 away from the top surface of bottom pan 46 at their forward portions in much the manner that the bosses 76, 76 accomplish this function at their rearward portions.
Rectilinear motion is imparted to reciprocating bar 82 by a crank lever 96 that is pivoted to bottom plate 46 on a boss 98 by a rivet 100. A washer 102 may be interposed between the head of the rivet 100 and the lever 96 to insure proper nonbinding action for the lever 96. At its inner end, crank lever 96 includes a rectangular groove 104 within which is nested a bent up, integral tab 106 on reciprocating bar 82, the groove 104 and tab 102 accommodating the pivoting action of lever 82 as it imposes rectilinear, reciprocating action to bar 82. Crank lever 96 is, of course, limited in its pivoting action by engagement of the integral tabs 84, 84 in opposite ends of the grooves 86, 86, with these portions shown in FIGS. 6 and 7, respectively.
Crank lever 96 also includes a foot or a hand extension portion 108, on which is mounted the outwardly disposed pedal 28, for ease in manipulation of reciprocating bar 82 by the user of powered nozzle 10. A slot 110 in upper shell 12 accommodates the extension portion 108 of crank lever 96 as it passes therethrough. Also mounted with crank lever 96 is an upwardly projecting indicator 112 of brush height adjusting means 30. The indicator may be attached by any conventional means to crank lever 96 such as by hook means (not shown) like the hook portions 70 and is desirably colored so that it is easily discernable as it extends through a viewing aperture 114 formed in upper shell 12 and comprising a part of brush height indicating means 28. By this structure, then, there has ben provided a dual-position resiliently mounted brush height adjustment means and connected indicating means both direct acting and direct reading and thereby thoroughly satisfactory to the user of the powered nozzle 10.
Powered nozzle 10 also includes a counterbalance spring means 116 tending to urge the rearward end of powered nozzle against the surface being cleaned during the backstroke of the nozzle (towards the user). Counterbalance spring means 116 takes the form of a torsion spring wound on an axle 118 for rear wheels 16, 16. This axle, in turn, is fixedly mounted to a pair of rearwardly extending portions 120, 120 of upper shell 12. The reaction points for the torsion spring are formed by an end 122 thereof engaging against a portion 124 of the hose coupling member 18 and an end 126 engaging against the bottom of powered nozzle 10 in the upper termination of a formed receiving groove 128. Thus, movement of the wand 20 during cleaning tends to increase or decrease spring pressure on the nozzle body so that, as the wand 20 is swingably lowered during the forward stroke (FIG. 3), greater spring pressure is imposed on the nozzle rearward end shifting some of its weight forwardly on the agitator. Moving the nozzle rearwardly raising the wand 20 decreases the spring force on the nozzle body but sufficient spring force (approximately 6 pounds) remains to overcome the natural inclinaton of lifting of the rearward portions of the nozzle from the surface being cleaned.
A nozzle lock means 130 is also provided, as is conventional to lock the wand 20 in upper storage position. This locking means includes a resilient spring steel finger 132 that abuts against a latch member 134 to urge the same generally vertically, the latch member being vertically slot mounted on rear wheel axle 118. A locking pawl 136 fixed with and carried by the hose coupling member 18, also pivoted on axle 118, upon pivoting thereof, engages against a latch portion 138 of latch member 134 when the same is urged upwardly under the control of resilient steel spring finger 132. To disable the latch member 134, foot actuated pedal 26 is moved downwardly carrying latch member 134 to which it is rigidly attached downwardly thus providing clearance between the latch member 134 and locking pawl 136 so that wand 20 may be placed in the non storage, cleaning mode position.
It should be clear from the foregoing description that a nozzle has been provided having all the desirable characteristics set out for it and, further, that the preferred embodiment is exemplary only, many modifications occurring to one skilled in the art still falling within its spirit and purview. | A vacuum cleaner nozzle is provided having resilient means, disposed between it and its handle, to prevent displacement of the nozzle from the floor during cleaning and also having a litter collecting brush that is spring biased into floor engaging position and height adjustable so that the nozzle is usable on bare floor and carpeted surfaces. Height adjustment is occasioned by a reciprocal bar having dimpled camming surfaces formed integrally in its top surface, with this bar being lever actuated and including an indicating means to guide the user during cleaning. | 0 |
BACKGROUND OF THE INVENTION
The invention relates to a display shelf organizer. More particularly, the invention relates to a simple and easy to use device for organizing and labeling items on display on a shelf.
The large number of consumers who daily examine and handle articles on retail display invariably results in items being misplaced and the display as a whole becoming generally disordered. Retailers must attempt to maintain an orderly arrangement of this multitude of variously sized and shaped articles being displayed. Time is consumed in rearranging articles back to their proper location.
Further, where items are displayed side by side, confusion of the consumer between similar items may result. The consumer may wrongfully select an item improperly placed.
Attempts have been made at remedying this problem by sectioning off specific areas of a shelf in different ways. These include use of baskets or cumbersome dividers which may significantly reduce the shelf space available for display. In addition, these methods often require special components and fixtures and/or articles on the shelves which complicate their usage and limit dividing capabilities to pre-set sizes and locations.
Therefore, it is among the objects of this invention to provide a simple, low-cost shelf divider and labeling unit offering greater flexibility in the positioning of dividers in order to accommodate the various sizes and shapes of items to be displayed, while reducing to a minimum the displacement of usable display space taken up by such a unit.
SUMMARY OF THE INVENTION
In accordance with the present invention, a display shelf organizer is formed by securing generally long, thin, parallel divider strips perpendicularly to a front base having a nameplate bearing member. The divider strips are secured in such a manner that the strips are slideable along the length of the nameplate member. The divider strips rest on a shelf to divide the space on the shelf, with the nameplate member hanging over the front edge of the shelf to display one or more labels.
The divider strips can be adjusted in position on the shelf so that the spacing between adjacent strips corresponds to an appropriate width for accommodating articles to be displayed.
The front nameplate bearing member rests against and overlaps the front edge of the shelf, providing a front planar surface at an appropriate viewing angle. A nameplate label or card may be inserted into the nameplate member to display information regarding the items on the shelf.
The nameplate member preferably has a front nameplate bearing surface with lipped flanges at its top and bottom edges, forming parallel upper and lower slots for slideably receiving a nameplate or nameplates.
The front base member, including the nameplate member, preferably is formed as one piece, and each divider strip is injection molded.
Other and further objects of the present invention will be apparent from the following description and claims and are illustrated in the accompanying drawings, which by way of illustration, show preferred embodiments of the present invention and the principles thereof and what are now considered to be the best modes contemplated for applying these principles. Other embodiments of the invention embodying the same or equivalent principles may be used and structural changes may be made as desired by those skilled in the art without departing from the present invention and the purview of the appended claims.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view showing a display shelf organizer or shelf divider constructed in accordance with one embodiment of the invention and installed on a shelf.
FIG. 2 is a front elevation view of the shelf divider of the invention.
FIG. 3 is a side elevation view in section, taken generally alon the line and in the direction indicated by the arrows 3--3 in FIG. 2.
FIG. 4 is an isometric view of one of the divider strips used in the shelf divider shown in FIG. 1.
FIG. 5 is a top plan view of a shelf divider constructed and assembled in accordance with the present invention. FIG. 5 shows a shelf divider with a different number of divider strips and with different spacings of the divider strips as compared with that shown in FIG. 1.
DESCRIPTION OF PREFERRED EMBODIMENT
A preferred embodiment of a display shelf organizer in accordance with the present invention is shown in FIG. 1, generally indicated by the referencenumber 10.
The display shelf organizer 10 includes a front base member 11 to which a plurality of generally long thin divider strips 12 are slideably secured.
The divider strips 12 are arranged side by side in spaced parallel fashion so as to extend perpendicularly back from the front base member 11.
The front base member 11 in the preferred embodiment is constructed from plastic and comprises a nameplate bearing member 14 which runs the length of the front base member 11 and is of a generally flat shape and elongatedin the horizontal direction. Both the top and bottom edges of the nameplatebearing member 14 have lipped flanges 16a and 16b which provide upper and lower slots 18a and 18b, respectively, as best seen in FIG. 3, to receive and hold a nameplate 22. The nameplate or label 22 may be changed to provide information concerning the items being displayed, simply by sliding the nameplate or label card in and out of the slots 18a and 18b.
On the front surface of the nameplate bearing member 14, as seen in FIGS. 2and 3, are a plurality of ribs 24 which slightly offset the nameplate 22 from the surface of the nameplate bearing member 14 in order to securely retain the nameplate within the slots 18a and 18b.
A lower horizontal flange 26 is attached to, preferably integrally formed with the nameplate bearing member 14, extending rearwardly from the nameplate bearing member and running the full length longitudinally of thenameplate bearing member, as shown in FIGS. 1 and 3. The nameplate bearing member 14 is adjoined obliquely to the lower horizontal flange 26, so thatthe nameplate bearing member 14 is oriented in a position tilted back somewhat from vertical, preferably about 30 degrees. This angle of inclination may follow a similar angularity between the top and front surfaces 28 and 30 of the shelf 32 on which the divider assembly 10 is installed.
Adhesive pads 33 may be secured to the surfaces of the horizontal flange 26and of the nameplate bearing number 14, as shown, to secure the front base member 11 to the shelf 32. These pads may be continuous throughout the length of the front base member 11, with adhesive on both sides of the pads and preferably including a release strip on the outer side of each pad, which is to be removed when the front base member is installed.
An upper horizontal flange 34 is in generally spaced parallel relation to the lower horizontal flange 26 and is also attached to or integrally formed with the nameplate bearing member 14, as best seen in FIG. 3. Gripping flanges 38 and 40, respectively, extend generally at right anglesfrom the upper horizontal flange 34 and the lower horizontal flange 26, as shown in FIG. 3, to provide a relatively narrow gap or slot 42 between them at the rear of the front base member. The gripping flanges 38 and 40 extend toward one another, as shown in the drawing, and provide a means for engagement with the divider strips 12, as further explained below. An internal space or cavity 43 is formed by the nameplate bearing member 14 and the upper and lower horizontal flanges 34 and 26, as shown in FIGS. 1 and 3.
As shown in FIG. 3 and also in FIG. 4, each divider strip 12 has a front end including a locking tab 46 which is generally spade-shaped in cross-section with an enlarged head portion. The locking tab 46 is of a somewhat elongated shape as shown in FIG. 4, integrally molded with the divider strip 12 via an end flange member 48. The spade-shaped locking tab46 extends perpendicular to the length of the divider strip 12, as shown.
The locking tab 46 and the adjacent flange member 8, on the one hand, and the gripping flanges 38 and 40 and the slot 42, on the other hand, cooperate to form a locking mechanism which secures each divider strip 12 to the front base member 11 and holds the divider strips 12 in the proper orientation while permitting deliberate sliding movement. As shown in FIG.3 and also in FIG. 1, the spade-shaped locking tab 46 of each divider stripslides tightly into the gap or slot 42 of the front base member 11, with the end flange member 48 of the divider strip 12 abutting closely against the back sides of the gripping flanges 38 and 40 of the front base member 11.
The divider strips 12 are thus securely gripped by the front base member 11, but may be moved laterally with a small amount of force, for adjustingthe respective positions of all the divider strips 12.
As shown in the drawings, the top of each divider strip, near the front, may have an angled or beveled portion 50, providing a transition between the height of the remainder of the divider strip and the height of the front base member 11.
As shown in FIG. 4, each divider strip 12 may include one or more lines of reduced thickness 52, transverse to the length at the divider strip, for making the divider strip easily breakable along that line to shorten the strip appropriately for the width of the shelf.
While I have illustrated and described the preferred embodiments of my invention, it is to be understood that these are capable of variation and modification, and I therefore do not wish to be limited to the precise details set forth, but desire to avail myself of such changes and alterations as fall within the purview of th following claims. | A display shelf dividing and labeling assembly includes a plurality of divider strips which extend back to divide the display space on a shelf, connected to a front base member overhanging the front edge of the shelf. The divider strips are slidably received in the front base member to lock them in position. Labels may be inserted into the front base member, which may be retained on the shelf with adhesive pads. | 0 |
PRIORITY CLAIM
[0001] This application claims priority from U.S. provisional application serial no. 60/195,212, filed Apr. 7, 2000, the contents of which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] This invention relates to instruments, particularly medical and research instruments that are used for assessing gas volumes of air cavities, particularly, air cavities that may exhibit a compliance to changes in pressure, such as in vivo volumes of the lung, thorax, oropharynx and/or nasopharynx.
BACKGROUND OF THE INVENTION
[0003] Over the years, a number of methods have been used to determine the functional residual capacity (FRC) of the lung and related thoracic gas measures of a patient. These methods have involved gas dilution techniques, body plethysmography, and radiographic techniques. Gas dilution techniques require the patient to inhale special gases and necessitate special ventilation facilities (see, for example, U.S. Pat. No. 6,139,506). Radiographic techniques require a patient to be exposed to radiation. Additionally, static chest wall and abdominal composure by the patient is required during imaging. Plethysmography requires enclosing the patient or most of the patient's body (see, for example, U.S. Pat. Nos. 5,513,648 and 5,159,935) in a sealed enclosure or at the very least outfitting the patient with impedance belts about the torso (see, for example, U.S. Pat. No. 5,857,459). For these methods, lung pressurization maneuvers are performed by the patient during which changes in lung volume are simultaneously assessed by the plethysmograph. The general gas equation, relating pressure and volume and changes in pressure and volume, is used to determine the unknown volume. Current plethysmographic techniques to assess thoracic gas volume suffer from artifacts due to stomach gas, which causes compliance during testing maneuvers.
[0004] A method to estimate “trapped” air volume (not absolute volume) in lung of paralyzed patients has been proposed by obtaining a volume/pressure curve upon forced ventilation of the patient's lung (see U.S. Pat. No. 4,844,085). The large volume of gas exchange with this method introduces errors that must be compensated and the forced pressurization/de-pressurization precludes normal breathing of the patient during testing. None of the above methods allow convenient isolation and measurement of the volume of the oral cavity and nasal pharynx.
[0005] U.S. Pat. No. 5,937,854 discloses a method and apparatus for ventilator pressure and optimization by administering fixed stepwise pressure changes to the lungs of a patient and measuring the lung volume change resulting from each pressure change. The lung volume change is measured by using the RIP technique. This utilizes two elastic cloth bands containing insulated wires, which encircle the patient's rib cage and abdomen and are connected to an oscillator module.
OBJECTS AND ADVANTAGES
[0006] It is accordingly a principal object of the present invention to provide a non-invasive device and method for measuring in vivo gas volumes of a patient, including lung and pharyngeal volumes and, particularly, to obtain volume measurement in the presence of compliance.
[0007] An additional object of the present invention is to provide an inexpensive device and method that measures the lung volume of a patient independent of a sealed chamber or ventilated airspace and that does not require outfitting the patient with respiratory bands.
[0008] A further object of the present invention is to provide a device and method to measure lung and airway volume of a patient by a means that is not dependent upon patient cooperation and participation. In other words, the patient is only required “to breathe” and not to perform specialized pressurization maneuvers to within a certain tolerance. Therefore yet another object of the present invention is to provide a device for measuring the lung volume of the immobile, paralyzed, and “intensive care” or “special care” patient.
[0009] Accordingly, as will be disclosed in detail below, several advantages of the present invention are the measurement of in vivo volumes with a device that is smaller and more portable than existing systems, a device and method that is less complicated for clinicians and less troublesome for patients, and a device and method that serves a greater patient population, including veterinary applications, than is heretofore possible.
SUMMARY OF THE INVENTION
[0010] The purpose of the present invention is to provide a non-radiographic, noninvasive, portable, and non-confining apparatus for measuring gas volumes of in vivo cavities, including but not limited to lung volume and volumes of the thorax, oral and nasal pharynx. Further, the apparatus does not require sophisticated lung pressurization maneuvers to be performed by the patient or the outfitting of patients with thoracic position transducers. The present invention is intended therefore to serve a comprehensive patient population, including the bedridden, unawake, paralyzed, and sedated patient. Further, the device does not require the patient to inhale special gases or be subjected to imaging radiation.
[0011] It is recognized that various methods exist for assessing lung volume. The present invention represents improvements in the apparatus of boxless measurement of lung volume that can take the form of several embodiments. The detailed embodiments described herein are taken as representative or exemplary of those in which the improvements of the invention may be incorporated and are not presented as being limited in any manner.
[0012] The invention is directed to an apparatus for measuring gas volumes of an in vivo cavity of unknown compliance in a subject, particularly a patient comprising:
[0013] (a) an air cavity with induction means for inducing calibrated volume changes in said air cavity;
[0014] (b) a means for interfacing said air cavity to the in vivo volume of the subject to be measured;
[0015] (c) a means connected to said air cavity for measuring air pressure variations; and
[0016] (d) a control means electrically coupled to said induction means and measuring and processing means for calculating the gas volume in said subject.
[0017] In one embodiment, the subject is a human patient; in another embodiment the subject is a mammal; in yet another embodiment, the subject is a non-living item with a cavity exhibiting compliance, such as a balloon, a tank containing a bladder, or a tank with an inverted floating cover such as one used to contain hydrogen or natural gas.
[0018] The apparatus interfaces an air cavity to particularly the patient by means of a facial mask, nasal mask, mouthpiece or tubes. In a preferred embodiment, the interfacing means is a facial mask so that a common air cavity is formed with the patient via the oral and/or nasal orifices. The apparatus includes a respiratory access valve connected to its inner cavity that, when open, permits the patient to exchange air with the external environment in the manner of ordinary breathing (means for interfacing said air cavity to ambient environment) and, when closed, permits artificial pressurization of the cavity by means of a calibrated volume-changing piston (means for inducing volume change). The apparatus includes a calibrated device to assess air pressure changes occurring inside the common air cavity and a device to assess air pressure of the ambient environment.
[0019] The valve interfaces between the external environment and the inner cavity of the apparatus, and is opened or closed by passive means according to breathing airway pressure of the patient. The valve is constructed in such a manner as to remain open while the patient is in the process of inhaling or exhaling, and to momentarily close during the period of time that the patient is changing breathing modality from exhalation to inhalation, when cavity pressure is beneath the shutter threshold. The pressure change in the system due to the induced change in volume is, in itself, insufficient to open the valve.
[0020] The invention is also directed to a method for measuring a gas volume of an in vivo cavity in a subject utilizing the apparatus of the present invention comprising
[0021] (a) attaching said apparatus to said subject;
[0022] (b) measuring the barometric pressure in an area near the subject;
[0023] (c) measuring changes in induced pressure and volume in said cavity during an induction and preferably at least two inductions, and
[0024] (d) calculating said gas volume.
[0025] The method may further comprise the step of calculating compliance of said cavity where compliance is present.
[0026] The control and processing unit monitors system pressure during the breathing cycle and is therefore programmed to determine if pressure is negative (indicating inhalation), positive (exhalation), or zero (peak of inhalation or trough of exhalation). When the processing and control unit assess that air cavity pressure is within the range that the respiratory valve has become closed and, further, that the breathing cycle is at the trough of exhalation, the control unit repositions the piston and thereby decreases the system volume by a small, known amount. Those versed in the art comprehend that pressure and volume of gas in a closed mass system are mathematically related by the general gas equation. Specifically, the pressure-volume product of the system gas prior to piston movement is equal to the pressure-volume product after piston movement, for the same gas temperature.
[0027] Compliance occurs whenever the volume under test changes as a result of increased inner forces due to pressurization of the air cavity. Possible sources of compliance are cheeks and lung wall. Of particular note is compliance of the lung wall due to stomach gas, which is an artifact of body plethysmography of all types. Those versed in the art will appreciate the difficulty of measuring a volume under the circumstances in which that volume might adjust itself to the increased pressure created by the measurement process. The invention proposes a means of determining compliance in the course of testing by applying a plurality of different induced gas volumes that result in different pressure measurements from which in vivo volume may be determined.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] [0028]FIGS. 1A to 1 D schematically show the invention in the various states of its operational cycle as described herein in the EXAMPLES.
[0029] [0029]FIG. 2 shows a typical embodiment of the invention.
[0030] [0030]FIG. 3 shows a second embodiment of the invention with added monitoring components.
DETAILED DESCRIPTION OF THE INVENTION
[0031] To enhance understanding of the present invention, it is noted here that the formulae used to determine system volume are identical to those used by the clinically prevalent method of whole body plethysmography. In the case of whole body plethysmography, a change in system volume is created by the patient, by panting against a valve that has been closed at the trough of inhalation during a normal breathing cycle. The resulting changes in lung volume that occur during the panting maneuver are determined by solving a similar formula for the closed air cavity that exists between the patient and the inner box. The estimates of volume change thus obtained are used in the gas-volume equation to determine an estimate of lung volume. In the case of the present invention, the change in induced volume is known precisely since it is supplied in metered portions to the in vivo volume under test, and does not require estimation by a separate plethysmograph. Thus, patient participation and cooperation is minimized in the present invention when testing for thoracic gas volume.
[0032] In a typical embodiment, the apparatus shown in FIG. 2 is interfaced to the patient, with facemask 20 forming an airtight seal between the inner cavity of the apparatus 21 and in vivo air volume of the patient. Normal breathing by the patient is vented through valve 22 . Valve 22 interfaces between the external environment and inner cavity 21 of the apparatus and is opened or closed by passive means according to breathing pressure of the patient.
[0033] The processing and control unit 23 monitors the pressure of the system via pressure transducer 24 . The processing and control unit (PCU) also drives linear motor 25 at the appropriate time to move piston 26 a calibrated amount. Pressure changes monitored by transducer 24 from two or more system cycles are processed by PCU 23 as described in the EXAMPLES to display the calculated volume and compliance.
[0034] In an alternative embodiment shown in FIG. 3, a valve 30 controlled by PCU 23 replaces passive valve 22 shown in the embodiment of FIG. 2. A control signal from PCU 23 signals the valve to vent the apparatus cavity to atmosphere when a preset differential pressure between system and atmosphere exists. This differential pressure is created by a pneumotach screen 31 located in the air stream of valve 30 . A pulse monitor 33 interfaces to PCU 23 allowing each induced volume change to occur at the same phase in the heart cycle.
[0035] Pneumotach screen 31 serves a further purpose in the alternative embodiment. It may be desirable to obtain measurements of volume at successively occurring troughs of the breathing cycle to enhance accuracy via signal averaging. However, the amount of air in the lungs at the trough of the breathing cycle, FRC, is slightly different for each cycle, even during ordinary breathing. Pneumotach screen 31 and differential pressure transducer 24 permit measurement of volumetric air flow during breathing, so that corrections to lung volume V 0 can be made during the averaging process. Volumetric air flow measurements via pneumotach screen 31 and differential pressure transducer 24 are calibrated prior to patient testing using known air flow values and other standards common to the industry. Therefore, the apparatus of the present invention further comprises means for measurement of volumetric air flow during breathing.
EXAMPLES
[0036] To facilitate understanding of the operation of the invention, a schematic drawing of a general embodiment of the invention is shown in FIGS. 1A to 1 D. The apparatus is shown interfaced to an air cavity 1 of unknown volume V 0 to be determined, containing a compliant wall 2 shown figuratively as a movable piston backed by a spring. A cylinder 3 fitted with, for example, a piston 4 contains a pre-determined volume 5 that communicates with air cavity 1 . The induction means may also be an acoustic speaker, gas mass injection or dilution. A pressure-measuring device 6 is coupled to the combined air cavity and contains transducer, offset, gain, calibration adjustment, and other instrumentation components common to the industry. Operation of the embodiment shown in FIG. 1 begins with calibration of pressure-measuring device 6 , using calibration equipment and techniques common to the industry. When accomplished, pressure-measuring device 6 will directly assess air pressure in a standard unit of absolute measure, such as centimeters of water.
[0037] At the start of the cycle, piston 4 is situated as shown in FIG. 1A, such that a small volume V f 5 is defined in cylinder 3 . The vent valve 7 is initially open such that the pressure of the system is atmospheric. In FIG. 1B, valve 7 is closed and piston 4 is pushed inward. Pressure in the combined cavity is increased from P 0 to P by virtue of the piston displacement, according to physical laws governing gas within a closed mass system. In turn, a sympathetic increase in volume, V c 8 , occurs due to the compliance of wall 2 in cavity 1 . Volume of the combined air cavity thus changes from V 0 +V f in FIG. 1A to V 0 +V c in FIG. 1B.
[0038] If the total change in system volume is known, the volume V 0 can be computed from Boyle's gas equation, V 0 =ΔV[P 0 /(P−P 0 )] where ΔV=V f −V c (P/P 0 ). In a non-compliant system, V c =0, ΔV=V f , and the original volume V 0 can be directly determined. In a compliant system, however, V c ≠0, and the value for volume obtained by directly applying the gas equation is incorrect. Since V c is unknown, sufficient information is yet unavailable to determine V 0 directly whenever compliance is present in the system.
[0039] In order to determine if compliance is present in the volume under test, the cycle is repeated using a different piston chamber volume V f ′≠V f (FIGS. 1C and 1D). The mass of the system has now changed so that the gas equation results in an independent system equation from which volume can again be computed from the new measured change in pressure P′−P 0 . In the event that the computed volume is different than that calculated from performing the previous maneuver, compliance has been determined to exist and contributions to the system volume due to V c must be acknowledged.
[0040] Although neither V c or V c ′ is known, compliance may be assumed linear when changes in pressure occur that are small relative to atmospheric. In other words, a compliance parameter C may be defined, where V c =C (P−P 0 ) and V c ′=C (P′−P 0 ). Thus, the two independent system equations can be written in terms of P 0 , P, P′, V f , V f ′, C, and V 0 , where the first five of these terms are known by way of measurement and the latter two are the unknown parameters of the system. By techniques familiar to those skilled in the art, C and V 0 can be determined by various numerical means, including methods of linear diagonalization and methods of variance, depending upon the degree of sensitivity among terms.
[0041] The volume of air 1 in FIG. 1A is at a constant (body) temperature prior to the movement of piston 4 in FIG. 1B. Small changes in gas temperature occur due to movement of piston 4 because of gas compression. The effect of temperature change can be neglected whenever sufficient time is allowed for temperature of the gas to dissipate in the tissues of the body prior to pressure data collection. In the case of in vivo volumes such as lung, this time period is very short (less than 500 ms) due to the large surface area and efficient heat transfer characteristics of lung tissue. Alternately, if rapid sampling is required, such as for purposes of data averaging, effects of temperature may be accommodated by including temperature terms into the general gas equation, P 0 (V 0 +V f )/T 0 =P(V 0 +V c )/T, where temperature is measured by a transducer with a sufficiently high frequency response and sensitivity adapted into pressure transducer 6 .
[0042] Operation of a typical embodiment of the apparatus shown in FIG. 2 begins with calibration of pressure transducer 24 as described above. The apparatus is interfaced to the patient, with face mask 20 forming an airtight seal between the inner cavity of the apparatus 21 and in vivo air volume of the patient. This results in a combined air cavity of yet unknown volume, V 0 . Normal breathing by the patient is vented through valve 22 . The valve interfaces between the external environment and the inner cavity of the apparatus, and is opened or closed by passive means according to breathing pressure of the patient. The valve is constructed in such a manner as to remain open while the patient is in the process of inhaling or exhaling and to momentarily close during the time the patient is changing breathing modality from exhalation to inhalation, when cavity pressure is beneath the shutter threshold. The pressure change in the system due to the induced change in volume is, in itself, insufficient to open the valve.
[0043] The processing and control unit 23 monitors the pressure of the system via pressure transducer 24 , which will be atmospheric at the trough of the breathing cycle. At that moment, the passive valve is closed, sealing the system. The processing and control unit (PCU) signals linear motor 25 to move piston 26 a calibrated amount, inducing a volume change in the system by an amount V f 27 . After a suitable settling time, PCU 23 measures the system pressure via transducer 24 . This procedure provides measures of V f , P 0 , P and a preliminary estimate for V 0 as described in previous paragraphs.
[0044] The sequence is repeated except that PCU 23 causes piston 26 to induce a different volume V f ′. PCU 23 thus obtains additional measures of V f ′, P 0 , P′ and a second estimate for V 0 to determine (a) if compliance exists in the system and (b) measures of V 0 and the compliance parameter C as described above. Calculated values for V 0 and C are displayed by a digital display unit on PCU 23 . Several breath cycles may be monitored for purposes of averaging.
[0045] In a practical application of the apparatus, when measuring complex and dynamic volumes such as the human lung, sources of artifact, in addition to that introduced by compliance, are often problematic. One potential problem is associated with the small changes in lung volume that eventuate by blood being forced into the lung by the heart. Although this volume change is very small in relation to the volume of the lung, it may be appreciable in relation to the volume change induced to the system by the apparatus by which measures are obtained. The volumetric action of the heart on the lung wall creates a similar source of change in system pressure. FIG. 3 shows an alternative embodiment of the invention with components added which address these physiologic phenomena.
[0046] A valve 30 controlled by PCU 23 replaces passive valve 22 shown in the embodiment of FIG. 2. A control signal from PCU 23 signals the valve to vent the apparatus cavity to atmosphere when a preset differential pressure between system and atmosphere exists. A pneumotach screen 31 provides a small resistance to airflow in and out of the mask to allow transducer 24 in conjunction with PCU 23 to monitor flow and thus control valve 30 as noted. Utilization of an active valve in the alternative embodiment of the apparatus facilitates management of the system measuring process and provides surety to PCU 23 about valve status.
[0047] At the trough of the breathing cycle, control signals from PCU 23 close valve 30 and signal motor 25 to drive piston 26 in such a manner to induce a known increase to system volume. This increase results in a decrease in pressure of the system, instead of an increased pressure as in the case of the previous embodiment. Utilizing a reduced system pressure in the alternative embodiment reduces the tendency for involuntary glottal closure that might otherwise result due to excitation of supralaryngeal baroreceptors during pressurization.
[0048] A pulse monitoring means, provided by a pulse monitor 33 , allows each induced volume change to occur at the same phase in the heart cycle, thereby reducing the volume artifact caused by blood flow into and out of the lung and the artifact generated by the heart pushing on the wall of the lung. The total system pressure is monitored by transducer 24 and processed by PCU 23 such that slowly-varying pressure artifacts induced by the sources described above can be reduced either by filtering or by providing control feedback to piston 26 in such a manner to continually move it in a fashion to oppose pressure artifacts.
[0049] A glottal monitoring means, provided by the glottal monitor 32 (an electroglottograph or similar device), monitors the status of the glottis to determine which volume is being measured. When the glottis is closed, the volume being measured is that of the pharnyx. A nasal mask can replace the facemask for use in measuring the nasal pharynx, and the difference between the two measures provides the volume of the orapharynx. For this measurement, the patient's velum must be closed as occurs during swallowing.
[0050] In addition to measuring volumes of these cavities, taking volume measurements of the lung at the peak of the breathing cycle provides PCU 23 with information required to determine spirometric measures such as functional expired volume (FEV) in addition to the volume obtained at the trough of the breathing cycle, which is functional residual capacity (FRC).
[0051] Calibration of the pneumotach formed by the resistance screen 31 located in valve 22 permits measures of volumetric air flow by PCU 23 , thus facilitating averaging of calculated in vivo volume measurements obtained over successive breathing cycles.
[0052] The specific embodiments herein disclosed are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
[0053] Various references are cited herein, the disclosures of which are incorporated by reference in their entireties. | This invention relates to instruments, particularly medical and research instruments that are used for assessing gas volumes of cavities, particularly, cavities that may exhibit a compliance to changes in pressure, such as in vivo volumes of the lung, thorax, oropharynx and/or nasopharynx. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. application Ser. No. 13/293,786, filed Nov. 10, 2011, which is a divisional of U.S. application Ser. No. 11/813,145, filed Jun. 29, 2007, the entire contents of which are incorporated herein by reference. U.S. application Ser. No. 11/813,145 is a National Stage of PCT/FR05/51093, filed Dec. 15, 2005, and claims the benefit of priority to French Application No. 0453290, filed Dec. 31, 2004.
BACKGROUND
Field
The invention relates to a method of bending glazing units by which the glass is sucked by openings passing through a solid concave mold to take the form of said concave mold. The method according to the invention is more particularly suited to a rapid industrial production process, leading to glazing units free of optical defects.
The invention relates most particularly to the simultaneous bending of superposed sheets of glass (usually two superposed sheets of glass) that are required to be assembled later into a laminated glazing unit, particularly of the type of sheets intended to serve as windshields of motor vehicles. The sheets are assembled in a manner known to those skilled in the art by inserting between the sheets of glass a layer of polymer, usually of the polyvinylbutyral type.
Description of the Related Art
EP0363097 teaches the suction of a single sheet through a bottom concave mold. After bending, the sheet is separated from the bottom mold by a frame surrounding the concave form and rising to carry the sheet with it. To be able to carry the sheet upward, the latter must protrude beyond all the edges of the concave mold. Such a protrusion is not satisfactory for bending the edges, which are not always precisely formed during the bending. The result of this is a risk of bending defects at the edges of the sheet. Furthermore, this document gives no information relating to the bending of several superposed sheets.
U.S. Pat. No. 3,778,244 teaches a top form fitted with a suction skirt placed above a bottom mold furnished with suction orifices through its solid full surface. These two bending forms work one after the other without carrying out any pressing of the glass, since, when a sheet has been partially bent against the top form, this sheet is allowed simply to fall on the bottom form (col 5 lines 3-6).
WO02064519 teaches the bending of superposed sheets through a bottom concave mold. A top oddside mold may squeeze the edges of the two sheets together at the time of suction by the concave form. Here also, it is a frame surrounding the bottom form which, when rising, picks up the sheets after bending. Consequently, the sheets must also protrude from the bottom form. Furthermore, even though this method represents notable progress, the desire is to be able to accelerate it in the context of an industrial usage. To be able to accelerate it, it is possible to work on the value of the vacuum used during the suction. The applicant has however observed that it was appropriate not to push the vacuum beyond a vacuum pressure of approximately 100 mbar (the difference between atmospheric pressure and the pressure in the bottom mold), because that could lead to optical defects visible to the naked eye, of the distorted vision type. It seems that this defect originates in fact from a clearance being created between the various sheets during the suction. This clearance may even reach 1 mm in the central region. The optical distortions that result therefrom may reach 90 mdpt (millidioptres).
SUMMARY
The invention resolves the aforementioned problems. According to the invention, upward suction means are used, particularly of the suction skirt type, to pick up the sheets of glass, before the suction bending step. It has been discovered that the use of this type of means of support procured a double advantage: 1) on the one hand, it is no longer necessary for the sheets to protrude beyond the bottom concave mold, 2 ) on the other hand, and unexpectedly, if the suction/holding step (upward suction) is correctly combined with the suction/bending step (downward suction) through the bottom mold, it is possible to push the vacuum in the bottom concave mold beyond a vacuum pressure of 100 mbar without, for all that, causing optical defect problems. As a result, the invention allows superposed sheets to be bent at very rapid production rates.
Without this explanation causing a limitation to the scope of the present invention, it seems that the upward suction removes a substantial portion of the air between the superposed sheets and contributes to a better combination of the superposed sheets. The consequence of this is that the sheets are all more accurately brought toward the concave bottom form during the suction/bending step on the bottom mold. Specifically, it seems that the presence of residual air between the sheets could prevent a sheet that is not in direct contact with the bottom mold from following the bottom sheet during the suction bending step.
Thus, the invention relates in particular to a method of forming superposed sheets of glass (usually two superposed sheets of glass) brought to their forming temperature, comprising:
a suction/holding step comprising the sheets being picked up by a top form furnished with suction means creating an upward airflow blowing over the rim (edge) of the sheets, said suction being sufficient to lift and hold the superposed sheets against said top form, then a pressing step comprising the pressing of the sheets between the top form and a full surface solid concave bottom form furnished with openings (holes), said pressing beginning while the suction of the preceding step is not yet finished or is finishing, then a suction/bending step comprising the forming of the superposed sheets, by suction of the main face of the bottom sheet through the openings of the bottom concave mold, said suction forming beginning while the pressing of the preceding step is not yet finished, then a cooling step comprising the cooling of the sheets.
According to the invention, it has been discovered that the suction exerted during the suction/holding step serves not only to hold the sheets in order to place them in the appropriate position above the bottom bending mold, but it also draws the air from between the sheets. That is why it is preferred according to the invention to begin the pressing step while the upward suction is still operating or is in the process of finishing, because the pressing step procures an intimate contact between the sheets and ensures the seal between them, at a time when the air has been drawn from between the sheets. In practice, the upward suction may be stopped as soon as the pressing step begins, so that stopping the upward suction may be virtually simultaneous with beginning the pressing step. Specifically, no elastic effect intervenes to separate the sheets. This pressing step therefore prevents air from returning between the sheets. The sheets are then ready to be bent by suction of the bottom sheet. This (downward) suction by the bottom mold begins although the pressing step is not yet finished. The absence of air between the sheets means that all the sheets correctly follow the bottom sheet while it is being formed. It was noted that it was possible to exert a vacuum pressure of 350 mbar at the suction/bending step which resulted in a maximum clearance between the sheets of 0.5 mm, and an optical distortion of less than 70 mdpt, these values being capable of varying depending on the geometry and the complexity of the bending forms sought. It is not necessary to continue the pressing throughout the bending by suction. Specifically, once the bending by suction has begun and once the viscoelastic stresses are relaxed, the pressing can be released because the superposed sheets remain well pressed together. Preferably, the suction of the suction/bending step is therefore executed for a sufficient period for the required shape to be obtained and for the viscoelastic stresses after obtaining this final shape to be relaxed.
The top form picking up the sheets may be a full surface solid form or preferably a frame. “Frame” means a strip of an appropriate material (usually metal) offering at the periphery of the sheet placed in the top position a contact surface usually from 0.5 mm to 10 cm wide. “Periphery” means the border zone, of annular shape, of a main face of the sheet situated at less than 15 cm from all the edges.
The pressure exerted during the pressing step may be very light. Specifically, it is usually sufficient to push the top sheet a little (while the upward suction is still being exerted or is in the process of stopping) so that the two sheets are more intimately juxtaposed. Preferably, this pressure is exerted in the peripheral zone of the sheets. Preferably, the pressure is exerted so as to prevent air passing between the sheets.
The bottom bending mold is concave and its concavity corresponds substantially to the desired final shape of the glazing unit. This bottom mold is solid and comprises, at its surface, openings allowing the suction of the sheet that is placed in the bottom position and with which it is in contact. This bottom mold is preferably at least as large as the bottom sheet, so that the superposed sheets do not protrude beyond the mold at any location.
Once the suction through the bottom mold has begun, it is possible to stop the pressure by separating the top form and the bottom mold from one another. At this moment, there is no more upward suction. The downward suction through the bottom mold usually lasts from 1 s to 40 s.
The suction forces exerted on the sheets on the one hand during the suction/holding step (upward) and on the other hand during the suction/bending step (downward) are therefore different. Specifically, the first case involves creating a vacuum pressure at the border of the sheets so as to lift the sheets upward and also suck the air out from between the sheets (high airflow, for example of the order of 25 000 m 3 of air per hour for a 1.8 m 2 windshield), and the second case involves pressing the sheet in the bottom position against the bottom mold (large vacuum pressure and low airflow). The upward suction therefore requires the creation of a strong airflow blowing over the rim of the sheets, whereas the downward suction (for bending) requires the air to be drawn off through openings distributed substantially over the whole surface of the bottom mold. Usually, the upward suction of the suction/holding step is generated through a skirt surrounding the top form. To be better able to pick up and raise the sheets, the skirt surrounding the top form may come into contact with the support on which the sheets rest. If this support is a frame, its central part allows the air to pass beneath the sheets of glass which are then lifted without difficulty. If the support is not a frame, at least one orifice can be provided in the support beneath the sheets so that the air sucked through the skirt more easily raises the sheets.
To be picked up at the suction/holding step, the superposed sheets may be flat or already pre-bent before said step and have a temperature allowing them to be bent (usually between 560 and 610° C.). They are preferably pre-bent. Usually, this pre-bending has been carried out by gravity collapsing on a pre-bending support, usually of the frame or skeleton type. When the bends to be applied during the pre-bending step are relatively major, an articulated skeleton or any type of skeleton subjecting the sheets to several shapes successively may be used. In particular, these may be the skeletons described in EP 448447, EP 705798 or application PCT/FR2004/050198. Any pre-bending step gives the sheets the shape of a rough, part way between the flat shape and the desired final shape. This pre-bending may also give the periphery of the glazing unit its final shape, whereas the central part is only roughed. The existence of a pre-bending step is preferred when the final shape has relatively accentuated curves, particularly when the final shape has curves in directions orthogonal to one another (double bending). Motor vehicle manufacturers are increasingly making use of this type of complex shape having considerable double bending. This pre-bending is usually achieved by gravity, the superposed sheets being placed on an appropriate support which travels through a tunnel oven toward the main bending zone comprising the top form and the bottom bending mold. The tunnel oven is used both for giving the sheets the bending temperature and for carrying out the pre-bending. The pre-bending supports travel through the tunnel oven for example by being mounted on wheeled trolleys placed on rails. The pre-bending supports pass beneath the top form, which then picks up the superposed sheets thanks to the upward suction as already explained.
As already mentioned, the pre-bending support, particularly of the skeleton type, may offer, as a surface of contact with the glass, a shape that changes as it moves. This change may take place during the movement toward the position beneath the top form, while the support carries the superposed sheets. In particular, the contact surface of the pre-bending support may take at the periphery the final shape desired for the glass, even before being picked up by the top form. This does not mean that the glass already takes the desired final shape before being picked up by the top form, because the collapsing of the glass at the periphery may not be finished at that time and furthermore, even if the periphery of the glass touches the pre-bending support everywhere, the central zone has not, at any rate, taken the final desired shape. If the pre-bending support has the desired final peripheral shape for the sheets when picked up by the top form, this support may also pick up the sheets after the final bending in order to take them to the cooling zone without it being necessary to change its shape again. It is also possible for the pre-bending support to keep a rough peripheral shape until picked up by the top form, then, when it is no longer supporting the sheets, take the final peripheral shape desired for the sheets. Specifically, if this support must pick up the sheets after the final molding by the bottom mold, in order to take the sheets to the cooling zone, it is preferable for this support to have a shape that corresponds well to the final shape desired for the sheets.
Before any heating of the sheets, it is possible to place between the sheets superposed in an assembly a powder preventing the various sheets from sticking together during the bending process. This powder (possibly being silica for example) is placed in a manner known to those skilled in the art.
The contact surface of the top form may correspond to that of the top sheet when it is ready to be picked up, that is to say it may be flat if the sheets arrive flat beneath it, or have a rough shape corresponding to that given to the sheets by any pre-bending process, or have, at least at the periphery, the desired final shape. Preferably, the top form has at the periphery the desired final shape. In any case, the top form has no curves less accentuated than those of the sheets that it must pick up.
When the bending is finished and the sheets are resting on the bottom bending mold, the sheets may be cooled. To do this, it is preferable to separate the sheets from the bottom mold in order to subsequently place them on a support called a cooling support. The sheets may for example be separated from the bottom mold by upward suction in a manner similar to that used during the suction/holding step. It is even possible to use the same top form to carry out the suction/holding step and the separation from the bottom mold. However it is also possible to use a second top form (which may be called FS 2 in the context of the present application) furnished with the necessary suction means (particularly of the skirt type), surrounding it, to carry out this separation operation. After separation from the bottom mold by picking up with a top form, the latter then releases the sheets on top of a cooling support which carries the sheets toward the appropriate cooling zone. When a second top form is used, the latter advantageously has a contact shape with the top sheet corresponding to the final shape of the glazing unit. In all cases, the cooling support advantageously has a contact shape facing the sheet placed in the bottom position corresponding to the final shape of the glazing unit. Usually the cooling process is close to natural cooling, of the type used on the sheets intended to incorporate a laminated glazing unit for a motor vehicle windshield.
Thus, according to the invention, the bent superposed sheets may be separated from the bottom concave mold after the suction/bending step, by being picked up with the aid of a top form furnished with suction means creating an upward airflow blowing over the rim of the sheets, said suction being sufficient to lift and hold the superposed sheets against said top form, said top form then letting the bent superposed sheets rest on a support taking them toward a cooling zone for the completion of the cooling step.
In particular, the top form separating the bent sheets from the bottom mold may be a second form (FS 2 ) distinct (but possibly having the same shape) from the first top form (FS 1 ) picking up the sheets at the suction/holding step, the sheets possibly being moved from a position beneath the form FS 1 to a position beneath the form FS 2 by the movement of the bottom mold supporting them.
The use of two top forms makes it possible to accelerate the rates of the process relative to the variant with a single top form. Specifically, when the second form (FS 2 ) lets a set of bent superposed sheets rest on a support that is to take it to a cooling zone for the completion of the cooling step, the bending of another set of superposed sheets may already begin, the bottom concave mold being placed beneath the first form (FS 1 ).
The support taking a set of superposed sheets to the bending unit may be the same support that collects the sheets after bending to take them to the cooling zone.
Usually, the top form and the bottom bending mold are placed in a bending unit taken to the bending temperature.
The superposed sheets in one and the same assembly (or package) have substantially the same shape. Their size may vary slightly in the direction of a diminution of their surface area when moving from the sheet placed in a bottom position to that placed in a top position, so that the borders of the sheets coincide after the bending.
The invention also relates to a device making it possible to apply the method according to the invention. The device according to the invention is a device for bending sets of superposed sheets of glass comprising
a convex top form FS 1 furnished with means of suction around it, creating an upward airflow blowing over the rim of the sheets, said suction being sufficient to lift and hold the superposed sheets against said top form, and a bottom solid concave mold furnished with openings on its main face and means of suction through these openings,
said top form and said bottom mold having complementary shapes and being able to move toward one another along a vertical axis to press the sheets of glass.
In particular, this device may comprise a train of pre-bending supports moving to pass one after the other beneath the top convex form (FS 1 ) so that the sets of superposed sheets may be picked up by said top form (FS 1 ).
This device may furthermore comprise another convex top form (FS 2 ) furnished with means of suction around it, creating an upward airflow blowing over the rim of the superposed sheets, said suction being sufficient to lift and hold the superposed sheets against it, the bottom concave mold being able to be moved to pass alternately beneath one and then the other of the top forms (FS 1 and FS 2 ).
For the case in which the device comprises two top forms, it may also comprise a train of pre-bending supports moving to pass beneath the two top convex forms.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of a top form of the annular frame according to an exemplary embodiment of the present disclosure;
FIG. 2 is a perspective view of the bottom mold according to an exemplary embodiment of the present disclosure;
FIGS. 3 a -3 d represent a sequence of a method of the invention using one top form according to an exemplary embodiment of the present disclosure;
FIGS. 4 a -4 d represent a sequence of a method of the invention using two top forms according to an exemplary embodiment of the present disclosure;
FIG. 5 depicts a part of the top form coming into contact with the glass.
DETAILED DESCRIPTION
FIG. 1 represents a top form 1 of the annular frame type coming into contact with the periphery of the top sheet of a set 2 of two superposed sheets. A skirt 3 surrounds the form 1 and is capable of exerting a suction (in the direction of the arrows) sufficient for the two superposed sheets to be held against the top form 1 . The sucked air blows over the rim 4 of the sheets. Usually, the top form is coated with a material made of refractory fibers (metal and/or ceramic fibers) of the felt, woven or knit type, softening the contact of the glass with it and reducing the risks of marking. In addition, the air can circulate inside the fibrous material in all directions which generates an additional diffusion of the airflow.
FIG. 2 represents a bottom concave mold 5 furnished on its main top face with a multitude of orifices (openings, holes) 6 . A suction created through these orifices bends the superposed sheets by pressing them against the main top face of the mold. Usually, this bottom mold is coated with a material made of refractory fibers (metal and/or ceramic fibers) of the felt, woven or knit type, softening the contact of the glass with it and reducing the risks of marking. In addition, the air can circulate inside the fibrous material in all directions which generates an additional diffusion of the airflow. This mold has the final shape desired for the sheets.
FIG. 3 represents a few sequences of an embodiment of the method according to the invention when it comprises only one top suction form. A train 7 of trolleys 8 each carrying two superposed sheets of glass, takes the sheets (traveling from right to left in FIG. 3 ) beneath a bending unit 9 whose interior is at the bending temperature. Each trolley carries a pair of sheets 13 by means of a pre-bending skeleton 14 . This skeleton may have its contact surface modified in the sense of an increase in the bends during its path toward the bending unit. On arrival beneath the unit 9 , each trolley has already covered a certain distance through a tunnel oven 10 so as to cause the pre-bending of the sheets. Beneath the unit 9 , the skeleton presents a surface of contact (only for the periphery of the sheets) corresponding to the desired final shape, and the sheets have taken this shape at the periphery but not in their central region. The unit 9 contains a top form 11 fitted with a skirt (on the principle of FIG. 1 ) that is able to move vertically, and a bottom concave mold 12 furnished with openings (on the principle of FIG. 2 ) capable of moving horizontally. The top form is a frame having the shape of a ring and whose shape corresponds to the final shape desired for the sheets. The bottom mold has the final shape desired for the sheets. At the time of FIG. 3 a , the train stops so that a trolley is just at the vertical of the top form. The top form 11 then descends toward the trolley 8 to pick up the two superposed sheets thanks to the suction of its skirt ( FIG. 3 b ). The top form 11 rises again with the sheets, sufficiently high for the bottom mold 12 to move just beneath it by horizontal translation. The top form then descends again slightly to lightly press the periphery of the sheets against the bottom mold (the skirt is again in operation at that time) as shown in FIG. 3 c . The downward suction through the openings of the main face of the bottom mold may then begin to produce the bending by flattening against said face. This suction usually lasts from 1 s to 40 s. When the bending is finished, the top form can rise again with the sheets 13 while the bottom mold 12 resumes its rest position on the left. The top form 11 can then descend again to deliver the two bent sheets 13 to the same trolley 8 as the one that brought it. The train 7 can depart leftward so that the next pair of sheets is positioned just beneath the top form 11 and undergoes the same bending cycle as the pair preceding it. The train 7 travels therefore intermittently, constantly stopping and starting, each start corresponding to a translation by a distance of one trolley. The sheets are progressively taken leftward in the direction of a cooling zone. A fixed horizontal wall 14 placed beneath the rest position (toward the left) of the bottom mold 12 helps to thermally insulate the bending unit from the tunnel leading to the cooling zone.
FIG. 4 represents a few sequences of an embodiment of the method according to the invention when it comprises two top suction forms FS 1 and FS 2 . The start of the method begins like the one explained for FIG. 3 : the train brings the pairs of sheets pre-bent by gravity on skeletons, and stops so that one of the trolleys (trolley 8 a ) carrying the pair of sheets 13 a stops just beneath the first top form FS 1 . The latter then picks up the pair of sheets 13 a and rises again with it sufficiently high for the bottom concave mold 12 to be able to be placed beneath the sheets 13 a . The form FS 1 then descends again to cause the sheets to be pressed between FS 1 and the bottom mold 12 . FIG. 4 a represents this moment in the method. During the pressing, then the suction exerted on the sheets 13 a , the train moves leftward by a distance of one trolley so that the trolley 8 a is beneath the top form FS 2 . After the bending begins, the form FS 1 rises without lifting the sheets 13 a , the latter remaining placed on the bottom mold 12 which continues the bending by suction. Specifically, even if no top form touches the sheets at this stage, the sheets remain well pressed together without separating because what is important is that a pressing action takes place at least at the very beginning of the bending suction. The bottom mold 12 is then moved leftward ( FIG. 4 b ) to be beneath the form FS 2 . The form FS 1 can then descend to pick up the next pair of sheets 13 b . For its part, the top form FS 2 descends to pick up the pair of sheets 13 a ( FIG. 4 c ). The form FS 1 rises again with the pair 13 b and the bottom mold 12 is then placed beneath the form FS 1 to press and bend by suction the pair of sheets 13 b in the same manner as has been described for the pair of sheets 13 a . The partition 14 which insulated the bending unit from the tunnel leading to the cooling zone is here a movable wall that has been retracted leftward at this stage of the method so that the form FS 2 carrying the pair of sheets 13 a can rest this pair on the trolley 8 a ( FIG. 4 d ). Naturally, the support 15 actuating the translation of the bottom mold 12 has the necessary orifice so that the form FS 2 can descend to the trolleys. Furthermore it is also possible to actuate the translation of the bottom mold 12 from the bottom of the unit, the support 15 then being perpendicular in FIG. 4 d . After the pair 13 a has been deposited on the support 8 a , the form FS 2 rises again, the movable partition 14 returns leftward beneath the form FS 2 in order to insulate the bending unit. The trolley train then moves leftward by a distance of one trolley. It can be seen that this embodiment is more efficient than that of FIG. 3 because it has been possible here to move the pair 13 a during its bending and begin to place in position a new pair 13 b while the bending of the pair 13 a was finishing. With this embodiment with two top forms FS 1 and FS 2 , the cycle time-saving corresponds to the trolley transfer time, because it is possible to press while the trolley train is moving.
FIG. 5 represents the part of a top form 16 coming into contact with the glass, said top form being fitted with a skirt 17 . The top form 16 is furnished with a felt element 18 softening the contact with the glass. The skirt 17 is also furnished with a felt element 19 to soften the contact with the support 20 . At the moment represented by FIG. 5 , the top form will pick up two superposed sheets of glass 21 and 22 resting on the support 20 . To make the sheets easier to lift, orifices (not shown) may be provided in the support and situated beneath the glass. The sheet 22 is slightly larger than the sheet 21 so that the borders of the sheets coincide fully after bending to the final shape. The represented part of the skirt 17 may be movable vertically relative to the form 16 . In this manner, when the skirt/top form assembly meets the sheets and the support, it is the skirt 17 that first comes into contact with the support 20 , said skirt then stopping its descent, but the top form continues to descend a little (usually 1 mm to 2 cm) to meet the top sheet 21 . This procedure provides the method with flexibility. In order to reduce the necessary flows in the skirt, the distance (d) between the skirt and the top form should be as small as possible. For example, this distance may be from 5 mm to 40 mm, for example approximately 20 mm. The rims 23 and 24 of the sheets are situated between the skirt and the top form. | A method and device for bending superposed sheets of glass. The sheets are picked up by a top form furnished with a suction creating an upward airflow blowing over the rim of the sheets, the suction being sufficient to lift and hold the superposed sheets against the top form, then the sheets are pressed between the top form and a full surface solid concave bottom form furnished with openings, the pressing beginning conducted while the suction is not yet finished or is finishing, then the superposed sheets are formed, by suction of the main face of the bottom sheet through the openings of the bottom concave mold, the forming by suction beginning while the pressing is not yet finished, and then the sheets are cooled. Windshields free of optical defects may thus be produced. | 2 |
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to baking ovens having an endless baking tong chain circulating in the baking oven, which contains baking tongs comprising baking moulds consisting of baking mould upper parts and baking mould lower parts, which can be locked in their openable and closable state and in the closed state, in which crispy-brittle baked products produced by a baking process are formed.
The baking ovens each have a front oven part, a rear oven part, an oven frame provided with an external thermal insulation, a baking chamber disposed inside the thermal insulation and an endless baking tong chain circulating continuously in the baking oven and moving through the baking chamber. The baking tong chain is disposed in the baking oven along an orbit which is closed in itself, which extends in two superposed transport levels through both oven parts. The baking tong chain contains baking tongs which can be opened and closed, and which can be locked in the closed state, in which baking moulds consisting of baking mould upper parts and baking mould lower parts are disposed, which are opened by opening the baking tongs and closed by closing the baking tongs. Located in the front oven part of the baking oven is a device for unlocking the baking tongs on the orbit of the baking tong chain and along the upper transport level, a device for opening the baking tongs, a dispensing station, a loading station and a device for closing the baking tongs and a device for locking the baking tongs are disposed consecutively in the running direction of the baking tongs. Located in the dispensing station is a product removal device which removes the baked products from the opened baking tongs, which is followed by an upper transport device for the removed baked products.
In these baking ovens, flowable baking preparations are processed and converted by a baking process into baked products which are crispy and brittle at room temperature.
The baking preparations are produced in a mixer. In the mixer the liquid ingredients of the baking preparation and the solid or powdery ingredients of the baking preparation are blended with one another. A shapeless mass is thereby produced. The shapeless mass is flowable. It has a liquid, i.e., thin-liquid to thick-liquid, and sometimes also a pasty consistency. The liquid ingredients are principally water comprising a fraction of 42.0 to 60.0 wt. % of the baking preparation. The powdery ingredients are principally a starch-containing main component comprising a fraction of 36.0 to 56.5 wt. % of the baking preparation. Usually wheat flour is used as the starch-containing main component. The starch-containing main component can also be a starch flour or a mixture of wheat flour and starch flour or a mixture of various grain or starch flours.
The baked products produced from these baking preparations can be edible baked products such as, for example, wafers, crispy-brittle wafer sheets for producing wafer slices filled with cream, etc.
The baked products produced from these baking preparations can however also be products not provided for consumption per se. These products include, for example, packaging articles such as, for example, packaging cups produced from a starch-containing baking preparation or parts of disposable crockery produced from a starch-containing baking preparation such as, for example, plates and cups and also knives, forks and spoons.
The baking preparations are supplied as shapeless, liquid to pasty masses to the baking ovens, the baking tong chain of which contains openable and closable baking tongs provided with a locking device.
In the baking oven, the shapeless mass is conveyed by means of a dough pump through dough lines to the loading station. In the loading station the shapeless mass is divided into dough portions and the dough portions are introduced into the opened baking moulds located in the opened baking tongs which pass the loading station in the upper transport level of the baking oven. After introducing the dough portions, the baking tongs are closed. When closing the baking tongs, the baking moulds are closed and the dough portions enclosed in the baking moulds. After closing the baking tongs, the closed baking tongs are locked. The circulating baking tong chain conveys the closed and locked baking tongs through the baking chamber into the rear oven part. Whilst the baking tongs pass through the baking chamber, the baking tongs together with the baking moulds are heated and thereby heated up to baking temperatures between 150° C. (degrees Celsius) and 250° C. (degrees Celsius). As a result, the dough portions enclosed in the closed baking moulds are subjected to a baking process and baked under pressure in the closed and locked baking tongs. The circulating baking tong chain conveys the closed and locked baking tongs into the front oven part. There the closed baking tongs are unlocked. The circulating baking tong chain conveys the closed and unlocked baking tongs into the upper transport level. During passage through the upper transport level, the baking tongs are opened and conveyed in the opened state through the dispensing station to the input station. In the dispensing station the baked crispy-brittle products are removed in the hot state from the opened baking moulds located in the opened baking tongs. The baked products are dispensed in the hot state from the baking oven. The circulating baking tong chain conveys the opened baking tongs with the opened empty baking moulds to the loading station. In the loading station, the dough portions formed recently from the shapeless mass are introduced into the opened baking moulds.
Baking ovens in which baking moulds consisting of baking mould upper parts and baking mould lower parts in which the openable and closable baking tongs provided with a locking device of an endless baking tong chain circulating in the baking oven and moving through the baking chamber are arranged are known, for example from the documents AT 378 470 B1 and U.S. Pat. No. 4,438,685 A.
BRIEF SUMMARY OF THE INVENTION
It is the object of the invention to improve a baking oven of the type mentioned initially.
According to the invention a new baking oven is proposed. The new baking oven has a front oven part, a rear oven part, an oven frame provided with an external thermal insulation, a baking chamber disposed inside the thermal insulation and an endless baking tong chain which circulates continuously in the baking oven and moves through the baking chamber. The baking tong chain is disposed along an orbit closed in itself, which extends through two superposed transport levels through the two oven parts. The baking tong chain contains baking tongs which can be opened and closed and which can be locked in the closed state, in which baking moulds consisting of baking mould upper parts and baking mould lower parts are disposed, which are opened by opening the baking tongs and closed by closing the baking tongs. In the front oven part a device for unlocking the baking tongs is disposed on the orbit of the baking tong chain. Along the upper transport level, a device for opening the baking tongs, a dispensing station, a loading station and a device for closing the baking tongs and a device for locking the baking tongs are disposed consecutively in the running direction of the baking tongs. In the dispensing station there is provided a product removing device which removes the baked products from the opened baking tongs, which is followed by an upper transport device for the removed baked products.
The new baking oven is characterised according to the invention in that the product removal device has a horizontally disposed rotary unit which is rotatable about a horizontal axis of rotation, which projects into the opened baking tongs, that the rotary unit carries removal elements disposed along its outer circumference, which are disposed consecutively on the outer circumference of the rotary unit in at least one longitudinal row extending along the circumference of the rotary unit and that the removal elements are configured as suction elements connected to a vacuum source.
In this baking oven it can further be provided according to the invention that the horizontally disposed rotary unit is disposed in a height-adjustable manner in the front oven part. Furthermore, the horizontally disposed rotary unit can have outwardly projecting drive lugs on its outer circumference, which in the baking tong chain engage in the intermediate spaces of the baking tong chain disposed between the baking tongs.
In the baking oven according to the invention, the baked products formed in the closed baking tongs are removed from the circulating opened baking tongs at the dispensing station of the baking oven. In the opened baking tongs the baked products lie on the baking mould lower parts of the opened baking moulds located in the tong lower parts of the baking tongs.
Removal is accomplished by the product removal device or by the horizontally disposed rotating rotary unit of the product removal device. The horizontally disposed rotary unit rotates about its horizontally disposed central axis and removes the baked products from the opened baking tongs without deforming the baked products.
The rotating rotary unit grips the product pieces lying on the baking mould lower parts with its removal elements. The removal elements of the rotary unit are configured as suction elements which are connected to a vacuum source. The vacuum produced by a vacuum source acts via the removal elements of the rotary unit configured as suction elements directly on the product pieces lying on the baking mould lower parts. The product pieces are gripped individually. Each product piece is gripped by at least one suction element and held firmly on the rotary unit. The product piece is removed from the opened baking tong by the rotating movement of the rotary unit and conveyed to the upper transport device by the rotating movement of the rotary unit. The product piece is gripped by means of the vacuum applied to the suction element. When transferring the product piece to the upper transport device, the vacuum acting on the product piece via the suction element is interrupted.
According to the invention, the horizontally disposed rotary unit can be arranged in a height-adjustable manner in the front oven part. This configuration allows the position of the horizontal axis of rotation of the rotary unit to be varied inside the oven frame. As a result, on the underside of the rotary unit the distance between the removal elements disposed on the circumference of the rotating rotary unit and the horizontally disposed tong lower parts of the opened baking tongs can be adjusted or varied.
The height-adjustable arrangement of the rotary unit allows the height position of the rotary unit to be adjusted on the upper side of the baked products which, in the opened baking tongs, lie on the baking mould lower parts disposed in the tong lower parts of the baking tongs.
According to the invention, the horizontally disposed rotary unit can have outwardly projecting drive lugs on its outer circumference which, in the circulating baking tong chain, engage in the intermediate spaces of the baking tong chain located between the baking tongs. This configuration provides a direct drive of the horizontally disposed rotary unit through the baking tong chain circulating in the baking oven which is driven and set in motion by the main drive of the baking oven.
According to a further feature of the invention, it can be provided that the rotary unit has at least two product carrying arms, which are disposed at a distance from one another along the circumference of the rotary unit and that each product carrying arm carries at least one removal element configured as a suction element.
The rotary unit with its product carrying arms is assigned to the baked product pieces located in the tong lower parts of the opened baking tongs which pass successively through the dispensing station of the baking oven. Each product carrying arm is assigned to a product piece. The product carrying arm grips the product piece with its removal element configured as a suction element. The product piece is removed from the opened baking tong by the rotating movement of the rotary unit and conveyed to the upper transport device.
The rotary unit can have product carrying arms arranged consecutively in the direction of rotation, which are assigned to the product pieces arranged consecutively in the tong lower part of an opened baking tong.
According to a further feature of the invention, it can be provided that the product carrying arm has at least one rod which carries at least two removal elements configured as suction elements, which are disposed along the rod at a distance from one another. In this configuration, each product piece is gripped by two or more removal elements of a product carrying arm configured as a suction element and held firmly by vacuum on the rotary unit. The product piece abuts against the product carrying arm and is removed from the opened baking tong by the rotating movement of the rotary unit.
According to a further feature of the invention, it can be provided that the product carrying arm has at least one longitudinal rod disposed parallel to the axis of rotation of the rotary unit, which carries at least one removal element configured as a suction element. In this configuration, the product carrying arms disposed along the circumference of the rotary unit at a distance from one another are aligned parallel to the axis of rotation of the rotary unit.
According to a further feature of the invention, the longitudinal rod of the product carrying arm parallel to the axis of rotation of the rotary unit can carry at least two removal elements configured as suction elements, which are disposed along the longitudinal rod at a distance from one another.
This configuration of the rotary unit allows a single broad product piece or two adjacently disposed product pieces to be removed with a single product carrying arm from a tong lower part of an opened baking tong.
According to a further feature of the invention, it can be provided that the product carrying arm has at least two longitudinal rods disposed parallel to the axis of rotation of the rotary unit, which are disposed in a reference plane parallel to the axis of rotation of the rotary unit, and that the longitudinal rods carry removal elements configured as suction elements, which are disposed perpendicular to the reference plane.
This configuration of the rotary unit is advantageous for the manipulation of plate-shaped product pieces which are gripped by the two longitudinal rods of the product carrying arm in each case close to the front or rear edge of the product piece. The product carrying arm can also have three or more longitudinal rods each carrying a plurality of removal elements configured as suction elements, which are arranged along the respective longitudinal rod at a distance from one another and are each arranged perpendicular to the reference plane formed by the longitudinal rods.
According to a further feature of the invention, it can be provided that the product carrying arm has a longitudinal rod arranged parallel to the axis of rotation of the rotary unit, which carries at least one transverse rod disposed transversely to the longitudinal rod, which is disposed in a reference plane parallel to the axis of rotation of the rotary unit, and that the transverse rod carries two or more removal elements configured as suction elements, which are disposed along the transverse rod at a distance from one another and are each arranged perpendicular to the reference plane.
This configuration is advantageous when manipulating broad product pieces. These are each gripped at two or more places by the product carrying arm and the removal elements configured as suction elements hold them firmly on the transverse rod of the product carrying arm.
According to a further feature of the invention, in a product carrying arm of the rotary unit, it can be provided that the longitudinal rod carries two or more transverse rods disposed at a distance from one another, which are disposed in a reference plane parallel to the axis of rotation of the rotary unit, and that each transverse rod carries at least two removal elements configured as suction elements, which are disposed at a distance from one another along the transverse rod and are each disposed perpendicular to the reference plane.
This configuration is advantageous for the manipulation of large plate-shaped product pieces. The product carrying arm grips each product piece at several places simultaneously. The removal elements exposed to vacuum, which are configured as suction elements, hold the product piece firmly on the transverse rods of the product carrying arm. The product piece held firmly on the product carrying arm is removed from the opened baking tongs by the rotating movement of the rotary unit.
According to a further feature of the invention, it can be provided that in a product carrying arm of the rotary unit, the product carrying arm has at least two longitudinal rods disposed parallel to the axis of rotation of the rotary unit, which are disposed in a reference plane parallel to the axis of rotation of the rotary unit and that the product carrying arm has at least two transverse rods disposed transversely to the longitudinal rods which each carry at least two removal elements configured as suction elements, which are disposed at a distance from one another along the transverse rod and are each disposed perpendicular to the reference plane.
This configuration is advantageous for the manipulation of large-area plate-shaped product pieces. For the manipulation of very large, plate-shaped product pieces, three, four, five or even more transverse rods arranged at a distance from one another can be attached to the longitudinal rods of the product carrying arm, which are each arranged parallel to the reference plane. Each transverse rod can carry three, four, five or even more removal elements configured as suction elements arranged at a distance from one another, which are each aligned perpendicular to the reference plane parallel to the transverse rods. The product piece gripped by this product carrying arm abuts against the transverse rods of the product carrying arm. The vacuum acting on the product piece via the removal elements attached to the transverse rods, which are configured as suction elements hold the product piece firmly on the product carrying arm. The product piece is removed from the opened baking tongs by the rotating movement of the rotary unit.
According to a further feature of the invention, it can be provided that the product-carrying arms are each configured as hollow profiles and form a part of the suction lines which lead from the removal elements configured as suction elements, attached to the product carrying arms, to a vacuum source. In this configuration of the rotary unit, the suction lines leading from the removal elements configured as suction elements to the vacuum source run inside the hollow rods of the product carrying arms.
According to a further feature of the invention, it can be provided that the removal elements disposed on the circumference of the rotary unit are configured as suction cups preferably each provided with an elastic bellows, which are attached to the product carrying arms and are connected via suction lines to a vacuum source.
According to a further feature of the invention, it can be provided that the removal elements disposed on the circumference of the rotary unit are configured as suction sleeves which can be pushed together elastically into themselves, which are attached to the product carrying arms and are connected via suction lines to a vacuum source.
According to a further feature of the invention, it can be provided that the horizontally disposed rotary unit has at least one vertically disposed rotary star which carries removal elements configured as suction elements, disposed on the circumference of the rotary unit, and that the horizontally disposed rotary unit possesses possibly two or more rotary stars disposed adjacent to one another at a distance, which carry removal elements configured as suction elements, disposed on the circumference of the rotary unit.
In this configuration of the rotary unit, the product pieces are removed from the opened baking tongs by the vertically disposed rotary star of the rotating rotary unit. The removal elements configured as suction elements, attached to the rotary star are each exposed to vacuum. The product pieces are gripped by the removal elements by means of vacuum and held firmly by means of vacuum on the rotary star. The product pieces are removed from the opened baking tongs by the rotating movement of the rotary star and conveyed to the upper transport device located downstream of the rotary unit.
According to the invention, the horizontally disposed rotary unit can have two or more rotary stars arranged adjacent to one another which carry removal elements configured as suction elements, disposed on the circumference of the rotary unit.
In this configuration, the removal elements of the rotary unit configured as suction elements are disposed on the outer side of the rotary stars. The removal elements are disposed consecutively on the outer side of the rotary stars in longitudinal rows extending along the circumference of the rotary unit. At the same time, the removal elements are disposed in transverse rows parallel to the axis of rotation of the rotary unit. Individual large-area product pieces or adjacently disposed smaller product pieces can be removed from the opened baking tongs with the adjacently disposed rotary stars.
According to a further feature of the invention, it can be provided that the vertically disposed rotary star has an outer circumference configured as a polygon, in which the removal elements configured as suction elements are disposed on the straight segments.
According to a further feature of the invention, it can be provided that in each case at least two removal elements configured as suction elements are disposed at a distance from one another on the straight segments of the outer circumference.
According to a further feature of the invention, it can be provided that the rotary star is configured as a hollow body and forms a part of the suction line which leads from the removal elements configured as suction elements to a vacuum source.
According to a further feature of the invention, it can be provided that the removal elements of the rotary unit configured as suction elements are configured as suction cups preferably each provided with an elastic bellows, which are attached to the outer circumference of a rotary star and connected via suction lines to a vacuum source.
According to a further feature of the invention, it can be provided that the removal elements of the rotary unit configured as suction elements are configured as suction sleeves which can be pushed elastically into themselves, which are attached to the outer circumference of a rotary star and connected via suction lines to a vacuum source.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
The invention is explained in detail hereinafter with reference to exemplary embodiments by means of the drawings. In the drawings:
FIG. 1 shows schematically a first baking oven from the side,
FIG. 2 shows schematically a second baking oven from the side,
FIG. 3 shows schematically a third baking oven from the side,
FIG. 4 a to 4 c show a first rotary unit
FIG. 5 a to 5 c show a second rotary unit
FIG. 6 a to 6 g show a third rotary unit
FIGS. 7 a to 4 d show a product carrying arm
FIGS. 8 a to 8 d show another rotary unit
FIGS. 9 a to 9 d show a first removal element and
FIGS. 10 a to 10 d show a second removal element.
FIG. 11 shows a plan view of a section of the baking tong chain and
FIG. 12 shows a view of a baking tong viewed in the direction of travel of the baking tongs.
FIG. 13 shows the side view according to arrow XIII in FIG. 11 and FIG. 14 shows a detail.
DESCRIPTION OF THE INVENTION
FIG. 1 shows schematically a first baking oven 1 from the side. The baking oven 1 has a front oven part 1 a , a rear oven part 1 b , an oven frame 1 d provided with an external thermal insulation 1 c , furthermore a baking chamber 2 located inside the thermal insulation and an endless baking tong chain 3 circulating continuously in the baking oven 1 and moving through the baking chamber 2 . The endless baking tong chain 3 is located in the baking oven 1 along an orbit which is closed in itself, which extends in two superposed transport levels 4 and 5 through both oven parts 1 a and 1 b . The baking tong chain 3 is driven by a drive wheel 6 located close to the front end of the baking oven 1 and is deflected by the drive wheel 6 from the lower transport level 5 upwards into the upper transport level 4 . The circulating baking tong chain 3 moves in the upper transport level 4 away from the drive wheel 6 in the baking oven towards the back. Close to the rear end of the baking oven 1 the baking tong chain 3 passes a rear baking tong chain deflecting device 7 . At the deflecting device 7 the baking tong chain 3 is deflected from the upper transport level 4 downwards into the lower transport level 5 .
The baking tong chain 3 contains openable and closable baking tongs 8 . The baking tongs 8 are arranged one after the other in the baking tong chain 3 . Located in the baking tongs 8 are baking moulds consisting of baking mould upper parts and baking mould lower parts, which are opened by opening the baking tongs 8 and closed by closing the baking tongs 8 . The baking tongs 8 each consist of a tong lower part 8 a and a tong upper part 8 b connected pivotably to this. A control roller 8 c is attached to the tong upper part 8 b by means of which the baking tong 8 is opened and closed. Flat baking plates are disposed in the tong lower parts 8 a , which contain the baking mould lower parts of the baking moulds. Flat baking plates are disposed in the tong upper parts 8 b which contain the baking mould upper parts of the baking moulds.
On their front sides, the baking tongs 8 are provided with locking devices, not shown in the drawing, which are actuated when the baking tongs are closed in order to keep the baking moulds disposed in the closed baking tongs closed during the entire baking process
The baking oven 1 is provided with an electrical induction heater. This includes an alternating current generator 9 located next to the front oven part 1 a and elongated inductors 10 , 11 located in the baking chamber 2 . The alternating current generator 9 is connected to the inductors 10 , 11 via power leads 12 , 13 and supplies these with current. The elongated inductors 10 , 11 are located in the baking chamber 2 above and below the orbit of the baking tong chain 3 . The flat baking plates contained in the baking tongs 8 are configured as susceptor plates which are heated inductively in a contact-free manner by the magnetic fields generated by the inductors 10 , 11 .
A lower actuating device 18 for unlocking the locking devices of the baking tongs 8 is located in the front oven part 1 a on the lower transport level 5 .
In the front oven part 1 a , a linkage 14 for engagement with the control rollers 8 c of the baking tongs 8 is provided along the upper transport level 4 . The linkage 14 provides three consecutive sections in the running direction of the baking tongs 8 . The linkage 14 provides a gradually ascending linkage section 14 a which forms a device for opening the baking tongs 8 . The linkage section 14 a is adjoined by an upper horizontal linkage section 14 b . This holds the opened baking tongs 8 in the opened state whilst they pass the dispensing station 15 of the baking oven 1 and the adjoining loading station 16 . The linkage section 14 b is adjoined by a gradually descending linkage section 14 c which forms a device for closing the baking tongs 8 . Located at the end of the linkage 14 is an upper actuating device 19 for locking the locking devices of the baking tongs 8 .
The product removal device 17 which projects into the opened baking tongs 8 , shown only schematically in FIG. 1 , is provided in the dispensing station 15 . The product removal device 17 removes the baked products from the tong lower parts 8 a of the opened baking tongs 8 and transfers them to an upper transport device, not shown in FIG. 1 , by which the baked products are conveyed out of the baking oven 1 .
During operation of the baking oven 1 a baking preparation is introduced in individual dough portions into the circulating opened baking tongs 8 in the loading station 16 . After leaving the loading station 16 , the baking tongs 8 with the control rollers 8 c move along the gradually descending linkage section 14 c . At the same time the tong upper parts 8 b are folded downwards to the tong lower parts 8 a and the baking tongs 8 are closed. During closure of the baking tongs 8 the baking moulds contained in the baking tongs 8 are closed and the dough portions enclosed in the closed baking moulds. After closure of the baking tongs 8 the locking devices of the baking tongs 8 are actuated by lower actuating device 19 and the closed baking tongs 8 are locked. The closed and locked baking tongs 8 are conveyed by the circulating baking tong chain 3 through the baking chamber 2 . In the baking chamber 2 the baking moulds are heated inductively in a contact-free manner and the dough portions enclosed in the baking moulds are baked. The closed and locked baking tongs 8 are conveyed with the baked dough portions contained therein by the circulation baking tong chain 3 in the lower transport level 5 in the baking oven 1 forwards to the drive wheel 6 . When passing the lower actuating device 18 , the locking devices of the baking tongs 8 are actuated by the lower actuating device 18 and the closed baking tongs 8 are unlocked. The closed and unlocked baking tongs 8 are conveyed along the drive wheel 6 into the upper transport level 4 . In the upper transport level 4 the baking tongs 8 with their control rollers 8 c move along the gradually ascending linkage section 14 a . At the same time, the baking tongs 8 are opened and the tong upper part 8 b folded upwards. The baked dough portions or the baked products remain in the tong lower part 8 a of the opened baking tongs 8 . In the dispensing station 15 the baked products are removed by the product removal device 17 from the tong lower parts 8 a of the opened baking tongs 8 .
FIG. 2 shows schematically a second baking oven 20 from the side. The baking oven 20 has a front oven part 20 a , a rear oven part 20 b , an oven frame provided with external thermal insulation 20 c , a baking chamber 21 disposed inside the thermal insulation 20 c and an endless baking tong chain 22 circulating continuously in the baking oven 20 and moving through the baking chamber 21 . The baking tong chain 22 is disposed in the baking oven 20 along an orbit which is closed in itself which extends in two superposed transport levels 23 and 24 through both oven parts 20 a and 20 b . The baking tong chain 22 is driven by a drive wheel, not shown in FIG. 2 , located near the front end 25 of the baking oven 20 and is deflected by the drive wheel from the lower transport level 24 upwards into the upper transport level 23 . The circulating baking tong chain 22 moves in the upper transport level 23 from the front end 25 of the baking oven 20 towards the rear to the rear end 26 of the baking oven 20 . The baking tong chain 22 is deflected near the rear end 26 of the baking oven 20 by a rear baking tong chain deflecting device 27 from the upper transport level 23 downwards into the lower transport level 24 .
The baking tong chain 22 contains openable and closable baking tongs 38 in which baking moulds consisting of baking mould upper parts and baking mould lower parts are disposed, which are opened by opening the baking tongs 28 and closed by closing the baking tongs 28 . The baking tongs 28 each have a tong lower part 28 a and a tong upper part 28 b connected pivotably thereto. Attached to the tong upper part 28 b is a control roller, not shown in FIG. 2 , by which means the baking tongs 28 are opened and closed. Flat baking plates are disposed in the tong lower parts 28 a which contain the baking mould lower parts of the baking moulds. Flat baking plates are disposed in the tong upper parts 28 b which contain the baking mould upper parts of the baking moulds.
The baking chamber 21 is disposed in the rear oven part 20 b . The baking chamber 21 is provided with an electrical induction heater which includes elongated inductors 29 , 30 each disposed above and below the orbit of the baking tongs 28 in the two transport levels 23 and 24 .
In the front oven part 20 a of the baking oven 20 , a device 31 for opening the baking tongs 28 , a dispensing station 32 , a loading station 33 and a device 34 for closing the baking tongs 28 are disposed consecutively in the running direction of the baking tongs 28 along the upper transport level 23 . Located in the dispensing station 32 is a product removal device 35 with a horizontally disposed rotary unit 36 . The rotary unit 36 rotates about its horizontally disposed central axis and removes the baked products from the opened baking tongs 28 a and conveys them to an upper transport device 37 which conveys the baked products out from the baking oven 20 .
FIG. 3 shows schematically a third baking oven 40 from the side. The baking oven 40 has a front oven part 40 a , a rear oven part 40 b , an oven frame provided with external thermal insulation 40 c , a baking chamber 41 disposed inside the thermal insulation 40 c in the rear oven part 40 b and an endless baking tong chain 42 circulating continuously in the baking oven 40 and moving through the baking chamber 41 . The baking oven 40 corresponds in its design structure to the baking oven 20 of FIG. 2 and only differs from this by the baking chamber heating which is configured as gas heating 43 in the baking oven 40 . The gas heating 43 includes elongated gas burners 44 and 45 which are disposed in the baking chamber 41 below the orbit of the baking tong chain 42 .
FIGS. 4 a to 4 c show a first embodiment of the horizontally disposed rotary unit of the product removal device. FIG. 4 a shows the rotary unit 50 in an oblique view from the rear side. FIG. 4 b shows the rotary unit 50 in its working position. FIG. 4 c shows the rear side of the rotary unit 50 .
The rotary unit 50 is mounted rotatably on its rear side in a retaining device 51 fastened to the oven frame. The retaining device 51 is fastened to the oven frame in a height-adjustable manner. The rotary unit 50 has a horizontally disposed hollow shaft 52 . The rear drive star 53 of the rotary unit 50 sits on the hollow shaft 52 , which has arms 54 arranged in a star shape, which carry drive rollers 55 mounted rotatably at their end sections, which engage in the intermediate spaces between the successive baking tongs of the circulating baking tong chain.
A vertically disposed rotary star 56 is fastened to the front end of the hollow shaft 52 . The rotary star 56 is configured as a hollow body. The interior of the hollow star 56 is connected to the cavity of the hollow shaft 52 . The outer circumference of the rotary star 56 is configured as a polygon. Respectively two adjacently disposed longitudinal rods 58 parallel to the hollow shaft 52 are fastened to the straight segments 57 of the polygon. The longitudinal rods 58 are configured as hollow profiles and each carry three removal elements 59 disposed at a distance from one another. Each removal element 59 is configured as a suction element and is connected via a suction line to a vacuum source. The suction line runs inside the rotary unit 50 from the removal element 59 through the hollow longitudinal rod 58 and the hollow rotary star 56 to the hollow shaft 52 and through the hollow shaft 52 out from the rotary unit 50 . The removal elements 59 fastened to the longitudinal rods 58 are configured as suction cups provided with an elastic bellows.
The two longitudinal rods 58 fastened to the straight segment 57 of the outer circumference in the rotary star 56 are disposed in a reference plane parallel to the axis of rotation of the rotary unit 50 . The suction cups attached to the two longitudinal rods 58 , which are provided with an elastic bellows are disposed perpendicular to the reference plane. The two longitudinal rods 58 together form a product carrying arm of the rotary unit 50 . The rotary unit 50 has nine such product carrying arms which are disposed at a distance from one another along the circumference of the rotary unit 50 .
FIGS. 5 a to 5 c show a second embodiment of the horizontally disposed rotary unit of the product removal device. FIG. 5 a shows the rotary unit 60 in an oblique view from the rear side. FIG. 5 b shows the rotary unit 60 in its working position. FIG. 5 c shows the rear side of the rotary unit 60 .
The rotary unit 60 is rotatably mounted at its rear side in a retaining device 61 fastened to the oven frame. The retaining device 61 is fastened in a height-adjustable manner on the oven frame. The rotary unit 60 has a horizontally disposed hollow shaft 62 . The rear drive star 63 of the rotary unit 60 sits on the hollow shaft 62 , which has arms 64 arranged in a star shape, which carry drive rollers 65 mounted rotatably at their end sections, which engage in the intermediate spaces between the successive baking tongs of the circulating baking tong chain.
The rotary unit 60 has two vertically disposed rotary stars 66 configured as hollow bodies, the interior of each is connected to the cavity of the hollow shaft 62 . The outer circumference of the rotary stars 66 is configured as a polygon. Respectively two removal elements 68 disposed at a distance from one another are attached to each straight segment 67 of the polygon, which are configured as suction cups provided with an elastic bellows and which are connected via the hollow rotary stars 66 to a vacuum source.
FIGS. 6 a to 6 g show a third embodiment of the horizontally disposed rotary unit of the product removal device. FIG. 6 a shows the rotary unit 70 projecting into the opened baking tongs of a baking oven in an oblique view from the rear side. FIG. 6 b shows the rotary unit 70 in its working position without baking tongs. FIG. 6 c shows the rear side of the rotary unit 70 . FIG. 6 d shows the rotary unit 70 projecting into the opened baking tongs of a baking oven in a vertical section perpendicular to the axis of rotation of the rotary unit 70 . FIG. 6 e shows the rotary unit 70 projecting into the opened baking tongs of a baking oven in a vertical section through the axis of rotation of the rotary framework 70 . FIG. 6 f shows, in a vertical section, a product carrying arm of the rotary unit 70 in an opened baking tong above the tong lower part of the baking tong. FIG. 6 g shows a side view of FIG. 6 f.
The rotary unit 70 shown in FIG. 6 a projects into three successive opened baking tongs 71 of a baking oven. FIG. 6 a only shows the opened baking tongs 71 schematically. The rotary unit 70 is disposed in the opened baking tongs 71 above the tong lower parts 71 a and extends with its front side close to the folded-upwards tong upper parts 71 b . The rotary unit 70 is rotatably mounted on its rear side in a retaining device 72 fastened to the oven frame. The retaining device 72 is fastened to the oven frame in a height-adjustable manner. The rotary unit 70 has a short horizontal hollow shaft 73 . A drive star 74 disposed on the rear side of the rotary unit 70 sits on the hollow shaft 73 , which has arms 75 arranged in a star shape which carry rotatably mounted drive rollers 76 at its end sections, which engage in the intermediate spaces between the consecutive baking tongs 71 of the circulating baking tong chain.
The rotary unit 70 includes product carrying arms 77 adjacent to its outer circumference which are disposed at a distance from one another in the circumferential direction of the rotary unit 70 and which carry removal elements 78 of the rotary unit 70 each configured as a suction element, disposed on the outer circumference of the rotary unit 70 .
Each product carrying arm 77 has a longitudinal rod 79 parallel to the axis of rotation of the rotary unit 70 . Located on the radially outward-pointing side of the longitudinal rod 79 in the rotary unit 70 are five transverse rods 80 which are connected to the longitudinal rod 79 by a radially disposed connecting rod 81 . Each transverse rod 80 carries three removal elements 78 disposed at a distance from one another on its radially outwardly pointing side in the rotary unit 70 . Each removal element 78 is configured as a suction cup provided with an elastic bellows, which is fastened to the transverse rod 80 . The longitudinal rod 79 , the five transverse rods 80 and the five connecting rods 81 are configured as hollow profiles. The longitudinal rod 79 is connected by a radial connecting tube 83 disposed close to the drive star 74 to a vacuum distributor 83 located at the end of the hollow shaft 73 . The product carrying arm 77 carries fifteen removal elements 78 configured as suction cups which are disposed in a plane parallel to the axis of rotation of the rotary unit 70 . The fifteen suction cups are connected the in the product carrying arm 77 . The suction lines run through the hollow transverse rods 80 and the hollow connecting rods 81 to the hollow longitudinal rod 79 and through the radial connecting tube 82 to the vacuum distributor 83 .
The rotary unit 70 has nine product carrying arms 77 disposed at a distance from one another in the circumferential direction of the rotary unit 70 . The rotary unit 70 rotates about its horizontal axis of rotation. In the region of the lower apex of the rotary unit 70 , one product carrying arm 77 after the other is placed with its suction cups each provided with an elastic bellows through the rotary movement of the rotary unit 70 onto the baked product pieces which lie on the tong lower parts 71 a of the opened baking tongs 71 which pass through the lower apex of the rotary unit 70 .
FIGS. 7 a to 7 d each show a product carrying arm 77 of the rotary unit 70 . FIG. 7 a shows the product carrying arm 77 from the side, FIG. 7 b shows said product carrying arm in front view, FIG. 7 c shows it from above and FIG. 7 d shows it in oblique view.
FIGS. 8 a to 8 d show another embodiment of the rotary unit of the product removal device in engagement with a circulating baking tong chain of the baking oven. FIG. 8 a shows three consecutive opened baking tongs of a baking tong chain with the rotary unit projecting into the opened baking tongs from the rear side. FIG. 8 b shows an oblique view of FIG. 8 a . FIG. 8 c shows the engagement of the rotary unit in the baking tong chain. FIG. 8 d shows an oblique view of FIG. 8 c.
The rotary unit 85 shown in FIGS. 8 a and 8 b projects into three consecutive opened baking tongs 86 of an endless baking tong chain of a baking oven. In FIGS. 8 a and 8 b the opened baking tongs 86 are only shown schematically. The rotary unit 85 is disposed in the opened baking tongs 86 above the tong lower parts 86 a and extends with its front side close to the folded-upwards tong upper parts 86 b . The rotary unit 85 is rotatably mounted on its rear side in a retaining device 87 fastened to the oven frame. The retaining device 87 is fastened in a height-adjustable manner on the oven frame. The rotary unit 85 has a drive star 88 disposed on the rear side of the rotary frame 85 which has arms 89 arranged in a star shape, which carry rotatably mounted drive rollers 90 on its end sections which engage in the intermediate spaces located in the baking tong chain between the tong lower parts 86 a of the baking tongs 86 . In the baking tongs 86 the tong lower parts 86 a are provided at the front and rear edges with strips 91 , 92 projecting over the tong lower parts 86 a against which the drive rollers 90 of the rotary unit 85 abut.
FIGS. 9 a to 9 d show a removal element of the rotary unit which is configured as a suction sleeve which can be pushed elastically into itself. FIG. 9 a shows the suction sleeve from the side, FIG. 9 b shows a vertical section through the suction sleeve, FIG. 9 c shows the suction sleeve in oblique view and FIG. 9 d shows a plan view of the suction sleeve. The suction sleeve 94 has two coaxial tube pieces 94 a and 94 b which can be inserted telescopically into one another and a compression spring 95 which pushes the two tube pieces 94 a and 94 b apart in the interior of the suction sleeve 94 . The inner tube piece 94 b carries a suction plate 96 disposed on the free end of the suction sleeve 94 .
FIGS. 10 a to 10 b show a removal element of the rotary unit which is configured as a suction cup 97 provided with an elastic bellows 96 . FIG. 10 a shows the suction cup from the side, FIG. 10 b shows a vertical section through the suction cup, FIG. 10 c shows the suction cup in oblique view and FIG. 10 d shows a plan view of the suction cup.
FIGS. 11 to 14 show an advantageous design for the lateral guidance of the baking tong carriage. It was known from the prior art to guide the running wheels of the baking tong carriage by means of wheel flanges on the running rails. This resulted in more rapid wear of the running bearings of the running wheels and the wheel flanges. The design shown in FIGS. 11 to 14 avoids the disadvantages described and extends the stability.
FIG. 11 shows the plan view of a section of an arrangement of two consecutively disposed baking tongs 8 along a baking tong chain 3 . For better and low-wear guidance of the baking tong carriage, laterally disposed running bearings 98 are provided which are mounted on vertical axles 99 and which laterally guide the baking tongs over guide lugs 100 . The axles 99 sit on receiving panels 101 and the exact positioning of the running bearing 98 on the angle carrier 102 can be adjusted by an adjusting screw or an adjusting plate. The guidance via the guide lugs 100 can be adjusted with an adjustable play as indicated in FIG. 14 .
The guide lugs 100 can be configured to be short or longer in their longitudinal extension and specifically adapted to the travel speed of the wafer oven. The number of laterally disposed running bearings 98 can also be increased to ensure a more exact lateral guidance. For example, in the region before the deflection of the tong carriage, the number of lateral guides and therefore the number of running bearings 98 can be increased in order to ensure a problem-free deflection.
Other than in the previously known running rollers with wheel flange, the ball bearings of the running rollers 104 running on the rails 105 are only radially loaded, with the result that the lifetime increases. The running bearings can easily be exchanged in the case of a malfunction.
The other machine parts shown in FIGS. 11 to 14 are self-explanatory in view of the above explanations. As can be seen from FIG. 12 , each baking tong comprises an upper baking plate 8 b and a lower baking plate 8 a . Both baking plates are pivotably connected via the joint 103 . The opening and reclosing of the baking tong 8 is accomplished via the running roller 8 c of the upper baking plate, as is prior art.
It can also be seen in FIG. 11 that the baking tongs 8 suspended on one another to form the baking tong chain are connected to one another by means of connecting lugs 104 . The length of the guide lugs 100 is shown completely in its short form. The dashed lines indicate that the guide lugs can also be configured to be sufficiently long that they almost touch the guide lugs of the neighbouring baking tongs. | An oven contains a continuous chain of baking tongs that can be opened and closed, and locked in the closed state. The chain circulates in the oven and moves through the baking chamber in two transport planes, one above the other. A device for opening the baking tongs, a delivery station, a loading station, a device for closing the baking tongs, and a device for locking the tongs are successively arranged in the running direction of the baking tongs, in the front part of the oven, along the upper transport plane. A product removal device contains a flatly arranged rotating support and is arranged in the delivery station. The rotating support carries removal elements embodied as suction elements along the outer periphery thereof, which it uses to remove the baked products from the open baking tongs. | 0 |
Background of the Invention
The present invention relates to acyl derivatives of glucosamines with amino acids or synthetic peptides, endowed with antitumor chemotherapeutic activity against transplanted tumors in animals, to pharmaceutical compositions containing said derivatives, to processes for their preparation, and to processes for their chemotherapeutic administration.
Antitumor chemotherapy has been and still is an object of intensive research. Certain positive results have undoubtedly been achieved, especially by means of polychemotherapy realized by associating different active substances according to carefully developed protocols. However, the ideal therapy has not yet been found. The need to find new active substances has been particularly emphasized. All the foregoing justifies continuous research directed towards preparing new chemotherapeutic compounds active against tumors. There are already known peptides having antitumor activity, consisting of both normal and antimetabolic amino acids, coupled by means of a peptide bond. Such peptides have for years been in therapeutic use with favorable results both in monochemotherapy and in polychemotherapy. However, their adoption encounters obstacles of various kinds, which are connected, among other things, with the impossibility of being administered by the oral route because of inactivation of the said peptides in the gastrointestinal tract.
It has now surprisingly been found that the said difficulty is overcome by a series of new compounds possessing antitumor activity against transplanted tumors in animals, characterized by the presence of a molecule of a glucosamine. The glucosamine is used as a carrier of an anti-tumor-active compound wherein the anti-tumor-active molecule is bound to the --NH 2 group of the glucosamine, said tumors being transplanted into animals. For example, the amino group of the glucosamine is acylated by the carboxyl group of an antitumor amino acid or peptide. The resulting acyl derivatives of the glucosamines of the present invention are not inactivated in the gastrointestinal tract and are useful in controlling transplanted neoplasms in animals.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide novel compounds which are effective in controlling transplanted neoplasms in animals.
It is another object of the present invention to provide novel compounds which can be administered orally without undergoing deactivation in the gastrointestinal tract.
It is a further object of the present invention to provide a process for preparing the N-acyl derivatives of glucosamines of the present invention.
It is still another object of the present invention to provide pharmaceutical compositions which are effective in controlling transplanted neoplasms in animals and which contain at least one of the novel compounds of the present invention as an active ingredient.
These and other objects of the present invention are accomplished by condensing a D-glucosamine with an amino acid or with a peptide to form via peptide linkage, a compound of the general formula (I): ##STR2## where R 1 is a hydrogen atom or an acetyl group,
R 2 is a hydrogen atom, an acetyl group, aliphatic (C 1 -C 6 ) group or a benzyl group
and R 3 is m-di(2-chloroethyl)amino-L-phenylalanine, or L-methionyl-m-di(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine, or p-fluoro-L-phenylalanyl-m-di(2-chloroethyl)amino-L-phenylalanyl-L-proline, or m-di(2-chloroethyl)amino-L-phenylalanyl-L-methionyl-p-fluoro-L-phenylalanine.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the present invention have the general formula (I): ##STR3## where: R 1 =--H; --COCH 3 (an acetyl group),
R 2 =--H; --COCH 3 ; a C 1 -C 6 alkyl group; or a benzyl group, ##STR4##
The salts of the compounds of formula I with organic or inorganic acids which are physiologically tolerated also exhibit antitumor activity and are contemplated by the present invention. The preferred inorganic acid for forming the salts of the present invention is hydrochloric acid. Acetic acid is the preferred organic acid for forming the salts of the present invention.
In the above general formula I, exemplary of the hydrocarbon groups that are represented by R 2 are the C 1 -C 6 alkyl groups (for example, the methyl, ethyl, isopropyl, n-butyl and 2-methyl-pentyl groups) and the benzyl group. However, other alkyl groups or aralkyl groups, or monovalent hydrocarbon groups which result in compounds which are chemotherapeutically active against neoplasms by the oral route are also covered by R 2 . The preferred monovalent hydrocarbon groups represented by R 2 are the C 1 to C 6 alkyl groups (--CH 3 , --C 2 H 5 , --C 3 H 7 , --C 4 H 9 , --C 5 H 11 , --C 6 H 13 ) and the benzyl group, ##STR5## The C 1 to C 6 alkyl groups are the most preferred groups for the R 2 position.
In other words, the novel compounds are constituted of a molecule of a glucosamine (actually, a mixture of the two α and β anomers the latter in general being prevalent) of the general formula II: ##STR6## where: R 1 =a hydrogen atom or an acetyl group,
R 2 =a hydrogen atom, an acetyl group, an aliphatic (C 1 -C 6 ) group or a benzyl group
which is bonded by peptide linkage (--NHCO--) to an amino acid molecule or an oligopeptide molecule of: ##STR7## The peptide bond is between the amine group of the glucosamines of formula II and the terminal carboxylic acid group of the amino acid or oligopeptide. In every case, the amino acid or one of the amino acids in the oligopeptide in m-di(2-chloroethyl)amino-L-phenylalanine. The glucosamines of Formula II are carriers of the amino acids or oligopeptides.
It is in particular noted that, to have good antitumor activity against transplanted tumors in animals, all of the amino acids (including m-di(2-chloroethyl) amino-L-phenylalanine) used for the peptide synthesis and so forming the peptide moiety, must belong to the L-configuration. Among the compounds according to the present invention, the following are preferred:
(a) 1,3,4,6-tetra-O-acetyl-D-glucosamyl-m-di(2-chloroethyl)amino-L-phenylalanine ##STR8## (b) D-ethyl-glucosamyl-m-di(2-chloroethyl)amino-L-phenylalanine hydrochloride ##STR9## (c) 1,3,4,6-tetra-O-acetyl-D-glucosamyl-p-fluoro-L-phenylalanyl-m-di(2-chloroethyl)amino-L-phenylalanyl-L-proline,acetate
(d) D-ethyl-glucosamyl-p-fluoro-L-phenylanalyl-m-di(2-chloroethyl)amino-L-phenylalanyl-L-proline, hydrochloride
(e) D-glucosamyl-p-fluoro-L-phenylalanyl-m-di(2-chloroethyl)amino-L-phenylalanyl-L-proline, acetate
(f) D-ethyl-glucosamyl-m-di(2-chloroethyl)amino-L-phenylalanyl-L-methionyl-p-fluoro-L-phenylalanine, dihydrochloride
(g) 1,3,4,6-tetra-O-acetyl-glucosamyl-L-methionyl-m-di(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine, hydrochloride
(h) D-glucosamyl-L-methionyl-m-di(2-chloroethyl)amino-p-fluoro-L-phenylalanine dihydrochloride
(i) D-methyl-glucosamyl-L-methionyl-m-di(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine hydrochloride
(j) D-ethyl-glucosamyl-L-methionyl-m-di(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine hydrochloride.
SYNTHESIS OF THE COMPOUNDS OF THE PRESENT INVENTION
The compounds of the present invention are prepared by protecting the terminal amino group of the amino acid or oligopeptide by acylation to form a Schiff base, as by reaction with carbobenzoxy chloride or formyl chloride. The thus acylated amino acid or thus acylated oligopeptide is reacted with a glucosamine of formula II in the presence of dicyclohexylcarbodiimide (DCC) whereby condensation to form the peptide linkage (--NHCO--) occurs. The terminal amino group is then deprotected by reagents which do not disturb peptide linkages. For example, deprotection may be achieved by catalytic hydrogenation with Pd/C and hydrogen gas or by hydrolysis with alcoholic hydrochloric acid. Use of the latter reagent also deacetylates the glucosamine derivative (at the R 1 and R 2 positions). See Examples 4 and 7 below.
D-glucosamine (R 1 =R 2 =hydrogen atom in formula II) can be condensed directly with the amino acid or oligopeptide; that is, without passing through 1,3,4,6-tetra-O-acetyl-D-glucosamine. In other words, D-glucosamine is dissolved in a slightly aqueous alkaline solution and is reacted with the protected amino acid (e.g., formyl-amino acid) or protected oligopeptide (e.g. formylpeptide) dissolved in dimethylformamide (DMF) in the presence of DCC.
Other N-acyl derivatives of glucosamines of formula I (i.e. where both R 1 and R 2 are not a hydrogen atom) can be obtained by deacetylation of the respective derivatives of 1,3,4,6-tetra-O-D-glucosamine by means of alcoholic hydrochloric acid. See Examples 4, 7, and 8. The 1,3,4,6-tetra-O-acetyl-D-glucosamine (R 1 =R 2 =acetyl in formula II) reagent is synthesized from D-glucosamine by reaction of the latter with a protecting agent for the amino group (e.g. p-anisaldehyde) to form a Schiff's base. See Example 1(a) . The Schiff's base is then acetylated with acetic anhydride (Example 1(b)), then hydrolized with hydrochloric acid (Example 1(c)) and treated with sodium acetate (for example) to obtain 1,3,4,6-tetra-O-acetyl-D-glucosamine. Examples 1(d) and 2(a). The resultant 1,3,4,6-tetra-O-acetyl-D-glucosamine is condensed with the acylated amino acid or oligopeptide in the presence of DCC as described above.
The peptide moiety of the N-acyl derivatives of the glucosamines of the present invention is synthesized according to methods already known. Synthesis of a dipeptide is by means of condensation via DCC between two amino acids blocked respectly at the amino group and the carboxyl group, followed by deprotection of the carboxyl group and condensation with the amino group of a third amino acid blocked at the carboxyl group by means of DCC. In this way an acylated peptide is obtained. For the purpose of selectively protecting the amino functional groups, the amino group is acylated, for example with formic acid or with carbobenzoxy chloride. The carboxyl groups are protected by means of esterification to the methyl, ethyl, hexyl or benzyl ester, which are then cleaved by cautious saponification.
The single compounds were analyzed and controlled by means of elemental analysis (chlorine-bonded, either with covalent or ionic bond--nitrogen, possibly sulphur), specific optical rotation, thin layer chromatography (silica gel G), UV spectrophotometry, IR spectrometry.
The chemotherapeutic activity was evaluated by means of two experimental models:
1. Determination of the MST (Mean Survival Time) of BDGI mice inoculated intraperitoneally with 10 6 cells of lymphoid Leukemia L 1210 deriving from regular implants in DBA2 mice. The MST was determined both on the controls and on the animals treated, and thereafter an evaluation was made of the ILS (increased Life Span) according to Cancer Chemotherpy Reports 1972, Volume 3, No. 2 (Protocols for screening chemical agents and natural products against animal tumors and other biological systems--Third Edition, National Cancer Institute, Bethesda, Md.
In this case, the compounds were tested only after oral administration (as afterwards described), starting from the 4th day after implant of the tumor and continuing on the 8th, 12th and 16th day. On the 30th day, any surviving animals were sacrificed and the surviving animals were sacrificed and the expermient discontinued and evaluated. It should at this point be specified that whereas the first experiments on Sa. 180 (see following paragraph) were performed with injection of the products parenterally, the subsequent experiments were performed with administration of the products by the oral route--which, for other peptides not containing aminosugars, had given negative results. As has been stated it was surprisingly found that the peptides containing an aminosugar in their molecule are active by the oral route; and this is considered a great advance in antitumor chemotherapy, among other reasons, because of the greater ease of administration.
2. Inhibition of the growth of Sarcoma 180 according to the procedure established by CCNSC (Cancer Chemotherapy National Service Centre, U.S. Dept. of Health, Education and Welfare, Cancer Chemotherapy Reports, No. 25, Decemeber 1962).
This test was performed on Swiss albino carrying Sarcoma 180, transplanted every week; the sterility of the inoculum was in every case strictly controlled. Aqueous solutions or suspensions, stabilized with carboxymethyl cellulose, were administered intraperitoneally and/or orally on the 1st, 3rd, 5th, 7th day after implant of the tumor; the animals were sacrificed on the 9th day and determination made of tumor weight, percent variation of tumor weight as compared with the control tumors, WBC, spleen weight and carcass weight.
Chemotherapeutic research showed that all the compounds are active. In case of Sarcoma 180, the activity is thus seen to range from a minimum of 50% inhibition for certain of the compounds up to 94-96% for others. In this latter case, therefore, there is effective elimination of the tumor. Such a result demonstrates that the present invention achieves a substantial advance in experimental chemotherapy. Similar results were obtained with Leukemia L 1210, in which, taking Increased Life Span as a parameter of evaluation of the activity of a product, the values range from minima of 137 up to maxima of 263 and beyond--given that there are often animals surviving on the 30th day.
The antitumor chemotherapeutic activity of the compounds of the present invention are reported in an article by the inventor entitled "N-Acyl Derivatives of Glucosamine with Oligo-Peptides," Current Chemotherapy, Amer. Soc. of Microbiol., p. 1183 (April 1978). The article is herein incorporated by reference in its entirety. Tables 1 and 2, as reported in the article, show the antineoplasmic activity of the compounds of the present invention:
Table 1__________________________________________________________________________Effect of N-acyl peptides of glucosamine, administered orally,on survival in tumor-bearing mice Doses in mg of MST* ILS** Survivors at Compound m-SL/kg (days) (days) 60th day***__________________________________________________________________________Leukemia L1210 Controls 10GlcN-p-FPhe-m-SL--Pro-acetate 5.7 14 140 0/8 8 14 140 0/8GlcN--Met-m-SL-p-FPbe 5.7 15 150 0/8 8 17.5 175 0/8Ec--GlcN--Met-m-SL-p-FPhe 5.7 16 160 0/8 8 20.5 205 0/8Me--GlcN--Met-m-SL-p-FPhe 5.7 17 170 0/8 8 18 180 0/8Sarcoma 180 solid Controls 18GlcN-p-FPhe-m-SL--Pro-acetate 5.7 18.5 103 0/8 8 14.5 80.5 0/8GlcN--Met-m-SL-p-FPhe 5.7 28.5 158 1/8 8 33.5 186 0/8Et--GlcN--Met-m-SL-p-FPhe 5.7 41.5 230.5 1/8 8 30 167 1/8Me--GlcN--Met-m-SL-p-FPhe 5.7 34.5 192 2/8 8 33 183 1/8__________________________________________________________________________ *Mean survival time **Increase in life span. ***Survivors were without tumor, i.e., cured animals.
Table 2__________________________________________________________________________Effect of N-acyl peptides of glucosamine, administered orally, on sarcoma180 solid % Variation of tumor wt. Deaths Compound 4.1* 5.7 5.7 i.p. 8 Orally i.p.__________________________________________________________________________4Ac--GlcN-m-SL** -6.92 04Ac--GlcN-p-FPhe-m-SL--Pro -17.41 -41.83 -58.31 0GlcN-p-FPhe-m-SL--Pro-acetate -22.66 -58.89 -70.36 -67.21 0 04Ac--GlcN--Met-m-SL-p-FPhe -34.23 -57.18 -72.40 0GlcN--Met-m-Sl-p-FPhe -41.99 -69.04 -83.19 -87.18 0 0Et--GlcN--Met-m-SL-p-FPhe -54.18 -80.24 -82.98 -91.17 0 8/12Et--GlcN-m-SL--Met-p-FPhe*** -27.74 -33.82 0Me--GlcN--Met-m-SL-p-FPhe -68.22 -84.2 -88.65 -90.12 0 2/12__________________________________________________________________________ *Dose in milligrams of mSL contained in the compounds. **At 16 mg/kg in m SL = -46.92. ***At 16 mg/kg in mSL = -55.42.
In Tables 1 and 2 above, all amino acids in the N-acyl derivatives of the present invention are in the L-configuration. Additionally, M-SL is used as an abbreviation for m-di(2-chloroethyl) amino-L-phenylalanyl. GlcN is used as an abbreviation for glucosamyl.
Some examples illustrating the synthesis of some of the claimed compounds are listed hereunder. All temperatures are in °C. unless otherwise indicateed.
EXAMPLE 1
1,3,4,6-tetra-O-acetyl-D-glucosamyl-m-di-(2-chloroethyl)amino-L-phenylalanine
(a) N-(p-methoxy-benzylidene)-D-glucosamine(anisal-glucosamine) Intermediate I
To a solution of 215 g (1 M) of D (+) glucosamine.HCl in 1 liter of NaOH, 1N, 121.2 ml of p-anisaldehyde are added. The solid product precipitated is washed first with cold water and then with a mixture of ethanol and diethylether. It is then dried to yield 250 g (80% theoretical) of a white product: m.p.=165° C. (dec.) [α] D 20 ° =+73.9° (c=1, acetic acid).
(b) N-(p-methoxy-benzylidene)-1,3,4,6-tetra-O-acetyl-D-glucosamine. Intermediate II
750 ml of acetic anhydride are added to a cooled mixture of 250 mg of Intermediate I in 1250 ml of anhydrous pyridine at 5° C. The obtained solution is poured into an ice water mixture. The separated solid is filtered, washed first with water and then with petroleum ether whereby 365 g of product (m.p.=176°-180° C.) are obtained. By crystallization from absolute ethanol, 310 g of product (m.p.=180°-1° C.) are obtained.
(c) 1,3,4,6-tetra-O-acetyl-D-glucosamine. HCl Intermediate III
125 ml of 5N HCl are added to a boiling solution of 302 g of Intermediate II in 2 liters of acetone: the precipitation of the product takes place and is completed by additon of ether. The solid product is washed with ether to yield 245 g of white product: m.p.=230° C.; [α] D 20 ° =+30.9° (c=1,H 2 O).
(d) Tetracetyl-D-glucosamine(1,3,4,6-tetra-O-acetyl-D-glucosamine). Intermediate IV
16.4 g of sodium acetate are added to a mixture of 38.4 g of intermediate III in 200 ml of water. The tetracetyl-D-glucosamine which is precipitated is extracted with chloroform and the chloroformic extract is evaporated under vacuum. The solid residue is suspended in ether and filtered. 30.5 g of product (m.p.=127°-9° C.[α] D 20 ° =+27.2° C. (c=1, chloroform)) is obtained.
(e) N-(N-carbobenzoxy-m-di(2-chloroethyl)amino-L-phenylalanyl)1,3,4,6-tetra-O-acetyl-D-glucosamine. Intermediate V
A solution of 17.4 g of intermediate IV, and 22 g of N-carbobenzoxy-m-di-(2-chloroethyl)amino-L-phenylalanine in 150 ml of chloroform at a temperature of 5° C., is added to a solution of 11.4 g of Dicyclohexylcarbodiimide in 50 ml of chloroform. Almost immediately the precipitation of the dicyclohexylurea takes place. The solid is removed by filtration and from the clear filtrate 34.5 g of solid are obtained by addition of 500 ml of ether. From ethyl acetate, 16 g of the product melting at 198°-9° C. are obtained. The product is chromatographically homogeneous and shows:
[α] D 20 ° =-13.6 (c=1, CHCl 3 )
[α] D 20 ° =+10.0° (c=1, acetic acid)
______________________________________Analysis for C.sub.35 H.sub.43 Cl.sub.2 N.sub.3 O.sub.12 : % calculated % found______________________________________N = 5.46 5.46Cl = 9.22 9.18______________________________________
(f) N-(m-di-(2-chloroethyl)amino-L-phenylalanyl)-1,3,4,6-tetra-O-acetyl-D-glucosamine
To a mixture of 40 g of Intermediate V in 600 ml of methanol, and 8 ml of glacial acetic acid: 12 g of 5% Pd/C are added. Under vigorous stirring a stream of H 2 at room temperature is passed through the mixture for 6 hours. The suspension is warmed to 45° C. and filtered. The filtrate is evaporated under vacuum and the white residue is suspended in ether and filtered. 24 g of product melting at 153°-5° C. are obtained. The product is chromatographically homogeneous with
[α] D 20 ° =+24.9° (c=1,CHCl 3 )
______________________________________Analysis for C.sub.27 H.sub.37 Cl.sub.2 N.sub.3 O.sub.10 % calculated % found______________________________________N 6.62 6.59Cl 11.17 11.12______________________________________
EXAMPLE 2
1,3,4,6-tetra-O-acetyl-D-glucosamyl-p-fluoro-L-phenylalanyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-N-carbobenzoxy-L-proline
(a) 1,3,4,6-tetra-O-acetyl-D-glucosamyl-p-fluoro-L-phenylalanyl-m-di-(2-chloroethyl)-amino-L-phenylalanyl-N-carbobenzoxy-L-proline
105.5 g of 1,3,4,6-tetra-O-acetyl-D-glucosamine chlorohydrate are dissolved in 600 ml of dimethylformamide (DMF). With stirring, 40 ml of triethylamine, then 175 g of N-carbobenzoxy-L-prolyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-phenylalanine and successively a 62 g solution of dicyclohexyl-carbodiimide in 50 ml of dimethylformamide are added to the DMF solution. Stirring is continued at room temperature overnight. The insoluble residue is then filtered off. The filtrate is diluted to 3 liters with ethylacetate. The organic phase is then washed with water. By concentration under vacuum and chilling a crystalline product is obtained which is filtered and washed with ether. The yield is 90 g.
The analysis for C 49 H 58 Cl 2 FN 5 O 14 gives:
______________________________________ % calculated % found______________________________________N = 6.8 7.1Cl = 6.9 7______________________________________
[α] D 20 ° =+30.87° (c=1,CH 3 OH);-50.12° (c=1,CHCl 3 )
(b) 1,3,4,6-tetra-O-acetyl-D-glucosamyl-p-fluoro-L-phenyalanyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-L-proline acetate
66 g of the product obtained in the preceeding step are dissolved in methanol and acetic acid and 30 g of 5% Pd/C are added. Then an H 2 stream under vigorous stirring at room temperature is passed through. The suspension is filtered and the filtrate evaporated under vacuum until almost dry. Then, by slowly adding ether and chilling, a white crop is formed. 46.5 g of 1,3,4,6-tetra-O-acetyl-D-glucosamyl-p-fluoro-L-phenylalanyl-m-di(2-chloroethyl)amino-L-phenylanyl-L-proline acetate are obtained (m.p. 148°-151° C.).
Analysis for C 43 H 56 Cl 2 FN 5 O 14 is:
______________________________________ % calculated % found______________________________________N = 7.3 7.1Cl = 7.2 6.98H.sub.2 O = absent absent______________________________________
[α] D 20 ° =-14.4° (c=1,methanol)
EXAMPLE 3
D-glucosamyl-p-fluoro-L-phenylalanyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-L-proline acetate
35 g of carbobenzoxy-L-prolyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine are dissolved in 250 ml of DMF. Then, 12 g of D-glucosamine hydrochloride dissolved in 40 ml of H 2 O are added. To this solution, 4.2 g of NaHCO 3 are added. After cooling at 5° C., 15.5 g of dicyclohexylcarbodiimide dissolved in 20 ml of DMF are added to the solution. Filtration to eliminate the separated dicyclohexylurea is next, followed by pouring the decolorized filtrate under stirring into crushed ice. The solid which precipitates is filtered, washed first with water and then with petroleum ether, dried and crystallized from absolute ethanol. The yield is 138 g (m.p.=138°-142° C.).
Analysis for C 41 H 50 Cl 2 FN 5 O 10 is:
______________________________________ % calculated % found______________________________________N = 8.1 7.9Cl = 8.2 7.92______________________________________
[α] D 20 ° =+14.4° (c=1, methanol)
Removal of the carbobenzoxy protective group
To 9.5 g. of the previous compound add a 5 g suspension of 5% Pd/C in 300 ml of methanol and 10 ml of acetic acid. Continue stirring with passage of an H 2 stream therethrough. The suspension is then filtered, the filtrate is evaporated under vacuum, and the residue after suspension in ether gives 7.1 g of crystals melting at 104°-105° C.
Analysis for C 35 H 48 Cl 2 FN 5 O 10 is:
______________________________________ % calculated % found______________________________________N = 8.9 8.7Cl = 9.0 9.1______________________________________
[α] D 20 ° =+14.6° C. (c=1, acetic acid)
EXAMPLE 4
Ethyl-D-glucosamyl-p-fluoro-L-phenylalanyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-L-proline, hydrochloride
20 g of the product obtained as per example no. 2 are dissolved in 100 ml of ethanolic solution 1.5 N HCl. The solution is kept at room temperature and protected from light until complete deacetylation is achieved. The solution is decolorized with carbon and is evaporated under vacuum. The dry residue is suspended in ether. The solid, crystallized from propyl alcohol, yields 8.5 g of product which melts at 140°-143° C.
Analysis for C 33 H 45 Cl 3 FN 5 O 8 is:
______________________________________ % calculated % found______________________________________N = 9.1 9.1Cl = 13.9 14.1Cl ionic = 4.6 5.2______________________________________
EXAMPLE 5
1,3,4,6-tetra-O-acetyl-D-glucosamyl-L-methionyl-m-di(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine hydrochloride
(a) N-formyl-p-fluoro-L-phenylalanyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-L-methionine ethyl ester
554 g of N-formyl-p-fluoro-L-phenylalanyl-m-di-(2-chloroethyl)amino-L-phenylalanine are dissolved in 4.5 liters of dimethyl formamide (DMF). The solution is heated slowly for the dissolution step and then cooled to 15° C. While stirring add: 172 g of N-hydroxysuccinimide+225 g of dicyclohexylcarbodiimide+1,235 g-moles of L-methionine ethyl-ester dissolved in DMF. After 16 hours of stirring at room temperature, the precipitated dicylcohexylurea is removed and to the stirred filtrate 18 liters of a mixture of water and ice are added. The white precipitate is filtered, washed with water and completely dried under vacuum. Yield: 710 g (97.2%); m.p.=180°-182° C.; [α] D 20 =-7.0°±1° (c=2, DMF).
______________________________________Analysis: % calculated % found______________________________________S = 4.86 4.84N = 8.52 8.51Cl = 10.78 10.72______________________________________
(b) N-formyl-p-fluoro-L-phenylalanyl-m-di(2-chloroethyl)amino-L-phenylalanyl-L-methionine.
100 g of ester obtained in (a) are dissolved in 600 ml of DMF around 40° C. The solution is left to cool to about room temperature. Then, over a period of 1/2 an hour a 170 ml NaOH 1 N aqueous solution is added. After 1 hour of stirring, the solution is neutralized by slowly adding 170 ml of 1N hydrochloric acid. The tripeptide acid starts to precipitate. After a few hours in a refrigerator the solid is filtered, washed with ether and dried to yield 90 g of product.
______________________________________Analysis: % calculated % found______________________________________N (Kjeld.) = 9.38 9.31Total Cl = 11.87 11.82S = 5.36 5.28______________________________________
m.p.=150°-155° C.; [α] D 20 ° =-3° (c=1, DMF)
U.V. spectrum: ε 257 =16,169
I.R. spectrum: complies with the intended structure.
(c) 1,3,4,6-tetra-O-acetyl-D-glucosamyl-m-di(2-chloroethyl)amino-L-phenylalanyl-N-formyl-p-fluoro-L-phenylalanine
10.5 g of peptide obtained as per step (b) are dissolved in 50 ml of DMF and to the solution thus obtained: 9.6 g of 1,3,4,6-tetra-O-acetyl-D-glucosamine hydrochloride and 2.5 g of triethylamine are added. To the cooled mixture 2.3 g of hydroxysuccinimide and 3.8 g dicyclohexylcarbodiimide in 24 ml of DMF are added. The mixture is stirred at room temperature for 3 days to complete the reaction. The product obtained is dissolved in ethyl acetate and the organic phase is washed with water. A compound precipitates which after purification shows: [α] D 20 ° =-15.4° (c=1, DMSO)
______________________________________Analysis: Calculated Found______________________________________N % = 7.30 7.30Cl % = 7.50 7.40______________________________________
I.R. spectrum complies with the intended structure.
(d) 1,3,4,6-tetra-O-acetyl-D-glucosamyl-L-methionyl-m-di-(2-chloroethyl)-amino-L-phenylalanyl-p-fluoro-L-phenylalamine.
10 g of the compound obtained in reaction (c) are dissolved in 60 ml of glacial acetic acid. While stirring, a stream of dry gaseous hydrochloric acid is passed through the solution up to saturation. The reaction mixture is then poured into 500 ml of ether kept under stirring. The white precipitate is washed with ether and dried yielding 9.2 g of product. The latter, after crystallization from isopropanol, gives a product with the following analytical figures:
______________________________________ % calculated % found______________________________________N = 7.24 7.27Cl ionic = 3.66 3.56Total Cl = 11.00 11.12H.sub.2 O = 1.7______________________________________
m.p.=136°-9° C.; [α] D 20 ° =+40.4° (c=1, AcOH)
ε258=16,608; ε302=2,447
The IR spectrum complies with the intended structure.
EXAMPLE 6
Ethyl-D-glucosamyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-L-methionyl-p-fluoro-L-phenylalanine
(a) N-formyl-p-fluoro-L-phenylanyl-L-methionyl-m-di-(2-chloroethyl)amino-L-phenylalanine ethyl ester
98 g of N-formyl-p-fluoro-L-phenylalanyl-L-methionine dissolved in 565 ml of tetrahydrofurane are admixed with 0.287 moles of m-di-(2-chloroethyl)amino-L-phenylalanine ethyl ester. 63 g of dicyclohexylcarbodiimide are added. After stirring, the dicyclohexylurea is filtered out and the solvent is evaporated under vacuum to 1 liter. Then, about 4 liters of ether are added. 144 g of product (melting at 146°-154°) are obtianed. By further crystallization from 6000 ml of methanol, 100 g of white product melting at 155°-158° C. are obtained.
______________________________________Analysis: % calculated % found______________________________________N = 8.52 8.90S = 4.875 4.95Cl = 10.78 10.76______________________________________
[α] D 20 ° =+11.8° (C=1, dioxane)
(b) N-formyl-p-fluoro-L-phenylalanyl-L-methionyl-m-di-(2-chloroethyl)amino-L-phenylalanine
32 g of ester obtained in (a) are dissolved in 200 ml of DMSO. The solution is cooled and then 52 ml of NaOH 1 N at pH 11-12 is added. The solution is cooled and then neutralized to about pH 4 by slow addition of 52 ml of 1 N HCl. 400 ml of water is added to the neutralized solution. The white solid which separates is filtered, decolorized and crystallized from acetone. 19 g of product melting at 144°-147° C.
[α] D 20 ° =+15.56 (c=1,DMSO) are obtained.
______________________________________Analysis: % calculated % found______________________________________N (Kjeldhal) = 8.90 8.82S = 5.09 5.10Cl = 11.26 11.16______________________________________
(c) 1,3,4,6-tetra-O-acetyl-D-glucosamyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-L-methionyl-N-formyl-p-fluoro-L-phenylalanine
Dissolved in 600 ml of DMF are: 24.18 g of 1,3,4,6-tetra-O-acetyl-D-glucosamine hydrochloride, 9 ml of triethylamine+37.8 g of the peptide obtained from the previous reaction (b). The solution is filtered. Added to the filtrate is 13.6 g of dicyclohexylcarbodiimide. After stirring, the precipitated dicyclohexylurea is filtered out. To the filtrate are then added 1800 ml of chloroform, followed by extraction with water. From the organic phase, chloroform is evaporated and the product is precipitated from the resulting solution by addition of 900 ml of ether. After crystallization from methanol, 7.8 g of pure product are obtained melting at 206°-208° C.
______________________________________Analysis: % calculated % found______________________________________N (Dumas) = 7.30 7.39S = 3.34 3.38Cl = 7.39 7.25______________________________________
[α] D 20 ° =+19° (c=1, DMSO)
(d) Ethyl-D-glucosamyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-L-methionyl-p-fluoro-L-phenylalanine
6.72 g of compound obtained as per the previous step (6c) are dissolved in 52.5 ml of 1 N HCl in absolute ethyl alcohol. The solution is stirred overnight, then filtered, followed by complete removal of the solvent under vacuum. The solid product is suspended in ethanol. 5.84 g of product are obtained, which decomposes at about 120° C.
______________________________________Analysis: % calculated % found______________________________________Total Cl = 16.97 16.31Cl (ionic) = 8.49 8.46S = 3.84 3.88N = 8.38 8.43______________________________________
[α] D 20 ° =+27.8° (c=1, EtOH 95°).
EXAMPLE 7
Ethyl-glucosamyl-L-methionyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine
11 g of 1,3,4,6-tetra-O-acetyl-D-glucosamyl-L-methionyl-m-di-(2-chloroethyl) amino-L-phenylalanyl-N-formyl-p-fluoro-L-phenylalanine (prepared according to example 5(c)) are suspended in 80 ml of 1.2 N HCl in ethanol. The mixture is kept stirred for 2 days at room temperature up to completion of the reaction. The reaction mixture is treated with charcoal, filtered and then poured into 400 ml of ether. A semi-solid mass is obtained which is washed with ether and then dissolved in warm ethanol. Upon cooling a precipitate is obtained. After drying, 6.5 g of product with m.p. 162°-4° C. (dec) results. Analysis for C 35 H 50 Cl 2 FN 5 O 8 S.HCl is
______________________________________ % calculated % found______________________________________Total Cl 12.84 12.63Cl ionic 4.28 4.20N (Kjeld) 8.46 8.42S total 3.87 3.82H.sub.2 O at K.F. 1.25______________________________________
EXAMPLE 8
D-glucosamyl-L-methionyl-m-di-(2-chloroethyl)amino-L-phenylalanyl-p-fluoro-L-phenylalanine bihydrochloride
5 g of 1,3,4,6-tetra-O-acetyl-D-glucosamyl-L-methionil-m-di-(2-chloroethyl) amino-L-phenylalanyl-p-fluoro-phenylalanine (obtained as in example 5d) are dissolved in 45 ml of 25% ethanol, admixed with 5 ml of conc. HCl. The mixture is stirred for 48 hours, filtered with charcoal, and the filtrate is poured, drop by drop, into 150 ml of ether. 2 g of solid product are obtained in which glucosamine is in hemiacetalic form (as is confirmed by its capacity to reduce Fehling reagent). m.p.=98° C.
[α] D 20 ° =25° (c=1, DMF). Analysis for C 33 H 46 Cl 2 FN 5 O 8 S 2 HCl is:
______________________________________ % calculated % found______________________________________Total Cl 16.97 16.89Cl ionic 8.49 8.68N (Dumas) 8.38 8.21S 3.84 3.75H.sub.2 O at K.F. 1.50______________________________________
The theoretical values were calculated for the bi-hydrochloride. The hemiacetalic form is verified by the reducing capacity of the product against Fehling's reagent. | N-Acyl derivatives of glucosamines made by linking an amino acid or oligopeptide having a m-di(2-chloroethyl)amino-L-phenylalanyl group, to the amino group of the glucosamines by a peptide bond, are endowed with strong anti-tumor action against transplanted neoplasma in animal. The compounds according to the present invention are of the general formula (I): ##STR1## where R 1 is a hydrogen atom or an acetyl group,
R 2 is a hydrogen atom, an acetyl group, aliphatic (C 1 -C 6 ) group or a benzyl group
and R 3 is m-di(2-chloroethyl) amino-L-phenylalanine, or L- methionyl -m-di(2-chloroethyl) amino-L-phenylalanyl-p-fluoro-L-phenylalanine, or p-fluoro-L-phenylalanyl-m-di (2-chloroethyl) amino-L-phenylalanyl-L-proline, or m-di (2-chloroethyl) amino-L-phenylalanyl-L-methionyl-p-fluoro-L-phenylalanine.
The antineoplasmic activity of the compounds of the present invention is not affected in the gastrointestinal tract and hence they can be effectively administered orally. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The current invention relates to a surgical device and, more specifically, to a surgical device containing one or more design features that allow to the device to be used safely.
2. Discussion of the Background
Most existing trocars used for endoscopic surgical procedures are incapable of truly effective prevention of injuries to internal organs during insertion and manipulation of the trocar. Despite intensive efforts to improve present trocar designs, the results are still dismal. Present procedures frequently injure internal organs, and the resulting wounds are sometimes serious or even fatal. The need for safer trocars is thus imperative, especially given that endoscopic surgical procedures are likely to become more widespread in the future.
Endoscopic or minimally invasive surgery presents an opportunity to improve present surgical procedures and instrumentation comparable only to the revolutionary effect of the introduction of anesthetics in the 19th Century.
Most present day trocars utilize a tip “shield”, or cover, for the cutting edges which is usually deployed immediately after penetration of the body cavity has taken place. Such a penetration is fraught with danger of injury to internal organs. However careful a surgeon may be during penetration of the body cavity, the resistance to penetration drops at the last instant prior to damage to the internal organs. This sudden drop in the resistance to penetration is called a “plunge effect” and occurs prior to any safety feature deployment. In some trocars, the penetration is controlled in some fashion, either taking place in small increments or under some form of approximate direct observation, estimate, or monitoring. In all cases, however, the designs result in much of the piercing tip being inserted to a dangerous depth before any protecting devices is deployed. This is perhaps not surprising since, after all, a hole must be made before any protection is deployed.
Since in most cases delicate organs are very close to the inside of the skin layer being pierced, it is advisable to perform the penetration after internal cavities have been filled with carbon dioxide to minimize the danger of accidental injury due to contact with the sharp piercing tip or the cutting edges of the instrument. In most cases, however, the force required or penetration and the elastic nature of the muscular layer cause a severe depression at the surgical portal, therefore bringing the penetrating tip of the instrument closer to the internal organs. In some of those cases, the sudden penetration of the cavity wall and the rapid drop in resistance allow the instrument to be propelled far deeper than desired or is possible to control. Furthermore, friction between the tissue walls and any protective device retards the deployment of the protective device, and an injury almost inevitably occurs.
SUMMARY OF THE INVENTION
Accordingly, one object of this invention is to insure that such events be avoided through a surgical device in which a penetrating tip or cutting edge(s) of the instrument be kept, at all times, sufficiently distant from delicate tissues. Thus, even under dynamic conditions, the probability of injury will be reduced.
A further object of this invention is to provide a surgical device wherein insufflation fluid can be driven into a patient during penetration of the body cavity by the surgical device to drive the internal organs away from the surgical device during penetration. The insufflation fluid of the present invention can either be supplied from an external pressurized reservoir, or compressed (and hence gathered) during penetration of the body cavity by the surgical device.
A further object of the invention is to provide a surgical device that contains one or more cutting edge that provides low frictional forces between the cutting edge and tissue during penetration of the body cavity, thus reducing the force needed to drive the surgical device into the body cavity.
A further object of the invention is to provide a surgical device that includes a protective device that deploys while remaining substantially out of contact with tissue, thus reducing frictional forces between the protective device and ensuring a controlled and advantageous deployment.
A further object of the invention is to provide a surgical device that includes a protective device such as safety guards, wherein the guarding elements have an apex and the angle subscribed at the apex is smaller than the angle subscribed by the blades or cutting elements of the surgical device, thus insuring progressive coverage of the blades or cutting elements during deployment of the protective device.
A further object of this invention is to provide a surgical device with a grip mechanism that allows convenient gripping and twisting of the surgical device during penetration of the body cavity.
A further object of this invention is to provide a surgical device that includes a locking system that prevents accidental reuse of the cutting elements after the tip has been used.
It is therefor desired that this invention, in general, improve surgical safety.
These and other objects of the invention are achieved by a surgical device such as a trocar tissue penetrator including a set of thin planar arrow-pointed cutting blades joined at a cutting point coaxial and within a hollow cylinder penetrator and having the cutting edges converge at a cutting angle at the cutting point. The back outside of the set of cutting blades can be fixed to the inside of the hollow cylinder penetrator with the cutting edges fully protruding. The hollow cylinder can have its front end slotted and each segment pointed in a triangular shape and bent to fit between the blades and having its edges substantially parallel to the edges of the protruding blades but axially recessed behind such edges to act as a tissue expander to prevent contact between inside moving guards and the outside tissue. The slots between the triangularly shaped bent section tissue expanders at the end of the hollow cylinder penetrator can be wide enough to permit the passing between them and the sides of the cutting blades of a guard sheet at least as thick as the blades. A set of elongated axially bent sheet guards can be set to slide freely within the space between the sides of the cutting blades and the triangular bent segments of the hollow cylinder and having their frontal end with a tip angle profile substantially more acute than the adjacent angle of the blade edges and terminating in a very small dull round tip. The angular frontal edges of the bent sheet guards can have shallow angle ends and curving slowly toward the edges so that at no time their angle exceeds that of the adjacent cutting edges. The elongated bent sheet guards inserted between the cutting blades and the triangularly bent segments of the hollow cylinder can be attached at their opposite end to a stem which is urged toward the frontal cutting edges by a coil spring.
The advantageous characteristics of this surgical device include, e.g., the following:
a multiple system of sharp planar knife edges that practically eliminate lateral friction and provide a reduced resistance to penetration, thereby reducing the penetration “plunge effect” and tissue springback.
a mechanical tissue protection device that includes a series of thin plastic guards sliding along the sides of the planar knives and, in a preferred embodiment, having an angle between their edges smaller than that of the cutting knife edges. It can then be shown that, with proper contouring of such plastic guard edges, it is possible to provide complete guarding between the cutting edges and the surrounding tissues from the very start of the penetration, and to do so in a truly progressive manner, without jerks or discontinuities. The progressive guarding action that results from the smaller angle between the sides of the guards than the angle between the edges of the cutting blades allows the guards to plunge into the tiny opening made by the cutting tip and instantly surround it, thereby preventing injury to internal organs during the most crucial instant of the trocar insertion. Therefore, guarding action takes place in a truly progressive manner in which, as the cutting blades continue expanding the tiny initial opening, the guards progressively advance keeping the cutting edges constantly covered outside the penetrating region and isolated from internal organs until the penetration is completed and the cannula fully inserted;
one or more fixed conical deflectors to expand the cut tissue passage leaving the guards to contact tissue only at their tips, thus isolating the guards from friction against the tissue at the sides of the point of penetration. Therefore, as soon as even a minute opening is made at the tip by the cutting blades, the guards instantly plunge into the opening and prevent the blade tips from any contact with internal organs. Thus, using tissue expanders outside the guards prevents friction between the guards and the tissue, which would retard the deployment action. The use of this tissue expander allows the safety device to function without restriction, thereby eliminating one of the major deficiencies of existing trocars. In other words, the dynamic response of the guards is inherently much faster than the rate of penetration of the blades. As a result, cutting edges are never dangerously exposed to, contact with internal organs, however fast the penetration rate may be;
an insufflation passage configured to transport fluid into the body cavity during penetration. The insufflation passage can be pressurized either using an external reservoir or by compressing gas contained in the passage during penetration. Once an initial penetration of the, epithelium has been made, fluid from the insufflation passage will drive the internal organs away from the cutting edge(s). In the case of an external carbon dioxide gas reservoir, a carbon dioxide gas valve is opened, thereby pressurizing the penetrator tubular body. Under such pressurization, since the front is enclosed by tissue, the cutting tip penetrates the tissues while the gas is prevented from exhausting, but as soon as the most minute opening starts to appear at the tip, the gas expands suddenly into the opening and forcibly deflects delicate internal organs away from the tip of the cutting surface while simultaneously the guard tips are forced through the opening by their spring. The use of a pressurized fluid (or gas) tissue deflector thus creates an organ-free zone in front of the cutting blade tips at the instant of the incipient penetration, even before the guard tips plunge into the opening. It must also be pointed out that a sudden gas expansion can also aid the deployment of the guards since the flow occurs between the cutting blades and the conical expanders, precisely where guards may be located. It could almost be said that the guards are spit out by the fluid flow. This increases the velocity of their deployment and hence the overall safety of the surgical device;
a locking system for the guards, which is located at the proximal end of the instrument, prevents accidental reuse of the cutting features after the tip has been safely introduced for the first time. The locking system for the trocar guards includes a locking cylinder attached to a locking button supported by a leaf spring and inserted into a socket. The cylinder has a conical tip and a circumferential groove at the bottom and can be depressed by way of the button and engaged by the groove into a U shaped spring that will hold it down permitting it sliding motion until it comes out of the U shaped spring and is ready for locking again on its return to the initial position. If a reset action is desired it is necessary to push hard downward against the locking button and deliberately reset it for another cycle. Since the locking button is located deep within a recess at the proximal section of the handle, it demands some effort to reach and actuate, and thus it is difficult to accidentally reset.
an ergonomic design which facilitates handling. The proximal hemispherical knob nestles easily into the hollow of the hand while the index and middle fingers control rotation by gripping the side horns, thereby permitting push, pull, rotation, and tilting in a very natural and comfortable manner.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same become better understood by reference to the following detailed description when considered in connection with the accompanying drawings, wherein:
FIG. 1 shows a general view of an example trocar in isometric pictorial form;
FIG. 2 illustrates a partial broken view of the penetrating end of the example trocar with guards removed to behind the tip knives to illustrate a shape of this embodiment more clearly;
FIG. 3 shows the same end of the example trocar with the guards installed but retracted as when penetration of an example embodiment starts, and thus, the knife edges are exposed and ready to start cutting;
FIG. 4 shows the tip of the guards protruding ahead of the cutting tip as when the tip had just started to pierce the abdominal cavity;
FIG. 5 shows the tip of the example trocar with the guards fully extended and covering the knife edges as when completely inside of the abdominal cavity;
FIG. 6 shows the example trocar tip at the moment it approaches the skin layer, and thus the guard tips are beginning to push against the skin and be retracted into the penetrator;
FIG. 7 illustrates the point when, in an example embodiment, the guards are completely pushed into the retracted position and the knife tips start to cut into the tissue;
FIG. 8 illustrates the point when, in an example embodiment, the knife tips have completed the passage across the tissue and begin to emerge across the endothelial layer into the abdominal cavity, and thus the tips of the guards begin to push into the incipient opening while a forceful jet of pressurized carbon dioxide gas pushes delicate internal tissues away from the immediate penetration region;
FIG. 9 illustrates the point when, in an example embodiment, the tips of the guards have penetrated the opening and prevent any contact between the knife tips and the surrounding internal tissues while the exposed knife edges behind the opening continue the cutting action, and the pressurized carbon dioxide gas expansion continues to hold delicate tissues away from the cutting region;
FIG. 10 illustrates, in an example embodiment, the continuing penetration, and thus the guards have penetrated almost completely, while behind them the still-exposed edges continue the cutting action and the passage of gas continues;
FIG. 11 illustrates the point in an example embodiment when the penetration has been completed. The knife edges are fully covered by the guards and the tissue opening allows for the passage of the cannula and the insufflation continues until completed and the penetrator assembly can be removed;
FIG. 12 shows the top view of an example trocar handle with a portion broken away to show some internal details;
FIG. 13 illustrates a longitudinal section along a vertical plane “A—A” to exhibit most of the internal details of an example trocar handle;
FIG. 14 illustrates a top view of the distal section of an example handle with the grasping horns to facilitate manipulation;
FIG. 15 illustrates an end view of the distal section of an example handle as seen from the right showing also a partial broken section detail of the flap valve pivot and lever;
FIG. 16 illustrates a partial isometric view of the example locking mechanism for the guards stem showing some of the elements within the proximal section of the handle as in Section “A—A” on FIG. 13;
FIG. 17 illustrates an exploded view of some of the example elements of the guards stem locking mechanism in an example spatial relationship;
FIG. 18 illustrates an example locking mechanism in a locked position;
FIG. 19 illustrates an example locking mechanism having been unlocked and ready for the start of penetration;
FIG. 20 illustrates how pushing the guards against the skin has forced their stem towards the right;
FIG. 21 illustrates a position of the stem where the guards are completely retracted and the knife edges fully exposed for cutting;
FIG. 22 illustrates a position of the locking mechanism after the full release of the guards into the abdominal cavity and the locking of their stem back to its initial position shown in FIG. 18 .
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views, and more particularly to FIG. 1 thereof, wherein a cannula 2 is firmly attached to a distal section of a handle which is formed from two segments, the distal one 6 externally containing gripping horns 6 a , insufflation device 11 , and flap valve lever 12 , and a proximal handle section 5 in the shape of a hemispherical knob to facilitate its pushing with the palm of the hand. This section also contains a depression 9 with a flat bottom 9 a , and external mechanisms including a button 7 inserted for sliding into a slot 8 to monitor and control the position of safety guards at the extreme distal end of cannula 2 . The safety mechanisms protruding distally from cannula 2 include conical tissue expanders 4 , and safety guards 3 intended to cover a set of knives (not visible in this FIG. 1 ). Those are the externally visible features of this invention.
FIG. 2 shows details at the penetrating distal end of the trocar. A hollow outside cylinder 2 is the cannula which is firmly attached to the distal section of the handle 6 as was described in FIG. 1 . Inside of the cannula 2 , there is another hollow cylinder 13 which is the penetrator. This is the removable part which is attached to the proximal section of the handle 5 , and can be removed after the penetration is completed to allow for the introduction of surgical instruments. The cannula 2 has its distal end beveled as shown by 2 a to facilitate its introduction across the tissue opening with minimal resistance. The penetrator hollow cylinder 13 has its distal end formed as a plurality of conical segment expanders 4 which are spaced by slots 4 a to allow for the protrusion of pointed flat knives 14 joined at the center of the instrument and resembling thin arrowheads joined at a center. As shown in FIG. 2, the knives are positioned into the penetrator hollow cylinder 13 to a depth shown at 14 a . The knife edges outside the slots 4 a between the conical segment expanders protrude a substantial distance to insure adequate cutting. The set of knives is assembled into the penetrator cylinder 13 by spot welds 15 , or by other similar mechanism. Right behind the crossing of the knife blades can be seen the plastic guard tips 3 a . In FIG. 2, the guards are shown as removed from the knives so as to facilitate the understanding of their shapes and relationship to the knives. The subassembly of the guards 3 is part of a support disk 16 which in turn is part of the guards hollow stem 17 connecting them to an actuator spring and locking mechanism at the proximal section of the handle (not shown here). In the real instrument, the guard tips 3 a are inserted around the knife blades which fit into the narrow spaces 3 b between the guards. The guards are then assembled by being pushed forward until they protrude between the blade sides and the conical expander slots 4 a as can be shown in FIG. 3 below. In FIG. 3, the tips of the guards are barely visible because the guards are retracted as when the trocar is first pushed against the skin.
FIG. 4 shows the tips of the guards 3 a protruding ahead of the tip of the knives and covering them. A short distance behind the tips of the guards 3 a the edges of the knives 14 are exposed and capable of cutting. FIG. 4 shows the configuration of the trocar cutting tip right after initiation of the penetration across the abdominal tissue. At that instant, the guard tiny tips 3 a plunge across the start of the opening and quickly cover the sharp cutting point while the exposed knife edges continue cutting inside the skin until the penetration is complete as shown in FIG. 5 . FIG. 5 shows how the front end of the example trocar looks after the penetration into the abdominal cavity has been completed. At that time all edges of the cutting knives are covered by the fully extended guards and the whole penetrator assembly can be pulled out with the proximal sector of the handle.
As will be shown later, in one embodiment, at the instant when the first perforation of the abdominal wall was made, a forceful jet of carbon dioxide gas issued across the perforation to deflect away any delicate organs close to the knives tip while simultaneously the guard tips entered the opening to cover the point of the knife edges.
The operations just described above are a critical part of this invention, therefore they will best be described through the sequence of figures from FIG. 6 through to FIG. 11 .
FIG. 6 represents the example trocar guard tips 3 a as they begin to contact the skin layer 20 . The internal organs are shown at the left side as 25 . At this instant, the skin outside layer is deflected under the force of the guard tips which are urged forward by their spring. As the trocar is pushed forward, the guards will be forced into the penetrator 13 and displace the base disk 16 and guard stem 17 toward the right against the force of their spring.
FIG. 7 shows the guards 3 already completely retracted into the penetrator 13 , and the knife edges 14 completely exposed. At that instant, the point of the knives begins to cut and penetrate at 21 into the outside tissue layer. As shown in FIG. 7, the cutting pathway of the cutting tip/knife edge is of a smaller diameter than the inner diameter of the cannula 2 such that the cut made by the blade results in a smaller lumen or bore than that of the cannula. At that time, the carbon dioxide gas is allowed to pressurize the inside of the penetrator 13 , and while some gas may escape at first, the tissues around the tip will seal the flow until the cutting tip starts to emerge across the internal abdominal wall.
FIG. 8 shows the onset of penetration. At that instant, the cutting tip point 14 b has made a very minute perforation 23 and, because of the presence of the guard tips 3 a , there is enough space to allow a fluid flow (shown here as a gas jet 24 ) to issue out and cause the displacement of nearby internal organ tissues 25 a , while simultaneously the guard tips 3 a expand the opening urged by their spring pushing at 17 and plunge through the perforation effectively covering the cutting tip 14 b.
FIG. 9 shows the result of the action described above. The gas jet 24 continues issuing and driving internal organs 25 a farther away while the guard tips 3 a completely enclose the cutting tip 14 b . All danger to internal tissues has passed. The extremely quick flow of the gas and the action of the guard tips make the manipulation factors of this trocar the safest to master easily. The force or speed of the penetration action are, within reason, almost immaterial.
FIG. 10 shows the penetration process. The cannula 2 is partly introduced across the tissue 27 and the guard tips 3 a continue advancing and protecting the internal tissues from the knife edges while the portions of the edges not yet covered by the guards 14 a are seen cutting the remainder of the opening ahead of the cannula, and the tissue expanders 4 facilitate penetration by protecting the guards from tissue friction. At this point of the penetration the flow of carbon dioxide gas 24 is fairly unimpeded and performs the insufflation stage of the process, driving internal organs 25 a farther away from the trocar portal.
FIG. 11 shows the trocar after full insertion and in the last stage of insufflation. The knife edges are now fully covered by the guards, and the cannula 2 is seen fully inserted across the tissue. The insufflation continues until completed and then the penetrator 13 is removed to allow the insertion of surgical instruments across the cannula.
Having described in sequential detail the insertion, guarding, and insufflation operations, and the mechanical parts that perform them it remains to describe the additional way by which all that is accomplished. The mechanisms that allow this are located in the handle of the instrument.
FIG. 12 is a top view of the trocar showing some of the external parts as well as a partial broken view of some interior parts. The body of the handle is made out of plastic and has two main segments. The proximal segment 5 is designated to fit into the palm of the hand and has a proximal end of hemispherical shape with a depression of arcuate profile 9 at the top terminating at a flat surface 9 a where the guard stem controls are located. Those controls are recessed into the flat depression 9 a to prevent unwanted actuation, and include a double slot with vertical slots 8 and 8 a into which is inserted a button 7 and its rectangular guiding shank 7 a . The button 7 is capable of vertical and horizontal movement, the latter movement being limited between arrows 7 ″ and 11 ″ as will be described later. The proximal segment 5 is assembled as an integral part of the penetrator system. Its distal end 51 forms the interface between the two segments of the handle.
The distal segment 6 of the handle has two lateral protruding horns 6 b to facilitate its manipulation during penetration and orientation. The two handle segments 5 and 6 are locked together during usage by way of a bayonet stud 29 and slot 29 a . During insertion the stud 29 on part 5 is aligned with the slot 29 a on part 6 , pushed, and turned clockwise, until the stud locks the two segments firmly, the knob on 5 and the horns 6 b provide a good grasp for that operation. The slot 29 a has a slant at the transversal direction running slightly away from the interface 51 so as to insure that the turning-locking motion will assure a firm and stable connection. This will be discussed further in reference to FIG. 14 .
The partial broken section at the top left of the distal segment 6 is intended to show the operation of the flap valve 32 , which acts as a check valve in the illustrated embodiment. The valve has a shaft 34 pivoted between the upper 6 and lower 6 a portions of the handle and is urged to rotate counterclockwise by a torsional spring 33 located around the shaft 34 . The shaft of the flap valve is firmly attached to the valve and can be rotated from outside the body segment 6 as will be shown later on FIG. 14 . An external lock allows the valve to remain open during desufflation if turned hard to its stop position 32 a shown in dotted lines. As shown in the embodiment illustrated in FIG. 12, the valve has been opened by the insertion of the penetrator 13 . In other cases, the valve could be opened for surgical or visualization instruments. When left to itself, the valve will turn counterclockwise and snap shut against the face of seal 35 which serves as face seal for the valve and lip seal for the penetrator 13 . The left end of FIG. 12 shows how the cannula 2 is attached to the handle segment 6 by way of a flange 37 , and prevented from leaking by an “O” ring 36 . In the same FIG. 12 is shown how the carbon dioxide gas spigot manual valve 11 is mounted at one side of the top of segment 6 .
FIG. 13 is a longitudinal vertical cross section along a plane “A—A” to show the internal details of the handle. As can be noticed, the two segments of the handle include a top and a bottom part split along a horizontal plane for fabrication, one becoming 5 and 5 a , and the other 6 and 6 a , and after each segment has been fitted with the internal parts at assembly the two halves of each segment are permanently bonded together. Each of the two segments is assembled separately since they must be detached and attached during usage. The penetrator segment is only used to make the entry portal, but it must be emphasized that it is such step that involves the greatest risk.
The distal segment made of parts 6 and 6 a houses the cannula 2 and all the gas infusion and valving. The connection of the cannula to the segment part 6 was described before. FIG. 13 shows the gas connector or layer 11 a to which the gas line is affixed. The valve system is bonded via a conical stem 11 b into a boss on plane 10 so the incoming gas flows in the direction of arrow 30 and pressurizes the space between the inlet and the seal 35 from where it can enter the openings 38 around the penetrator 13 walls and fill the space between lip seals 40 and 41 . Since the lip seals are oriented toward the front the pressure will open lip seal 40 but not lip seal 41 and the gas will fill and pressurize the entire space along the penetrator 13 , not being able to escape when the trocar tip has been inserted into the tissue, however, as soon as the smallest opening is made by the point of the blades the gas will escape as a jet and deflect the surrounding internal organs away from the entry portal. Lip seal 40 is intended to prevent back flow from the penetrator in case of accidental opening or leakage across the gas valve during a procedure. In such a case, the pressurized volume of gas within the penetrator 13 will suffice to insure the safe deflection of nearby tissues even before the tips of the guards 3 a plunge into the opening. The guards stem 17 is completely sealed at the front by disk 16 and thereby its interior can be at atmospheric pressure, however, since it must slide back and forth with the guards it must also be supported at the proximal end and must be guided over a stationary hollow steel stud 44 inserted into it to a minimal depth of four diameters. The proximal end of stud 44 is flared to provide fixation between parts 5 and 5 a of the proximal hemispherical knob. A hole 56 on the hollow stud 44 serves to provide air passage in and out of the stud when the guards stem moves back and forth acting as a piston pump. The hole 56 should pass through the stud and be of a diameter such as not to impede flow and dampen the sliding action of the guards' stem. Compression coil spring 47 mounted around stud 44 serves to provide the required force to urge the guards stem in the distal direction. The proximal end of the penetrator outside cylinder 13 is flared at 43 for fixation onto the proximal handle segment parts 5 and 5 a . It is also sealed at the front by an “O” ring 42 to insure that no leakage of gas would occur even if seal 35 should leak: flared tubular assemblies like 43 are not reliable seals.
The proximal handle segment formed by 5 and 5 a is attached to the penetrator 13 and contains all its functional and control elements. The guards stem 17 has at its proximal end a shallow cylindrical depression into which a thin ring 45 a which is part of leaf spring 45 is affixed. The exact configuration of the locking system to which the spring 45 belongs can be seen in FIGS. 16 and 17, and its function in the sequence of FIGS. 18 through 22. FIG. 17 is an exploded view of some of the elements of the locking system in their proper relationship. At assembly, the button 7 is inserted across slot 8 on the top surface 9 a on FIG. 13 and the locking cylinder 48 , which has a circumferential groove 48 a and a conical end 48 c is pushed up along the stem 7 b against the bottom of the rectangular guide 7 a thereby assembling button 7 into the slot 8 a . As the assembly continues the lower tip of stem 7 b is pushed hard against the punched hole 45 d of the leaf spring until groove 7 c is gripped by the lateral tabs at 45 d and the assembly of the button is complete. If now the open hollow cylinder 45 a is snapped onto the surface depression at the proximal end of stem 17 , the button 7 becomes axially fixed to stem 17 and will follow its back and forth motion in response to coil spring 47 and the forces at the tip of the guards. FIG. 16 shows the assembly of the U spring 46 to the lower inside of 5 by the use of screw 50 . FIG. 16 does not show button 7 for the sake of clarity, but it shows flat spring 45 pushing up against the bottom of the U spring 46 . If the assembly of the button 7 and the locking cylinder 48 was shown there, it would be evident that the button would be pushed upwards and the locking cylinder 48 would be forcibly inserted into the round socket 8 b , thereby preventing any motion of the flat spring 45 and the guards stem 17 attached to it by ring 45 a . That is the situation depicted on FIG. 13 .
FIGS. 18 through 22 describe an operation of an example locking system in detail, as follows. In the position illustrated in FIG. 18 the system is locked: the guards stem and the guards cannot move at all since the cylinder 48 is inserted into the round socket 8 b . FIG. 19 shows what happens when button 7 is pushed down. When that is done the conical end 48 c of cylinder 48 opens the U spring 46 and the spring then snaps close into the groove 48 a thereby disengaging the locking cylinder from the round socket 8 b . The system is then unlocked. The trocar is said to be “armed”, and able to permit the motion of the guards backwards, exposing the cutting blades for penetration of the skin. That is the position depicted on FIG. 6 . The following discussion is directed to the embodiment shown in FIG. 20 . The penetrating force against the skin pushes on the guards and the guards stem 17 , and the connecting flat spring 45 moves the button 7 proximally. The rectangular slide section 7 a enters the space between guides 8 a , and soon afterwards, the locking cylinder groove 48 a disengages from the open end of the U spring 46 , and the spring 45 pushing upwards against the stem groove 7 c forces the top of the locking cylinder to snap against the underside of the groove 8 a . In that position, the locking cylinder 48 is free to continue sliding along the underside of groove 8 a as shown in FIG. 21 until the initial penetration is made and the force of the coil spring 47 urges the guards stem 17 and the flat spring 45 to return the button 7 to its initial position, at which time the locking cylinder will pass freely over the U spring 46 and snap back into the round socket 8 b locking the system into the “safe position” where the guards cannot move accidentally. FIG. 22 shows the completion of the cycle back to the initial configuration of FIG. 18 .
A quick review of the provided example locking system from the user viewpoint reveals that the operations include “arming” the trocar by pushing down on the button at the top of the handle at position 7 ′ shown in FIG. 12, until it “snaps” down; then pushing the trocar against the skin and watching or listening to the position of the button as it slides towards 7 ′ and then “snaps” to its initial position 7 ′. That will be the indication of having completed the penetration. If, for any reason, button 7 were pushed down accidentally, it could be reset to the “safe” condition by merely moving it in the direction to 7 ′ and then releasing it. It should then get snap-locked at a high level in position 7 ′, and could not be moved without first pushing it down.
The details of operation of the example flap valve, its design, and locking for deflation are seen in FIGS. 14 and 15. FIG. 14 shows the top view of the handle distal segment, previously presented in FIG. 12 as a partial broken section to show the interior details. FIG. 14, however, is intended to show the external operative controls on this segment of the handle in the interest of the user. The flap valve lever 12 is shown in the closed position as it should be when the penetrator is removed. The lever is attached to a shaft 34 whose opposite end is attached to the flap 32 as seen in FIG. 15 . The insertion of the internal trocar elements is performed when the top 6 and bottom 6 a of each handle segment are separated prior to their being bonded along plane 6 d.
FIG. 15, as explained before, is the end view of the example embodiment previously illustrated in FIG. 14 as seen from the right side. That is how the distal segment of the handle will appear when the proximal segment is removed. The flap valve external lever knob 53 is provided with a small depression 54 at its bottom to allow it to be held open when the depression is forcibly made to engage a small knob 54 a protruding from the flat surface 10 after the lever has been turned in the direction of arrow 52 . That is the desufflation position of the valve which allows the surgeon to use both hands to massage the insufflated region and expel the gas retained by the patient at the end of the procedure. The arc of rotation needed for the lever to engage the protruding knob 54 a is labeled as 55 . This locking position is not reached by the lever when the valve is opened by the insertion of the penetrator. The locking of the valve has to be done by the forceful and deliberate action of the surgeon. The small angle 52 shown at the bayonet locking stud 29 refers to the desirable slant for the groove 29 so as to insure that the locking force increases sufficiently to prevent accidental loosening between the proximal and the distal segments of the handle. The elasticity of the locking elements determines the exact angle to be used, which should be somewhere between 2 and 5 degrees to account for tolerance errors. The infusion valve 11 , its lever 11 c , and its lever connector 11 a are shown on FIG. 14 . In FIG. 15, the opening of the valve is indicated by arrow 11 d . FIG. 15 also shows a broken section of the valve shaft 34 , its top “O” ring seal 34 a , and its torsion spring 33 inserted into a slot in the operating bracket of valve 32 . In the same FIG. 15, the seal 35 is seen, as well as the front surface 51 a of the distal handle segment, which contacts the mating surface 51 of the proximal segment.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. In particular, it is understood that the present invention may be practiced by adoption of aspects of the present invention without adoption of the invention as a whole. | A surgical device for endoscopic surgical procedures capable of preventing injuries to internal organs during insertion. The surgical device can include one or more of the following: a multiple system of sharp blade edges, a mechanical tissue protection device that includes a series of thin plastic guards sliding along the sides of the planar knives and having an angle between their edges smaller than that of the cutting knife edges, one or more fixed conical deflectors to expand the cut tissue passage leaving the guards to contact tissue contact only at their tips, an insufflation passage configured to transport fluid into the body cavity during penetration, a locking system for the guards that prevents accidental reuse of the cutting features, and/or an ergonomic design which facilitates handling. | 0 |
BACKGROUND OF THE INVENTION
The invention relates to chromoionophore comprising an chromophore and an ionophore capable of selectively binding sodium ions for determining sodium ion in a sample. The present invention also relates to a method of determining the concentration of sodium ions in a sample wherein the chromoionophore is contacted with sodium ion in a sample, wherein the intensity of at least one absorption maximum in the visible region changes and the concentration of sodium ion is calculated based on the change in the intensity of the absorption maximum.
The accurate measurement of physiologic cations, such as sodium, potassium, lithium, calcium, and magnesium, is essential in clinical diagnosis. Traditionally, these ions were determined in plasma or serum using ion-selective electrodes (ISE), which are very cumbersome to use and costly to maintain. Serious drawbacks of electrochemical measuring arrangements are the requirement of a reference element, sensitivity towards electrical potentials and electromagnetic interference.
An alternative enzymatic method is based on the activation of β-Galactosidase by cations (Berry et al., Clin. Chem., 34/11, 1988 2295-2298). The high cost and poor stability of the enzyme preclude its extensive application in clinical laboratories. Therefore, the development of practical and inexpensive calorimetric reagents for the clinical determination of these ions in biological fluids remains an important area of research.
U.S. Pat. No. 4,367,072 describes a process for the determination of metal ions using simple crown ethers as ion-binding units. However, the binding is too weak to be useful for many practical applications, such as clinical applications, in which the indicator has to discriminate between ions with very similar properties, e.g., sodium versus potassium or magnesium versus calcium.
U.S. Pat. No. 5,011,924 and U.S. Pat. No. 4,994,395 describe cryptands (or cryptohemispherands) linked with an ionizable chromophore, which changes its color upon binding of ions based on charge interaction between the bound cation and the anion of chromophore. Although all nitrogen atoms in these cryptands are aliphatic, and not electronically conjugated with the chromophore, the results of measurement of serum samples using these chromoionophores are impressive and promising (Helgeson et. al. J. Am. Chem. Soc ., vol. 111, 1989, 6339-6350). However, the syntheses of these cryptands, especially of those cryptohemispherands, are lengthy and tedious. Consequently, the manufacturing cost of these reagents remains prohibitively high even in the decades following their discovery. The cost factor could be a reason why these reagents have not replaced those ISE modules in most large clinical analyzers, in which the ISE methods are still dominating (see Burtis et. al. ed. “Tietz Textbook of Clinical chemistry and Molecular Diagnostics” Elsevier Sauders, St. Louis, Mo., USA 2006, page 986).
U.S. Pat. No. 5,952,491 report sodium ionophore, which has π-electron conjugated nitrogen and is coupled to a fluorophore to make luminophore-ionophore sensors where the respective ions are detected by measuring luminescence emission. All three ionophores has been proven to be very effective in determination of sodium in whole blood in which sodium is the major cation. (see He et. al. Anal. Chem . Vol. 75, 2003, 449-555), thus showing that the ionophore is effective under physiological conditions.
By coupling to a chromophoric moiety, the ionophore can be converted into colorimetric sensors. The chromophoric moieties can be a nitro-substituted styryl or phenylazo, substituted thiazolevinyl or thiazoleazo, substituted naphthothiazolevinyl or naphthothiazoleazo, substituted naphthylvinyl or naphthylazo, substituted quinolinovinyl or quinolinoazo and their quartemized salts. To date, there has been no systematic investigation of these types of colorimetric reagents. Gunnlaugsson et al. ( J. Chem Soc., Perkin Trans. 2, 2002, 141-150) describe use of a sodium ionophore with a nitrophenylazo chromophore. The water solubility of this dye is so poor that one has to use organic solvent to solubilize it. The water solubility can be improved dramatically if a charge is introduced into the dye molecules. The absorption wavelength can be red-shifted by replacing the nitrophenyl with a nitrothiazole or larger chromophore-generating substituent.
The present invention provides sodium chromoionophores that are water soluble and can be reliably used for detection of ions in samples that absorb at wavelengths longer than about 400 nm. Examples of such samples are biological fluids including plasma, serum and urine.
For the chromoionophores of the present invention, the amount of ion present is determined by measuring changes in the intensity of at least one absorption maximum of the chromoionophore upon contacting the chromoionophore with an ion. The measurements are done by using standard centralized instruments, such as ultraviolet-visible spectrometers. A calibration curve for an ion is generated from a series of empirically determined absorption spectra. A calibration curve is useful for at-once determining the concentration of ion in a sample from the measured absorbance.
The chromoionophores of this invention absorb visible light (about 400 nm or greater) with reasonable extinction coefficient, thus avoiding those practical problems associated with variable background absorption from optical components, cuvette polymer materials, and biological samples. Further, the invention is well suited for practice in the determination of sodium ion in the presence of physiological concentrations of other alkali ions.
SUMMARY OF THE INVENTION
In brief, the present invention relates to novel chromoionophores, comprising a chromophoric moiety and an ionophoric moiety. The invention further relates to a method of determining sodium ions in a sample, wherein the ions are contacted with a compound having chromophoric moiety and an ionophoric moiety, where the ionophoric moiety interacts with the sodium ions present in the sample, resulting in the chromophoric moiety changing its radiation absorption properties in the ultraviolet and visible regions of the spectrum. In one embodiment, a change in an intensity of an absorption maximum is measured and the ion concentration is determined accordingly.
In one embodiment, the chromoionophores of the invention comprise an ionophore having one or more chelating moieties that is capable of selectively binding sodium ions and a chromophore having a plurality of conjugated unsaturated bonds. The chromoionophore exhibits at least one absorption maximum having a wavelength in the visible region having a first intensity and wherein the absorption maximum has a second intensity that is different from the first intensity in an amount that is by proportional to the concentration of sodium ion present in a mixture comprising sodium ions and the chromoionophore.
In other embodiments, the chromoionophores of the invention are compounds having the Formula (I)
wherein, r and s independently are selected from the group consisting of 0, 1 or 2, and L is a chromophoric moiety. It should be understood that compounds wherein r is 1 and s is 0, and L is
are excluded from the scope of this invention.
The invention further provides a method of determining the concentration of potassium ions in a sample comprising
(a) measuring the intensity of at least one absorption maximum of a solution of a chromoionophore sensitive to the presence of sodium ions in solution to obtain a first intensity; wherein the concentration of the chromoionophore in solution is known; and
wherein said at least one absorption maximum has a wavelength in the visible region;
(b) contacting the solution of the chromoionophore with the sample; whereby the first intensity changes;
(c) measuring the intensity of at least one absorption maximum to obtain a second intensity;
(d) deriving the concentration of sodium ion in the sample based, in part, on the difference between the first and second intensities.
In one embodiment, at least one absorption maximum occurs at a wavelength that is in the visible region.
In another embodiment, the difference between the first and second intensities results in a colorimetric change in the solution sample comprising the chromoionophore and sodium ions.
In another embodiment, at least one absorption maximum occurs at a wavelength of about 400 nm or greater.
In another embodiment, at least one absorption maximum occurs at a wavelength between about 400 nm and about 800 nm.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of synthetic pathway to sodium calorimetric indicator.
FIG. 2 is a graph illustrating the absorbance of a sodium colorimetric indicator in accordance with the invention versus sodium concentration in serum sample.
FIG. 3 is a graph illustrating a calibration curve a sodium calorimetric indicator in accordance with the invention versus sodium concentration in serum sample.
DETAILED DESCRIPTION OF THE INVENTION
As used herein, the terms have the following meanings:
The term “alkyl” as used herein refers to a straight or branched chain, saturated hydrocarbon having the indicated number of carbon atoms. For example, (C 1 -C 6 ) alkyl is meant to include, but is not limited to methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, hexyl, isohexyl, and neohexyl. An alkyl group can be unsubstituted or optionally substituted with one or more substituents.
The term “alkylene” refers to a divalent alkyl group (e.g., an alkyl group attached to two other moieties, typically as a linking group). Examples of a (C 1 -C 7 ) alkylene include —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, and —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 —, as well as branched versions thereof. An alkylene group can be unsubstituted or optionally substituted with one or more substituents.
The term “alkoxy” as used herein refers to an —O-alkyl group having the indicated number of carbon atoms. For example, a (C 1 -C 6 ) alkoxy group includes —O-methyl, —O-ethyl, —O-propyl, —O-iospropyl, —O-butyl, —O-sec-butyl, —O-tert-butyl, —O-pentyl, —O-isopentyl, —O-neopentyl, —O-hexyl, —O-isohexyl, and —O-neohexyl.
The term “alkenyl” as used herein refers to a straight or branched chain unsaturated hydrocarbon having the indicated number of carbon atoms and at least one double bond. Examples of a (C 2 -C 8 ) alkenyl group include, but are not limited to, ethylene, propylene, 1-butylene, 2-butylene, isobutylene, sec-butylene, 1-pentene, 2-pentene, isopentene, 1-hexene, 2-hexene, 3-hexene, isohexene, 1-heptene, 2-heptene, 3-heptene, isoheptene, 1-octene, 2-octene, 3-octene, 4-octene, and isooctene. An alkenyl group can be unsubstituted or optionally substituted with one or more substituents.
The term “Ar” as used herein refers to an aromatic or heteroaromatic moiety. An “aromatic” moiety refers to a 6- to 14-membered monocyclic, bicyclic or tricyclic aromatic hydrocarbon ring system. Examples of an aromatic group include phenyl and naphthyl. An aromatic group can be unsubstituted or optionally substituted with one or more substituents. The term “heteroaromatic” as used herein refers to an aromatic heterocycle ring of 5 to 14 members and having at least one heteroatom selected from nitrogen, oxygen and sulfur, and containing at least 1 carbon atom, including monocyclic, bicyclic, and tricyclic ring systems. Representative heteroaromatics are triazolyl, tetrazolyl, oxadiazolyl, pyridyl, furyl, benzofuranyl, thiophenyl, benzothiophenyl, quinolinyl, pyrrolyl, indolyl, oxazolyl, benzoxazolyl, imidazolyl, benzimidazolyl, thiazolyl, benzothiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, cinnolinyl, phthalazinyl, quinazolinyl, pyrimidyl, azepinyl, oxepinyl, naphthothiazolyl, quinoxalinyl. A heteroaromatic group can be unsubstituted or optionally substituted with one or more substituents.
The term “halogen” as used herein refers to —F, —Cl, —Br or —I.
As used herein, the term “heteroatom” is meant to include oxygen (O), nitrogen (N), and sulfur (S).
The term “chromoionophore” as used herein refers to a compound comprising at least one ionophore and at least one chromophore.
The following abbreviations are used herein and have the indicated definitions: LAH is lithium aluminum hydride; DMF is dimethylformamide; NMR is nuclear magnetic resonance; THF is tetrahydrofuran.
Compounds of the Invention
The present invention provides compounds of Formula (I) referred to as “chromoionophores”
wherein r and s are as defined above.
In one embodiment, the chromophoric moiety L is selected from the group consisting of —NO 2 , Formula (II) and (III),
wherein, Ar is a (C 6 -C 10 ) aromatic moiety or a (C 5 -C 14 ) heteroaromatic moiety containing one or more heteroatoms selected from N, O, and S, and wherein Ar is substituted with one or more substituents selected from the group consisting of hydrogen, —NO 2 , —NO, —CN, (C 1 -C 8 ) straight chain or branched alkyl, (C 2 -C 8 ) alkenyl, halogen, —SO 3 H, —W—COOH, —W—N(R 1 ) 3 , —C(O)OR 1 , —C(O)R 1 ; W is (C 1 -C 8 ) alkylene; and R 1 is selected from the group consisting of hydrogen and (C 1 -C 8 ) straight chain or branched alkyl.
In another embodiment, Ar is selected from the group consisting of Formula (IV), (V), (VI), and (VII)
wherein X is O or S, and Y is N or C;
R 2 , at each occurrence, is independently selected from the group consisting of hydrogen, —NO 2 , —NO, —CN, C 1 -C 8 straight chain or branched alkyl, (C 2 -C 8 ) alkenyl, halogen, —SO 3 H, -Q-COOH, -Q-N(R 4 ) 3 , —C(O)OR 4 , —C(O)R 4 .
R 3 is -Q-SO 3 − or -Q-COO − .
Q is (C 1 -C 8 ) alkylene.
R 4 is selected from the group consisting of hydrogen and (C 1 -C 8 ) straight chain or branched alkyl;
Variable l is an integer selected from 1 to 3; m is an integer selected from 1 to 7; n is an integer selected from 1 to 5; and p is an integer selected from 1 to 6.
Specific examples of compounds of Formula I are provided below:
The invention further provides methods of determining sodium ion in a sample comprising a chromoionophore according to Formula (I) and sodium ions, where the chromoionophore has the general Formula (I)
wherein r and s are as defined above.
The invention further provides methods of determining sodium ion in a sample comprising a chromoionophore according to Formula (I) and sodium ions, where the chromophoric moiety L is selected from the group consisting of —NO 2 , Formula (II) and (III),
wherein, Ar is a (C 6 -C 10 ) aromatic moiety or a (C 5 -C 14 ) heteroaromatic moiety containing one or more heteroatoms selected from N, O, and S, and wherein Ar is substituted with one or more substituents selected from the group consisting of hydrogen, —NO 2 , —NO, —CN, (C 1 -C 8 ) straight chain or branched alkyl, (C 2 -C 8 ) alkenyl, halogen, —SO 3 H, —W—COOH, —W—N(R 1 ) 3 , —C(O)OR 1 , —C(O)R 1 ; W is (C 1 -C 8 ) alkylene; and R 1 is selected from the group consisting of hydrogen and (C 1 -C 8 ) straight chain or branched alkyl.
The invention further provides methods of determining sodium ion in a sample comprising a chromoionophore according to Formula (I) and sodium ions, where Ar is selected from the group consisting of Formula (IV), (V), (VI), and (VII)
wherein X is O or S, and Y is N or C;
R 2 , at each occurrence, is independently selected from the group consisting of hydrogen, —NO 2 , —NO, —CN, C 1 -C 8 straight chain or branched alkyl, (C 2 -C 8 ) alkenyl, halogen, —SO 3 H, -Q-COOH, -Q-N(R 4 ) 3 , —C(O)OR 4 , —C(O)R 4 .
R 3 is -Q-SO 3 − or -Q-COO − .
Q is (C 3 -C 8 ) alkylene.
R 4 is selected from the group consisting of hydrogen and (C 1 -C 8 ) straight chain or branched alkyl.
Variable l is an integer selected from 1 to 3; m is an integer selected from 1 to 7; n is an integer selected from 1 to 5; and p is an integer selected from 1 to 6.
The invention further provides methods of determining sodium ion in a sample comprising a chromoionophore according to Formula (I) and sodium ions, where the sample is a biological fluid. Examples of biological fluids are whole blood, plasma, serum, and urine.
The invention further provides methods of determining sodium ion in a sample comprising a chromoionophore according to Formula (I) and sodium ions, where the sample has a pH of 6.5 or above.
Preparation of the Compounds of Formula (I)
Those skilled in the art will recognize that there are a variety of methods available to synthesize molecules described herein. The synthesis of the chromoionophore (Na6) and (Na12) from commercially available compounds is illustrated in FIG. 1 . o-Anisidine (Na1) was di-alkylated with 2-chloroethanol then reacted with bis[(2-chloro-ethoxy)]ethane. The resultant phenylazacrown ether (Na3) was coupled with diazonium (Na5) to afford chromoionophore (Na6). Na3 was also converted to (Na12).
Example 1
N,N-Bis(2-hydroxylethyl)-2-methoxyaniline (Na2). Na1 (452 g, 4 mol) was dissolved in 2-chloroethanol (1,932 g, 24 mol) and heated to 80° C. for 15 min. K 2 CO 3 (608 g, 4.4 mol) was slowly added such that the temperature of this exothermic reaction was kept below 110° C. The mixture was heated at 95° C. for 22 h., cooled and approximately 800 mL of unreacted 2-chloroethanol was removed under vacuum. The residue was diluted with water (1 L) and extracted with CHCl 3 (2×1 L). The CHCl 3 solutions were back-washed with water (5×1.5 L), dried over K 2 CO 3 and the solvent evaporated to afford 404 g (48%) of a light brown oil. 1 H NMR (CDCl 3 ): δ=3.18 (t, 4H), 3.50 (t, 4H), 3.60 (m, 2H), 3.82 (s, 3H), 6.90 (m, 2H), 7.10 (m, 1H), 7.19 (m, 1H). Anal. Calcd. for C 11 H 17 NO 3 : C, 62.54; H, 8.11; N, 6.63. Found: C, 61.33; H, 8.28; N, 6.43.
Example 2
2-Methoxyphenylaza-15-crown-5 (Na3). Na2 (403 g, 1.91 mol) was dissolved in dioxane (2.21 L) and heated at 80° C. for 20 min. Powdered NaOH (168 g, 4.20 mol) was added slowly within about 3 h. The temperature was then increased to 95° C., bis(2-chloroethanoxyethane) (300 mL, 1.93 mol) added in one portion and the mixture kept at 95° C. for 30 h. The suspension was then filtered hot, the solvent evaporated, and the residue treated with a solution of NaClO 4 (234 g, 1.91 mol) in methanol (640 mL). The mixture was stirred at 60° C. for 30 min and concentrated to about 300 mL. Ethyl acetate (860 mL) was added, the mixture stirred at room temperature for 20 min then allowed to stand at room temperature for 2 h. The resulted precipitate was filtered, washed with ethyl acetate (2×200 mL) and dried at room temperature for 30 min to give 199 g of azacrown-sodium perchlorate complex as a soft white powder. This powder was dissolved in a mixture of CH 2 Cl 2 (600 mL) and water (600 mL), the layers separated and the aqueous phase was extracted with CH 2 Cl 2 (400 mL). The organic solutions were combined, washed with water (8×600 mL), dried over Na 2 SO 4 then evaporated to afford 100.4 g (16%) of pale yellow oil. 1 NMR (CDCl 3 ) δ=3.49 (t, 4H), 3.68 (t, 16H), 3.82 (s, 3H), 6.88 (m, 3H), 7.12 (m, 1H). Anal. Calcd for C 17 H 27 NO 5 : C, 62.70; H, 8.36; N, 4.30. Found: C, 61.63; H, 8.44; N, 4.26.
Example 3
4-(2′,4′-Dinitrophenylazo)-2-methoxyphenylaza-15-crown-5 (Na6, R═NO 2 ). Na3 (1.62 g, 5 mmol) was dissolved in 50 mL tetrahydrofuran and the resulting solution was diluted with 50 mL methanol. To this solution 2.54 g (10 mmol) 2,4-dinitrophenyldiazonium tetrafluoroborate was added in three portions. The suspension was stirred at room temperature for 2 hours. When TLC showed that Na3 was gone, the solvent was evaporated and the residue was dissolved in 500 mL chloroform, washed 500 mL water. The solvent was evaporated to get about 3.32 g oily gum. This crude product was purified with a short column, packed with 25 g silica gel, eluted with chloroform to remove front impurities, then using chloroform/methanol (99/1, v/v) to get 0.84 g dark red gum product. 1 H NMR (CDCl 3 ) 3.60 (t, 16H), δ=3.70 (t, 4H), 3.82 (s, 3H), 6.78 (d, 1H), 7.36 (d, 1H), 7.52 (m, 1H), 8.22 (d, 2H), 8.80 (s, 1H).
Example 4
Synthesis of Na8 (R═CH 2 COOEt). Under the cooling of ice-water bath, sodium nitride 1.39 g (20 mmol) was added to 16 g (40.8 mmol) concentrated sulfuric acid and stood for five minutes, then warmed to 60° C., the solution became clear. The solution was cooled to under 0° C. with ice-salt bath; then 3.72 g (20 mmol) ethyl 2-aminothiazole-4-acetate was added in one portion. The solution was kept at under 0° C. and stirred for two hours. KI-starch paper monitored the free nitrous acid until reaction completed. Used immediately for next step.
Example 5
Synthesis of Na9 (R═CH 2 COOEt). Under the cooling of ice-water, the solution of Na8 was slowly transferred into the solution of Na3 (4.87 g (3 mmol) and sodium acetate 8.10 g (82 mmol) in 50 mL acetic acid. The resulting suspension mixture was stirred overnight and poured into stirring 400 mL DI water, extracted with 200 mL chloroform. The organic layer was washed with 200 mL sat. sodium carbonate, 200 mL DI water, dried over anhydrous sodium sulfate. The solvent was evaporated and the residue was further purified with 10 g silica gel 60 using chloroform:methanol 9:1 (v/v) as elution to afford 2.53 g dark red product. 1 H NMR (CDCl 3 ) 1.25 (t, 3H), 3.60 (t, 16H), δ=3.70 (t, 4H), 3.82 (s, 3H), 4.20 (q, 2H), 6.75 (d, 1H), 7.35 (d, 1H), 7.48 (m, 1H), 8.20 (s, 1H).
Example 6
Synthesis of Na10 (R═CH 2 COOH). To a solution of 2.50 g Na9 in 50 mL methanol was added 10 mL water and 10 mL 1 N KOH. The resulting solution was warmed to 60° C. and let it cooled to room temperature for 1 h. The solvent was evaporated and the residue was dissolved in 5 mL methanol. This solution was directly used as stock solution.
Example 7
Synthesis of Na11. Na3 (100 g, 308 mmol) was dissolved in DMF (145 mL, 1850 mmol) in a 500 mL three-neck flask and cooled to −5° C. POCl 3 (57.4 mL, 616 mmol) was added dropwise via an addition funnel such that the solution temperature did not exceed 5° C. After stirring at room temperature for 16 h, the solution was heated to 60° C. for 1 h, cooled, poured into 500 g ice, the flask rinsed flask with 70 mL water, and the combined aqueous solutions adjusted to pH 7 (by pH paper) with saturated K 2 CO 3 . The solution was extracted with CHCl 3 (2×500 mL), the CHCl 3 phase washed with water (2×500 mL) then dried over MgSO 4 (100 g) for 1 h. Evaporation of the solvent afforded 85 g light yellow oil that crystallized upon standing overnight. Re-crystallization from ethyl acetate/hexane (1:4) afforded 56 g (51%) light orange crystals. 1 H NMR (CDCl 3 ) δ=3.68 (t, 16H), 3.78 (t, 4H), 3.82 (s, 3H), 7.05 (m, 1H), 7.28 (m, 2H), 9.78 (s, 1H). Anal. Calcd for C 18 H 27 NO 6 : C, 61.17; H, 7.70; N, 3.96. Found: C, 61.05; H, 8.01; N, 4.04.
Example 8
Synthesis of Na12. Na11 (0.35 g, 1 mmol) was dissolved in 10 mL 10 mL ethanol. To this solution 0.35 g (1.1 mmol) 2-methyl-1-(3-sulfopropyl)naphtho[1,2-d]thiazolium inner salts and 0.11 g (1.1 mmol) triethylamine were added. The resulting solution was stirred under reflux for 18 h. after cooling. The solvent was evaporated and the residue was purified by a silica gel column with CHCl3/methanol (99/1,v/v) as eluent to give 0.48 g dark brown powder. 1 H NMR (CDCl 3 ) δ=2.1 (m, 2H), 3.45 (m, 4H) 3.68 (t, 16H), 3.78 (t, 4H), 3.82 (s, 3H), 6.9-8.3 (m, 9H).
Example 9
Method of Determining Sodium Ions: Solvents and reagents are purchased from Aldrich (Milwaukee, Wis.) and used without further purification. Analytical grade buffer and inorganic salts are purchased from either Fluka AG (Buchs, Switzerland) or Sigma Co. (St. Louis, Mo.). Absorption measurements are performed with a Shimadzu UV2101PC spectrophotometer equipped with a jacketed cuvette holder for controlling of temperature. Titration of a chromoinophore is carried out in the following manner: A methanolic solution of a chromoionophore is diluted with buffer, deionized water or deionized water with organic co-solvent in a volumetric flask to make about 30 μM final solution, the required amount of solid salt is added and the solution's absorption spectrum is measured. The typical titration spectra are shown in FIG. 2 .
A sodium colorimetric reagent used for FIG. 3 is formulated as follows: a methanolic solution containing of about 2.3 mg of calorimetric sodium indicator Na10 (R═CH 2 COOH) is mixed with 0.905 g tetramethylammonium hydroxide pentahydrate and 0.0292 g ethylenediaminetetraacetic acid. The resulting mixture is dissolved in methanol and bring the total volume to 100 ml. 2.7 ml of this solution is mixed with 0.3 ml serum or aqueous sample, incubated at 37° C. for 5 min. The absorption values are recorded at wavelength of 486 nm, and are used to plot the chart shown in FIG. 3 . | The invention relates to methods of determining sodium ions in a sample, wherein the ions are contacted with a compound having chromophoric moiety and an ionophoric moiety, where the ionophoric moiety interacts with the sodium ions present in the sample, resulting in the chromophoric moiety changing its radiation absorption properties in the ultraviolet and visible regions of the spectrum. For example, a change in an intensity of an absorption maximum is measured and the ion concentration is determined accordingly. | 2 |
RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Serial No. 60/972,798 filed on Sep. 15, 2007 entitled “Vehicle Launcher Assembly,” which is hereby incorporated by reference as if set forth in full in this application for all purposes.
BACKGROUND OF THE INVENTION
[0002] Toy vehicles that can be launched from another object are a source of amusement for children and adults alike. Some examples of previous vehicle launching platforms include motorcycles launched from carrying cases, aircraft launched from space vehicles, and cars or trucks launched from helicopters, tractors, or other cars. The ways in which a vehicle departs its carrier object have included launching from a split-open front end of a vehicle, exiting the trunk area at the rear of a truck, and dropping from the bottom of a carrier. Regarding the mobility of vehicle launchers, launched vehicles have been configured to be spring-launched from a carrier, to have an independent power source from its mother vehicle, or to be the power source for enabling its carrying vehicle to move. There is a continuing demand for novel features and developments in vehicle launchers to provide new and exciting modes of entertainment.
SUMMARY OF THE INVENTION
[0003] This invention sets forth a vehicle launcher assembly comprising an inner vehicle carried within an outer vehicle. The outer vehicle has movable panel components which allow an inner vehicle to be released from the outer vehicle when the panel components are opened. Operation of the toy assembly involves a first actuation step to open the panels of the outer vehicle, and second actuation step to launch the inner vehicle. The outer vehicle is operable as a moving vehicle with or without the inner vehicle enclosed inside. In one embodiment, the outer vehicle is in the form of a car and the inner vehicle is in the form of a motorcycle. The vehicle launcher assembly may also include projectile launchers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0004] Other advantages of the present invention will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein:
[0005] FIG. 1 provides a perspective view of an embodiment of the vehicle launcher assembly with an inner vehicle having been launched;
[0006] FIG. 2 depicts a perspective view of the outer vehicle of FIG. 1 in a closed state;
[0007] FIG. 3 illustrates a projectile launching mode of the vehicle launcher assembly of FIG. 1 ;
[0008] FIG. 4 is a top view of another embodiment according to the present invention, in which the outer vehicle is expanded; and
[0009] FIG. 5 provides a top view of the outer vehicle of FIG. 4 in a closed state.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0010] FIG. 1 provides a perspective view of one embodiment of a vehicle launcher assembly 10 according to the present invention. An outer vehicle 11 of vehicle launcher assembly 10 includes a base 12 , a top panel 13 hingedly attached to the rear of base 12 , two front wheels 14 , two side panels 15 pivotally coupled to front wheels 14 , rear wheels 16 , a projectile launching bay 17 mounted at the rear of top panel 13 , and a launching mechanism 18 mounted on base 12 . An inner vehicle 20 , depicted here as a motorcycle with a rider, has a back end 21 . Back end 21 of inner vehicle 20 mates with launching mechanism 18 , which in this embodiment comprises a spring-release mechanism for ejecting inner vehicle 20 . The spring-release mechanism may incorporate a compressed spring released by a push button on the rear of outer vehicle 11 , not shown in this view of FIG. 1 , or may incorporate other means known in the art for releasably ejecting objects. Outer vehicle 11 in FIG. 1 is depicted in an expanded state, in which top panel 13 is pivoted upward as shown by arrow 22 , and side panels 15 are swung outward and upward as indicated by arrows 23 and 24 , respectively. When outer vehicle 11 is in this expanded state, the inner vehicle 20 may be ejected as depicted by directional arrow 25 .
[0011] FIG. 2 shows a perspective view of the outer vehicle 11 from FIG. 1 in a compacted or closed state, in which top panel 13 and side panels 15 have been manually closed by a user. Alternatively, top panel 13 and side panels 15 may be closed with a lever, button, sliding mechanism or the like, which are mechanically coupled to top panel 13 and side panels 15 . In this closed state, outer vehicle 11 takes the form of a car. However, other types of vehicles such as trucks, aircraft, or water vehicles are also possible. The compacted outer vehicle 11 of FIG. 2 may be rolled on its wheels 14 and 16 to be operated as a vehicle either with or without inner vehicle 20 inside. In this view, an actuation button 26 , a projectile mode button 27 , and a trigger button 28 can be seen on top of outer vehicle 11 . To return the outer vehicle 11 of FIG. 2 to an expanded state, the user presses actuation button 26 . Actuation button 26 may alternatively take the form of a lever, a rocker switch, or the like. Actuation button 26 is coupled to actuation means within outer vehicle 11 to release top panel 13 and side panels 15 as previously shown by arrows 22 , 23 , and 24 in FIG. 1 . The actuation means for releasing top panel 13 and side panels 15 may comprise means known in the art such as springs, latches, and arm linkages.
[0012] To operate the vehicle launcher assembly 10 of FIGS. 1 and 2 , a user inserts the inner vehicle 20 into the interior of outer vehicle 11 . The user pushes inner vehicle 20 rearward along base 12 until back end 21 engages and locks into launching mechanism 18 . The user then closes top panel 13 as well as side panels 15 , and may proceed to play with outer vehicle 11 with inner vehicle 20 loaded inside. A user may eject inner vehicle 20 by first pressing actuation button 26 to open outer vehicle 11 to an expanded state. Next, the user presses a release button, not shown, on the rear of outer vehicle 11 to actuate launching mechanism 18 . An actuation component, such as a compressed spring or other means known in the art, within launching mechanism 18 propels inner vehicle 20 forward. Once it is released from outer vehicle 11 , inner vehicle 20 moves forward under its own inertia. Outer vehicle 11 may additionally include a seat pocket, not shown, within base 12 such that a play figure may be inserted after inner vehicle 20 is launched.
[0013] FIG. 3 shows an additional, optional mode of the vehicle launcher assembly 10 from FIG. 1 . The mode shown in FIG. 3 depicts a projectile launching mode, in which a user may launch projectiles 29 from projectile launching bay 17 . A user may transform the vehicle launcher assembly 10 from the compacted form of FIG. 2 to the projectile launching mode of FIG. 3 by pressing projectile mode button 27 located on the top of outer vehicle 11 . In the projectile launching mode, side panels 15 are displaced outward as shown by the arrows 30 , projectile launching bay 17 is extended upward from its stored position as shown by arrow 31 , and top panel 13 remains stationary. Inner vehicle 20 is seen to remain inside outer vehicle 11 in this mode. To launch projectiles 29 , the user presses trigger button 28 located near projectile mode button 27 . Although this embodiment of FIG. 3 is configured to launch two projectiles 29 , it may be configured to house only one projectile or more than two, as allowed by the space available within projectile launching bay 17 . In the case where multiple projectiles 29 are present, a single trigger button 28 may launch all projectiles simultaneously, or multiple trigger buttons 28 may be utilized to individually control each projectile. Furthermore, a single trigger button 28 may be coupled to an indexing mechanism to launch projectiles 29 sequentially.
[0014] FIG. 4 depicts another embodiment according to the present invention, in which side panels shift laterally outward rather than angling outward and upwardly as in the embodiment of FIG. 1 . Similar to vehicle launcher 10 of FIG. 1 , this vehicle launcher assembly 40 of FIG. 4 comprises an inner vehicle 41 and an outer vehicle 42 , with outer vehicle 42 including a top panel 43 , a plurality of wheels 44 , and side panels 45 . However, side panels 45 shift laterally outward as indicated by arrows 53 . Additionally, outer vehicle 42 includes a launching tube 47 above each side panel 45 , and also includes an actuation button 48 and a launching button 49 at the rear of outer vehicle 42 . A projectile 51 is loaded into each launching tube 47 , and each launching tube 47 further includes a back end 52 . Launching tubes 47 may include a trigger button, not shown, located at back end 52 for launching projectiles 51 . The outer vehicle 42 of FIG. 4 is shown in an expanded state in which side panels 45 are displaced laterally outward as shown by arrows 53 , and the front of top panel 43 hinges upwardly as shown by arrow 54 .
[0015] FIG. 5 shows the corresponding closed outer vehicle 42 from FIG. 4 , in which a user has manually closed side panels 45 and top panel 43 by pushing them inward and downward, respectively. Alternatively, top panel 43 and side panels 45 may be closed using a lever, a button, or the like mechanically coupled to top panel 43 and side panels 45 . With the inner vehicle 41 loaded inside outer vehicle 42 , a user operates the vehicle launcher assembly 40 by first pressing actuation button 48 . Pressing actuation button 48 causes top panel 43 and side panels 45 to open to the expanded state of FIG. 4 . When the launching button 49 is pressed, a spring-release mechanism within the outer vehicle 42 is released, and the inner vehicle 41 is launched from outer vehicle 42 . Inner vehicle 41 and outer vehicle 42 may operate independently using their own set of wheels, or outer vehicle 42 may be operated with inner vehicle 41 encased inside. The interior of outer vehicle 42 may be configured with a seat pocket to accommodate a play figure when inner vehicle 41 is not occupying the interior of outer vehicle 42 .
[0016] The present invention may include variations of the movable top and side panels which have been disclosed. For instance, a side panel of the outer vehicle may have a hinged joint across its width so that it accordion-folds when actuated. In another example, a top panel may be split along its length such that its two halves rotate outwardly rather than upwardly as previously described. Furthermore, while the figures depict the invention in the form of wheeled vehicles, other types of vehicles such as spacecraft and water vehicles are applicable.
[0017] While the specification has been described in detail with respect to specific embodiments of the invention, it will be appreciated that those skilled in the art, upon attaining an understanding of the foregoing, may readily conceive of alterations to, variations of, and equivalents to these embodiments. These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention. Thus, it is intended that the present subject matter covers such modifications and variations as come within the scope of the appended claims and their equivalents. | This invention sets forth a vehicle launcher assembly comprising an inner vehicle carried within an outer vehicle. The outer vehicle has movable panel components which allow an inner vehicle to be released from the outer vehicle when the panel components are opened. Operation of the toy assembly involves one actuation step to open the panels of the outer vehicle, and second actuation step to launch the inner vehicle. In one embodiment, the outer vehicle is in the form of a car and the inner vehicle is in the form of a motorcycle. The vehicle launcher assembly may also include projectile launchers. | 0 |
[0001] This application claims the benefit of U.S. Provisional Application 61/869,471, filed Aug. 23, 2013.
BACKGROUND
[0002] On the surface of bodies of water, or below the surface, debris can accumulate, such as refuse, algae and floating aquatic vegetation.
[0003] U.S. Pat. Nos. 3,811,325; 3,863,237; 5,450,713; 5,705,058; 7,111,741 and 7,603,836 disclose various skimming or raking screens that are pulled through the water by handles or ropes, some floating and others non-floating.
[0004] U.S. Patent Applications 2012/0124957 and 2010/0263347 U.S. Pat. No. 7,771,593 disclose floating pond raking or skimming devices.
[0005] It would be desirable to provide a pond rake that is light weight and able to be handled and deployed by a user, while also being effective in collecting floating vegetation, algae and other debris.
SUMMARY
[0006] A water rake is provided that is lightweight and effectively handled and deployed by a user. The rake provides an apparatus that not only effectively screens water surfaces, and below, but provides a mechanism to retain debris or collected material in the rake for removal and disposal. When held in a vertical orientation debris or collected material can be released by gravity. The rake is adjustable in buoyancy to collect materials at or below the water surface.
[0007] A water rake is provided that includes a handle and a frame attached to the handle. The handle extends rearward from the frame. The frame has an open area closed by a net. A plurality of prongs extends from the frame generally in a rearward direction. The prongs help retain debris and other collected material in the net or otherwise collected by the frame.
[0008] The frame is preferably rectangular. The open area of the frame defines a plane and the prongs are arranged at an oblique angle relative to the plane.
[0009] Prongs along a top area of the frame are declined from the frame and prongs along a bottom area of the frame are inclined from the frame.
[0010] The handle and frame comprise tubular members.
[0011] The frame can be entirely sealed from ingress or egress of water.
[0012] A valve is provided on the rake to selectively accept water into the frame and retain the water in the frame, i.e., in the tubular members of the frame.
[0013] An angled brace is connected between the handle and the frame, wherein the brace is also tubular and in flow communication with the frame and mounts the valve.
[0014] Alternately, only selected portions of the rake can receive and retain water, such as the frame, or the brace and the frame. The handle, for example can be sealed from the inside of the frame and could be sealed from ingress or egress of water within the handle, or not.
[0015] Numerous other advantages and features of the present invention will become readily apparent from the following detailed description of the invention and the embodiments thereof, from the claims and from the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a perspective view of a rake according to the invention;
[0017] FIG. 2 is a sectional view taken generally along line 2 - 2 of FIG. 1 ;
[0018] FIG. 3 is an enlarged elevation view taken from FIG. 1 ; and
[0019] FIG. 4 is a sectional view taken generally along line 4 - 4 of FIG. 2 .
DETAILED DESCRIPTION
[0020] While this invention is susceptible of embodiment in many different forms, there are shown in the drawings, and will be described herein in detail, specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated.
[0021] FIG. 1 illustrates a rake 10 having in a rectangular collecting frame 14 connected to an elongated handle 18 . The handle extends rearward from the frame toward a user. An angular brace 20 is connected between the frame 14 and handle 18 .
[0022] A tension wire 26 forms a triangle between three fixed fastening locations 30 , 32 , 34 located on the handle 18 and frame 14 respectively. The tension wire 26 structurally stabilizes the frame with respect to the handle, and prevents bending or breaking of the frame 14 subject to vegetation resistance as the frame 14 is pulled through and out of the water by the handle. The locations can be fasteners that are fastened into the frame and handle, wherein the wire is tightly wound a few turns around the fastener.
[0023] The frame 14 includes a top member 40 , and a parallel bottom member 42 connected together by opposite side members 44 , 46 . The members 40 , 42 , 44 , 46 are preferably hollow tubes and can be connected together by 90° hollow tube joints 52 .
[0024] The handle 18 can be attached to the member 40 using a clamp or a tee joint such as a tubular tee member 56 . In the case of using a tee member, the member 40 is cut and fit into the tee member such that the handle, tee member and upper member 40 are open to each other on the inside.
[0025] The brace 20 can be attached to the frame member 42 using a clamp joint or a tubular tee member 56 . In the case of using a tee member, the lower frame member 42 is cut and fit into the tee member such that the brace 20 , the tee member 56 and the lower frame member 42 are open to each other on the inside.
[0026] The handle 18 is preferably a hollow tube and is closed at a distal end to the frame 14 by a cap 60 . A faster such as an eye-bolt 62 is fixed to an end of the cap 60 and is used for attaching a rope 64 to the handle 18 . The rope 64 is sufficiently long for the user to cast the rake out into the pond at a distance from the user. The user can then draw back the rake toward the user handle side first, by reeling in the rope, to rake through the pond.
[0027] FIGS. 1 and 2 show that the upper frame member 40 mounts downwardly angled prongs or rods 70 . The prongs are spaced apart along the frame member 40 . The rods 70 extend perpendicularly from the frame member, in parallel, in a direction generally toward the distal end of the handle. The lower frame member 42 mounts upwardly angled prongs or rods 72 that are spaced apart along the frame member 42 . The rods 72 extend perpendicularly from the frame member 42 , in parallel, in a direction generally toward the distal end of the handle. The rods 70 , 72 can be tubular. The rod 70 in FIG. 2 is shown in section to show the attachment method for the rods 70 , 72 . Each of the rods 70 , 72 is mounted to the frame by a screw 70 a with a head diameter similar to the diameter of the rods 70 , 72 . The screw 70 a freely extends through the rod and is threaded through the wall of the tubular frame member adjacent to the rod and is threaded into but does not penetrate the opposite side of the tubular frame member. Other ways of fastening the rods 70 , 72 to the frame are encompassed by the invention.
[0028] A net 80 closes a rectangular open side of the frame 14 defined between the members 40 , 42 , 44 , 46 , opposite the handle 18 . The net has openings sufficiently large to allow water and small objects to past therethrough as the rake is pulled through the water, but small enough to capture the desired vegetation and debris to be removed from the water. The net openings are square with sides parallel to the respective frame sides and can have a width dimension of ¾ to 1″. Alternatively, a lacing or webbing can be provided by lacing or criss-crossing rope or the like between the rods 70 , 72 .
[0029] FIG. 3 illustrates the connection area of the brace 20 in the handle 18 . The brace 20 terminates in a valve 90 having an open/close mechanism 94 , and an oblique angle fitting such as a 22.5° fitting or a 45° fitting 98 connected to the valve 90 . The fitting has an open end 100 covered by a fine screen 100 a to prevent debris from entering the open end 100 . The fitting 98 is tightly clamped by a pipe clamp 102 or the like. The pipe clamp 102 includes a fastener 104 that penetrates through holes through the handle 18 and is tightened by a nut 106 to fasten the pipe clamp 102 and brace 20 tightly to the handle 18 . Preferably, the handle 18 , the frame 14 and the brace 20 are all in flow communication via the hollow insides of the tube members. The elbow joints 52 and the tee joints 56 are also in flow communication with the members attached thereto.
[0030] The valve 90 allows for the entry of a desired amount of water into the rake 10 . By opening the valve while the valve and fitting are submerged, water can pass into the rake through the valve. This can be used to set a desired buoyancy for a desired skimming depth of the frame in the water as a rake 10 is pulled through the water.
[0031] FIGS. 2 and 4 illustrate some advantageous dimensions. The overall length L of the frame 14 can be 52, 46 or 40 inches, but the invention encompasses other sizes as well. The handle can be 5 feet, 6 inches. The overall width W of the frame 14 can be 8 inches. The spacing of the upper prongs 70 along the member 40 can be 3 inches. The spacing of the lower prongs 72 along the member 42 can be 3 inches. The upper prongs are preferably in line with the lower prongs along the length of the frame. The number of upper prongs can be 16. The number of lower prongs can be 16. The prongs preferably have a length L3 of about 2 inches and a diameter of about ¼ inch. With the handle 18 held horizontal and the frame 14 oriented vertically, the angle β of the prongs 70 , 72 to horizontal is preferably about 35 degrees.
[0032] Advantageously, the members 20 , 40 , 42 , 44 , 46 , and 52 are tubular plastic pipe elements having a nominal diameter of ¾ inches. Advantageously, the member 18 can be tubular plastic pipe element having a nominal diameter of 1 inch. The upper member 56 can be a tubular plastic pipe element having nominal diameters of 1 inch×¾ inch×¾ inch. The lower member 56 can be a ¾″ by ¾″ by ¾″ tee.
[0033] From the foregoing, it will be observed that numerous variations and modifications may be effected without departing from the spirit and scope of the invention. It is to be understood that no limitation with respect to the specific apparatus illustrated herein is intended or should be inferred. | A water rake for skimming vegetation and debris off ponds includes a handle and a frame. The frame is attached to the handle and the handle extends rearward from the frame. The frame has an open area closed by a net or web to capture the vegetation or debris as the rake is pulled through the water. A plurality of spaced-apart prongs are connected at base ends to the frame and extend from the frame generally in a rearward direction to retain collected vegetation and debris in the net or web, or otherwise collected in the frame. | 0 |
FIELD OF THE INVENTION
[0001] This invention is in the field of compositions and methods of treatment for dental bleaching agents, and more specifically in the prevention of post-bleaching induced hypersensitivity.
BACKGROUND OF THE INVENTION
[0002] The process of dental bleaching is an increasingly popular practice in dentistry to combat the problem of staining or discoloration of teeth.
[0003] The enamel layer of teeth is composed of hydroxyapatite. It is believed that the porous nature of the enamel is attributed to the crystalline structure of hydroxyapatite, which allows staining agents and discoloring substances to permeate the enamel, thereby discoloring teeth. Substances that come in contact daily with teeth and that can stain or reduce the “whiteness” of teeth include foods, tobacco products, tea, coffee, betel nut, plants and food products. These substances permeate the enamel of the teeth and with continued contact impart noticeable discoloration to the teeth.
[0004] In addition, teeth may become stained from excessive intake of fluoride (endemic fluorosis). In young persons, the administration of tetracycline during tooth formation may cause staining. Generalized intrinsic staining can result from systemic conditions and diseases such as cystic fibrosis, congenital hematoporphia and dentinogenesis imperfecta.
[0005] Since white or unstained teeth are considered to improve a person's appearance, it is generally desired by patients to try to increase the whiteness of the teeth. Methods of improving the whiteness of teeth include bleaching methods which can be used to ameliorate the staining of teeth. However, known effective bleaching procedures for teeth also result in the undesired effect of tending to produce hypersensitivity or supersensitivity of the teeth. It has been reported that 74% of incidents of dental bleaching result in post-bleaching pain (hypersensitivity) to the patient. Bleaching compositions generally use peroxide or peroxide yielding compounds which have tended to involve the activation of peroxide by light sources such as photo flood light, ultraviolet light, or by heat methods such as convection heat or by the application of heat directly to teeth. These methods require the use of high concentrations of peroxide, such as in the form of Superoxol® or a 35% peroxide composition, which not only cause hypersensitivity but also have the potential to damage oral and facial tissues.
[0006] Passive bleaching involves the use of bleaching agents supplied directly in dentrifice compositions for brushing the teeth, or gels, foams, creams or pastes which are applied in prefabricated trays and/or in custom trays fabricated with reservoirs to hold bleaching preparations in extended intimate contact with the teeth for longer periods of time. Passive bleaching agents have been used with photo flood lights and with lasers. It is now understood that the teeth can be made whiter by passive bleaching methods using peroxide releasing compounds such as carbamide peroxide, also known as urea peroxide, usually in the amount of 10% to 20% by weight of the composition. The higher concentrations of the peroxide yielding compounds are used to effect faster and more effective bleaching (power bleaching). Other peroxide releasing compounds that have been known in the prior art include sodium perborate, zinc peroxide, calcium peroxide and magnesium peroxide, and other compounds which can release peroxide effectively with bubbling oxidizing force.
[0007] In general, higher concentrations of peroxide yielding compounds improve the efficacious bleaching capabilities of the composition. However, the higher peroxide concentrations exacerbate the sequelae of hypersensitivity or supersensitivity. The pain resulting from hypersensitivity or supersensitivity is considered to be a warning that the tooth and pulpal tissues have experienced a severe insult. Faster and more aggressive bleaching techniques, such as with the use of higher concentrations of peroxide yielding compounds, results in more severe and higher incidence of post-bleaching hypersensitivity to thermal, chemical and tactile stimuli.
[0008] Dental bleaching compositions are described in a number of-references, including U.S. Pat. No. 5,098,303; U.S. Pat. No. 5,234,342; U.S. Pat. No. 5,376,006; and U.S. Pat. No. 5,409,631, all to Fischer, which are hereby incorporated by reference. The Fisher patents describe tooth bleaching dental gel composition comprising carbamide peroxide, water, glycerin carboxypolymethylene (Carbopol) and sodium hydroxide. Dental bleaching compositions are also described in U.S. Pat. No. 5,631,000, to Pellico et al., which is hereby incorporated by reference.
[0009] The use of potassium nitrate as a compound for desensitizing teeth is disclosed in U.S. Pat. No. 3,863,006, which is hereby incorporated by reference. Potassium nitrate has also been disclosed as useful for treatment of canker sores in U.S. Pat. No. 4,191,750, hereby incorporated by reference, useful for preserving dental pulp, in U.S. Pat. No. 4,343,608, hereby incorporated by reference, useful for treating gingival and periodontal tissues, in U.S. Pat. No. 4,400,373, hereby incorporated by reference, and useful for treating post-restoration dental pain, in U.S. Pat. No. 5,153,006, hereby incorporated by reference.
[0010] Other patents, including for example U.S. Pat. No. 5,256,402 and U.S. Pat. No. 5,648,399, have described the use of potassium nitrate in dentrifice compositions as a treatment for hypersensitivity. However, the use of potassium nitrate incorporated into dental tray bleaching compositions has not been previously described as being capable of preventing tooth hypersensitivity.
[0011] Another patent, U.S. Pat. No. 5,522,726 has described the use of a composition having a high concentration of potassium, such as potassium nitrate, for anesthetizing teeth requiring preparation, caries removal or manual manipulation thereof.
SUMMARY OF THE INVENTION
[0012] It has now been surprisingly discovered that the use of 1% to 35% of a potassium containing composition, such as potassium nitrate, by weight in passive bleaching materials comprising a peroxide releasing material prevents the frequently seen (up to 75% of the time) tooth hypersensitivity from occurring. The potassium nitrate contemplated by the invention is uniquely compatible with peroxide yielding bleaching compounds such as peroxide, carbamide peroxide, calcium peroxide, zinc peroxide, magnesium peroxide and sodium perborate.
[0013] In another aspect of the invention, it has-also been found that the potassium-containing composition, specifically potassium nitrate, which is known to be an oxidizing agent, is complimentary and synergistic with the peroxide bleaching agents contemplated by the invention and actually enhances the release of oxygen to the tooth enamel.
[0014] Preferred compositions of the invention may include from 1% to 35% by weight of potassium nitrate. In more preferred compositions of the invention, the potassium nitrate is present in the amount of 1-20%. In even more preferred embodiments, potassium nitrate is present in the amount of 1-8%. In a most preferred embodiment, potassium nitrate is present in a composition in the amount of about 5% by weight. The invention contemplates the use of higher amounts of potassium nitrate with higher amounts of peroxide releasing compounds.
[0015] The invention also contemplates the use of a potassium-containing composition comprising a compound other than potassium nitrate such as potassium bicarbonate, potassium biphthalate, potassium bromide, potassium chromate, potassium dichromate, potassium phosphate, potassium sulfate, potassium chromium sulfate, potassium thiocyanate, potassium alum, potassium bitartrate, potassium bromate, potassium carbonate, potassium chlorate, potassium chloroglatinate, potassium hydroxide, potassium perchlorate, potassium persulfate, potassium oxalate, potassium azide, potassium flouride, potassium hydrogen sulfate, potassium iodate, potassium chloride, potassium acetate or potassium tartrate. For the purposes of the invention and the description herein, these potassium-containing compounds may be used instead of potassium nitrate.
[0016] The invention contemplates the use of the potassium-containing compound such as potassium nitrate in liquids, gels, creams, pastes, foams and ointments with tooth bleaching compositions for the prevention of tooth hypersensitivity from occurring. In an additional embodiment, the invention is in the form of a lacquer or varnish or other surface coating that is painted to the teeth, thereby providing a longer contact/coating period. In all embodiments of the invention, the use of the potassium-containing compound such as potassium nitrate is a unique one-step method of preventing hypersensitivity when combined with the bleaching compositions known in the art, and is different from known methods of using potassium-containing compounds potassium nitrate for the treatment of hypersensitivity that has already occurred. This is an improvement over the known use methods of this technology, and the invention is directed to a method of preventing the usual tooth hypersensitivity from occurring following the application of the dental bleaching composition of the invention to teeth.
DETAILED DESCRIPTION OF THE INVENTION
[0017] By “orally compatible” is meant compositions and ingredients which are generally regarded as safe for use in the oral cavity.
[0018] By “oral compositions” is meant a product which in the ordinary course of its use is retained in the oral cavity for a time sufficient to contact substantially all of the dental surfaces and/or oral tissues for purposes of oral activity.
[0019] By “safe and effective amount” is meant a sufficient amount of material to provide the desired benefit while being safe to the hard and soft tissues of the oral cavity.
[0020] By “carrier” is meant a suitable vehicle which is orally compatible and can be used to apply the present compositions in the oral cavity.
[0021] It is to be noted that the composition of the invention is a dental bleaching composition, and can be distinguished from dentrifices. A “dentrifice” is a substance, such as a liquid, paste, gel or powder, used with a toothbrush or similar instrument for the purpose of cleaning the accessible parts of teeth. Dentrifices generally contain a fluoride releasing compound and an abrasive.
[0022] The bleaching composition of the invention may take the form of liquids, gels, pastes, creams, ointments or foams. In each of these forms, the bleaching composition of the invention includes a peroxide releasing compound, such as carbamide peroxide (Peroxomer®), and potassium nitrate in the amount of from 1% to 35% by weight. Other potassium-containing compounds instead of potassium nitrate, such as those listed above, may be used instead of potassium nitrate in the bleaching composition.
[0023] The bleaching compositions of the present invention can also include ancillary ingredients such as orally compatible carriers or matrices, to provide commercially acceptable products. The carrier for the dental bleaching compositions of the invention include water. The water used in the compositions of the invention is preferably deionized and free of impurities. Water may comprise up to about 50%, preferably from about 20% to about 40%, byoweight of the dental bleaching composition herein.
[0024] The composition of the invention may also include glycerin, which acts as a humectant and flavoring agent, or sorbitol, aloes such as aloe vera, polyethylene glycols, propylene glycols, polyols or polypropylene. Flavoring agents which may be included in the composition of the invention include mint flavorings, oil of wintergreen, oil of peppermint, oil of spearmint, oil of sassafras, and oil of clove. Sweetening agents may also be used, and include xylitol, aspartame, acesulfame, saccharin, dextrose, levulose and sodium cyclamate. Flavoring and sweetening agents are generally included in the dental bleaching compositions of the invention in the amount of from about 0.005% to about 2% by weight. Combinations of one or more humectants, flavoring agents or sweetening agents is also contemplated by the invention.
[0025] The composition of the invention may comprise a high viscosity matrix material, such as carboxypolymethylene (Carbopol).
[0026] A water soluble cellulosic ether, such as hydroxyalkyl celluloses such as hydroxypropyl cellulose, hydroxypropyl ethylcellulose, or hydroxypropyl methylcellulose, or carboxymethyl cellulose, may also be included in the dental bleaching composition. Further, the composition may comprise a base, such as sodium hydroxide.
[0027] The composition may also comprise orally compatible preservatives of the type commonly used in dental compositions, such as sodium benzoate.
[0028] The composition may also comprise orally compatible coloring agents or colorants of the type commonly used in dental compositions.
[0029] In the form of a gel, glycerin may be present in the amount up to about 64% by weight; proplyene glycol may be present in the amount of up to about 55% by weight; polyethylene glycol may be present in the amount of up to about 50% by weight; deionized water may be present in the amount of up to about 50% by weight; carboxypolymethylene may be present in the amount of up to about 12% by weight; hydroxyalkyl cellulose may be present in the amount of up to about 15% by weight; carbamide peroxide may be present in the amount of about up to about 30% by weight; and potassium nitrate may be present in the amount of about 1% by weight to 35% by weight. Other potassium-containing compounds instead of potassium nitrate, such as those listed above, may be used instead of potassium nitrate in the gel.
[0030] The composition of the invention in its liquid form, such as in the form of a solution, includes an orally compatible solvent, such that the solvent may come into contact with the dental and gingival tissues of a person. Suitable solvents include water and water-immiscible solvents, such as ethanol, isopropyl alcohol, propylene glycol, polyethylene glycol, glycerol, methylcellulose, cellulose, esters, morpholines, dioxane, dimethylsulphoxide and the like. The composition of the invention in the form of a liquid may also comprise a stabilizer, such as calcium disodium edetate, deforoxamine mesylate or tetrasodium edetate.
[0031] In its embodiment as a foam, the composition of the invention may include any of the various types of emulsifying agents or surfactants commonly used in dental compositions. Exemplary emulsifying agents are those which are reasonably stable and foam throughout a wide pH range, including non-soap anionic, nonionic, cationic, zwitterionic and amphoteric organic synthetic detergents.
[0032] In addition to the higher fatty acid soaps, other synthetic anionic organic detergents may be used as replacements or partial replacements. Among the useful anionic detergents are the higher alkyl sulfates, higher alkyl sulfonates, higher alkyl benzene sulfonates, ethoxylated higher fatty alcohol sulfates, monoglyceride sulfates, higher fatty acid amides of amino-lower carboxylic acids, such as sodium lauroyl sarcoside, phosphates and phosphonates corresponding to the above mentioned sulfates and sulfonates, and sulfates and sulfonates of the well-known nonionic surface active agents, such as those of polyoxyethylene glycols, of block copolymers of ethylene oxide and propylene oxide, chain terminated with propylene glycol and of polyethoxylated middle alkyl phenols. Specific examples of useful anionic synthetic organic detergents or surface active agents for inclusion in this formula are triethanolamine lauryl sulfate; linear dodecyl benzene sodium sulfonate; potassium coconut oil monoglyceride sulfate; ammonium paraffin sulfonate; and ammonium paraffin sulfonate and ammonium polyoxyethylene stearyl alcohol sulfate.
[0033] The foam composition of the invention may also include a foam stabilizer or mixture of such stabilizers. Such materials may include organic gums and colloids, serving as thickening agents to maintain the foam in the shape in which it was applied, but it will often be found preferable to utilize the lower alkanolamides of higher fatty acids for this purpose. An exemplary foam stabilizer is lauric-myristic diethanolamide, or LMDEA.
[0034] In its various embodiments, the composition of the invention may be within a range of pH's which are safe for the hard and soft tissue of the mouth. Such pH's are generally from about 3 to about 10, preferably from about 4 to about 8.
[0035] The dental bleaching composition of the invention is designed for application to teeth by methods commonly used in the art. For example, the composition may be disposed in a applicator tray which is insertable into the mouth as a mouthpiece surrounding respectively the upper and lower teeth and adjacent periodontal tissue. Such trays are commonly rigid and made of the vinyl plastic material and are in the form of an arcuate U-shaped mouth piece. Applicator trays are described in U.S. Pat. No. 5,575,654, to Fontenot, which is hereby incorporated by reference.
EXAMPLES
[0036] The following Examples illustrate various exemplary formulations of the compositions of the invention in the form of gels.
TABLE I Example 1 2 3 Carbamide 10% 20% 14% peroxide Water (deionized) 21% 20% 10% Potassium Nitrate 5% 7% 6% Glycerin 52% 33% 64% Hydroxyalkyl 7% 12% 3.5% Cellulose Sodium 5% 8% 2.5% Hydroxide
[0037] Set forth in Table I above are three examples of formulations of the invention in the form of gels. It is noted that Example 2, with the highest concentration of carbamide peroxide, has similarly higher percentages of potassium nitrate for best effects. For maximum results a dental tray holds these preparations adjacent to discolored tooth surfaces.
[0038] The use of hydroxyalkyl cellulose results in bleaching compositions of high viscosity. As a result, the dilution of compositions by saliva is difficult, and the composition stays within the tray longer providing a sustained relief of the effect of the peroxide releasing properties of the carbamide peroxide to the patient's teeth.
[0039] A fourth example of the composition of the invention in the form of a gel is set forth below at Table II with its components in weight percent.
TABLE II Example 4 Water (deionized) 6% Propylene Glycol 32% Glycerin 38% Xylitol 9% Peroxomer ® 407 7% Potassium Nitrate 3% Aloe Vera 3% Mint or other 2% flavoring
[0040] Example 4 is used preferably with a dual chamber dental tray as hydrogen peroxide is stable at lower pH's but is effective at higher pH's. The dual chamber tray contains an activator and mixes the compositions together.
[0041] A fifth example of the composition of the invention in the form of a gel, is set forth below in Table III with its components in weight percents.
TABLE III Example 5 Carbamide Peroxide 17% Water (deionized) 2% Hydroxyethyl cellulose 14% Potassium nitrate 33% Carbopol 30% Flavoring agents 2% Coloring agents 2%
[0042] The compositions of the invention may be formed by any of the methods commonly used in the art, such as by adding and admixing the ingredients in a suitable vessel, for example a stainless steel tank. Mixers may be used to mix the ingredients to form a homogeneous dispersion such as a gel. The components that are mixed to-ether are added in amounts to produce a resulting composition with the weight percents disclosed in this specification, for example in the above Examples 1 to 5.
[0043] It is understood that upon prolonged storage or upon use, such as upon disposal into dental trays or upon contact with a patient's teeth, the compositions of the invention may undergo chemical or physical, reactions so that the chemical nature of the components are changed. For example, as described above the carbamide peroxide or other peroxide releasing compound decomposes over times so that peroxide is released. Further, the humectants such as propylene glycol, may absorb water to form new compounds. It is understood that these chemical and physical reactions may change the weight percents of the composition that are present at formation.
[0044] While there have been described particular embodiments of the invention, those skilled in the art will realize that changes and modifications can be made thereto without departing from the spirit of the invention and it is intended to claim all such changes and modifications that fall within the true scope of the invention. | Dental bleaching compositions, for example in the form of liquids, gels, creams, pastes and ointments, comprising a peroxide releasing compound and from 1% to 35% by weight of a potassium-containing compound such as potassium nitrate, wherein the potassium nitrate is present in a safe and effective amount to prevent tooth hypersensitivity in the patient during the bleaching process. The potassium nitrate contemplated by the invention is compatible with peroxide yielding bleaching compounds such as peroxide, carbamide peroxide, calcium peroxide, zinc peroxide, magnesium peroxide and sodium perborate. Potassium nitrate is complimentary and synergistic with the peroxide bleaching agents contemplated by the invention and enhances the release of oxygen to the tooth enamel. Also contemplated are methods of bleaching teeth comprising application of the dental bleaching compositions of the invention. | 0 |
BACKGROUND OF THE INVENTION
The invention pertains to the field of motion damping devices used with submerged marine instrumentation for damping instrumentation movement and displacement due to wave and water motion.
In underwater transducer and hydrophone installations, such as in a sonobuoy system for detecting submarine sounds and the like, the provision of a substantially stable platform for the hydrophone is of prime importance in order to reduce extraneous noises and signals and permit the most accurate sound pressure wave input characteristics.
The purpose of sonobuoy suspension systems is to attenuate the vertical motion imparted by surface wave action to a hydrophone platform as motion of the hydrophone due to surface wave action will result in the generation of spurious low frequency signals. The attenuation system itself must not produce low frequency lateral motion oscillation such as those commonly found in objects suspended in ocean currents resulting from periodic shedding of vortices in the flowing fluid.
In a free floating sonobuoy system it is also important that a high drag concentration in the vicinity of the hydrophone platform be produced to reduce the relative velocity of the flow past the hydrophone to minimize the magnitude of any occurring flow noise as well as reducing the frequency of the noise associated with boundry layer transition on the hydrophone surfaces. Additionally, the magnitude and frequency of any unavoidable motion associated with vortex shedding is simultaneously reduced.
Improved transducer suspension systems have been achieved by the utilization of complaint members such as shown in the assignee's U.S. Pat. No. 3,377,615. Additionally, the utilization of specialized configurations in floating and buoy systems for stabilization purposes are known as shown in U.S. Pat. Nos. 3,191,202, 3,500,783, 3,510,892 and 3,543,228. However, a damper assembly for use with submerged hydrophone assemblies wherein a mass damper of an effective construction capable of being concisely stored has not been previously successfully achieved.
SUMMARY
It is an object of the invention to provide a low cost damper for the purpose of stabilizing the position of a hydrophone platform in order to reduce the introduction of spurious noises and signals into the hydrophone. The damper of the invention utilizes both mass, drag and hydrodynamic mass damping characteristics, and while the mass of the damper is significant when deployed, its weight when stored is very small and its unique construction utilizes entrapped water to produce the desired damping mass.
Additionally, the damper assembly of the invention isolates the hydrophone platform from any direct input of residual strumming produced by the compliant cable spring suspension utilized in conjunction with the hydrophone, and the construction of the damper is such as to minimize the occurrence of vibration due to water current and flow past the damper components.
The damper assembly in accord with the invention includes a long cylinder of flexible synthetic plastic film closed at each end by a check valve of unique configuration which permits water to enter, but not leave the tube. Disks having a diameter substantially greater than that of the tube are attached to each tube end at the check valves transversely disposed to the tube length to produce hydrodynamic damping and the disks are canted with respect to each other to minimize adverse effects produced by vortex shedding. An inelastic strip is affixed to the tube extending its length causing the tube to be warped or curved in an arc in the longitudinal direction minimizing rotation of the damper due to waterflow, and elimination of such rotation is important as rotation will aggravate the instability of the damper assembly in a shear current.
The disks located at the tube end are formed of synthetic plastic film and their shape is maintained, when deployed, by a flexible, resilient ring formed of a spring steel material which forms an expanded cylindrical configuration as soon as the damper is deployed and removed from its storage cannister.
Assembly of the damper is simplified by the utilization of retaining members defined on the check valve wherein a mechanical interconnection between the tube and associated disks is simultaneously achieved by the assembly of the check valve structure. Also, suspension means are defined on the check valve permitting the damper to constitute a component in the hydrophone suspension system.
BRIEF DESCRIPTION OF THE DRAWINGS
The aforementioned objects and advantages of the invention will be appreciated from the following description and accompanying drawings wherein:
FIG. 1 is a perspective view of a deployed sonobuoy system utilizing the damper of the invention,
FIG. 2 is an elevational view of the damper in accord with the invention as deployed,
FIG. 3 is a view taken from the right of FIG. 2,
FIG. 4 is a top plan view as taken of FIG. 2,
FIG. 5 is a cross-sectional view taken through the tube along Section V--V of FIG. 2,
FIG. 6 is an enlarged cross-sectional view taken through the disk and check valve along Section VI--VI of FIG. 4,
FIG. 7 is an enlarged cross-sectional view taken through the check valve rim region illustrating the retaining ring construction, and FIGS. 8 through 10 illustrate the folding of the disk and tube for packing into the sonobuoy cannister.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 illustrates a deployed sonobuoy system using a damper and improved transducer platform for providing high quality transmission of underwater sound vibrations. The sonobuoy float 10 floats upon the surface of the water and the cannister 12 depends from the float. The cannister is of a hollow cylindrical configuration and prior to deployment houses the sonobuoy components. In those cases where the sonobuoy is dropped from aircraft the cannister serves to protect the transducer, damper and other components upon impact with the water. A cable 14 depends from the cannister and is attached to the upper end of the damper assembly generally indicated at 16. A second cable 18 depends from the lower end of the damper assembly and is attached to the hydrophone assembly generally indicated at 20. The assembly 20 includes instrumentation housing 22, housing 23, compliant expansion cables 24 and 26, hydrophone 28, and weight 30. The housing 23 and hydrophone 28 are located within a mesh tube 32 which reduces flow noises and electrical conductors, not shown, interconnect the hydrophone with its transmitter housings 22 and 23 and the transmitter located within the cannister 12. The assembly 20 constitutes no part of the invention and is described in detail in the assignee's copending application, Ser. No. 111,410, filed Feb. 1, 1971. It is to be understood that the purpose of the damper assembly 16 is to provide a stable platform for the hydrophone assembly 20 and does so in the manner described below.
The damper assembly 16 includes a mass cylinder 34 formed by a tube or sleeve of flexible synthetic plastic film of only a few thousandths of an inch thickness whereby the cross-sectional configuration of the tube is cylindrical and the tube may be concisely folded.
The ends of the tube 34 are cut at substantially right angles to the tube length, when deployed, and are connected to check valve structure in a manner later described. The check valve structure 36 is identical at each end of the tube and each check valve includes retaining ring members whereby the tube and disk members associated at each tube end may be mechanically connected simultaneously to the check valve.
The disks 38 are also each formed of synthetic plastic film having an upper layer 40 and a lower layer 42, FIG. 6. When deployed, the annular configuration of the disks is maintained by an annular resilient spring-like ring 44, and the disks are formed by a heat sealing process resulting in a peripheral seam 46.
Stabilizer straps 48 of plastic film are connected to each of the peripheries of the disks 38 at one end, and connected to the central region of the tube 34 at the other end, and the length of the stabilizers is such that the disks 38 are canted with respect to each other as will be apparent in FIGS. 2 and 3.
The check valve structure 36 will be appreciated from FIGS. 4, 6 and 7. As appreciated from FIG. 4, the check valves are of an annular configuration including a peripheral rim region 50. The body of the valve is formed of a synthetic plastic material and is of a cylindrical configuration including a passage 52. centrally defined therein through which water may flow into the tube 34. Webs 54 diametrically extend across the passage 52 and the inner surface 56 of the rim region serves as a valve seat for the resilient, flexible flap valve 58 riveted to the valve body at 60. Thus, it will be appreciated that water may flow through the passage 52 against the valve element 58 and around the valve element into the tube 34. However, the water may not flow from the tube in that the valve 58 seats against the surface 56, and that portion of the valve disposed over the passage 52 is supported by the webs 54.
The valves 36 are connected to the tube 34, and serve to interconnect the tube and disks by means of a retaining ring assembly 62 which consists of an outer annular ring 64 and annular inner ring 66. The ring 64 and an L cross-sectional configuration including a radial surface 68 for opposed relationship to the peripheral rim region surface 70. Also, the ring 64 is recessed at 72 whereby the ring 66 overlays the ring 64 to maintain the assembly thereof to the valve body.
The valve body peripheral rim region is provided with a conical "undercut" surface 74 and a radial surface 76 for cooperation with corresponding conical surface 78 and radial surface 80 defined upon the ring 66. The ring 66 is split at 82, FIG. 4, wherein once the ring 64 is positioned as shown in FIG. 7, the ring 66 may be inserted into the recess 72 defined by the ring 64 and the conical surface 74. Due to the presence of the conical surfaces 74 and 78 the ring 66 will be maintained in position, and thereby maintain the assembly of the retaining ring assembly 62 upon the valve body.
The tube material adjacent the tube end is disposed between the surfaces 68 and 70, the surfaces 76 and 80 and the surfaces 74 and 78 as appreciated from FIG. 7. Likewise, the synthetic plastic film layers constituting the layers 40 and 42 of the disks 38 are disposed between the aforementioned surfaces as illustrated whereby compression upon the material of the tube and disks is maintained between the valve body and the retaining ring assembly to form an effective sealing mechanical connection between the tube, associated disk and check valve structure.
The aforementioned check valve structure constitutes the subject matter of the assignee's pending U.S. Pat. application, Ser. No. 145,133, filed May 20, 1971.
An inelastic plastic strip 84 is adhered to the tube 34 throughout its length and electrical conductors 86, FIG. 5, are sandwiched between the tube 34 and the adhesive strip 84 wherein such conductors interconnect the hydrophone assembly 20 below the damper with the cannister 12 located vertically above. The disks 38 may be provided with vent holes 88, and loop anchors 90 formed of a reinforced fabric, FIG. 6, are defined on each of the valve structures 36, and affixed thereto by rivets 92, FIG. 6, to serve as the mounting for the suspension cables 14 and 18.
In that the tube 34 and disks 38 are formed of a highly flexible lightweight synthetic plastic film material it is possible to fold the entire damper assembly 16 in a space only slightly greater than that occupied by the valves 36 when stacked one upon the other. Such concise packaging is illustrated by the folding procedure shown in FIGS. 8 through 10. Each of the disks may be folded as illustrated due to the resilient nature of the annular rings 44 wherein each ring is folded and "wound" to a diameter substantially equal to that of a check valve body. FIG. 10 illustrates the configuration of the disk once the ring is folded in the described manner. Thereupon the tube material may be sandwiched between the folded disks and check valves and the damper assembly is inserted into the cannister 12 intermediate the float 10 and the hydrophone assembly 20.
When the cannister 12 engages the water surface, the release mechanism permits the assemblies 20 and 16 to deploy from the cannister. The weight of the assembly 20 will pull the damper assembly 16 from the cannister and as the assembly 16 is removed from the confines of the cannister the rings 44 will, due to their resilient nature, "open" to form the disk configuration apparent in FIGS. 2 and 3. Additionally, as the damper assembly is pulled down through the water the water will be forced into the interior of the tube through the lower check valve passage 52. Any air trapped in the tube 34 will soon escape the tube upon wave motion causing an upward movement of the damper assembly wherein the upper check valve 36 will momentarily open and permit entrapped air to be released. The mass of the water entrapped within the tube 34 is significant and thus a mass damping is achieved.
The inelastic strip 84 causes the tube to form an arc rather than a straight line, and the strip 84 is located at 180° with respect to the stabilizer straps 48.
The configuration of the damper due to the presence of the inelastic strip 84 and the canting of the disks 38 stabilizes the damper in the presence of a shear current in that the curved configuration employed in conjunction with the offsetting of the points of attachment occurring at the attachment rings 90 located adjacent the check valve edge regions minimizes rotation of the damper, and as such rotation would aggravate the instability of the damper in a shear current such features are of significance.
Additionally, vortex shedding is greatly reduced due to the presence of the stabilizer straps 48 and the canting of the disks. This combination disrupts the normal waterflow around the tube breaking up the pattern of vortex shedding. Thus, the damper may be used in close proximity to a hydrophone platform without adverse effect.
Accordingly, it will be appreciated that the damper of the assembly effectively produces mass, drag and hydrodynamic mass damping with the utilization of economically produced structure easily stowable in a restricted volume container. Advantageous waterflow characteristics are achieved wherein the damper does not introduce extraneous vibrations into the hydrophone suspension system, and assembly of the damper components is minimized due to the mechanical interconnection thereof achieved by the check valves 36.
It is appreciated that various modifications to the inventive concept may be apparent to those skilled in the art without departing from the scope and spirit of the invention. | A damper for use in submerged hydrophone suspension systems including an elongated mass cylinder defined by a tube of flexible synthetic plastic film utilizing a check valve located at each end permitting water to enter the tube and preventing egress. Additionally, each tube end is provided with a disk transversely disposed to the tube length and of a diameter substantially greater than that of the tube to provide drag and hydrodynamic mass damping. The tube and disk are of a configuration to eliminate vortex shedding and the entire damper assembly is capable of being folded and packed within a concise configuration prior to deployment. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of International Patent Application No. PCT/EP2008/004281 filed on May 29, 2008, which claims priority to European Application No. 07 111 423.5, filed on Jun. 29, 2007, the entire contents of both of which are incorporated herein by reference.
BACKGROUND
The present invention relates to devices for delivering, injecting, infusing, administering or dispensing a substance, and to methods of making and using such devices. More particularly, it relates to a device for preventing a flow through a catheter, and more particularly to a catheter formed such that a flow of a fluid through the catheter due to a hydrostatic pressure of the fluid or liquid flowing through, channeled in or conducted through the catheter is blocked or prevented. The present invention also relates to a system comprising such a catheter and an administering device, e.g. an infusion pump.
Known infusion systems store a drug to be administered in a container, usually an ampoule, in which a carrier fluid with the drug dissolved in it—referred to in the following simply as the drug fluid—is situated between a movable stopper and a container outlet. One end, which may be thought of as the rear end, of a catheter is connected to the container outlet. A needle, which is introduced into the human or animal body to administer the drug fluid, is placed on the other, front, end of the catheter and in most cases remains there for an administering period which is often several days, wherein if the container with the drug fluid is situated at a greater height than the front end of the catheter and/or the needle, there exists the danger, if the difference in height between the container and the front end of the catheter is large enough, of the container gradually emptying itself due to the force of the column of fluid.
In insulin therapy using portable infusion apparatus, for example pump apparatus, the catheters used can exhibit lengths of more than 1 m. If the apparatus, including the container, is arranged vertically above the user, for example at night or when showering, a hydrostatic ground pressure of about 0.1 bar is generated, if no other effects—for example friction losses, discharge effects or capillary action—are taken into account in addition to the purely static pressure due to the inherent weight of the drug fluid, and if the density of water is assumed for the drug fluid.
To prevent any undesirable discharge due to the pressure of the column of fluid, the wall friction between the stopper, which is accommodated in the container such that it can slide freely, and the container wall could be increased; however, this would incur other disadvantages. Another solution would be to fix the stopper to the driven member of an infusion pump, such that the stopper prevents the surface of the fluid from dropping in the container and so prevents it from emptying itself. Known systems involving screwing the stopper to the driven member. This, however, increases the cost of the apparatus. Also, this solution cannot be used with prefabricated ampoules, since the stopper is not prepared for a screw connection.
International application WO 97/02059 relates to an infusion pump comprising a pump casing and a safety valve which is intended to prevent delivery of the drug from being caused by gravity alone. The connecting casing of the pump is detachably fastened to the pump casing. Also, its upstream end is connected to a sack-like drug reservoir via a catheter and an inlet connector.
International application WO 95/16480 discloses an infusion device comprising a drug container, a catheter leading away from it, a clamp arranged on the catheter, a pump connected to the catheter, another catheter leading from the pump to the patient, and a safety valve arranged in said other catheter. By means of the clamp for the first catheter and the safety valve, the intention is to prevent the drug fluid from being undesirably conveyed due to gravity.
EP 0 882 466 A2 discloses a device for administering, in particular infusing, a drug fluid in doses, comprising a container from which the drug fluid is displaced in doses through an outlet when a stopper is advanced, to administer it, and comprising a catheter which is connected to the container at the outlet, wherein the front end of said catheter facing away from the outlet is or can be connected to an administering needle, wherein a valve is arranged between the outlet and the administering needle in a flow cross-section of the drug fluid, and the valve only allows a flow toward the front end of the catheter when the fluid pressure acting in this direction is greater than a pressure bearing on the valve as a result of the inherent weight of a column of fluid in the device, to prevent the container from emptying itself.
SUMMARY
An object of the present invention to provide a catheter and a system comprising the catheter and an administering device which prevent a drug fluid or substance to be dispensed through the catheter from being dispensed or discharged in an uncontrolled manner.
In one embodiment, the present invention comprises a catheter for connecting an administering device to an administering needle, the catheter including a catheter wall, a flow region limited by the catheter wall, and at least one catheter portion at which at least one partial piece of the catheter wall abuts at least one other partial piece of the catheter wall to releasably block or obstruct the flow of a medium through the catheter, wherein the flow is unblocked or opened when the medium exhibits a pressure above a predetermined blocking pressure.
In one embodiment, a catheter in accordance with the present invention for connecting an administering device, for example an infusion pump which is known in its own right, to an administering needle which can be included in a so-called infusion set, comprises a catheter wall which is provided as a continuous one-part wall of a tubular or flexible tubular catheter made from an elastic material. The inside of the catheter wall (or walls) limits or defines the flow region of the catheter, through which a drug fluid or substance, dispensed from an infusion pump, is conveyed to an administering point and to an administering needle. In one embodiment, in accordance with the present invention, the catheter comprises at least one catheter portion at which at least one partial piece of the inner wall of the catheter abuts at least one other partial piece of the inner wall of the catheter, to automatically block or obstruct the flow through the catheter, wherein the flow is re-enabled and the catheter opened when the fluid being guided in the catheter exhibits a pressure above a predetermined minimum pressure of, for example, more than 0.1 bar or more than 0.2 bar.
Providing a catheter portion comprising an inner wall of the catheter which, in its normal state without the application of a predeterminable minimum pressure of the fluid being guided by the catheter, is automatically deformed—for example by correspondingly shaping the catheter wall and/or using specific, for example elastic, materials or by applying an external force such as for example attaching one or more clamping pieces—such that a flow through the catheter is only possible once a predeterminable minimum pressure of, for example, more than 0.1 bar is exceeded, has the advantage that additional valves do not have to be provided at the end of the catheter or in the catheter to control and/or prevent a free flow. A self-blocking catheter in accordance with the present invention can thus be designed very simply and also prevents incorrect use, since additional valves do not have to be connected and therefore also cannot be forgotten when using the catheter.
In some preferred embodiments, a catheter in accordance with the present invention may advantageously comprise two or more catheter portions which are, for example, spaced apart from each other in the longitudinal direction, i.e. along a length of, and/or in flow direction of the catheter, to form two or more zones to prevent a free flow through the catheter when a pressure below the predetermined minimum pressure is applied. For example, two or more zones can be formed in immediate succession, within which the inner walls or surface(s) of the catheter abut each other, wherein preventing a free flow at a pressure below the predeterminable minimum pressure can be realized by an individual zone, e.g. by the inner walls of the catheter abutting each other, or by automatic sealing within an individual region or zone, or also by a number of successively arranged zones co-operating, in which the catheter walls abut each other, spaced apart from each other in the longitudinal direction of the catheter, at a number of portions and thus form a number of blocking or securing elements along the length of the catheter.
In some embodiments, the minimum pressure which has to be applied to re-open the self-blocking or self-sealing on the catheter is around at least 0.1 bar and, in some preferred embodiments, above 0.1 bar, i.e. in the range above 0.15 bar or 0.2 bar or above 0.3 bar or 0.7 bar.
When the ampoule is biased, i.e. a minimum impact force is applied to the stopper, it may be that the fluid pressure at the outlet region of the ampoule is around a higher pressure of, for example, 0.5 bar. Accordingly, in some embodiments, the opening pressure of the catheter should be around this higher pressure, plus a safety pressure of, for example, 0.1 bar or 0.2 bar.
In some preferred embodiments, to obstruct administering the drug in doses as little as possible, but still securely prevent discharge, the catheter is configured such that it only allows the flow toward the front end of the catheter when the fluid pressure in this direction (the flow direction) exceeds the maximum possible pressure of the column of fluid, in some embodiments, multiplied by a safety factor. Since, in the present case, the valve is being used in the medicinal field, the safety factor may correspond to the value 3. For a maximum catheter length of about 1 m and a negligible column of fluid in the container, the maximum fluid pressure at the free end of the catheter measures about 0.1 bar, such that in this case, the catheter is configured such that it only opens when the fluid pressure exceeds 0.3 bar. These are also the dimensions for an exemplary preferred use in a portable infusion pump.
In some preferred embodiments, the catheter is self-closing or self-blocking below the aforementioned blocking pressure or minimum pressure and can thus effectively prevent a substance or drug fluid from unintentionally flowing through it due to the pressure of the column of fluid within the catheter.
In some preferred embodiments, a catheter in accordance with the present invention comprises regions or portions in which the walls of the flexible tube are biased against each other. This can, for example, be achieved by only one partial piece being biased toward another, for example opposing inner wall of the catheter in the circumferential direction of the catheter, or by two regions of the catheter wall which oppose each other being biased toward each other, to abut each other when there is a lack of pressure in the medium being guided in the catheter, such that the flow is blocked below the mentioned minimum pressure which enables a flow. A partial piece of the catheter or a region of the catheter wall can, for example, be biased by using an elastic material which is provided on or in the catheter or as a part of the catheter wall, such that one or more catheter walls are biased in a direction which reduce and, in some embodiments, completely seal the flow region, i.e. an opening within the catheter.
Alternatively or additionally, an external element, for example a clip or clamping device, which is formed as a suitably-shaped, e.g. U-shaped, spring element can generate an external force which acts on the outer wall or walls of the catheter, to press together the catheter between or by the clip element or spring element. When the predeterminable minimum pressure is applied, for example generated by an infusion pump, a fluid passing through the catheter can press the external element apart far enough to enable a flow through the catheter, which is limited in accordance with the pressure being applied or which is unobstructed.
In some embodiments, the catheter can also be reshaped by a production process or by an external element, such as a clamping element, such that the catheter is not annular in cross-section like known catheters but rather exhibits a different shape which is advantageous for blocking a flow, for example, in some embodiments, a catheter in accordance with the present invention may have the shape of a flat flexible tube in which the wall halves abut each other and can thus prevent a flow at a low pressure.
Furthermore, in some embodiments, it is also possible for the catheter to be embodied so as to be bent or sharply bent and for this bent or sharply bent shape to be realized either by the catheter materials, by catheter geometry used, and/or by an external element such as a clamping piece which holds the catheter in a bent or sharply bent shape.
In accordance with another aspect of the present invention, the invention comprises a system comprising a catheter such as has been described above and an administering device, e.g. an infusion pump, for administering a drug fluid in doses, wherein the drug fluid is contained in a container from which it is displaced, to be administered, in doses by advancing a stopper which is movably accommodated in the container toward a container outlet. The rear end of a catheter such as has been described above can be connected directly to the outlet of the container, where an outlet piece and/or outlet support for connecting a catheter is provided. The catheter is usually a flexible tubular catheter. It would, however, be equally possible to use a rigid catheter comprising elastic partial pieces. The front, free end of the catheter is or can be connected to a needle for administering the drug. “Administering” is understood to mean both infusing and injecting and/or a combination of the two types of administering. Thus, in some embodiments, the present invention is intended to be used in infusion devices and/or infusion apparatus, which may be portable pump apparatus for insulin treatment.
In some preferred embodiments, the self-blocking element or partial piece of the catheter is arranged between the container outlet and the needle for administering the drug, in a flow cross-section of the drug fluid. The catheter is dimensioned such that, to prevent it from emptying itself, it only allows a flow toward the front end of the catheter when the fluid pressure acting in this direction is greater than a pressure bearing on the self-blocking portion as a result of the inherent weight of the column of fluid in the device. If the device is a mass-produced device, for which a whole range of catheters having different lengths are available, then the self-blocking portion is dimensioned for using the longest catheter, i.e. for the maximum possible column of fluid.
Although the self-blocking portion or the self-blocking partial regions of the catheter can in principle be placed at any point between the container outlet and/or infusion pump and the administering needle, in some preferred embodiments the portion or region is arranged as near as possible to the outlet of the container or as near as possible to the infusion pump.
In accordance with another aspect of the present invention, it comprises a method for preventing a free flow through a catheter, wherein at least a partial region of the catheter or the catheter wall prevents the flow of a medium below a predetermined minimum pressure, and wherein the catheter is pressed open to enable the flow when the medium exceeds the minimum pressure.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top view onto a partial piece of one embodiment of a catheter in accordance with a first embodiment of the present invention, comprising a clip;
FIG. 1A is a sectional view along the line A-A in FIG. 1 ;
FIG. 1B is a sectional view along the line B-B in FIG. 1 ;
FIG. 2 depicts a second embodiment of a self-blocking catheter in accordance with the present invention comprising two blocking regions;
FIG. 2A is a cross-sectional view along the line A-A in FIG. 2 ;
FIG. 3 is a schematic representation illustrate the working principle of one embodiment of the present invention;
FIG. 4 depicts a third embodiment comprising a number of successively arranged, sharply bent regions; and
FIGS. 5A , 5 B, and 5 C depict another embodiment of a self-blocking catheter in accordance with the present invention comprising a separate pressure element.
DETAILED DESCRIPTION
With regard to fastening, mounting, attaching or connecting components of the present invention, unless specifically described as otherwise, conventional mechanical fasteners and methods may be used. Other appropriate fastening or attachment methods include adhesives, welding and soldering, the latter particularly with regard to the electrical system of the invention, if any. In embodiments with electrical features or components, suitable electrical components and circuitry, wires, wireless components, chips, boards, microprocessors, inputs, outputs, displays, control components, etc. may be used. Generally, unless otherwise indicated, the materials for making embodiments of the invention and/or components thereof may be selected from appropriate materials such as metal, metallic alloys, ceramics, plastics, etc. Unless otherwise indicated specifically or by context, positional terms (e.g., up, down, front, rear, distal, proximal, etc.) are descriptive not limiting. Same reference numbers are used to denote same parts or components.
FIG. 1 shows a first embodiment of a blocking valve 2 which is formed on a catheter 1 , directly on or in the flexible catheter tube and in the vicinity of the outlet point of a pump (not shown). The blocking valve 2 is configured such that it blocks or prevents flow when an interior pressure of the flexible tube or a pressure of the medium being guided in the flexible tube 1 is 0.1 bar or less, and opens at higher pressures and allows a flow through the flow region 1 b of the catheter 1 .
The first embodiment of the catheter 1 shown can, for example, be obtained by reshaping the catheter or flexible tube in the region of the valve 2 by a thermal reshaping method, wherein the annular or tubular cross-section of the catheter 1 is reshaped in the region of the valve 2 into a flat flexible tube, as shown in the sectional view in FIG. 1A , such that the wall halves 1 a of the catheter 1 abut each other and can thus prevent a flow when a low interior pressure is being applied. If the pressure of the medium being guided in the catheter 1 rises above a predetermined minimum pressure of, for example 0.1 bar, the inner wall 1 c of the catheter is pushed open and the valve 2 is opened, such that a flow through the catheter 1 is possible.
As can be seen from FIGS. 1A and 1B , the valve 2 can be fitted with a clip 3 which is formed as a U-shaped spring element and comprises pressing pieces 3 a and 3 b . The clip 3 is arranged around the catheter 1 and can bias the catheter halves and therefore the inner walls 1 c of the catheter against each other via its clamping force. By using the clip 3 , it is possible to set a defined blocking force or blocking pressure. The greater the force with which the clip 3 presses the catheter walls 1 c onto each other, the greater the minimum pressure of the medium which has to be applied to enable a flow through the catheter 1 .
If such a catheter 1 , comprising one or more valves 2 successively arranged in the longitudinal direction of the catheter 1 , is connected to an administering device, for example an infusion pump, the catheter 1 is connected to a reservoir 4 for a substance or medium to be administered. Usually, a stopper 5 is inserted into the reservoir 4 or an ampoule 4 by an infusion pump, such that the interior pressure in the ampoule 4 is increased and a substance contained in the ampoule 4 is dispensed from a dispensing opening 4 a of the ampoule 4 . This causes a rise in pressure in the connected catheter 1 , which ensures that the catheter walls 1 a , which are biased against each other, are pushed open and that a desired amount of the substance, such as for example insulin, can thus be dispensed to a patient. As soon as the desired amount of the substance has been administered, and the stopper 5 of the reservoir 4 is at rest again, the valve 2 closes due to the force of the clip 3 which presses the catheter 1 together again, automatically. The opening pressure for the valve 2 is thus set or defined by the biasing force of the clip 3 .
FIG. 2 shows a second embodiment of a catheter 1 in accordance with the present invention, comprising two valves 2 . The two valves 2 are arranged in two zones spaced apart from each other in the longitudinal direction of the catheter 1 , i.e along the length of the catheter, and comprise catheter walls 1 a which are respectively biased against each other, wherein one catheter wall 1 a of a first side, shown on the left in FIG. 2A , is biased toward the second side (in the drawing, downwardly), such that the inner walls 1 a of the catheter abut each other and prevent a flow of a medium when a predetermined minimum pressure is not being applied. In the region of the second valve, shown on the right, the bias relative to the first valve is reversed, i.e. the opposing second side is biased toward the first side, such that the desired valve blocking effect occurs.
Each bias of a catheter wall 1 a can thus be regarded as an aperture. If a number of apertures are arranged in series, the overall difference in pressure is divided into stage differences in pressure, such that the drop in pressure per valve zone can be reduced. Reducing the overall difference in pressure is advantageous, since the closing force per valve zone can then be reduced and the functional reliability of the overall valve, formed from a number of valve zones, can thus be increased.
In accordance with another embodiment of the present invention, a valve function using a catheter 1 can be achieved by moving the catheter 1 into a sharply bent region using a defined path-force element (spring). When the pressure rises, for example between 0.5 and 0.8 bar, the catheter 1 is released from the sharply bent region and so releases the flow.
FIG. 3 schematically shows an ampoule 4 comprising a stopper 5 which can be shifted within it in the direction of the arrow and using which a substance contained in the ampoule 4 can be dispensed from a dispensing opening 4 a to the catheter 1 connected to the ampoule 4 . If, for example, the difference in height between the lower and upper end of the catheter 1 measured one metre, then a partial vacuum of 0.1 bar would be applied at the upper end of the catheter 1 , which could cause a substance to be unintentionally dispensed from the ampoule 4 in an uncontrolled manner, solely due to the hydrostatic pressure generated by the column of fluid in the catheter 1 .
It is therefore advantageous, in some embodiments, to arrange a valve in the upper region of the catheter, since a partial vacuum of 0.1 bar in relation to a relative exterior pressure of 0 bar causes the catheter walls 1 a to be automatically pressed together. If the catheter walls 1 a are elastic, the partial vacuum in the upper catheter portion can therefore be utilized such that in the event of a hydrostatic pressure distribution in the catheter, the valve is automatically closed.
If the above-described catheter 1 in accordance with the present invention is used, then it is possible to prevent a substance from being unintentionally dispensed from the ampoule 4 through the catheter 1 .
In some embodiments, a number of sharply bent regions 1 d can also be successively arranged, as shown in FIG. 4 , wherein a catheter or flexible tube 1 is accommodated in a clamping piece or clip 3 which can consist of an upper part 3 c of the clamping piece and a lower part 3 d of the clamping piece, which can be connected to each other. The catheter 1 is inserted into the catheter guides, which are, for example, formed by a number of mutually parallel partition walls 3 e , such that the catheter 1 is held meandering, or snaking or winding, in the clamping piece 3 , wherein linear regions of the catheter 1 are parallel to each other, separated by the wall pieces 3 e , wherein a sharply bent region 1 d is provided in each region in which the catheter 1 transitions from one guide, formed by two adjacent wall pieces 3 e , to the next guide. FIG. 4 shows the open-catheter state, in which the sharply bent regions 1 d are open, due to an applied pressure of, for example, more than 0.7 bar, and so enable a flow of a medium through the catheter 1 . If a pressure below 0.7 bar is being applied, the catheter 1 is deformed in the region of the sharp bends 1 d , such that a medium is prevented from passing through the catheter 1 .
The clamping piece 3 can, for example, be formed to be rigid, such that when the pressure of the medium being guided in the catheter 1 rises above 0.7 bar, a flow is enabled solely by the deformation of the catheter 1 . Alternatively, the clamping piece 3 can also be formed to be elastic or flexible, such that when the pressure of the medium being guided in the catheter 1 rises, the clamping piece 3 is deformed or expanded and so releases the flow for the fluid being guided in the catheter 1 .
Although the clamping piece 3 could in principle be formed in one piece, in some preferred embodiments it is formed—to more easily insert the catheter 1 —from two partial pieces 3 c and 3 d which can be placed onto each other or connected to each other, after the catheter 1 has been inserted into the clamping piece 3 d in the manner shown in FIG. 4 , such that the catheter 1 exhibits a number of successive sharply bent regions 1 d on two opposing sides of the clamping piece 3 .
FIG. 5A shows another embodiment of a blocking mechanism for a catheter 1 , wherein a catheter blocking valve can be both integrated into the catheter 1 and formed as a separate valve piece which can be inserted between two catheter pieces 1 . In the embodiment shown in FIG. 5A , a valve base body 4 made from a thermoplastic elastomer (TPE) can be seen which is formed in the shape of a disc or plate and is flat. The body 4 has been inserted between two catheter pieces 1 , wherein the body 4 has been placed onto the catheter pieces 1 in the region of a fusing zone 4 a and connected or fused to the catheter pieces 1 , so as to be an integrated part of the catheter. A sealing or covering element 4 b , in the form of a film which is likewise formed from a thermoplastic elastomer, is placed onto the valve base body 4 and can be formed double-layered and from a different material than the valve base body 4 . The film 4 b is connected to the valve base body 4 in the region of a fusing zone 4 c.
A bent clip 3 formed from spring steel may be slid or placed onto the valve base body 4 connected to the film 4 b , in a similar way to the embodiment described with respect to FIG. 1 . The clip comprises two mutually opposing pressure surfaces 3 f and 3 g , such that the upper pressure surface 3 f can press onto the film 4 b and the lower surface 3 g can press onto the lower side of the valve base body 4 . FIG. 5C is a top view onto the clip 3 which is shown in a lateral view in FIG. 5B .
If a pressure of, for example, less than 0.7 bar is being applied to the medium being transported in the catheter 1 , then the film 4 b is pressed into the valve base body 4 or the valve base body 4 is pressed together with the film 4 b , such that a flow of a medium cannot occur. If the pressure of the medium rises above 0.7 bar, then the clip 3 is pressed or urged apart by the pressure of the medium, i.e. the pressure surfaces 3 f and 3 g are urged away from each other enabling a flow of the medium.
The blocking pressure of the valve shown in FIG. 5 can be altered by the configuration of the clip 3 , and/or by its manufacture, deformation and material constants or processing, such that the valve can also open at a lower pressure of, for example, 0.1 bar or 0.2 bar or at a higher pressure of, for example, 1 bar or above.
Embodiments of the present invention, including preferred embodiments, have been presented for the purpose of illustration and description. They are not intended to be exhaustive or to limit the invention to the precise forms and steps disclosed. The embodiments were chosen and described to illustrate the principles of the invention and the practical application thereof, and to enable one of ordinary skill in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth they are fairly, legally, and equitably entitled. | A catheter for connecting an administering device to an administering needle, the catheter including a catheter wall, a flow region limited by the catheter wall, and at least one catheter portion at which at least one partial piece of the catheter wall abuts at least one other partial piece of the catheter wall to releasably block or obstruct the flow of a medium through the catheter, wherein the flow is unblocked or opened when the medium exhibits a pressure above a predetermined blocking pressure. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of pending application 07/984,995 filed Dec. 02, 1992 now U.S. Pat. No. 5,282,587.
FIELD OF THE INVENTION
The present invention relates to a protective cover for the wing of an aircraft, a novel cover-to-fuselage connecting means, and to the method for installing the cover.
BACKGROUND OF THE INVENTION
The airfoil or wing surfaces of an aircraft are subject to the effects of transient atmospheric conditions posed by the weather systems of the winter season. The effects may manifest as frost, snow or ice, normally upon the upper and vertical surfaces of the aircraft skin. It is well known in the aircraft industry that such contamination of the wings has serious detrimental effects upon aircraft aerodynamics with the potential danger for loss of lift and control. A recent 1988 example of the tragic consequences of attempting flight with affected wing surfaces was unfortunately demonstrated in the Air Ontario crash of a Fokker F-28 at Dreyden, Ontario, Canada.
For some decades, protective covers have been provided to protect the surfaces of aircraft wings. Generally their use has been limited to light aircraft such as smaller, privately owned aircraft. An early example of such a device is disclosed in U.S. Pat. No. 3,044,516, issued to Stoll in 1962. This reference describes a wing covering device as an envelope-like receptacle for snugly fitting over a wing tip in a glove-like relation.
The commercial passenger aircraft industry uses large aircraft comprising narrow and wide body jets with typical wing spans of 100 feet and 200 feet respectively. Use of protective covers for this case of aircraft has been tried, but has not been commercially successful due in part to the size and installation difficulties. Such early covers were fabricated from heavy fabrics which absorbed water and tended to become unwieldy when wet. The cover could freeze into a stiff shape or worse, freeze to the wing surface.
Modem commercial aircraft surfaces are highly engineered components with surface finishes and structures which are particularly delicate and susceptible to damage and stresses other than those imposed by flight. Access for maintenance personnel to walk on the wing surfaces, for installation or removal of a cover, is now severely restricted and with the increased use of composite materials construction, walking loads are not allowed at all. Contact of the surfaces with metal fasteners, and the like, such as grommets disclosed by Stoll, is unacceptable. On many aircraft, delicate instruments and devices are mounted on the wing surfaces. These devices are fragile and must avoid mechanical damage. As an example of such a device, static wicks are located on the wing tips, which are adapted to discharge static during flight.
The airline industry is regulated under the auspices of the FAA in the United States, the MOT in Canada and similar agencies in other countries. These regulatory bodies require preventative de-icing and similar safety measures be performed for aircraft flight surfaces under certain weather conditions prior to takeoff. Presently, a typical treatment comprises applying a heated glycol solution to the wings. Generally, this is accomplished with a truck and boom arrangement whereby a water cannon directs a 160° F. glycol solution onto the wings, removing snow, ice and frost with a combination of mechanical force and melting action. For smaller narrow body aircraft such as the McDonnell Douglas 80 (MD-80) or the Boeing 737, the amount of glycol used could be 20 to 200 US gallons per wing, dependent upon the level of contamination. A wide bodied aircraft such as the Boeing 747 could require up to 2000 US gallons per wing. The spent glycol flows to the tarmac surface where it can eventually cause damage to the concrete, or can pose a serious environmental impact if it reaches permeable ground. Glycol may be collected for recycling or an ash-like absorbent material is used to absorb the spent glycol and the waste is shipped to an industrial landfill. In some cases, the glycol is simply left on the tarmac with the attendant results.
The disadvantages to the glycol de-icing system include:
the significant cost of the glycol and procedures;
serious delays and interruption of the airline departure schedule; and
the environmental impact.
With this background in mind, it was the objective of the present invention to provide a wing cover, suitable for use with large aircraft, which could be easily installed and removed and which would result in reduced consumption of glycol.
SUMMARY OF THE INVENTION
In accordance with the invention, an improved protective cover for an aircraft wing is provided.
More particularly, the cover comprises a generally wing-shaped panel having leading and trailing portions which overhang the leading and trailing edges of the wing. The panel has a length sufficient to extend along most of the length of the wing, from its root to adjacent its tip. A plurality of strap means are provided at spaced points along the length of the cover. The strap means are connected to the cover's overhang portions and are operative to secure them together and to cinch the panel snugly to the wing surface.
The design of the cover has been influenced by the solution of unforeseen problems which were discovered in connection with prototypes in the course of the development of the product. More particularly, it was found:
That it was desirable to anchor the root or inner end of the cover to the fuselage as otherwise the outwardly tapering characteristic of the wing and the action of the wind getting between cover and wing can work the cover out toward the wing tip or twist it around one wing edge or the other;
That it was necessary to form cut-outs in the overhang portions so that the cover would have a form-fit around the wing's protuberances located adjacent the wing edges, such as vortex generators, fairings, engine mounts and air dams. If this was not done and the cover was simply stretched or "tented" over the protuberance, air would enter through the openings created and would form frost and snow on the wing surface;
That it was desirable to space the strap means less than 12 feet apart along the length of the panel, to enable two workers to efficiently install the cover. If the spacing was too great and conditions were windy, the workers had difficulty reaching back to a cinched portion to grasp the loose portion to cinch it at the next station; and
That it was necessary to form the panel of lightweight ultraviolet stabilized material which would not absorb water. A suitable material was found to be woven polyethylene, commonly used as lumber wrap. The woven nature of the material lends it the ability to resist propagation of tears--a useful feature in this application. However, this type of material was found to be relatively weak. It was liable to tear if the connecting straps were secured directly to the cover material and cinching stress was applied. It was therefore found desirable to form an anchoring "base" for the connecting straps.
More particularly, the base comprised first and second lengths of webbing extending parallel and adjacent to the cover edge with one overlying the other, so that they sandwiched the cover between them. The anchor base further preferably comprised a third length of webbing extending laterally and inwardly from the first and second lengths, along the intended line of the cinching force. The cinching strap was secured to the T-shaped anchor so formed.
In one broad aspect then, the invention is a protective cover for an airplane wing, comprising:
a substantially wing-shaped panel having a root portion and leading and trailing edges, said panel being adapted to cover the upper surface of an airplane wing along part of its length, said panel having sufficient width so that a portion overhangs the leading edge of the wing and preferably overhangs both edges;
the panel being formed of lightweight, ultraviolet-stabilized material which does not absorb any significant amount of water;
the leading overhang portion being cut-out so as to form-fit around edge protuberances of the wing to be covered; and
an array of strap means being positioned along the length of the cover in spaced-apart relation, for extending beneath the wing to secure the leading and trailing edges of the panel and to cinch the panel to the wing;
said strap means being located at points spaced apart less than about 12 feet.
In a second aspect of the invention, a novel combination of a protective cover and a fuselage restraining means is provided, said cover being adapted to cover the upper surface of a tapered wing of an aircraft having a fuselage, comprising a substantially wing-shaped panel having a root portion and leading, trailing and root edges, said restraining means comprising:
a strap means formed into a loop about the fuselage and being secured to the panel at its root edge, adjacent to the panel's leading edge for anchoring the root portion of the panel to the aircraft fuselage; or alternately
a strap means secured to the panel substantially along a path of shortest distance extending from the panel's trailing edge, adjacent the fuselage, to the panel's leading edge and connecting to a belly strap extending beneath the fuselage for anchoring the root portion of the panel to the aircraft fuselage; and
one or more rib means being secured to the panel, extending laterally from the strap means towards the panel's root edge to assist in fort-fitting the root portion of the panel to the wing.
The protective cover lends itself to a novel and efficient process of installation on the wing of a low wing aircraft. This process comprises:
(a) rolling the wing tip end of the panel toward its root portion to form a single roll having a longitudinal axis and bottom portion with the root portion free;
(b) placing the roll up onto the root area of the wing's upper surface, the roll axis being oriented transverse to the lateral extension of the wing, the roll further being oriented such that the root portion of the panel projects from the bottom portion of the roll and faces the wing root whereby the roll may be directly unrolled along the wing;
(c) securing the root portion of the panel to the fuselage;
(d) securing the root portion of the panel to the wing by connecting a first pair of associated strap members, respectively attached to the leading and trailing edges of the panel and extending beneath the wing, and cinching the panel's leading and trailing edges together using the strap members to form-fit the root portion to the wing;
(e) unrolling the panel away from the wing root and exposing a second pair of associated strap members, spaced from the first pair, and an unrolled panel portion;
(f) securing the unrolled panel portion to the wing by connecting and cinching the second pair of associated strap members to form-fit the unrolled panel portion to the wing; and
(g) repeating steps (e) and (f) of unrolling and securing the unrolled panel portions until the panel has been completely rolled out and covers the wing with a form-fit.
In a fourth aspect of the invention, an installation process is provided for covering the wing surface of a high wing aircraft, such as a De Havilland DH-8. The wing is attached at its root and extends laterally outwards from both sides of an an aircraft fuselage having a longitudinal axis. In this case, the wing may be defined as having a longitudinal axis and an upper surface comprising a central root area and first and second wing tips. The protective cover is a wing surface-shaped panel having a central root portion and first and second wing portions extending outwardly therefrom and ending with first and second tip portions.
The process comprises:
rolling each of the tip portions toward the root portion to form a double-roll having first and second sides and a longitudinal axis;
placing the double-roll up onto the root area of the wing's upper surface, the longitudinal axis of the double-roll being oriented transverse to the longitudinal axis of the wing and being centered on the fuselage longitudinal axis, whereby the first and second roll members may be unrolled along the wing surface, in both directions toward the wing tips; and
unrolling and securing each side of the double-roll as previously described with the low-wing version of the cover.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a low-wing jet aircraft;
FIG. 2 is a perspective view of a cover panel shaped to conform to the wing of the aircraft according to FIG. 1;
FIG. 3 is a top plan view of the cover of FIG. 2 showing cut-outs and strap assemblies;
FIG. 4 is a perspective view showing a cover in place on a wing with the straps undone and a cut-out fitted to a protuberance;
FIG. 4a is a sectional view of FIG. 4;
FIG. 4b is a sectional view of FIG. 4, but with the straps done up;
FIG. 5 is a view similar to FIG. 4, but with the straps done up;
FIG. 5a is a view similar to FIG. 4, but with the straps done up and the panel being connected to the collar;
FIG. 5b is a view similar to FIG. 5a, but with the panel being fitted with ribs and being connected to a fuselage belly strap;
FIG. 5c is a perspective view of part of the cover and the strap and rib restraining means, with particular detail of the ribs;
FIG. 6 is a perspective view of part of the cover fitted around a protuberance;
FIG. 7 is a perspective view from below of a strap assembly secured to edges of the panel;
FIG. 8 is a perspective view of part of a strap assembly;
FIG. 9 is a perspective view of a panel (strap assemblies not shown) being rolled up in preparation for installation;
FIG. 10 is a perspective view of the panel of FIG. 9 in a fully rolled up state, ready for installation;
FIG. 11 is a perspective view of the roll of FIG. 10 in place on the wing, connected to the collar;
FIGS. 12-17 show in simplified form the installation of the cover;
FIG. 18 is a perspective view of a high-wing aircraft;
FIG. 19 is a top view of a panel for the wing of the aircraft of FIG. 18;
FIG. 20 is a perspective view of the panel initially being rolled up in preparation for installation;
FIG. 21 is a perspective view showing the panel of FIG. 20 fully rolled up to provide a double roll;
FIG. 22 is a perspective view showing the double roll of FIG. 21 in place on the wing; and
FIG. 23 shows the cover installed on the aircraft of FIG. 18.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In one version of the invention, a separate protective cover 1 is provided for each wing 2 of a low-wing passenger jet aircraft 3, such as the MD-80.
The upper surface 31 of the wing 2 has a root portion 4 adjacent the fuselage 5 and extends laterally in tapering fashion out to the wing tip 6. The edges and undersurfaces of the wings of most passenger jet aircraft have protuberances 7, such as air-dams, vortex generators, engine mounts and fairings.
The cover 1 is formed of lightweight, woven, ultraviolet-stabilized, tear-resistant material which will not absorb water. A suitable material is woven polyethylene available from Bonar Inc. and marketed under the trade-mark FLEXENE PLUS.
As shown in FIGS. 1, 2 and 3 the cover 1 incorporates a panel 8 that is wing-shaped. The panel 8 is wider that the aircraft wing 2 so that it has overhang portions 9, 10 at the leading and trailing edges 11, 12 of the wing.
Cut-outs 13 are formed in the overhang portions 9, 10. These cut-outs 13 correspond with the wing protuberances 7 and function to enable the panel 8 to have a form-fit when it is cinched to the wing 2. This is illustrated in FIGS. 4, 6.
Having reference to FIGS. 4, 7 and 8, the cover 1 includes associated pairs of strap assemblies 14, comprising fastener means, for securing and cinching the panel 8 to the wing 2. More particularly, each strap assembly 14 comprises a T-shaped anchor 16 formed by overlain top and bottom lengths of edge webbing 17, 18, sandwiching the panel edge 19 between them, and inwardly extending overlain lengths 20, 21, which also extend out beyond the panel edge to form a strap 22 which carries a buckle 23 or fastener 24. Each strap 22 is aligned substantially parallel to the forces generated by the cinching action of each strap assembly 14. The overlain, paired lengths of webbing are sewn to each other and the panel 8, to provide an anchor 16 that distributes stress so that tearing is avoided. There are thus provided strap means for securing and cinching together the leading and trailing overhang portions 9, 10, to pull the panel 3 into close form-fit with the wing 2. The strap means are located at points spaced apart along the panel edges at distances of less than about 12 feet.
The tapered nature of the wing 2 encourages the panel 8 to creep away from the fuselage under cinching and wind loads, exposing the root portion 4 of the wing's upper surface 31. Retaining means are provided as shown in FIG. 5a for retaining the panel 8 in place with respect to the fuselage 5. More particularly, the retaining means comprises strap assemblies 25, located at the root areas of each panel 3, for connection with a loop or collar 26. The collar 26 is adapted to extend around the fuselage 5 and, when connected to the strap assemblies 25, it holds the cover 1 in place longitudinally and helps to restrain it from twisting due to wind action.
Alternately as shown on FIGS. 5b and 5c, the retaining means may comprise a root strap assembly 100 and resilient ribs 101. The root strap assembly 100 is secured to the root portion of the panel 8. The strap assembly 100 extends substantially along a path which represents the shortest contiguous distance from the trailing edge 12, adjacent the fuselage 5, over the upper surface 31 of the wing, and to the leading edge 11 for connection to a belly strap 102. The belly strap 102 extends beneath the fuselage 5 for connection to a belly strap from a panel covering the opposing wing. When tensioned by cinching the belly strap 102, the root strap assembly 100 and attached panel 8 are disinclined from movement relative to the fuselage 5.
The ribs 101 are secured to the panel 8, substantially perpendicular to the panel's edge; one near the wings's leading edge 11, and additional ribs being placed in spaced-apart relation along the wing root 4, as required. The ribs 101 act to press the root portion of the panel 8 into close fit with the root portion 4 of the wing 2. The ribs 101 are suitably constructed of resilient material 103 such as neoprene tubing, enveloped in an elongated pocket of webbing 104 sewn to the panel 8.
In addition, strap assemblies 27 are provided on each side of the cut-outs 13 to secure the overhang portion edges to provide a firm, tight fit of the cut-out edge to the wing 2. Reinforcing webbing 28 is also provided around the cut-outs 13 to distribute stress.
Turning now to the method for installing the cover 1, have reference to FIGS. 9 to 17. In preparation for installing the cover 1 on the wing 2, the panel 8 is laid out with its upper surface facing upwards and then is rolled up from the tip end toward the root portion 29, to form a roll 30 having its root portion 29 free. The roll 30 is placed on the root area of the wing 2, adjacent the fuselage 5, with its longitudinal axis transverse to the longitudinal projection of the wing 2 and with the root portion 29 extending along the upper surface 31 of the wing 2, as shown in FIG. 11. The collar 26 is positioned around, or the alternate belly strap 102 is positioned under the fuselage 5. The panel root portion 29 is secured to the collar 26 or belly strap 102 by strap assemblies 25 or 100 respectively. The roll 30 is then unrolled toward the wing tip 32. In windy conditions, it may be necessary to stretch each panel portion between adjacent pairs of strap assemblies 14 into good fit with the wing 2 and immediately cinch up the exposed strap assembly 14. Alternatively, as shown in the Figures, in calm conditions the roll 30 may be totally unrolled before cinching the strap assemblies 14.
As a result of the combination of the cinching capability, the fuselage connection, the custom fit of the panel to the wing involved and the cut-outs, a tight form-fit between panel and wing can be obtained, which essentially prevents wind entering between wing and panel.
To remove the cover, the strap assemblies are undone and the panel is pulled by the straps down over the trailing edge of the wing.
A cover 50 suitable for high-wing aircraft 55 (FIG. 18) is shown in FIG. 19. In this case, the panel 51 can extend the full length of both wings. With respect to installation, the panel 51 is formed into a double roll 52 and placed at the center of the fuselage 53 for unrolling each roll 54 toward one of the two wing tips, as shown in FIGS. 19 to 23.
To illustrate the effectiveness of the invention and its glycol-saving capability, one wing of an MD-80 passenger jet was protected with a cover 1 and the other wing was left uncovered, on a test basis under mild winter conditions. A heavy frost was generated on both the uncovered wing and the cover of the covered wing. The cover was removed. A solution of 50/50 water/ethylene glycol was then applied to both top and bottom surfaces of both wings, to clean the wings to an acceptable condition. 20 gallons of solution were necessary for the uncovered wing. 5 gallons were necessary for the covered wing. | A device and method is disclosed whereby a protective cover is positioned on the upper surface of an aircraft wing. The cover comprises a lightweight, ultraviolet stabilized material which is resistant to propagation of tears and does not absorb water. Cover material, overhanging the leading or trailing edges of the wing, is locally cutout in the area of protuberances to assist in providing a form fit when a plurality of cinch straps, attached to the leading and trailing edges, are tightened under the wing. Additional straps may be employed to secure the cover to the fuselage. The cover, when tightened, prevents significant ingress of air, protecting the upper surface. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to shoe manufacturing machinery, and more particularly to an apparatus for applying heat and pressure to a shoe upper for molding thereof.
2. Description of the Prior Art
Shoe manufactures have long used pressure and/or heat in one arrangement or another to form shoe uppers to specific contours of toe or heel portions of a foot. U.S. Pat. No. 2,983,934 describes an inflatable die arrangement to shape an upper about a heated heel mold. This is an early attempt to use heat and pressure to conform an upper about a mold. It is more complicated and hence expensive than what has been developed since. Other inventors using just pressure, as shown in U.S. Pat. No. 3,017,645, form an upper about a heel die, wherein rigid wings that collectively define the surface of the heel, pivot about the heel of the mold and force the upper material thereto. A still further attempt at upper molding and also back seam pressing is shown in U.S. Pat. No. 3,039,288 wherein a heated convex form mates with a heated concave form, with a back seam stitched upper pressed therebetween. This method is costly using built-in heaters with each mold, since separate molds are necessary for variations in shoe size or style, and the die members are susceptible to wear. A recent U.S. Pat. No. 3,464,073, describes a flexible band arrangement comprised of elastomeric material having radiant heating elements disposed adjacent the band but lacking a powdered metallic filler.
The mold members, or dies, exemplified by the above cited examples, should be flexible to permit a slight yielding when pressed and they should conduct heat while not permitting excessive elongation during long periods of use. Some materials used in dies or pressure bands lack good heat transfer characteristics and have "sticky" properties. That is, the upper material and/or the color of upper material adheres with the band, and undesirably transfers it to the next upper being operated upon.
The present invention is designed to overcome the above cited shortcomings of the prior art.
SUMMARY OF THE INVENTION
In accordance with the invention, there is provided an elastomeric molding member having a dispersion of aluminum particles therein. The elastomeric molding member is comprised of a U-shaped flexible band that mates with a male die. The male die and flexible band are movable with respect to one another. The flexible band has heating elements against the external portions of its leg sections. A heel portion of a shoe upper is placed between the male die and the flexible band. The heating elements are activated and the male die and flexible band are mated, pressing the upper therebetween, conforming it to the desired shape of the heel. The molding members conduct the heat uniformly throughout, aided by the heat transfer capacity of the aluminum particles.
The flexible band is constructed as to be the movable member whose resilient legs wrap around the male die in a pressure activated heat transfer relationship. The heat aids in molding a thermoplastic stiffening element within the shoe upper which helps maintain the contours therein.
BRIEF DESCRIPTION OF THE DRAWING
The objects and advantages of the present invention will become more apparent when viewed in conjunction with the following drawings, in which:
FIG. 1 is a side elevational view of a shoe upper preshaping machine having flexible, externally heated bands constructed according to the principles of the present invention;
FIG. 2 is a side elevational view similar to FIG. 1, with the elements of the machine in another phase of operation; and
FIG. 3 is a side view of the flexible, externally heated, impregnated band.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to the drawings, and particularly to FIG. 1, there is shown a portion of a shoe upper preshaping machine 10 having a pair of shoe upper molding mechanisms 12. Each shoe upper molding mechanism 12 is comprised of a generally U-shaped flexible band 14, a male die member 16, a heater 18 of any suitable type on each leg of the flexible band 14. The male die members 16 may be of a heel or a toe form. Each heater 18 is mounted on a back plate 20. The back plate is bolted to a metal plate 22 (preferably aluminum) that is attached to the outward portion of each leg of the U-shaped flexible band 14. Each heater 18 is energized electrically through a cable 24 attached to a power supply, not shown.
Each flexible band 14 is movable with respect to the male die member 16. A pressurizable fluid piston, not shown, motivates a piston rod 26 toward and away from the die member 16. A cross arm 28 is attached to the piston rod 26, as shown in FIG. 2, and has a link 30 on each end connected to the lower end of each leg of the flexible U-shaped band 14. Upon pressurization by the fluid piston, not shown, the piston rod 26 is extended toward the male die member 16. It may be seen that the die member 16 could be alternately movable rather than the band and/or a wide variety of moving means could be used without departing from the scope of the invention. It is understood that a shoe upper 28, indicated by dashed lines in FIG. 1, is disposed between the molding members 14 and 16. A metal band 34 is fastened across the exterior of the flexible band 14, and is connected to the back plate 20. As the cross arm 28 is forced to move with the piston rod 26, the links 30 cause the legs of the flexible band 14 to wrap about the shoe upper 28 and around the male die 16, as shown in FIG. 2. A pressure activatable upper tensioning gripper arrangement 32 is disposed adjacent the male die 16 to pull the shoe upper snugly over the male die 16 just prior to the movement of piston rod 26 toward the male die 16.
A heating element, not shown, may also be located within the male die 16. The heater 18 heats the plate 22 which is embedded into the surface of the flexible band 14 and transmits heat from the heater 18, across a broad area, as shown in FIG. 3, into the flexible band 14. The flexible band 14 in its preferred embodiment is comprised of silica gum rubber which is uniformly mixed with a metallic powder filler, aluminum, in this example. Aluminum is used because it has good heat transfer properties but other metal powders and/or particles could be used without departing from the scope of the invention. The aluminum powder is added to the silicone rubber, giving it the thermal conductivity the silicone rubber does not have by itself, although this type of rubber does have capabilities of withstanding high temperatures with minimum elongation and color transfer.
Silicone rubber has a relatively high elongation factor and, by using metal particles as filler, that elongation factor, elasticity, will not decrease markedly. Elasticity is very important in bands of this type. A rubber successfully used was prepared from SE-7501U which is a General Electric Company silicone rubber compound. The compound was cured with Bts (2, 4Di Chlorobenzoyl) peroxide using 1.2 parts per 100 at a temperature range of about 220°F to 270°F for about 15 to 30 minutes, preferably 20 minutes. The aluminum particles used were generally spherical, having a diameter range of 10 to 15 microns, preferably 13 microns. The amount of aluminum particles in the compound ranges from 50 to 75% by weight with 60% being the preferred quantity by weight of aluminum particles. Additionally, an increase in tear strength of the band 14 is obtained with the 50 - 75% aluminum particle filler.
The external heaters 18, which may be of the cartridge type, are utilized in the range of about 300°- 400°F, preferably 350°F, which permits an extended service life of the bands 14. The aluminum plate 22, shown in FIG. 3, may be sandblasted, cleaned, and coated with a silicone primer to promote adhesion with the silicone rubber with which it will be mated. The bond formed between the two materials, the aluminum plate 22 and the silicone rubber which comprises the band 14 will resist temperatures up to 480°F. The externally heated band 14 thus provides a long lasting arrangement for heating and molding shoe uppers. It is to be noted that the band could be formed to mold toe portions of shoe uppers as well as heel portions thereof.
Though the invention has been described with a certain degree of particularity, it is to be understood that the description was exemplary only, and that the scope of the invention is to be defined by the following claims. | A heat conductive band movably mounted on a machine for preshaping shoe parts. Each band is comprised of silicone rubber compounds with a dispersion of metal particles therein. Metal plates are bonded to external surfaces of the band with heating elements attached thereto. The metal particles in the band aid in heat conduction through the bands, and the silicone rubber bands permit efficient heat transfer and extended life for shoe molding apparatus. | 0 |
This application is a continuation-in-part of copending U.S. patent application Ser. No. 814,365, filed Dec. 30, 1985 now U.S. Pat. No. 4,667,461.
BACKGROUND OF THE INVENTION
The field of the present invention is hand rakes, particularly skid or runner type ground support adapted to be attached to standard tined (or "lawn") rakes so to alleviate damage caused to the lawn and rake tines during the raking action while easing the raking effort.
A common problem in the raking of leaves and other materials using a lawn rake is that the tines of the rake grip more than just the material to be moved. This can severely damage both new and existing grass roots and scar a lawn. Additionally, the raking of leaves from a substrate of gravel or mulch using conventional lawn rakes often results in considerable relocation of the substrate--thus drastically increasing the task of raking by requiring separation and spreading of the substrate once the raking is completed. Also, the tines of the rake itself are battered during the raking process which decreases the useful life of the rake. Moreover, the pulling required to move the tines of a lawn rake through a lawn is burdensome and tiring.
Through the years, various devices have been employed as runner attachments for cast iron toothed (or "garden") rakes. A search of skids or guards for all types of rakes produced the following:
______________________________________U.S. Pat. No. 464,802 to PinkhamU.S. Pat. No. 885,252 to HughesU.S. Pat. No. 1,174,317 to HeimerlU.S. Pat. No. 1,318,079 to HoagU.S. Pat. No. 1,536,742 to Anderson et alU.S. Pat. No. 2,137,608 to FlavinU.S. Pat. No. 2,790,297 to Gardner______________________________________
These all involve using a variety of skids or wheels attached to the teeth, head, or handle of a garden rake to help prevent the teeth from ripping through the raking surface. Additionally, a lawn rake of unusual construction, U.S. Pat. No. 2,083,922 to Roessel, has been disclosed having modified tines which support the rake above the raking surface.
Although the foregoing devices may function reasonably well, each is deficient in a number of respects. Some of these devices are not readily and cleanly removable to permit standard raking action. Some of the devices add unnecessary weight, complexity, and cost to the rakes. Additionally, most of these devices support the rake at a fixed position above the raking surface and do not permit the user to exert pressure to achieve progressively increased amounts of raking action. Further, none of the devices provide an elongated skid surface for maximum glide across the lawn. Most importantly, none of the devices disclose a skid for attachment to the present standard form of spring steel, bamboo or plastic lawn rakes.
In light of the foregoing, it is an object of the present invention to provide a skid for a lawn rake which supports the tines of the rake above the raking surface so both to protect the rake tines and the lawn or other substrate by positioning the rake tines to grip only the material being moved and not the substrate, and to decrease vastly the effort required to pull the rake.
A further object of the present invention is to provide a skid device for a lawn rake which is lightweight, installs easily and securely, and is quickly retracted and stored to permit standard raking action.
An additional object of the present invention is to provide a skid device for a lawn rake which incorporates all the foregoing objects, is inexpensive to produce, and can be readily installed onto any standard lawn rake.
SUMMARY OF THE INVENTION
The present invention is directed to a skid device adapted to be attached to standard lawn rakes. The invention comprises: a flexible contoured skimmer element, which provides reinforcement for the tines of the lawn rake and two skid arms to support the rake tines above the substrate surface; and a mounting bracket and restraint arm, which both attach to the handle or upper tines of the rake and cooperate to retain removably the skimmer element on the rake.
Employing the present invention provides effective yet effortless raking action over a variety of substrate surfaces, including lawns, gravel, and mulch. The tines of the lawn rake are supported above the substrate s to avoid undesirable snagging of substrate which can damage the substrate, unduly complicate the raking procedure, and destroy the tines of the rake. However, the skimmer element is flexible and permits the user to exert added pressure to create standard raking action whenever it is desired. Additionally, the skimmer element is easily removed or swung out of use when extended standard raking action is necessary.
The present invention is designed to be inexpensively added to any standard lawn rake and can be readily installed by either a manufacturer or a consumer.
DESCRIPTION OF THE DRAWINGS
The operation and features of the present invention should become apparent from the following description when considered in conjunction with the accompanying drawings, in which:
FIG. 1 is an overhead view of one embodiment of the present invention attached to a standard lawn rake;
FIG. 2 is an exploded perspective view of one embodiment of the present invention in relationship to a standard lawn rake;
FIG. 3 is a perspective view of the mounting bracket and restraint arm of another embodiment of the present invention.
FIG. 4 is an exploded perspective view of a standard lawn rake incorporating a restraint arm and a unified skimmer element and mounting bracket of a further development of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a skid device to be used on common lawn rakes. Illustrated in FIGS. 1 and 2 is a modified standard metal tined lawn rake 10 incorporating the present invention and having the standard features of a handle 12, a plurality of tines 14 which are attached to the handle 12 by a tine support bracket 16, and a tine reinforcement plate 18. As is true of many rakes of this kind, the tine reinforcement plate 18 contains two support arm receptacles 20. In normal operation, additional bracing is provided by a support arm (not shown) which attaches to each of the support arm receptacles 20, 20 and is held to the tine support bracket 16 through a combination of: a bolt 22, which passes through the tine support bracket 16 via orifice 23; an upper fitting 24, which seats on top of the support arm and holds it firmly against the tine support bracket 16; a lower fitting (not shown); and a nut 26.
To practice the present invention, the standard support arm is replaced by a mounting bracket 28 which, similar to the support arm it replaces, attaches to the tine support bracket through use of the bolt 22 and upper fitting 24. Also similar to the support arm, the mounting bracket 28 passes through the support arm receptacles 20, 20 in the tine reinforcement plate 18. Unlike the support arm, the mounting bracket 28 has two extended legs 30, 30 which legs 30, 30 pass through the receptacles 20, 20 and beyond the tine reinforcement plate 18.
A restraint arm 32 is added which engages via a downward bend 33 the tine support bracket 16 through a hole 34 added on the raking side of the orifice 23. The restraint arm 32 passes through an added opening 36 in the tine reinforcement plate 18 and ends in a downward facing hook 38 before reaching the ends of the tines 14. It should be noted that the restraint arm 32 may be adapted to pass over the tine reinforcement plate if desired, although some structural integrity may be lost by doing so. For reasons of flexibility and tine support, discussed below, the restraint arm 32 should be as long as possible, but it should be significantly shorter than the length of the tines so not to interfere with the use of the rake during normal raking action.
A contoured skimmer element 40 is provided, having a substantially rectangular upper section defined by a cross brace 42 and a pair of lower protruding skids 44, 44. The tips of the skids 44, 44 should bend upwards or should double back on themselves so to avoid snagging of the substrate.
The skimmer element 40 attaches to the rake by placing its rectangular side opposite the cross brace 42 under the two extended legs 30, 30 so to cause the skimmer element 40 to be held snuggly between the tines 14 and the extended legs 30, 30. The skimmer element 40 locks into this position by placing the cross brace 42 into the downward hook 38 of the restraint arm 32. Once installed, the skids 44, 44 should extend well beyond the ends of the tines 14 and should support the tines 14 of the rake approximately 1/2" above the substrate when the rake is held in the normal raking position.
The mounting bracket 28, the restraint arm 32, and the skimmer element 40 may be constructed from any desired material which provides sufficient support and flexibility, including plastic or metal. In light of their weather resistant smooth finish, 1/8" stainless steel or nickel plated steel are particularly desirable. The final configuration should provide sufficient f exibility in the skimmer element 40 and the restraint arm 32 both to permit the user to exert only relatively minor pressure to cause the tines 14 to contact the substrate, and to permit the user to bend the cross brace 42 to easily engage and disengage the hook 38.
Although the skimmer element may be readily removed to permit normal raking action, by providing a modified lower fitting 46 with a curved catch 48 (or merely a separate curved catch component 48 attached to the lower handle 12 or to an existing lower fitting), the skimmer element 40 may be disengaged easily from the restraint arm 32 and be swung back to engage the cross brace 42 onto the curved catch 48. This securely retains the skimmer element 40 with the rake but permits completely normal raking action. Equally effective storage of the skimmer element 40 may be accomplished by removing it entirely and then repositioning the cross brace 42 beneath the legs 30, 30 and attaching the opposite rectangular side of the skimmer element 40 to the curved catch 48.
The above embodiment of the present invention works well with little or no modification on many of the lawn rakes presently available on the market, including the Disston steel rake produced by Sandvik Group, Danville, Va. However, although this embodiment can be installed by consumers, the main modification work necessary may make it more amenable to addition by an original or after-market manufacturer. Moreover, there are certain lawn rakes, such as the common bamboo or plastic types, that do not use a support arm attached to a tine reinforcement plate. Accordingly, a modified mounting bracket and restraint arm has been provided which can be installed easily by consumers on any lawn rake.
FIG. 3 illustrates a modified mounting bracket 28a having two modified legs 30a, 30a constructed from a piece of sheet metal. A modified restraint arm 32a is provided attached to a sheet metal attachment piece 50. The modified mounting bracket 28a and the attachment piece 50 each have two corresponding oblong openings 52. Attachment is accomplished by placing the modified mounting bracket 28a beneath the tines 14 and positioning the attachment piece 50 directly above it on top of the tines 14 and then anchoring the two together via nuts and bolts or other attachment means passing through each of the oblong openings 52, 52. By attaching the modified mounting bracket 28a so that its legs 30a, 30a are in approximately the same position as the legs 30, 30 in the embodiment disclosed above, the skimmer element 40 can be used unchanged on any lawn rake. The addition of a curved catch 48 allows the skimmer element 40 to be stored as discussed above.
FIG. 4 illustrates a further development of the present invention. In an effort to concentrate the present invention into the least number of component parts, the functions of the skimmer element 40 and the mounting bracket 28 may be combined into a self-attaching skimmer element 60.
The self-attaching skimmer element 60 looks similar to skimmer element 40 but it has two attachment members 62 extending rearward. The attachment members 62 are formed so to fit between the tines 14 of a rake and secure over the standard tine reinforcement plate 18 found on most common metal, plastic, and bamboo-tined rakes. The attachment member 62 holds the self-attaching skimmer element 60 in position for supported raking.
All that is required to secure the self-attaching skimmer element to a rake having a tine reinforcement plate 18 is a restraint arm 32. Attachment is accomplished in the same manner as that employed with skimmer element 40. In order to avoid completely the need for modification of a standard rake, a modified restraint arm 32a may be used.
The modified restraint arm 32a comprises an arm member 64, having a hook 65, attached to an arm fastener 66. The arm member 64 is similar in shape and construction to restraint arm 32. The arm fastener 66 comprises an arm holder piece 68, a fastener plate 70, washers 72 and bolts 74. The holder piece 68 is provided with threaded holes (not shown) or with nut means to receive and secure the bolts 74. The arm member 64 may be affixed to the arm holder piece 68 through any known method, such as injection molding, cementing, or threaded attachment. The holder piece 68 and the method of arm member 64 attachment should be able to withstand the stresses inherent at the base of any restraint arm of the present invention; accordingly, injection molded plastic holder arms permanently affixed to the arm member is preferred.
As is shown in FIG. 4, the modified restraint arm 32a attaches to the upper rake tines through placement of the arm holder piece 68 on top of the tines, and placement of the fastener plate 70, and washers 72 beneath the tine. The bolts 74 pass through the washers 72, the fastener plate 70, and the tines and anchor into the holes in the arm holder piece 68, thus securing the arm fastener 66 firmly to the rake. It should be understood that any other suitable fastening means, such as clasps or latches, may be substituted for the bolts and threaded holes.
In all other respects the self-attaching skimmer element 60 functions the same as the standard skimmer element 40. However, the self-attaching skimmer element 60 has some distinct advantages over other forms of skimmer elements. Some of the advantages include: it is cheaper to manufacture; it requires fewer components; and it can be very readily attached to most rakes with no modifications to the rake itself.
While particular embodiments of the present invention have been disclosed herein, it is not intended to limit the invention to such a disclosure and changes and modifications may be incorporated and embodied within the scope of the following claims. | A skid device adapted to be removably attached to standard tined lawn rakes is provided. The device maintains the tines of the rake above the surface to be raked so to ease both the effort required to pull the rake and the damage caused to the substrate under the material to be raked, while allowing thorough raking action. The device is readily removable to allow standard raking action when desired. | 0 |
[0001] This application claims benefit under 35 USC §119(e) of the Provisional Application No. 60/380,563 filed May 14, 2002.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates generally to toaster ovens and particularly to toaster ovens that transport bread products through a toasting chamber during the cooking process. More particularly, the invention relates to a microprocessor-based method and device for controlling such toaster ovens so as to adjust the degree of toasting, to adapt to different types of bread products, to compensate for line-voltage fluctuations, to enable power-conservation, and to effect other desired oven characteristics.
[0004] 2. Description of the Prior Art
[0005] Conveyor toasters are popular convection ovens in which items of food stuff, usually bread-related, are transported on a motor-driven conveyor. Such ovens range from small counter-top bread/bagel/sandwich toasters to the large commercial ovens common at pizzerias. Typically, the conveyor's food-bearing surface moves along a substantially horizontal plane through a toasting chamber positioned between upper and lower heating elements. The toasting is effected by a combination of radiative and convective heat generated by upper and lower heating elements, either working in concert to provide uniform toasting on both sides of the (generally planar) food item, or alone, for those products that need be toasted on only one side. Because of the range of what people consider to be a proper degree of toasting, and because different types of bread products have different toasting susceptibilities, there must be some means available to the operator of the toaster for adjusting the “toasting energy” to which an item is exposed. The toasting energy (the quantify of heat) received by an item will be jointly dependent on the heat flux it exposed to (where heat flux will be dependent on the air temperature within the oven and the level of radiation from the heater, both determined by the heater temperature) and the length of time for which it is exposed. This being the case, one can vary the degree of toasting by changing the heater temperature, the conveyor speed, the rate at which the oven exchanges air with the outside, or a combination of all three. Only the heater temperature and the conveyor speed will be addressed here, though it is noted that the convection fan with which the typical toaster oven is equipped is far from a passive element in the operation.
[0006] Consider first changing the heater temperature while maintaining the conveyor speed constant. Presuming that the desired mode of operation is such that the throughput of toasted products is maintained at its maximum rate, this approach would require that the highest heater temperature be used for the products, such as bagels, that require the most toasting energy. For items, such as slices of white bread, requiring the lowest toasting energy, the lowest heater temperatures would be used. Typically the heating elements are energized by the mains electric power (the “line voltage”), either via a single-phase 117 Vac or 234 Vac line, by a 208 Vac three-phase-line, or, rarely, by a three-phase 480 Vac line. Since the typical heating element presents just a passive resistance (R) to the applied voltage (V), the current through the elements will be directly proportional to the applied voltage, and heating of the heating elements occurs through simple Joule heating, varying as the square of the heater-element current or, equivalently, as the square of the voltage (V) applied across the heater element. (The Joule power dissipated per cycle will be proportional to the mean square of that applied voltage.) For maximum temperature on the heater elements and hence in the toasting zone, the full line voltage would be placed across the heating element(s) all of the time. Reducing the mean voltage across the elements lowers their temperature. Although the electrical power dissipated by an element is directly proportional to the mean square of the voltage, the temperature response is more complicated, because of the manner in which heat is transferred from the elements into the toasting zone, by radiation, by convection, and by conduction. It is noted that once one is positioned to vary the heater-element temperature, by whatever means, one has the capacity to compensate for one of the banes of commercial toaster ovens: line voltage fluctuation and drift (drift being just a long-period fluctuation, “fluctuation” will generally be taken to refer to both short-term fluctuation and to drift).
[0007] Controlling the mean voltage across a heater element is commonly done by placing a phase controller in series with the line voltage to the heater element to be controlled. The phase controller is tantamount to a fast switch that is “on” for an adjustable fraction of each cycle of the line voltage and “off” for the rest of the time, so as to vary the mean square voltage across the heater element. The usual phase controller incorporates a triac and a circuit that will gate the triac at a determinable point in the line voltage cycle. The triac is the switchable component placed in series with the heater element; specifically, it is switched by voltage input to its gate electrode. In order to avoid a dc component to the voltage placed across the heater element output in this technique, equivalent portions of the negative- and positive-going halves of the cycle are applied to the element. With no gate input, the triac presents a blocking resistance to the ac voltage, but when a small dc voltage is applied to the gate, the triac freely passes the ac line voltage. Because of its high input impedance, the triac gate draws negligible power.
[0008] The triac is essentially a pair of SCRs wired in an antiparallel configuration and their gates tied together. That is, the “forward” direction of current for one of SCRs is in the opposite direction from the forward direction for the other. When a gate voltage is applied to switch them “on,” the line current will pass through one of them for the first half of the ac cycle and through the other for the other half. The nature of the SCR is that once turned “on” (so as to pass forward current) by a voltage pulse to the gate it will remain “on” as long as forward current is flowing. With a 60 Hz ac voltage, the forward voltage will fall to zero every {fraction (1/120)}th of a second. The zero-crossing point of the forward current will be delayed by an interval determined by the reactive component of the load. For a purely resistive load, such as is represented by a heater element, the line current phase is the same as the live voltage phase. Because of this, the phase controller switches the triac “on” during the second half of either the positive- or negative-going cycle, with a short voltage pulse to the gate. When the voltage falls through zero (the zero-crossing point), the triac switches off and current ceases. Then the gate is pulsed “on” again at the analogous position in the other half of the 60-Hz cycle. Adjusting the mean voltage in this manner involves setting the “delay angle” on the phase controller. As the delay angle is varied from zero to 180, the mean voltage applied to the heater element goes from full to zero.
[0009] This simple system of maintaining and/or adjusting the heater-element temperature provides a simple way of compensating for the inconstancy of the line voltage, the magnitude of which can typically varying over time by up to ±10% without being considered out of spec or as violating any performance standards. One means of compensating for this drift in phase-controller-based temperature regulation is to install within the oven an electronic temperature sensor coupled into an error-signal generator. The error signal is then fed into the phase controller so as to periodically adjust the delay angle so as to maintain a set temperature regardless of the variation in line voltage and other environmental conditions. The phase controller can thus be made into a very sensitive thermostat for the oven, without the need to resort to anything other than well-known circuit elements and sensors.
[0010] More typically, because of the lower cost, a relatively insensitive bimetallic-based temperature sensor is used to control an on-off switch in the line leading to the heater element, with the result that the voltage across the heater element cycles between full on and full off. That, combined with the bimetallic sensor's requirement of a relatively large temperature deviation from the set point for it to respond, leads to a relatively large oscillation in the oven temperature about that set point, much greater than the triac-based methods and other electronic approaches allow. Under the right circumstances, the performance advantage of the electronic approach and in particular the approach using the phase controller in combination with the electronic temperature sensor more than offsets the cost advantage of the bimetallic-switch control. For obvious reasons, the methods that rely on a feedback signal being generated by direct temperature measurement are referred to as “closed-loop” systems.
[0011] Regardless of the approach used, there are some serious disadvantages to controlling the toasting energy delivered to an item solely by varying the oven temperature. Most seriously it reduces the overall rate at which a distributed range of products can be toasted, since it requires the conveyor speed to be set so as to ensure that those items requiring the most toasting energy (e.g., bagels) are properly toasted with full power applied to the heater elements. This means that for the other food items, which will constitute the majority of the food types toasted in establishments not specializing in bagels, the heater power will have to be cut back so that they do not get burned during the long transit time through the toasting chamber. Obviously, the optimum production rate across all items will be attained by always maintaining the heating elements at their highest temperature and varying the time that the items spend in the toasting chamber (though this will not in general result in the lowest per-item cooking cost). Traditionally, this time control has been accomplished by varying the conveyor speed, the highest speed being used for the products that toast most readily and the lowest speeds for items like bagels.
[0012] Cost of manufacture is one of the paramount considerations going into the design of toaster ovens, especially those that will be used in large numbers in commercial establishments. This consideration underlies the decisions made about many of the oven components. For example, a typical toaster oven conveyor is driven by an inexpensive universal motor to which it is coupled through a gearbox and chain linkage. This setup permits the conveyor speed to be varied mechanically by changing the gear ratio, even as the simple motor continues to operate at a fixed speed. Of course, it is much more convenient to provide for electric or electronic control of the conveyor speed, an approach that is also more readily and flexibly automated than is the mechanical approach. The simplest method of controlling the conveyor speed electrically is to vary the voltage to the motor and hence the motor speed; this is the approach in many of the existing systems. Unfortunately, the inexpensive motors traditionally used with conveyor-based toasters do not function well at speeds that differ significantly from their synchronous speed. (For a line frequency of 60 Hz, the synchronous speed for a two-pole universal motor is 3600 RPM.)
[0013] For those systems that vary the ac motor speed in order to vary conveyor speed, the motor-voltage control is typically exercised through a variable resistance in series with the motor or by a phase controller (as discussed above) in series with the motor. Both the series resistance and the series phase controller approaches are relatively simple and low in cost, though the series resistance results in wasted Joule heating when the motor is being operated at any but the highest speeds. Both approaches falter when very low motor speeds are attempted, for the reason set out above. At motor speeds lower than the synchronous speed, the torque produced by the motor falls off, and at speeds significantly lower than the synchronous speed, the torque falls to the point where variable frictional forces in the motor's mechanical load become significant, and erratic operation of the motor (and the conveyor) can result. For example, the motor may stop completely even when a non-zero speed is desired and the corresponding non-zero voltage applied to the motor. Furthermore, as discussed elsewhere, the line voltage available in most facilities can fluctuate over a considerable range and still be considered “normal,” meaning that even if the motor is running at a speed high enough to ensure continuous operation, a drop in the line voltage may cause it to stall—and the toast to burn.
[0014] An alternative to the above approach is to use a dc motor in place of the universal ac motor. This gets away from the constraints on low-speed operation, though at a higher cost. Rosenbrock et al. (U.S. Pat. No. 5,197,375; issued Mar. 30, 1993, and U.S. Pat. No. 5,253,564; issued Oct. 19, 1993) discloses an advanced system incorporating a dc motor to drive the conveyor. Incorporating a microprocessor and various sensor/feedback loops, the Rosenbrock et al. system reportedly maintains the conveyor speed and the oven temperature at operator-selected levels, even as the line voltage varies irregularly. Conveyor speed is maintained in the system taught by Rosenbrock et al. through a control loop incorporating a motor-speed-monitoring sensor (optical-based or otherwise). This sensor generates an error signal whenever the conveyor speed begins to deviate from the speed selected, an error signal that causes an increase or decrease in voltage applied to the motor so as to counter an unwanted decrease or increase, respectively, in the conveyor speed. In this manner, all external influences, including line voltage fluctuation, tending to vary conveyor speed are compensated for. The voltage to the dc motor in the Rosenbrock et al. system comes from a power supply energized ultimately by the ac line voltage. The conveyor speed is controlled by toggling this power-supply-generated dc voltage to the motor on and off, so as to produce a train of similar voltage pulses at the motor input. Each pulse has a height corresponding to the full dc voltage and a width that is adjustable; the average voltage input to the motor is then varied by varying the pulse width in this Pulse Width Modulation (PWM) speed control. In Rosenbrock et al. the interval is never so long that the motor stops. For that matter, the circuitry in Rosenbrock et al. appears to be such that, because of induction and other mechanisms, the motor speed for a given PWM is essentially constant, not responding to the discreteness of the individual pulses. This method of maintaining conveyor speed through PWM and a speed-sensing feedback loop has the potential to provide very close control of the oven operation. However, it is very expensive compared to the traditional means of varying conveyor speed in toaster ovens. The cost is increased in part because of the additional feedback circuitry, including the sensor network, and the fact that dc motors of the type incorporated in the Rosenbrock et al. system are significantly more expensive than the universal motors traditionally-used in the industry. In general, the closed-loop toaster-oven systems of the prior art are capable of providing good temperature and conveyor speed control, but at a high monetary cost compared to the prior-art open-loop systems.
[0015] With the line voltage available at the toaster oven allowed to vary as much as ten percent about its nominal level, nominal 117 Vac single-phase line voltage can be as high as 129 Vac or as low as 105 Vac and still be acceptable under the rules governing the local utility responsible for delivering electricity. Since the heater elements are normally just wires or bars of resistance R, a simple expression gives the rate at which the elements give off (dissipate) energy, namely the Joule heating expression (V 2 /R). This means that the power dumped into the heating chamber increases by 21% when the line voltage increases by 10%. Although, as mentioned above, the temperature does not follow the power-dissipation level directly, a 21% increase in power dissipated increases the temperature in the oven significantly. The power radiated by the heaters varies with the fourth power of the heater temperature. Thus the temperature of the heating element has to increase only by 5% to increase radiative power by 22%.
[0016] Line voltage variations may be short lasting, but they may also endure for hours, reflecting demand elsewhere in the power network supplying the toaster-oven site. Thus, a large demand for air-conditioning may result in the line voltage at the toaster oven being reduced by as much as 10% for the entire afternoon. It is normally at the onset of the change in the line voltage that the most mischief is wrought with toaster ovens. A line-voltage reduction can result in untoasted bread emerging from the oven, and a line-voltage increase can result in carbonized toast and a smoke-filled eating establishment.
[0017] An important, though often slighted, component in the toaster oven is the convection fan used to circulate air within the oven. In a properly designed system, the convection fan increases the efficiency with which energy dissipated at the heater elements is delivered to the products being toasted. Historically, this function has been served by the simple, inexpensive muffin fan.
[0018] Traditionally, toaster-oven muffin fans have alternated between operating at full speed and not operating at all, as the voltage applied to them cycles between the full line voltage and zero voltage. Finer control over the fan speed would offer several advantages. For example, during inactive periods, when the heaters are placed on reduced-power standby mode, it would be useful to also reduce the fan speed to a lower, yet non-zero, level. Also it would be beneficial to maintain fan speed at its set level regardless of voltage fluctuation. Although there are ways that this can be achieved by the use of dc fans, it is again desirable for reasons of economy to achieve this control with the inexpensive ac muffin fans.
[0019] In addition to the quantitative improvements in toaster ovens that are described above, certain qualitative departures from traditional operation are also desirable. All of these improvements can be achieved by the use of microprocessors for toaster oven control. For example, one can set up the control unit at the beginning of each day or at the start of the season, or at the manufacturing plant, with criteria for placing the oven on stand-by operation. This may be as simple is having the shift to stand-by to occur at the same time or times each day, based on historical information regarding slow periods in the business. Alternatively, the shift to stand-by may be triggered whenever no toasting has taken place for a pre-selected time interval. The advantage of this approach is that it is automatic, with no need for a conscious decision on the part of the operator every time the shift to energy-conserving stand-by is made. Similarly, various start-up and shut-down modes may be built into the oven control and, with the flexibility provided by microprocessors, the toaster operator can easily set the various triggering criteria to meet the conditions at the specific establishment where the toaster is located, conditions that may vary throughout the year. As a yet-further improvement, the microprocessor-based control system could enable the operator to introduce a slight increase or slight decrease in the degree of toasting (the darkness) for a few items out of a large number that receive the “default” degree of toasting. The challenge is to introduce the numerous microprocessor-mediated improvements in a manner that avoids significant increases in the cost of manufacturing the toaster ovens.
[0020] Therefore, what is needed is a toaster-oven controller that permits easy operator-mediated control over the level of toasting energy supplied to the items to be toasted, while providing the capacity of maximizing the average throughout of a variety of items. What is further needed is such a controller that permits efficient control of the speed of the convection fans used with toaster ovens. What is yet further needed is a method of using such a controller so as to implement a wider range of start-up, shut-down, and stand-by protocols than have been used previously. What is still further needed is such a controller and method that can provide toasting processes impervious against short- or long-term line voltage variation. Moreover, what is needed is that the controller and method achieving these objectives do not add significantly to the cost of production of toaster ovens.
SUMMARY OF THE INVENTION
[0021] An objective of the invention is to provide a control system for conveyor-based toaster ovens that guards such ovens and the products they produce against adverse effects from line-voltage fluctuations. Another objective is to provide such a control system that permits easy adjustment in the degree to which a given item in the oven is toasted, and that permits the accommodation of a large variety of food items with their concomitant range in toasting-energy requirements. It is a further objective that this control system provide the oven operator the ability to make these choices and also to make the choice between maximizing product throughput, on the one hand, and minimizing operating cost, on the other. Yet another objective is to introduce to such ovens' operation improved power-up, shut-down, and shift-to-standby protocols. An overriding objective is that all these objectives be achieved without significantly increasing the complexity nor the cost of the individual components of the control system.
[0022] The present invention meets the stated objectives by introducing particular microprocessor-based oven-control circuitry that does not incorporate the complexity of closed-loop systems. The invention also introduces a new philosophy regarding conveyor speed, one that emphasizes not conveyor speed per se but rather the dwell time within the toasting chamber of the items to be toasted. By such an emphasis, the present invention is able to avoid completely the problem of operating conveyor motors at very low speeds, a problem that the prior art has addressed by going to more expensive motors and/or to complex, expensive circuitry. Once it is realized—that for a toasting chamber presenting heating characteristics that are either uniform or slowly varying as a function of location, it can be seen that the exact nature of the transit of the bread items through the chamber is not important. In particular, since the degree of toasting is basically a function of the total toasting energy that the item receives, an item can move through in a stop/start fashion with no detriment to the final product, providing that the item's total dwell time is commensurate with its toasting-energy needs and the distribution of convective and radiative heating within the chamber. With this approach, there is clearly no upper limit to the dwell time in the cooking region, that is no lower limit to the average speed with which the conveyor moves. In an extreme example, the conveyor can mimic the toasting procedure of the simple home toaster, by moving the food item into the toasting chamber, halting the conveyor motor for the duration of time required for the item to be toasted, and then moving the item on out the exit. However, as a practical matter, the demands on the typical commercial conveyor toaster are such that a quasi-continuous transit of the food through the chamber is required. The word “microprocessor” is used throughout this discussion as a concise reference to any digital processing and control device or collection of devices, including without limitation those devices sometimes referred to as “microprocessors” or “microcontrollers.” Further, the term should be taken to encompass as well the support circuitry necessary for carrying out various peripheral functions including, but not necessarily limited to, analog-to-digital conversion, digital-to-analog conversion, timing, memory, digital input and output, watchdog, and reset or initialization. In summary, the use of the label “microprocessor” should not be taken as limiting in any way the range of embodiments of the invention described and claimed herein.
[0023] By permitting stop and start motion of the conveyor, one can retain the economic advantage provided by the inexpensive universal motors without having to be concerned with the erratic behavior of such motors under low-speed operation. In the present invention the motor receives either full line voltage or no voltage at all. Apart from the transient periods while the motor is getting up to speed and coasting to a stop, respectively, the motor (and conveyor) either operates at maximum speed or is at rest. The system controlling the motor must provide a duty cycle to the motor reflecting the dwell time required by whatever food item is then being toasted.
[0024] The on/off sequencing that the invention uses is based on the stable 60 Hz line frequency provided in the U.S. and most countries. Corresponding to this frequency is a period of one-sixtieth of a second (approximately 0.016 sec). In its Preferred Embodiment, the invention ensures the proper dwell time by alternating between applying the full ac voltage (or substantially the full voltage) for an integral number of such periods and completely removing the voltage from the motor for an integral number of periods. The motor sees bursts of ac line voltage. The shorter the bursts are (i.e., the fewer cycles for which the voltage is applied) the shorter distance the conveyor advances during each “on” interval. Similarly, as the time between bursts is made longer the conveyor is stopped for a longer time between bursts. The toasting operation depends on the conveyor's average speed while the item-to-be-toasted is within the toasting chamber, a joint function of the duration of the “on” intervals and the length of time between the “on” intervals. At one extreme, the controller applies the full ac line voltage to the motor without any interruption as the item travels through the oven. This defines the maximum conveyor speed for that line voltage, and the minimum dwell time (toasting time). In contrast, the controller may apply the voltage for a very small number of complete periods (say 5 ) and then wait for a large number of cycles (say 120 ) before applying the voltage again. In this case, the conveyor will move forward a small distance, say one-quarter inch, then pause for two seconds before moving another quarter-inch. It is easily understood that with this control scheme there is no lower limit to the average conveyor speed nor, consequently, no upper limit to the dwell time.
[0025] There are various ways in which the dwell-time approach of this invention can be implemented. This is particularly true for embodiments that devote one or more microprocessors to translating the independent parameter—total dwell time—to the on/off sequencing of the conveyor. Furthermore, with a microprocessor-based control unit, it is straightforward to increase or decrease the dwell time from its default value so as to comply with the customer's taste and also to adjust the dwell time so as to compensate for environmental factors, in particular line-voltage fluctuations. The latter function will require in one way or another a comparison of the line voltage magnitude with some fixed voltage reference. The invention depends on automatic electronic shifting of the on/off sequence to compensate immediately for a detected deviation of the line voltage. This might be a deviation up or down (usually down) from the nominal value or a shift from an erstwhile voltage level back to the nominal value for the line voltage. Alternatively, the measured change in line voltage can be compensated for by adjusting current through the heating elements so as to ensure that their temperature does not change, thus eliminating the need to adjust the dwell time in response to a change in the line voltage. Finally, some combination of dwell-time adjustment and heater current adjustment may be made to compensate for the change in line voltage. The present, microprocessor-based, invention provides the flexibility needed to select whichever combination is most beneficial, whether it is to minimize operating costs or to maximize production rates. If the establishment operating the oven is extremely busy, the emphasis will presumably always be maximizing output. Under those circumstances, for example, an increase in line voltage will be seized upon as an opportunity to cut down on dwell time. Of course, when the voltage dips, the only response can be to increase the dwell time, that is to decrease output.
[0026] Once a microprocessor has been introduced into the system, the other objectives of the present invention can be achieved by properly programming the microprocessor so as to provide the protocols for turning on the oven, for shutting down the oven, and for putting the oven on a pre-programmed stand-by mode. These protocols relate primarily to powering the heating elements, the fan motor, and the conveyor motor. For the purposes of controlling the fan, one can exercise the same type of start-and-stop operation as used with the conveyor motor, thus permitting the oven to use the traditional inexpensive muffin fan. In the alternative, if there is not a need to operate the fan at very low speeds, the traditional voltage-lowering can be used to vary fan speed. The most important aspect of the invention is the line-voltage-fluctuation compensation achieved by adjusting conveyor speed, heat settings, and/or fan speed. In practice the compensation is based on providing the microprocessor information gained by monitoring the line voltage or surrogate for the line voltage. Here the surrogate can be derived from the line voltage itself through any combination of discrete or integrated passive and active semiconductor devices (including without limitation, resistors, capacitors, inductors, diodes, transistors, and semiconductor controlled rectifiers). The surrogate itself can take the form of a voltage, current, frequency, phase angle, pulse width, pulse position, temperature, resistance, reactance, and so on, indeed any physical parameter detectable by the microprocessor. The choice made in the Preferred Embodiment is to generate for the surrogate a voltage derived directly from the line voltage by a step-down, isolating transformer. That approach also entails isolating the entire control circuit from the line voltage, the front end by a power transformer and the output end by optical-isolation devices. Alternatively, one could establish insulating barriers between the control circuit and the user, in which case there would be no need for isolation in the line-voltage surrogate generation path.
[0027] The commentary of the previous paragraph is provided so as to emphasize the many embodiments that a person skilled in the field and art can devise once the details of the present invention are known and the fact that the invention claimed is far broader than any particular detailed embodiment described in this document.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] [0028]FIG. 1 is a block diagram of the invention's Preferred Embodiment, exclusive of the conveyor and the circuit that switches the conveyor motor on and off.
[0029] [0029]FIG. 2 is a diagram of the circuit used to turn the conveyor motor on and off in response to the on/off signals generated by the control unit logic in the Preferred Embodiment, as well as a block diagram of the conveyor motor and equipment linking the motor to the conveyor.
[0030] [0030]FIG. 3 depicts waveform representations illustrating various aspects and consequences of turning the conveyor motor voltage on and off.
[0031] [0031]FIG. 4 is a schematic depiction of the Preferred Embodiment keypad by which the operator selects the toaster operations desired and causes the system to deviate from any default values built into it.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0032] The following discussion is best followed with reference to FIG. 1, which is a block diagram of a number of the invention's components that are configured by long-known techniques and circuits. The invention is designed to use standard ac line voltage such as is available in most homes and business establishments. The Preferred Embodiment is configured in particular to be energized by single-phase ac power such as is available in the United States and Canada (referred to alternately as ac line voltage, ac line power, or simply line voltage). In the Preferred Embodiment, the line voltage is introduced over a first ac line L 1 and a second ac line L 2 to several input points in the system. These input points are isolated from one another, and the line voltage is isolated from ground. In particular, and most importantly, the line voltage is isolated from the low-voltage dc voltages produced within the system as control signals.
[0033] As can be seen from FIG. 1, the line voltage is introduced to a converter 300 . The converter 300 is a standard ac-to-dc converter that includes a step-down transformer so that it converts the nominal line voltage of 117 Vac to an unregulated dc voltage with a nominal voltage of 8 Vdc which is output on unregulated-dc line 2 . In addition to stepping down the ac voltage, the step-down transformer portion of the converter 300 isolates the line voltage from the stepped-down ac and hence from the unregulated dc voltage appearing on unregulated-dc line 2 . Also produced by the converter 300 is a zero-crossing pulse train 7 consisting of a 120-Hz train of positive-going pulses each pulse synchronized to the instant that the ac line voltage passes through zero (120 times a second for the 60-Hz signal) in such a way that half of each pulse precedes the zero-crossing and half follows it. The individual pulses have a fixed width of approximately 1 ms, a height on the order of one volt, and are output over a zero-crossing line 3 . (See FIG. 1 and FIG. 3.) It is the zero-crossing pulse train 7 that provides the synchronizing and counting means for the control system. Both the rising and the falling pulse edges are used, the rising edge serving to “wake up” the controller and the falling edge to cause the motor's turn-on signal to be issued. This permits a well-defined turn-on time, and hence minimizes jitter in the triggering point location from one turn-on phase to the next.
[0034] The unregulated-dc line 2 is connected to a digital control unit 10 and to a dc regulator 400 . The dc regulator 400 converts the unregulated voltage from the unregulated-dc line 2 to a regulated (constant) 5 Vdc output on regulated-dc line 1 that is coupled directly to the control unit 10 , to which it provides operating power. The digital control unit 10 is in major part a microprocessor. Note that in addition to the regulated-dc line 1 and the unregulated-dc line 2 , the control unit 10 has as an input the zero-crossing line 3 ; the zero-crossing pulse train 7 plays a clock and synchronizer role for the control unit 10 .
[0035] As further depicted schematically in FIG. 1, a keypad 12 is coupled to the control unit 10 . The keypad 12 is the means by which the oven operator interacts with the control unit 10 either to enter specific operational commands or to vary certain pre-programmed tasks. As will be discussed further below, there are buttons corresponding to the most common food types expected to be placed in the oven for toasting. In addition, there is a button to depress to slightly increase the dwell time, whatever the pre-programmed protocol calls for, and another to decrease the dwell time slightly. The keypad 12 and its configuration with the control unit 10 also provides the operator more advanced control options such as the capacity to change default settings for the power-up and shut-down procedures, respectively. Further, in the Preferred Embodiment, the keypad 12 allows the operator to select 30 min, 60 min, or 90 min as the time interval that must pass with no operator input before the oven enters stand-by. For monitoring the operation and changes in the oven, the system is equipped with a visual display 14 coupled to the control unit 10 . Visual information presented by the display 14 includes such things as (a) the time remaining (during power-up or start-up from standby) until the oven reaches operating temperature, (b) the time remaining before the oven goes into standby mode absent an input, (c) time remaining in standby mode before complete shut-down occurs absent input, and other time information useful to the operator in planning his/her production.
[0036] Additional control signals generated by the control unit 10 include a top-heater-control signal, which is output on a top-heater-control line 9 , a bottom-heater-control-signal which is output on bottom-heater-control line 11 , a fan-control signal, which is output on a fan-control-signal line 13 , and a conveyor-control signal, which is output on a conveyor-motor control signal line 15 . All of these control signals are binary in nature, with a HI-to-LO difference being on the order of a few volts. These control signals all look into high-impedance inputs, details of which are set out below.
[0037] As can be seen with further reference to the block diagram of FIG. 1, the Preferred Embodiment includes a top-heater control circuit 18 , which is basically a switch interposed between the first ac line L 1 and a first end of a top-heater element 16 , a second end of the top-heater element 16 being connected directly to the second ac line L 2 . In the Preferred Embodiment, the top-heater control circuit 18 incorporates a phase controller (not shown) such was described earlier. The control unit 10 determines the delay angle of the phase controller and hence the fraction of each cycle for which full power is to be applied to the top-heater element 16 . The top-heater element 16 being a simple resistance, with no reactive component, the power that top-heater element 16 dissipates is directly proportional to the mean square voltage applied to it, the mean square voltage value being determined by the delay angle. The full ac line voltage is turned on by a brief logic HI signal, but turns off by itself when next the current through the phase controller passes through zero. Because the top-heater element 16 constitutes a non-reactive load for the top-heater control circuit 18 , the current through it will pass through zero at essentially the same instant that the voltage applied to the it passes through zero.
[0038] A similar arrangement determines the average power dissipated in a bottom-heater element 20 , which is also a simple resistive element. The bottom-heater-control line 11 provides control input to a bottom-heater control circuit 22 which is interposed between first ac line L 1 and a bottom heater element 20 . The current through the bottom heater element 20 is controlled in the same manner as described above for the top-heater element 16 .
[0039] The fan-control line 13 is connected to a fan control circuit 26 which in turn is coupled to a muffin fan 24 . The speed of the muffin fan 24 is controlled by the fraction of the line voltage cycle that is applied to it. This fraction in turn is controlled in the same manner as described above in the description of the control of the current through the top-heater element 16 and the bottom-heater element 20 .
[0040] The monitoring of the unregulated-dc signal by the control unit 10 is the key to the steps taken by the control unit 10 in compensating for variations in the line voltage amplitude. In other words, the signal on unregulated-dc line 2 is a fluctuation surrogate for the ac line voltage. The unregulated-dc signal will have an amplitude (magnitude) that is directly proportional to the ac line voltage amplitude. For example, a variation in the ac line voltage amplitude by ±10% about its nominal peak-to-peak amplitude of 117 volts will result in the unregulated-dc voltage on unregulated-dc line 2 also varying by ±10%, with a resulting range of 7.2 to 8.8 Vdc.
[0041] In order to use the varying amplitude of the voltage on the unregulated-dc line 2 directly to determine line voltage drift, it is necessary to recognize and take account of variations in the unregulated-dc voltage that arise from sources unrelated to the ac line voltage variation. The most significant such source in the Preferred Embodiment is the change in the unregulated-dc voltage that occurs because of changing current demands put on it by the regulator 400 . The regulator 400 has as its sole function the maintenance of a constant 5 Vdc output on regulated-dc line 1 in the face of the current demands put on the regulated-dc line 1 by the load it powers. As the regulator 400 meets this function, its demand for current from the unregulated-dc voltage line 2 varies causing the voltage on the unregulated-dc voltage line 2 to vary also, as a function of the output impedance of the converter 300 . The visual display 14 is the major cause of the variation in current demand placed on the regulated-dc line 1 , primarily because of the varying information the visual display 14 is called on to present. (All the other outputs of the control unit 10 go to high impedance connections.) The Preferred Embodiment deals with this effect by ensuring that the measurement of the variation of voltage on the unregulated-dc line 2 is always done with the same load on regulated-dc line 1 , by returning the visual display 14 to a specific reference mode for the fraction of a second that the variation is measured. That is, the interval for which the circuit must be held at the reference mode is very short, only long enough for the voltage on unregulated-dc line 2 to arrive to a level reflective of the ac line voltage, a small fraction of a second, and hence not enough to interfere with the operator's visual observation of the visual display 14 .
[0042] As stated above, the “clock” for the control unit 10 is provided by the signal on the zero-crossing line 3 , the zero-crossing pulse train 7 on that line providing 120 Hz “ticks” of the clock, with the individual pulses synchronized to the zero-crossing times of the ac voltage input to the power supply. Everything that is done by the system is done for an even number of such ticks.
[0043] The key control signal from the control unit 10 is a motor-control signal 70 output on motor-control-signal line 15 . The motor-control signal 70 reflect all the information that the control unit 10 has been given or has calculated regarding the demand for the quantity of energy that the bread items are to be exposed to. This motor-control-signal line 15 can be seen in FIG. 1, where it is shown as an output from the control unit 10 , and also in FIG. 2, where it is shown as the input to a motor control circuit 100 .
[0044] As depicted schematically in FIG. 2, a conveyor 28 is driven by a conveyor motor 30 coupled to the conveyor 28 through a gearbox 32 and a chain drive 34 . The motor 30 is powered by the ac line voltage, the first ac line L 1 being connected directly to the motor 30 and the second ac line L 2 being connected to the motor 30 through the motor control circuit 100 .
[0045] The control unit 10 monitors the zero-crossing pulse train 7 with pulses synchronized to the zero crossings is shown in FIG. 1. A zero-crossing pulse will appear every 8.33 ms for a 60 Hz line voltage. The zero-crossing pulses identify the cycles of the ac line so that the control unit 10 can produce the pulse that switches the motor 30 on or off to within a precision of {fraction (1/120)} of a second. That is, the control unit 10 counts pulses on the zero-crossing pulse train 7 and, when the total equals a number predetermined based the desired dwell time, it outputs an appropriate signal on the motor-control-signal line 15 to the motor control circuit 100 so as to interrupt the ac line voltage to the motor 30 . Then the pulse count by the control unit 10 begins again and when the total reaches a predetermined number, the control unit 10 , again acting on the control circuit 100 , allows the full ac line voltage to be applied once again to the motor 30 . This pattern continues to repeat until the operator changes the dwell time through inputting new information to the control unit 10 through the keypad 12 . The details about the way in which the motor control circuit 100 operates are given in the next paragraphs.
[0046] As with the other control signals in the Preferred Embodiment, the motor-control signal 70 is binary in nature. When the motor-control signal 70 is HI, it causes the control circuit 100 to interrupt completely the ac line voltage to the motor 30 . This is the low-voltage regime. When it is LO, it causes the control circuit 100 to permit the full ac line voltage, the high-voltage regime. FIG. 3 illustrates this sequence. The top line in FIG. 3 represents the zero-crossing pulse train 7 ; the second line is the motor-control signal 70 output by the control unit 10 on motor-control line 15 ; the line below that depicts a motor input voltage 80 ; and the bottom line roughly depicts a motor speed 90 . The four lines are synchronized and indicate the following. The motor-control signal 70 is initially HI, resulting in the motor input voltage 80 being zero, holding the motor speed 90 to zero. Coincident with the second pulse in the zero-crossing pulse train 7 , the control unit 10 causes the motor-control signal 70 to switch from HI to LO at a turn-on point 71 . As a consequence the control circuit 100 causes the full ac line voltage to be applied to the motor 30 , as depicted by the motor input voltage 80 trace between a voltage start 81 and a voltage stop 82 , all as set out in FIG. 3. With continuing reference to FIG. 3, it can be seen that coinciding with the voltage start 81 , the motor speed 90 becomes non-zero and, after going through a speed-up phase 91 , the motor speed 90 reaches full speed 92 . Similarly, when, after four zero-crossing pulses, the motor-control signal 70 switches back from LO to HI at a turn-off point 72 , all input voltage is removed from the motor at a voltage stop point 82 , and the motor 30 coasts to a stop during a coast-down phase 93 .
[0047] [0047]FIG. 2 depicts the control circuit 100 , for the purpose of illustrating the means by which commands from the control unit 10 cause the motor input voltage 80 to the motor 30 to be switched between zero and the full ac line voltage, that is, for the line voltage to the motor 30 to be switched on and off. The motor-control signal 70 from the control unit 10 , carried on conveyor-motor-control signal line 15 , effects these changes in a series of steps designed to isolate the ac line voltage from the control unit 10 and its associated circuits. The conveyor-motor-control signal line 15 is connected directly to the negative side of a light-emitting diode D 1 , as can be seen in FIG. 2. The positive side of the diode D 1 is biased to +5 Vdc by regulated-dc voltage line 1 (connection not shown) through a first current-limiting resistor R 1 , 330 ohms in the Preferred Embodiment. When the motor-control signal 70 is switched from HI to LO, current flows through diode D 1 , causing it to emit light which, in turn, activates (turns on) a light-activated switch Q 2 (a triac) so that light-activated switch Q 2 becomes freely conducting in both directions. Once light-activated switch Q 2 is fully conducting, the full ac line voltage appears at node 150 , causing a coupling triac Q 1 to turn on, so as to complete the circuit between first ac line L 1 and second ac line L 2 through the motor 30 . The full ac line voltage continues to be applied to the motor 30 as long as diode D 1 is emitting light, that is as long as conveyor-motor-control signal line 15 is held at LO.
[0048] The control circuit 100 also includes a snubber circuit consisting of snubber capacitor C 1 , 0.05 pF in this embodiment, and snubber resistor R 3 , 100 ohms in this embodiment, shunting the coupling triac Q 1 . The function of this snubber circuit is to reduce or eliminate oscillations in the control circuit that otherwise would tend to occur at the turn-on and turn-off times.
[0049] In the Preferred Embodiment, the light-emitting diode D 1 and the light-activated switch Q 2 are included in a standard off-the-shelve device of the type used to provide optical coupling (and electrical isolation) between two electrical circuits. The part number of this unit is TLP 160J, manufactured by TOSHIBA.
[0050] The control unit 10 is configured by well-known techniques to incorporate the algorithms needed to effect the various toasting protocols called for by the particular toaster specifications. In the Preferred Embodiment, it is configured to allow the operator to vary the duty cycle from essentially 100% (conveyor running continuously at full speed), down to 5% (resulting in products spending 20 times as long in the cooking zone as they do at 100% duty cycle). Also in the Preferred Embodiment, the operator is able to set up a shift-to-stand-by protocol whereby if the toaster has not had any inputs from the operator for some multiple of 30 minutes, it goes into standby mode, causing the heaters to be cut back to half power and causing the fan speed to be cut back as well. If a further predetermined period (typically 30 minutes) passes after it enters standby mode, the toaster is shut off completely.
[0051] [0051]FIG. 4 shows the keypad 12 in the Preferred Embodiment. It includes an “on” button 201 and an “off” button 202 . Also on the keypad 12 is a status display 203 , which indicates various key time intervals, such as time-to-standby, time-to-shutdown, and time-to-full-turn-on (during power-up), and also provides the operator information about the current status of the toaster, such as the type of bread item it is set to toast. Below the status display 203 is a step-down button 204 for making the toast one-half step darker, on the fly. Depressing it causes a slight reduction in the duty cycle of the motor. Similarly, a step-up button 205 enables the operator to make the toast in process one-step lighter. In the Preferred Embodiment, the step-down button 204 is labeled “DARKER” and the step-up button 205 “LIGHTER. The oven is pre-programmed for several common types of bread products, permitting the operator to simply press the button corresponding to each of those types in order to obtain the-proper toasting parameters. Thus, there is a toast button 206 , a bagel button 207 (which will cause a long dwell time while limiting heat to just the top-heater), and a muffin button 208 (calling for a heater/dwell time combination appropriate for most English muffins). Also there is a particular-pre-programmed-protocol button 209 for calling up a particular protocol that has been programmed by the operator or, during original set-up, by the manufacturer. Closely related to this function is the control provided by a protocol-choice button 214 , which enables the operator to make a menu-based choice from a number of pre-programmed protocols, the difference being that the protocols accessible through the protocol-choice button 214 are more difficult to modify than is that accessible through the pre-programmed-protocol button 209 .
[0052] The keypad 12 also allows the operator to easily introduce variants to the pre-programmed protocols. Perhaps the most used of these variants will be the LIGHTER and DARKER commands. For example, with the bagel button 207 depressed, and the legend BAGEL displayed on the status display 203 , the operator may push the step-down button 204 (DARKER) once. This has two effects. One is to extend the toasting time by approximately 10% and to cause the display on the status display 203 to begin to alternate between BAGEL and DARK. After a time interval sufficient for the operator to load the untoasted bagel and for the item to pass through the toasting chamber, the control reverts automatically to the default dwell time for bagels. If the operator pushes the step-down button 204 twice, the dwell time is extended for approximately 20% and while the piece is toasting the display on the status display 203 alternates between BAGEL and XDARK—until the appropriate time interval has elapsed, and the controls go back to the bagel default dwell time and the display goes by to a continuous BAGEL. A similar variant is available for making the item one or two stages lighter than the default dwell time for the species of bread item would result in. Although in the Preferred Embodiment, each step lighter or darker results in a change of about 10% in the dwell time, this increment can be modified by the supervisor to be any desired step. As a safeguard, the apparatus can only be re-programmed through password-protected access, presumably limited to managers and the like.
[0053] Also, through a top-heat button 210 and a bottom-heat button 212 , the operator can choose to have one or the other of the heaters (or both or neither!) operating. Through a power-saver button 211 , the operator can determine whether the standby-mode option is activated. A manual dwell-time-adjust button 213 permits a manual adjustment of the dwell time over a continuous range (in contrast with the single discrete change in dwell time available through either the step-up button 205 or the step-down button 206 ), by adjusting the motor duty cycle over a continuous range.
[0054] The details of one particular embodiment, the Preferred Embodiment, have been set out above. In so doing, there is no intention of limiting the invention claimed to this Preferred Embodiment. The full scope of the invention is defined in the Summary; those skilled in the art can readily develop alternatives to the Preferred Embodiment while staying within the invention's scope. | A control system for a toaster oven incorporating a conveyor driven by an inexpensive ac motor, where the control system allows the entire range of toasting demands to be met while also compensating for variations in the line voltage. The heart of the toasting control is the reliance on the total dwell time of the bread products within the toasting zone of the oven, rather than on the speed of the motor. The control system also provides for a convection fan of varying speed without the need to replace the inexpensive muffin fan with more elaborate devices. Among the advantages offered by the dwell time approach is on-the-fly adjustment upward or downward of the degree of toasting, there being no need to await for the toasting zone to heat up or cool down to achieve this. | 0 |
FIELD OF THE INVENTION
This invention relates to compound use for controlling weight and, more particularly, relates to use of 5-Thio-D-glucose to bring about a loss in body weight.
BACKGROUND OF THE INVENTION
The area of medicine and particularly that field of human medicine devoted to individual and public health has long sought a non-toxic compound which would permit the control of body weight and which would act in such a way as to permit persons to eat in a normal fashion but still lose weight, the usual intent of such weight reduction being to reduce personal weight within the weight range recommended by the medical profession as desirable for particular heights and ages.
While various compounds have heretofore been suggested and/or utilized with a view toward causing loss of body weight, none of these compounds have proved to be completely successful in accomplishing the desired end and more particularly in providing a non-toxic compound that controls body weight yet permits the person to eat in that person's normally accustomed manner.
A few years ago, this inventor invented a novel sulfur-containing compound and method for the preparation of the same, and U.S. Pat. No. 3,243,425 was issued to me on Mar. 29, 1966, the invention being assigned to Purdue Research Foundation. The sulfur compounds of that invention are based upon the replacement of an oxygen atom in a sugar molecule by a sulfur atom, and, more specifically, are based upon the replacement of the ring oxygen of the sugar by the sulfur atom and oxidized forms of the sulfur atom and thus may be described as thiosugars.
While the compounds described in my U.S. Pat. No. 3,243,425 were recognized to be of both chemical and biochemical interest as sugar analogs, the then recognized use of the compounds was primarily in the preparation of resins by reaction with a diisocyanate or other polyisocyanates, with usefulness as radiation absorbers and as chain terminators in free radical polymerizations being mentioned. It has remained until now, however, to find and develop usefulness for particular forms of such compounds, and particularly to find and develop 5-Thio-D-glucose for the purposes hereinafter described.
SUMMARY OF THE INVENTION
This invention provides a particular compound use for controlling body weight. 5-Thio-D-glucose has been found to be useful in causing loss of weight without disrupting normal eating habits, and may be administered orally or by intravenous injection.
It is therefore an object of this invention to provide a novel compound use for controlling body weight.
It is another object of this invention to provide a novel use of 5-Thio-D-glucose for controlling body weight.
It is yet another object of this invention to provide compound use for causing loss of body weight due to reduced appetite.
It is still another object of this invention to provide administration of 5-Thio-D-glucose to thereby reduce carbohydrate assimilation and thereby cause reduction in calorie intake.
It is yet another object of this invention to provide a method for administering -Thio-D-glucose to effect weight reduction.
With these and other objects in view which will become apparent to one skilled in the art as the description proceeds, this invention resides in the novel composition and use thereof substantially as hereinafter described, and more particularly defined by the appended claims, it being understood that such changes in the precise embodiment and use of the herein disclosed invention are meant to be included as come within the scope of the claims.
DESCRIPTION OF THE INVENTION
As a result of research, a compound has been found that is useful in controlling body weight, and this compound is 5-Thio-D-glucose. This compound may be used in the daily diet to effectively bring about weight reduction even though otherwise normal food intake occurs.
The structural formula for 5-Thio-D-glucose is as follows: ##STR1##
5-Thio-D-glucose is the nearest analog of D-glucose (see U.S. Pat. No. 3,243,425). It may be looked upon structurally as D-glucose in which the ring oxygen atom has been replaced by a sulfur atom. The sugar analog is the nearest analog of D-glucose ever prepared, and this analog has nearly the same chemical and physical characteristics as does real D-glucose.
While the sugar analog is somewhat sweeter than real D-glucose, is has been found to be non-toxic with a LD 50 (i.e., a lethal dose as measured by a 50% kill of test animals) of 14,000 mg of compound per kg of animal body weight when administered to rats in a single dose. In mice feeding trials, some extending to 48 days, the animals were observed to be fully normal.
An example of results achieved in use of 5-Thio-D-glucose is shown in the following table:
______________________________________ Average Weight Average WeightExperiment In Grams In GramsTime Of Mice Of Mice(in weeks) Fed 5-Thio-D-glucose Fed Normal Diet______________________________________0 38.30 37.301 36.45 37.202 34.75 37.153 35.70 37.404 35.75 38.755 34.75 39.256 34.75 39.257 29.00* 37.75______________________________________ Notes: Initial age of mice at start of experiment - 6 weeks *2 mice - exposed to food only 4 hours 1 day After mice fed 5-Thio-D-glucose were put on normal diet at end of 7 weeks these mice showed weight increase of 4-5 gms in 2 days.
In this example, daily doses of 5-Thio-D-glucose were administered to a first control group of test mice while a second control group of test mice were administered only a normal diet. The 5-Thio-D-glucose was administered at the following level:
average weight of mice = 40 g fed at 50 mg 1 kg of body weight; ##EQU1##
one dose lasts 6 hours, therefore, need 4 doses in a 24 hour period;
4 × 2 mg = 8 mg/day/mouse.
Since mice eat about 7 g of food per day, each mouse was given 10 g of food each day with the first control group having 11.4 mg of 5-Thio-D-glucose mixed into the food. Corrections were made to provide 200 mg/day when it was determined that the first control group averaged only 405 g of food eaten per day.
The control group mice were fed daily and weights recorded daily for the first month and once a week for the remainder of the 48 days. Urine glucose levels were determined using the Glucostat method with no differences being noticed between the control groups. A measure of water intake showed no significant differences between control groups.
Tests were also made of excretion in the urine of both mice and rats and indicated a low rate of metabolism. This was confirmed by feeding the rats 5-Thio-D-glucose in which the carbon atoms were radioactive. Using radioactive techniques, it was observed that 98% of the 5-Thio-D-glucose was eliminated unchanged within a 6 hour period. However, while the 5-Thio-D-glucose was in the animal's system, it inhibited the body cells from using real D-glucose from the blood. This prevention of the body cells from using real D-glucose caused this normal blood sugar to increase in concentration in the blood. A small increase in blood sugar caused the animal to feel less hungry and the amount of food eaten was therefore reduced. This loss of appetite, clinically known as anarexia, reduced the food intake and therefore greatly contributed to reduction and even loss in body weight.
If very large doses of 5-Thio-D-glucose are eaten, or otherwise taken into the system, the utilization of real D-glucose may be so greatly inhibited as to cause the normal blood sugar to rise to very high levels which exceed the threshold at which blood sugar is excreted by the kidney. When this threshold value is exceeded normal blood sugar, real D-glucose is excreted into the urine. No harm occurs with this phenomena and it is conceivable that large amounts of 5-Thio-D-glucose given just before a meal rich in carbohydrate would cause most of the carbohydrate to be excreted in the urine and thereby eliminated from the system. This loss in dietetic calories would in itself produce a weight reduction effect when real D-glucose is prevented from entering the cells by the presence of 5-Thio-D-glucose, the cells no longer depending upon carbohydrates for their energy supply, but instead turning to the utilization of fats and proteins. This, of course, leads to a reduction in body weight.
Therefore, as indicated hereinabove, there are two ways in which 5-Thio-D-glucose can and does effect weight gain or weight loss in the body. The first of these requires only a very little intake of 5-Thio-D-glucose. In fact, as little as 1-4 mg/kg of body weight per day is sufficient to reduce the food intake and weight gain. Slightly greater effects on weight loss and food intake are observed at higher levels in the range of 4-50 mg/kg of body weight per day and experiments with as much as up to 200 mg/kg of body weight per day have been conducted without observing ill effects in the physiological condition, but still experiencing the effect of reduced appetite and lowering of total body weight. In the implementation of the use of 5-Thio-D-glucose for the control of body weight and food intake the smallest amounts necessary to effect a desirable condition should be administered, of course, even though the 5-Thio-D-glucose is non-toxic and larger amounts could be given without adverse effects. The subject wishing to control weight would preferably take the 5-Thio-D-glucose either at periods when hunger begins to be present or one to two hours prior to normal meal times.
The second method for using 5-Thio-D-glucose for the control of appetite and particularly for the control of weight gain would be to provide dosages 1 to 2 hours prior to meals. In certain subjects and under particular conditions, it may be only necessary to provide 5-Thio-D-glucose 1 or 2 hours before normally heavy meals are taken such as lunch or dinner. In the event that large doses of 5-Thio-D-glucose are taken 1 to 2 hours prior to lunch or dinner when fairly large consumption of carbohydrates would be taken at these meal times, it would appear feasible, although not necessary, to take fairly large amounts of 5-Thio-D-glucose, preferably in the range of 4-50 mg/kg of body weight. Such a large amount of 5-Thio-D-glucose would cause the carbohydrate taken in with the meal to be largely excreted in the urine since it would raise the blood sugar level to values that would cause large amounts of blood sugar to be removed from the blood and placed in the urine where it would be excreted from the body. During this period in time the body would use as it's energy source mainly fats and proteins from the diet or from depots in the body. Since the effect of 5-Thio-D-glucose reaches its maximum effective peak between 11/2 and 41/2 hours after the dose is taken orally, the time of giving the weight controlling 5-Thio-D-glucose can be established with a fair degree of certainty. Furthermore, since the major amount of the 5-Thio-D-glucose which is given to the subject is eliminated unchanged in the urine within approximately a 6 hour period the effect of the 5-Thio-D-glucose is no longer present after approximately 6 hours. Thus, when given in large doses, 5-Thio-D-glucose administration should be programmed to have its largest effect during and immediately following digestion of a carbohydrate meal.
If only sufficient amounts of 5-Thio-D-glucose are to be given to produce a decrease in hunger, smaller quantities of 5-Thio-D-glucose may be given 2 to 3 hours prior to a normal meal, or it may be given at any appearance of hunger or at periodic times over the day such as once every 4 to 6 hours to cause a continuous loss of appetite and carbohydrate assimilation.
In view of the foregoing, this invention provides a novel compound use for controlling body weight. | A particular compound, namely 5-Thio-D-glucose, and use thereof, is disclosed herein for control of body weight. 5-Thio-D-glucose is administered to thereby cause loss of weight without disrupting normal eating habits, the 5-Thio-D-glucose reducing carbohydrate assimilation to thereby cause reduction in calorie intake. | 0 |
BACKGROUND
The present disclosure relates to a throttle or accelerator pedal, and an associated method of developing more holding power resulting from simultaneously depressing a brake pedal and a throttle pedal by modifying a ratio of the throttle pedal. It finds particular application in conjunction with a variable ratio throttle pedal. However, it is to be appreciated that the present exemplary embodiment is also amenable to other like applications that encounter similar problems or require similar solutions.
Currently, an accelerator pedal is pivotally moved relative to a mount or mounting stay. A throttle cable is, in turn, secured to the accelerator pedal so that pulling of the throttle cable matches the movement of the accelerator pedal. That is, the cable stroke or cable pull ratio matches the ratio of pedal stroke movement throughout the actuation/deactuation of the pedal. There is only a small incidental variation in the ratio so that the cable pull ratio is dictated by the accelerator pedal ratio. Typically, a line of action for the cable is aligned with a top of the accelerator pedal. The intent is to maintain a linear accelerator pedal input and as a result the cable end follows an arc controlled by a pivot location of the pedal. This ensures minimal change to the pedal to cable stroke ratio.
It is desirable to assure that brake force builds faster than engine torque when both brake and accelerator pedals are simultaneously depressed. Variable ratio throttle systems are per se known. The change in rate, however, is usually practical due to the environment the pedals are subjected to. For example, water, ice, mud, etc. could potentially lodge in the cam and as a result the throttle cable would become dislodged from its desired line of action. Thus, a simplified structure that assures that opening of an engine throttle is slower than application of the brake is required. Also, with a variable ratio pedal, is desirable that the operator/driver not detect the slower action of the accelerator at small pedal angles and assure that action of the accelerator at normal driving modes be in the range of traditional or more normal pedal to cable pull ratios.
This disclosure remedies these problems in a simple, reliable, effective, and inexpensive manner.
BRIEF DESCRIPTION
There is provided a pedal assembly, namely an accelerator pedal assembly, in which a throttle cable attaches to an accelerator pedal at an angle so that the throttle cable provides a variable angle as the pedal is actuated or depressed, and wherein the pedal is a one-piece member without moving linkages to provide the variable angle.
More particularly, the pedal assembly includes a mounting stay and a pin fixedly secured to the mounting stay. The one-piece accelerator pedal without moving linkages is mounted to the pin for rotational movement about the pin relative to the mounting stay. The throttle cable is operatively connected to the accelerator pedal for movement thereby as the pedal rotates, at least one of the pedal and mounting stay configured to provide a first ratio of pedal stroke movement relative to cable stroke movement at initial depression of the accelerator pedal, and a different, second ratio of pedal stroke movement relative to cable stroke movement upon further depression of the accelerator pedal.
The throttle cable is secured to the accelerator pedal for initial movement at an angle relative to a tangent of the pedal travel path.
The angle ranges from approximately 45° to approximately −7° relative to the tangent of the pedal travel path.
The throttle cable is substantially tangent to the pedal travel path at the end of the cable stroke.
The mounting stay includes a mounting region that receives the throttle cable and orients the throttle cable substantially perpendicular to an initial portion of the angled pedal travel path.
The accelerator pedal includes a mounting region that receives a first end of the throttle cable.
The pedal assembly further includes a brake pedal assembly that is configured to provide a brake force that is greater than an engine torque.
The brake force is greater than the engine torque during the first ratio of pedal stroke movement relative to cable stroke movement at initial depression of the accelerator pedal.
A method of varying a ratio of pedal stroke movement relative to cable stroke movement during actuation of an accelerator pedal includes mounting an accelerator pedal to a pin for rotational movement about the pin. The method further includes connecting a throttle cable to the accelerator pedal for movement in different first and second ratios of pedal stroke to cable stroke movement during actuation of the accelerator pedal.
The method includes securing the throttle cable to the accelerator pedal for initial movement at an angle relative to a tangent of the pedal travel path.
The method includes providing a first ratio of pedal stroke movement relative to cable stroke movement at initial depression of the accelerator pedal, and a different, second ratio of pedal stroke movement relative to cable stroke movement upon further depression of the accelerator pedal.
The method includes providing a greater ratio of pedal stroke movement relative to cable stroke movement during initial depression of the accelerator pedal than later in the pedal stroke movement.
The method includes providing greater braking force than engine torque during the first ratio of pedal stroke movement relative to cable stroke movement at initial depression of the accelerator pedal.
The method includes forming the pedal as a one-piece component without moving linkages.
One benefit of the present disclosure is assuring that the brake force builds faster than the engine torque when both brake and accelerator pedals are simultaneously depressed.
Yet another advantage is the ability to address this issue without substantially altering the remaining components of the current system.
Still another benefit is the simple, less complex manner of achieving a variable ratio throttle/accelerator pedal assembly.
Still other benefits and advantages will become apparent those skilled in the art after reading and understanding the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic elevational view of an accelerator pedal assembly known in the art.
FIG. 2 is an enlarged detail view of a portion of FIG. 1 .
FIG. 3 is a representation of a line of action of a throttle cable associated with the arrangement of FIGS. 1 and 2 .
FIG. 4 is a graphical representation of pedal stroke versus cable stroke/pull.
FIG. 5 is a schematic elevational view of an accelerator pedal assembly of the present disclosure.
FIG. 6 is a representation of a line of action of the throttle cable associated with the accelerator pedal assembly of FIG. 5 .
FIG. 7 is an enlarged detail view of a portion of FIG. 5 .
FIG. 8 is a schematic elevational view of a mounting stay and accelerator pedal.
FIG. 9 is an elevational view taken generally from along the right-hand side of FIG. 8 .
FIG. 10 is an enlarged cross-sectional view taken generally along the lines 10 - 10 of FIG. 8 .
FIG. 11 is a schematic of a brake pedal assembly including a brake pedal.
DETAILED DESCRIPTION
The description and drawings herein are merely illustrative, and various modifications and changes can be made in the structures disclosed without departing from what is defined in the appended claims. All references to direction and position, unless otherwise indicated, refer to the orientation of the structures and components illustrated in the drawings and should not be construed as limiting the claims appended hereto. Like numbers refer to like parts throughout the several views.
With reference to FIG. 1 , there is shown a pedal assembly 100 such as used in an associated vehicle (not shown). In this particular instance, the pedal assembly 100 is an accelerator pedal assembly which includes an accelerator pedal 110 having a first arm or portion 112 through which a force is applied to the pedal, e.g. through application of a force via the foot of the vehicle user, and a second arm or portion 114 that connects with an accelerator or throttle cable 120 , particularly a first end thereof. The pedal 110 is mounted for rotation on pin 124 that is secured to a mounting surface or mounting stay 130 . The mounting stay 130 is commonly secured to a firewall or panel (not shown) in a manner generally known in the art so that it is common for the mounting stay to be secured to a substantially vertical wall of the vehicle. The pin 124 is thus disposed in spaced relation relative to this vehicle wall and allows pivotal movement of the pedal 110 .
Applying a force through the first arm 112 rotates the pedal 110 around the pin 124 (in a clockwise direction as shown) and likewise results in the same rotational movement of the second arm 114 (again, in the clockwise direction as shown). As a result of the rotational movement, the first end 122 of the throttle cable 120 is pulled as the accelerator pedal 110 rotates about the pin 124 . As shown in FIGS. 1 and 2 , the full extent of rotation of the pedal 110 is illustrated by the two positions of the pedal.
The first end 122 of the throttle cable 120 travels along a substantially linear path 140 as the pedal is actuated ( FIG. 3 ). This travel is also represented in FIG. 1 by reference numeral 142 as a stroke length or pull distance of the throttle cable 120 . The throttle cable end 122 follows arc 144 ( FIG. 3 ) controlled by the pin 124 or pedal pivot location. This has a minimal change to the pedal to cable stroke ratio. The line of action for the throttle cable 120 is aligned with the top of the accelerator pedal 110 , i.e., with the top of the second portion 114 of the accelerator pedal 110 . Although there may be a small variation in the ratio, the design intent with the current technology is to maintain a linear accelerator pedal input. Thus, the cable pull ratio traditionally matches the top of the accelerator pedal 110 , and there is only a small incidental variation in the ratio, so the cable pull ratio is driven by the pedal ratio. This is represented by a linear plot 146 in FIG. 4 .
Where the accelerator pedal 110 , 1120 and the brake pedal 100 are depressed at the same time, i.e. simultaneously, it is desirable that the vehicle not move. Therefore, it is desirable that the engine throttle opening is slower than the brake application. It becomes necessary to design the brake force to increase faster than the engine torque when both brake and accelerator pedals are depressed at the same time. This can be achieved with a variable ratio accelerator pedal, one output of which is illustrated by plot 150 in the graphical representation of FIG. 4 . As mentioned in the Background, it is preferable to limit the complexity and number of changes to incorporate a variable ratio accelerator pedal. To that end, a new pedal assembly 200 , 1100 is shown in FIGS. 5-11 in order to achieve the variable ratio, preferably a first ratio 152 where there is an increased or greater pedal stroke relative to cable stroke through an initial portion of accelerator pedal depression, and then a second ratio 154 shown in FIG. 4 as having the same ratio as that of the prior art arrangement of FIGS. 1-3 . Of course the particularly selected ratio may vary without departing from the scope and intent of the present disclosure, although these are preferred ratios.
Reference numerals in the “100 series” (such as pedal assembly 100 in FIGS. 1-3 ) now identify like components by reference numerals in the “200 series” (such as pedal assembly 200 in FIGS. 5-11 ), and new components are also referenced by new numerals in the 200 series. Here, pedal assembly 200 is an accelerator pedal assembly which includes an accelerator pedal 210 having a first arm or portion 212 (through which a force is applied to the pedal) and a second arm or portion 214 that connects with an accelerator/throttle cable 220 , particularly a first end 222 thereof. The one-piece pedal 210 is mounted for rotation on pin 224 that is secured to a mounting surface or mounting stay 230 . The mounting stay 230 is secured to a firewall or panel (not shown) and the pin 224 allows pivotal movement of the pedal 210 . Rotation of the first arm 212 rotates the pedal 210 around the pin 224 (in a clockwise direction as shown) and likewise results in the same rotational movement of the second arm 214 (again, in the clockwise direction as shown).
As a result of the rotational movement, the first end 222 of the throttle cable 220 is pulled as the accelerator pedal 210 rotates about the pin 224 . The first end 222 of the throttle cable 220 travels along a path 240 ( FIG. 6 ) when the accelerator pedal 210 is actuated and this path is initially oriented at an angle “α” relative to the arc stroke or movement 242 of the accelerator pedal. By way of example, angle α may range from approximately 45° (for instance as shown in FIG. 6 ) to approximately −7°. At the end of the stroke, the throttle cable 220 is virtually tangent (see reference numeral 260 in FIG. 6 ) to the arc stroke 242 of the accelerator pedal 210 . Thus, the ratio of the pedal stroke to the cable stroke varies as illustrated in FIG. 4 , from an initial ratio 152 to a second ratio 154 . Consequently, the cable pull ratio 152 transitions to a second ratio 154 resulting from the purposeful, initial positioning of the throttle cable 220 at an angle α to the arc path of the pedal 210 that then transitions to become tangent with the arc path of the accelerator pedal.
In this manner, where the accelerator pedal 210 , 1120 and the brake pedal 1110 are depressed at the same time, i.e. simultaneously, the engine throttle opening is initially and desirably slower than the brake application. The new pedal assembly 200 effectively achieves the desired variable ratio by angling a surface 270 of the mounting stay that is oriented perpendicular to the initial path 240 defined by angle a. If the angle a is changed, then likewise the angle of surface 270 is altered to provide proper orientation of the throttle cable end 222 with accelerator pedal 210 .
Preferably the pedal 210 is a one-piece member without moving linkages. This eliminates undesired complexity, yet purposeful angling of the throttle cable 220 at the attachment point 222 with the accelerator pedal 210 still provides the desired variable ratio. This is also accomplished in a manner that does not require undue alteration of surrounding components in an existing vehicle design.
This written description uses examples to describe the disclosure, including the best mode, and also to enable any person skilled in the art to make and use the disclosure. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims. Moreover, this disclosure is intended to seek protection for a combination of components and/or steps and a combination of claims as originally presented for examination, as well as seek potential protection for other combinations of components and/or steps and combinations of claims during prosecution. | A pedal assembly includes a one-piece accelerator pedal without moving linkages that is mounted to a pin for rotational movement relative to a mounting stay. The throttle cable is operatively connected to the accelerator pedal for movement thereby as the pedal rotates, at least one of the pedal and mounting stay configured to provide a first ratio of pedal stroke movement relative to cable stroke movement at initial depression of the accelerator pedal, and a different, second ratio of pedal stroke movement relative to cable stroke movement upon further depression of the accelerator pedal. | 1 |
RELATED APPLICATIONS
[0001] This is a continuation of U.S. Ser. No. 09/607,567 filed Jun. 29, 2000, which is a divisional of U.S. Ser. No. 09/201,929 filed Dec. 1, 1998, now U.S. Pat. No. 6,176,992, incorporated herein by reference.
BAGKROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a Method and Apparatus for Electro Chemical Mechanical Deposition, and more particularly, to a method and apparatus that provides for both the deposition and polishing of a conductive material on a semiconductor wafer.
[0004] 2. Background of the Invention
[0005] Metallization of semiconductor wafers, i.e. deposition of a layer of metal on the face of wafers over a barrier/seed layer of metal has important and broad application in the semiconductor industry. Conventionally, aluminum and other metals are deposited as one of many metal layers that make up a semiconductor chip. More recently, there is great interest in the deposition of copper for interconnects on semiconductor chips, since, as compared to aluminum, copper reduces electrical resistance and allows semiconductor chips using copper to run faster with less heat generation, resulting in a significant gain in chip capacity and efficiency.
[0006] Conformal thin film deposition of copper into deep submicron via holes and trenches is becoming more difficult in ULSI chip processing, especially when the feature sizes are decreasing below the 0.25 μm with aspect rations of greater that 5 to 1. Common chemical vapor deposition and electroplating techniques have been used to fill these deep cavities etched into silicon substrates. These processes so far have yielded a very high cost and defect density for developing and integrating local interconnects for ULSI technology.
[0007] One of the factors that contributes to the high cost is the manner in which the conductive material, and particularly copper, is applied, Specifically, it is well known to apply certain contaminants, known as leveling agents, in the electrolyte solution that prevent or slow down the rate of deposition of the metal to the surface of the wafer substrate. Since these contaminants have a large size in comparison to the size of the typical vie that needs to be filled, deposition of the metal on the surface of the wafer is, in part, prevented. This prevention, however, is achieved at the expense of adding contaminants to the electrolytic solution, which results, in part, in vias that do not have the desired conductive characteristics. In particular, the grain size of the deposited conductor, due to the use of such contaminants, is not as large as desired, which thereby results in quality problems for the resulting device, as well as increased expense due to significant annealing times that are subsequently required.
[0008] Further, the cost of achieving the desired structure, in which the conductive material exists in the via, but not on the substrate surface, still required separate deposition and polishing steps. After the conventional deposition of the metal using an anode, a cathode and electrolytic solution containing metal as is known, there is then required a polishing step, which polishing step is, for high performance devices at the present time, typically a chemical-mechanical polishing step. While chemical mechanical polishing achieves the desired result, it achieves it at considerable expense, and requires a great degree of precision in applying a slurry in order to achieve the desired high degree of polish on the conductive surface.
[0009] Accordingly, a less expensive and more accurate manner of applying a conductor to a semiconductor wafer is needed
SUMMARY OF THE INVENTION
[0010] It is an object of the present invention to provide a method and apparatus that both deposits and polishes a conductive material on a semiconductor wafer.
[0011] It is an object of the present invention to provide a method and apparatus that simultaneously deposits and polishes a conductive material on a semiconductor wafer.
[0012] It is an object of the present invention to provide a method and apparatus that simultaneously deposits a conductive material in deep cavities of a semiconductor wafer and polishes/starves electrolytic solution from the top surface area of the semiconductor wafer.
[0013] It is a further object of the present invention to provide a method and apparatus that recirculates the electrolytic solution used in depositing the conductive material on the semiconductor wafer.
[0014] These and other object of the present invention are obtained by depositing a conductive material form an electrolyte solution to a predetermined area of a wafer. The steps that are used when making this application include applying the conductive material to the predetermined area of the wafer using an electrolyte solution disposed on a surface of the wafer when the wafer is disposed in proximity to an anode, and preventing accumulation of the conductive material to areas other than the predetermined area by mechanically polishing, protecting, or reducing form electrolyte contact to the other areas while the conductive material is being deposited.
[0015] An apparatus that performs this method includes an anode capable of receiving a first potential upon application of power, A cathode or the wafer is spaced from the anode and is capable of receiving a second potential opposite the first potential upon application of power. A pad or a multiple number of pads is/are disposed between the anode and the cathode, the pad being movable with respect to a surface of the wafer and inhibiting or reducing application of the conductive material to certain other areas when power is being supplied to the anode and the cathode. Further, a fluid chamber allows an electrolyte solution to be disposed on the surface of the wafer or the pad and the conductive material to be formed on desired areas of the wafer upon application of power.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] These and other objects and advantages of the present invention will become apparent and more readily appreciated from the following detailed description of the presently preferred exemplary embodiment of the invention taken in conjunction with the accompanying drawings, of which:
[0017] [0017]FIGS. 1A and 1B illustrate a first embodiment of the present invention;
[0018] [0018]FIG. 2 illustrates a second embodiment of the present invention;
[0019] [0019]FIG. 3 illustrates a representative via to be filled with a conductor according to the present invention; and
[0020] FIGS. 4 A- 4 C illustrate a third embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0021] The preferred embodiments of the present invention will now be described. As noted above, conventional processing uses different equipment, at different times, in order to obtain conductive material within vias or at other desired locations on the surface of a semiconductor wafer that contains many different semiconductor chips, but not have the conductive material disposed at undesired locations. Accordingly, the equipment cost needed to manufacture a high quality semiconductor integrated circuit device can be exorbitant.
[0022] The present invention contemplates different embodiments which allow for the same device, termed a “electro chemical mechanical deposition apparatus”, to be used to both deposit a conductive material as well as then polish or reduce the rate of deposition of that conductive material. The “electro chemical mechanical deposition apparatus” can also be used to simultaneously deposit and/or polish the conductive material. While the present invention can be used with any conductive material or any workpiece suitable for plating it is especially suited for use with copper as the conductor, and for use in the fabrication of ULSI integrated circuits having submicron features with large aspect ratios. In the various embodiments, the present invention uses conventional components, arranged in a unique manner, in order to achieve the functionalities described herein.
[0023] [0023]FIG. 3 is first referred to in order to illustrate a portion of an integrated circuit chip that includes an area in which a via is to be formed, The via, as known in the semiconductor arts, being a conductive material that electrically connects different circuit layers together. AS shown in FIG. 3, a via contains a conductor 2 that can connect a lower level conductive area 4 with an upper level conductive area 6 , with insulative material 8 disposed there around. Of course, it is understood that the present invention can operate upon any metal layer of a multi-layer integrated circuit chip.
[0024] [0024]FIGS. 1A and 1B illustrate a first embodiment of the invention, which embodiment has two different modes of operation. In a first mode, a conductive metal, preferably copper, or other conductive material, is applied in vias and/or other desired areas using an electrolyte solution, while build-up of the conductive material on undesired areas is eliminated, or at least minimized, due to the mechanical polishing and/or electrolytic solution deprivation to top surface areas of the semiconductor wafer that is described hereinafter. In a second mode of operation, polishing of the wafer, using a conventional chemical mechanical polishing, can be performed using the same device, to the extent that such chemical mechanical polishing is needed. It is contemplated that according to this embodiment of the present invention that in most circumstances only the first mode of operation will be needed. The second mode of operation, and the structure corresponding thereto, are included for circumstances in which an extremely high degree of polish is desired.
[0025] [0025]FIG. 1A illustrates an overview of the electro chemical mechanical deposition apparatus 10 according to the first embodiment of the invention, illustrating in perspective view the mechanical pad assembly 12 that has a mechanical pad 32 that rotates around a first axis 14 , and a wafer head assembly 16 that has a wafer that rotates around a second axis 18 . As illustrated, the wafer rotates within an area that is covered by the mechanical pad 32 , as will be described in further detail hereinafter, which area is within container 20 that keeps various solution disposed therein. Although shown as operating upon a single wafer, it is understood that a plurality of wafer lead assemblies 16 could be associated with each mechanical pad assembly 12 , and that the apparatus 10 could include a plurality of mechanical pad assemblies 12 as well, each operating on different wafers.
[0026] [0026]FIG. 1B illustrates a side cross sectional view of the apparatus 10 taken along line A-A of FIG. 1A according to the present invention. As illustrated, the system 10 is capable of depositing thin metal films onto the wafer.
[0027] Each wafer head assembly 16 includes a nonconductive, preferably circular, head assembly 22 with a cavity that is preferably a few millimeters deep at its center and which cavity may contain a resting pad 25 . The semiconductor wafer is loaded into this cavity 22 , backside first, against the resting pad 25 using a conventional type of transport or vacuum mechanism to ensure that he wafer is stationary with respect to the wafer head assembly while in use. A nonconductive retaining ring 24 at the periphery of the wafer head assembly 16 includes at least one O-ring or other rubber type seal 26 and a spring loaded cathode contact electrode 28 , which each push against the face of the wafer and hold the wafer in place at its very edge. A liquid-tight seal is thus obtained so that the cathode contact electrode 28 is kept isolated from the solution within the container 20 , as described hereinafter, The entire back side of the wafer which pushed against resting pad 25 and the front surface areas (typically the outer 1-10 mm surface of the front surface area) which are under this retaining ring 24 will thus be protected from any and all solution, including electrolyte, as discussed hereinafter.
[0028] The mechanical pad assembly 12 is disposed within container 20 , which container 20 holds the various solutions that will be introduced, as described previously and hereinafter. Mechanical pad assembly 12 included an anode plate 30 that preferably has a thin flat circular shape and is made of a porous or solid conductive material such as copper and/or platinum and is mounted so that it rotates about the second axis 18 , and rests upon a table and bearing support as is known. A mechanical pad 32 , as is known is the art and used, as example, in chemical mechanical polishing, and preferably one that is made of a nonconductive porous type material such as polyurethane, is mounted onto the face of the anode plate 30 . The mechanical pad 32 preferably has a circular shape, but may be shaped in any other form so long as it can effectively polish the wafer. The electrolyte can be fed to the pad 32 from a reservoir (not shown) located behind the anode plate 32 via a chamber 31 , which chamber 31 then feeds the electrolyte up through the anode plate 30 and pad 32 using the in-channel 34 . Alternatively, in-channel 44 can also be used to dispense the electrolyte directly down onto the surface of the pad 32 .
[0029] The wafer head assembly 16 faces toward the mechanical pad assembly 12 , and is pushed down with a controlled force. The wafer head assembly 16 rotates around axis 18 using a conventional motorized spindle 36 , whereas the mechanical pad assembly 12 rotates around axis 14 using a conventional motorized spindle 38 .
[0030] Proper drainage channels 40 provide a safe recycling or disposal of electrolyte. Thus, once the electrolyte is placed onto the pad 32 as described above, it can be drained via the drainage channels 40 to a resuscitating reservoir, also not shown, that can replenish and clean the electrolyte, thereby allowing re-sue and being environmentally safe.
[0031] The inlet 44 can also be used to apply deionized water when operating in the second mode of the invention, as discussed hereinafter.
[0032] In operation according to the first mode of the invention, the apparatus 10 applies, using a power source, a negative potential to the cathode contact 28 and a positive potential to the anode 30 . The electrolytic solution is introduced through one or both of the in-channels 34 and 44 to the surface of the mechanical polishing pad 32 . When an electric current is established between the two electrodes, molecules of metals in electrolyte are deposited on the surface of the wafer, being attracted thereto by the negative voltage applied to the cathode contact 28 . While this is taking place, there is also performed a mechanical polishing using the mechanical pad assembly 12 . This mechanical pad assembly 12 substantially prevents molecules of metals from becoming permanently deposited on surfaces of the wafer where such a deposit is undesired, due to the polishing or rubbing action of the mechanical pad 32 . Thus, the contaminants or additives referred to above that are presently used to prevent or reduce such depositing are not needed, or alternatively can be used in much smaller percentages. Accordingly, at the conclusion of the first mode of operation, metal is deposited in vias and the like where desired, and is substantially prevented from being deposited in undesired areas.
[0033] In a second mode of operation, a number of different conventional operations can be performed, depending upon the chemicals introduced via the in-channel 44 . If chemical mechanical polishing is desired, a slurry can be introduced, although this specific mode of operation is not preferred since it increases the amount of impurities introduced into the apparatus fluid chamber substantially. In the preferred second mode of operation, the apparatus 10 can be used to buff polish the seed layer or be used as an electro polisher by reversing the current polarity (cathode and anode polarity), Further, the apparatus 10 can also be purged with water if it is necessary to leave the wafer clean but wet with deionized water, and polishing using the mechanical pad 32 with the deionized water can take place. Thereafter, after lifting the wafer off the pad 32 , spin drying of the wafer on the rotating wafer head assembly 16 can take place.
[0034] [0034]FIG. 2 illustrates another embodiment of the present invention. Like reference numerals are used to indicate structure that corresponds to that of FIGS. A 1 and 1 B described above. In this embodiment of the invention, the wafer is stationery, and electro chemical mechanical deposition apparatus 100 is disposed within a container (not shown) that collects spent solutions. The electro chemical mechanical deposition apparatus 100 corresponds in structure in large part to the wafer head assembly 16 previously described with reference to FIG. 1B. In this embodiment, however, the electro chemical mechanical deposition apparatus 100 includes a mechanical pad 32 , which is rotated by the spindle shaft 36 . Spindle shaft 36 is illustrated as being rotated and moved side to side and held in proper position using DC motor 102 , weights 104 , bearing sets 106 and 108 an springs 110 , all of which are conventional.
[0035] The electrolyte solution is introduced using in passage 34 , and it flows to the desired surface of the wafer through the porous anode 30 and mechanical pad 32 . It is expelled through out-channel 40 .
[0036] Operation of the FIG. 2 embodiment is very similar to that of the first mode described with respect to FIGS. 1A and 1B. Specifically, deposition of a conductive material using an electrolyte, such as described previously, in desired vias and/or other areas, is obtained at the same time that mechanical polishing of the surface of the wafer using rotating pad 32 , which may be the shape of a rectangle, a circle, or a pie or the like, takes place.
[0037] The electro chemical mechanical deposition apparatus according to the present embodiment also reduces the need for pulse generating power supplies because the mechanical pulsing that is generated from the movement of the pad creates sufficient pulsing. This mechanical pulsing is created as a result of the wafer being in contact with the pad as it is moved in relation to the wafer. The benefit of the mechanical pulsing is that it improves grain size and copper film integrity without the need for power supplies with pulsing capabilities.
[0038] FIGS. 4 A- 4 C illustrate yet another preferred embodiment of the present invention. Like reference numerals are used to indicate structure that corresponds to that of FIGS. 1A, 1B, and 2 described above, In this embodiment of the invention, the electro chemical mechanical deposition apparatus 200 contains a mechanical pad assembly 210 that corresponds to the mechanical pad assembly 12 and a wafer head assembly 240 that corresponds to the wafer head assembly 16 . In this embodiment, the electro chemical mechanical deposition apparatus 200 includes a circular or square mechanical pad 212 mounted on a cylindrical anode 214 that rotates abut a first axis 216 as illustrated in FIGS. 4A and 4C, whereas the wafer rotates abut a second axis 242 as illustrated in FIG. 4B.
[0039] The mechanical pad 212 can have a size that either polishes the entire usable portion of the wafer, or only a section of the wafer at any given time. If only a portion of the wafer is polished at any given time, a drive assembly (not shown) must also be included in order to move the anode 214 , and thereby the mechanical pad 212 , so that it is in contact with the portion of the wafer that needs to be acted upon at that moment in time.
[0040] In operation, it will be appreciated that the belt-shaped mechanical pad 212 polishes the wafer similar to the manner in which a roller paintbrush paints a wall. While operating, the electrolyte or other solution is introduced to the mechanical pad 212 from a reservoir (not shown) located in proximity to the anode 214 . In one specific embodiment, the anode 214 contains an in-channel 224 that includes a passageway 226 within anode 214 and holes 228 that are made in the anode 214 , which together provide a path for the solution to be fed to the mechanical pad 212 . Alternatively, the electrolyte solution can be dispensed directly onto the pad 212 through a channel 213 in accordance with the methods described earlier herein. The solution will be contained with a non-conductive chamber 230 that is created around the wafer head assembly 240 , and an nonconductive solution containment housing 250 , which housing contains an out-channel 252 . O-rings and other conventional structures, as described earlier herein, to seal the solution within the solution containment housing 250 may be used in this embodiment.
[0041] Again, the electro chemical mechanical deposition apparatus according to the present invention reduces the need for pulse generating power supplies because the mechanical pulsing that is generated from the rotating movement of the pad and wafer creates sufficient pulsing.
[0042] According to the present invention, in any of the embodiments, since mechanical action is used to prevent undesired build-up of a conductor on undesired areas of a wafer surface, leveling agents are not typically needed, or needed in a much smaller percentage than conventionally used. Further a polished smooth and shiny conductive surface can be obtained.
[0043] Although only the above embodiments have been described in detail above, those skilled in the art will readily appreciate that many modification of the exemplary embodiment are possible without materially departing from the novel teachings and advantages of this invention. | The present invention deposits a conductive material from an electrolyte solution to a predetermined area of a wafer. The steps that are used when making this application include applying the conductive material to the predetermined area of the wafer using an electrolyte solution disposed on a surface of the wafer, when the wafer is disposed between a cathode and an anode, and preventing accumulation of the conductive material to areas other than the predetermine area by mechanically polishing the other areas while the conductive material is being applied. | 2 |
BACKGROUND
[0001] Shellfish or crustaceans such as shrimp and crabs may be frequently prepared for eating by boiling the shellfish in water and then serving the cooked products still in the shell. The shell may have to be removed or broken away from the meat before the meat can then be extracted for consumption. Boiling or broiling of a shellfish or crustacean, such as a crab, may not change the characteristics of the shell in that it may still be relatively hard and brittle.
[0002] It may have been common practice for many years to use a nutcracker-type instrument to crack the shells of crab legs or other types of shellfish in order to facilitate removal of the shellfish meat from the protective shell. These utensils may have found wide-spread acceptance for opening of shellfish shells, primarily because there may have been no reasonable alternative system or method. However, the nutcracker-type utensils may be relatively expensive and present restaurants with a cost problem because of the relatively high percentage of loss that is experienced as a result of customer pilferage. Furthermore, these utensils may not be particularly useful in the case of shells that are somewhat soft, and mere cracking of the shell often does not allow a person to easily remove meat from the cracked shell.
[0003] Many persons experiencing frustration with the inadequacy of nutcracker-type utensils for opening crab leg shells, particularly in circumstances where the shell is somewhat soft but of tough characteristics, may resort to the use of a common table fork in an effort to sever the shell. One of the tines of the fork may be inserted under the shell and the user may then lift up on the fork handle in an effort to tear the shell body. Although this may accomplish the intended result in certain instances, many times such misuse of the fork may result in bending of the fork tine, thus again causing the restaurant losses because of the cost of replacing bent forks.
[0004] Furthermore, once the shell is cracked, it may be difficult to extract the meat portion and/or other items from the crustacean. What is needed is a system and method for opening the shell, and extracting the meat portion and other items from a crustacean.
SUMMARY
[0005] Exemplary embodiments provided herein may include a system and method for opening shellfish shells and extracting items therefrom, including a body having a first end, a second end and a middle portion therebetween, wherein the first end includes a first and second protuberance in spaced relation to each other to facilitate the opening of a shellfish shell, and wherein the second end comprises a probe portion configured to facilitate extracting items from the shellfish.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 is a perspective view of a system according to an exemplary embodiment.
[0007] FIG. 2 is a side elevational view of a system according to an exemplary embodiment.
[0008] FIG. 3 is more detailed, inverted perspective view of a second end of a system according to an exemplary embodiment.
[0009] FIG. 4 is a sectional view of a second end of the exemplary embodiment of FIG. 2 along line 4 - 4 .
[0010] FIG. 5 is a more detailed view of a first end of a system according to an exemplary embodiment.
[0011] FIG. 6 is a side elevational view of a system according to an exemplary embodiment.
[0012] FIG. 7 is a perspective view of a second end of a system according to an exemplary embodiment.
[0013] FIG. 8 is a sectional view of a second end of the exemplary embodiment of FIG. 6 along line 8 - 8 .
DETAILED DESCRIPTION
[0014] The detailed description set forth below in connection with the appended drawings is intended as a description of exemplary embodiments and is not intended to represent the only forms in which the exemplary embodiments may be constructed and/or utilized. The description sets forth the functions and the sequence for constructing and operating exemplary embodiments in connection with the illustrated embodiments. However, it is to be understood that the same or equivalent functions and sequences may be accomplished by different embodiments that are also intended to be encompassed within the spirit and scope of this disclosure.
[0015] A shellfish and/or crustacean opening and extracting system is shown in FIG. 1 , generally at 10 . System 10 may include a body 12 which may include a first end 14 and a second end 16 . Body 12 may further include a middle portion 18 between first end 14 and second end 16 .
[0016] First end 14 may include a first protuberance 20 and second protuberance 22 in a spaced relation to first protuberance 20 . Second protuberance 22 may have an edge 24 which may have a generally knife-like or cutting configuration. First protuberance 20 may include a flat portion, which may generally face second protuberance 22 . With this configuration, second protuberance 22 may extend underneath the shell of, or into the shellfish and/or crustacean, and the shell may slide along the flat portion of first protuberance 20 .
[0017] Second protuberance 22 may be configured to cut, break and/or otherwise open the shell of the shellfish and/or crustacean. Protuberances 20 and 22 may be one to five centimeters in length extending away from the system 10 however other dimensions may be utilized as desired. Similarly the protuberances 20 and 22 may be in different spaced relationships such that they will facilitate different uses for different types, and/or thicknesses of shellfish and/or crustacean shells, and the like.
[0018] Middle portion 18 may include indentions 40 which may be configured to receive fingers of a user such that torque and/or other forces may be applied to system 10 , and consequently transferred to the shell of the shellfish and/or crustacean to aid in the opening of the shell.
[0019] Second end 16 may include a probe portion 30 which may be configured to extend into the shellfish and/or crustacean to remove the meat portion or other items and/or portions, as desired. The second end 16 may also include an aperture 42 which may be utilized to hold a security chain or other device, as desired. Aperture 42 may also be utilized to attach some other device, such as a securing and/or security device, to system 10 such that a restaurant patron may not easily steal or remove the system 10 from a restaurant or other establishment.
[0020] With this configuration a user may break the shell of a shellfish and/or crustacean, such as a crab leg, then reverse the system 10 to utilize probe portion 30 to more easily extract the meat or other portion of the shellfish and/or crustacean. This may allow the user to not use their fingers or other devices to extract the meat and/or other items from a shellfish and/or crustacean.
[0021] FIG. 2 shows a side elevational view of an opening and extraction system, generally at 10 . Again system 10 includes a body portion 12 which may have a first end 14 , a second end 16 , and a middle portion 18 therebetween. Again front portion 14 may include a generally knife-like second protuberance 22 . It will be appreciated that other configurations for protuberance 22 may be utilized to facilitate the opening of the shellfish and/or crustacean. As shown, second protuberance 22 slopes gradually from the outward edge of the system 10 toward the inner portion. This may facilitate insertion into a shellfish and/or crustacean, or portion of a shellfish and/or crustacean, as well as facilitate the opening, cutting and/or cracking action of the system.
[0022] Middle portion 18 again may include indentions 40 which may be configured to receive the fingers of a user. Typically a user may place their thumb on the top of the system 10 and their index finger on the bottom of system 10 to impart torque upon the shellfish and/or crustacean. Again second end 16 may include a probe portion 30 and an aperture 42 .
[0023] First protuberance 20 may include a generally flat portion 26 , which may facilitate the system 10 sliding along the outer portion of the shellfish and/or crustacean shell. This configuration may enhance the opening ability of the system 10 to enable a user to better utilize system 10 .
[0024] FIG. 3 shows a more detailed perspective view of second end 16 . As shown probe portion 30 may be generally scoop, spoon or cup-shaped to facilitate the removal of meat and/or other items from the shellfish and/or crustacean however, other configurations may be utilized without straying from the concepts disclosed herein.
[0025] FIG. 4 is a sectional view of second end 16 along lines 44 from FIG. 2 . As shown probe portion 30 may have a depth of more than half of the thickness of probe portion 30 . It will be appreciated that different lengths, widths and depths, among other characteristics, may be utilized for probe portion 30 without straying from the concepts disclosed herein, as desired.
[0026] FIG. 5 shows a more detailed perspective view of first end 14 along line 5 from FIG. 1 . As shown first protuberance 20 may have a flat portion that faces second protuberance 22 to facilitate the device sliding along the outer shell of a shellfish and/or crustacean. Again, second protuberance 22 may have a generally knife-like or other configuration that may be utilized for cutting or cracking the shell of a shellfish and/or crustacean, as desired.
[0027] FIG. 6 is an exemplary embodiment of a shellfish and/or crustacean cracking and meat removal system, generally at 60 . System 60 may include a body portion 62 which may include a first end 64 and a second end 66 . Furthermore body portion 62 may include a middle portion 68 between first end 64 and second end 66 .
[0028] First end 64 may include a first protuberance 70 and a second protuberance 72 in a similar configuration to exemplary embodiments disclosed above. First protuberance 70 may include a generally flat portion 76 , which may generally face second protuberance 72 . Second protuberance 72 may include a generally knife-like portion 74 , which may facilitate the opening of a shell or other item. It will be appreciated that although second protuberance 72 is shown as generally knife-like, other configurations, such as serrations, wedges, etc. may be utilized without straying from the concepts disclosed herein.
[0029] In this exemplary embodiment second end 66 includes a probe 80 which has a generally shovel-shape, or open-ended configuration. It will be appreciated that other configurations for probe 80 may be utilized without straying from the concepts disclosed herein. This configuration may facilitate the removal of meat and other portions from the inside of a shellfish and/or crustacean. Middle portion 68 may include indentions 90 which may facilitate the user imparting torque upon the shell of a shellfish and/or crustacean to more easily crack or break it open to reveal the contents therein, or to more easily extract the meat or other portion, as desired.
[0030] FIG. 7 shows a more detailed perspective view of second end 66 . As shown probe 80 may have a generally three-sided, shovel-type configuration. With this configuration the inside of the shell of the shellfish and/or crustacean may be more easily scraped to remove meat and other portions, as desired.
[0031] FIG. 8 shows a sectional view along line 8 - 8 from FIG. 6 of second end 66 . As shown the bottom of probe 80 may slope gradually from the exterior toward the interior of the system. It will be appreciated that other configurations may be utilized for probe portion 80 without straying from the concepts disclosed herein.
[0032] System 10 may be made from disposable plastic or durable stainless steel and/or other materials and/or combinations thereof. The disposable plastic embodiment may be utilized as a giveaway or one-time-use system. Stainless steel may be utilized as a reusable tool for restaurant-grade use. It will be appreciated however, that other materials such as plastics, woods, polymers, metals, and/or combinations thereof may be utilized, as desired.
[0033] System 10 may be approximately 4 to 7 inches long and 0.25 to 1.25 inches thick. The system may be a convenient disposable plastic or durable stainless steel tool used to facilitate the removal of meat in crab legs and other shellfish and/or crustaceans and portions of shellfish and/or crustaceans, as desired. It will be appreciated that other dimensions may be utilized for different uses, such as, but not limited to, different types of shellfish and/or crustaceans.
[0034] The first end of the system may slide into a leg or other portion and while the user presses upward, may split the shell, exposing the meat inside. The probe portion of the second end of the system may aid in removing the crab meat or other portions without the necessity for digging into the shell with fingers. Exposure of the shell contents may be further enhanced by splitting the shell at both the top and the bottom edges.
[0035] It will be appreciated that other dimensions may be utilized for different sized shellfish and/or crustaceans. It will also be appreciated that many different colors and materials may be utilized, along with advertising, without straying from the concepts disclosed herein. Some embodiments may be produced inexpensively with advertising such that restaurants and/other advertisers may use them as a giveaway item, similar to chopsticks and other utensils.
[0036] In closing, it is to be understood that the exemplary embodiments described herein are illustrative of the principles of the exemplary embodiments. Other modifications that may be employed are within the scope of this disclosure. Thus, by way of example, but not of limitation, alternative configurations may be utilized in accordance with the teachings herein. Accordingly, the drawings and description are illustrative and not meant to be a limitation thereof. | Exemplary embodiments provided herein may include a system and method for opening shellfish shells and extracting items therefrom, including a body having a first end, a second end and a middle portion therebetween, wherein the first end includes a first and second protuberance in spaced relation to each other to facilitate the opening of a shellfish shell, and wherein the second end comprises a probe portion configured to facilitate extracting items from the shellfish. | 0 |
This application is a continuation of parent application Ser. No. 621,032 filed Oct. 9, 1975 now U.S. Pat. No. 4,028,338.
BACKGROUND OF THE INVENTION
The present invention relates to a block copolymer having excellent solvent resistance, as well as desirable processability and more particularly the present invention relates to a block copolymer composed of alkylperfluoroalkylethylenesiloxy blocks and diphenylsiloxy blocks which block copolymer has desirable processability properties and excellent solvent resistance.
Dimethylpolysiloxane polymers which are cured with peroxide curing catalysts to produce heat vulcanizable silicone rubber elastomers are well known in the art. Such heat vulcanizable elastomers have the desired low and high temperature stability that is well known of silicone elastomers. However, one difficulty in the production of such elastomers is that the diorganopolysiloxane gums that are utilized have viscosities of 1,000,000 to 200,000,000 centipoise at 25° C. Such materials with the incorporation of the necessary amounts of filler in them tend to be very viscous, as can be appreciated, and very tacky. Accordingly such polymers are very difficult to process because of their tackiness on standard processing equipment in the preparation of such compositions prior to curing them at elevated temperatures.
There have been many attempts to alleviate the processing problems in the treating of such uncured heat vulcanizable silicone rubber compositions. One approach to the problem is to utilize process aids. Another approach is that disclosed in the foregoing Bostick, U.S. Pat. No. 3,337,497 which is to form a block copolymer having diphenylsiloxy blocks in the copolymer along with dimethylsiloxy blocks. The advantages of having such diphenylsiloxy blocks is that such blocks depending on the number of siloxy units in the block are crystalline at temperatures up to 200° C and above. Accordingly, they impart to the diorganopolysiloxane block copolymer a certain amount of stiffness which prevents the polymer from being tacky and accordingly facilitates the processing of heat vulcanizable silicone rubber compositions in the uncured state. However, such polymers while being processable in the uncured state do not have as high a solvent resistance in hydrocarbon fluids as would be desired.
Solvent resistant heat vulcanizable silicone rubber compositions having fluorinated substituent groups in the polymer are well known -- see, for instance, U.S. Pat. No. 2,979,519 of Pierce et al and U.S. Pat. No. 3,179,619 of Brown.
However, one disadvantage of such polymers which are utilized to produce heat vulcanizable silicone rubber compositions, such as the disclosed in the above patents, is that the fluorinated gums are even more tacky than dimethylpolysiloxane gums and thus are extremely difficult to process even at temperatures below room temperature. To alleviate this problem, certain process aids have been developed for fluorosilicone polymers. However, these process aids have not completely alleviated the problem. Further, the Bostick, U.S. Pat. No. 3,337,497, specifically discloses that this block copolymer be free of halogen hydrocarbon substituent groups. Accordingly, little, if any, attempt has been made up to the present time to produce such block copolymers with fluorinated substituent groups.
It is one object of the present invention to produce a solvent resistant block copolymer having desirable processability properties in the uncured state.
It is another object of the present invention to provide a solvent resistant block copolymer composed of diphenylsiloxy blocks and alkylperfluoroalkylethylenesiloxy blocks.
It is an additional object of the present invention to provide an economical process for producing solvent resistant block copolymers with excellent processability properties wherein the block copolymer is composed of diphenylsiloxy blocks and alkylperfluoroalkylethylenesiloxy blocks.
It is yet an additional object of the present invention to provide a process for producing high yields of a solvent resistant block copolymer having desirable processability properties.
It is still an additional object of the present invention to provide a heat vulcanizable silicone rubber composition having as the main polymer a block copolymer composed to diphenylsiloxy blocks and alkylperfluoroalkylethylenesiloxy blocks wherein the cured elastomer that is formed from the composition has excellent solvent resistance.
These and other objects of the present invention are satisfied by means of the disclosure set forth herein below.
SUMMARY OF THE INVENTION
In accordance with the above objects, there is provided by the present invention a solvent resistant block copolymer having excellent processability properties in the uncured state comprising a copolymer of the formula, ##STR1## where R is an alkyl radical of 1 to 3 carbon atoms, R 1 is a perfluoroalkyl radical of 1 to 8 carbon atoms, Vi is vinyl, B is selected from the class consisting of lithium and hydrogen, x varies from 20 to 400, y varies from 700 to 6000 and z varies from 0 to 100. The above block copolymer is produced by reacting in the anhydrous state a trimer of the formula,
[(R) (R.sup.1 CH.sub.2 CH.sub.2) SiO].sub.3 ( 2)
in the desired molar proportions in the presence of a solvent promoter selected from the class consisting of tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide, tetramethyl urea and a catalyst which is a dilithium compound and then after the fluorinated block is formed to add a trimer of the formula,
[(C.sub.6 H.sub.5).sub.2 SiO].sub.3 ( 3)
and complete the reaction.
At this point, there may optionally be added along with the fluorinated trimer a methylvinyl trimer to add various amounts of methylvinylsiloxy units in the fluorinated block to facilitate the curing of the final block copolymer with a peroxide catalyst.
In the preferred embodiment, the reaction is carried out in two stages where in the first stage the reactants are heated at a temperature of 55° to 85° C for a period of time varying from 0.5 to 4 hours and in the second reaction period the solvent promoter is stripped off and there is added to the reactants the diphenyl trimer in a high boiling solvent and the reaction is completed at a temperature varying anywhere between 85° to 180° C for an additional period of time varying from 1 to 8 hours. The high boiling solvent may be such solvents as dichlorobenzene, and the dimethoxyether of ethylene glycol and diphenylether. When the reaction is completed the dilithium compound is neutralized with any well known neutralizing agent for lithium but is preferably neutralized with compounds such as water, acetic acid, or an aliphatic alcohol. The solvent promoter or high boiling solvent is then stripped off to yield the block coplymer. The catalyst is utilized at a concentration of 0.7 to 8.0 millimoles per mole of trimer reactants and more preferably utilized at a concentration of 1.1 to 6.0 millimoles per mole of trimer reactants. Further, it is only necessary that the solvent promoter be in sufficient quantities in the initial part of the reaction so as to dissolve the trimer reactants and more preferably it is utilized in considerable excess since it facilitates the promotion of the reaction. As can be understood in the reaction, the fluorinated trimer is first added to the solvent promoter in the presence of a catalyst and allowed to react to form a fluorinated block and then the diphenylsiloxy trimer is added to form the terminal blocks on the block copolymer.
Once the block copolymer is prepared it may then be taken and mixed with the well known ingredients utilized in heat vulcanizable silicone rubber compositions to produce a solvent resistant elastomer. With the diphenylsiloxy blocks in the block copolymer, the polymer with the filler mixed in and any process aids, pigments, flame retardants and other additives has stiffening properties in the composition such that it is not very tacky. Thus, the entire uncured composition has good processability properties.
DESCRIPTION OF THE PREFERRED EMBODIMENT
In formula (1) of the block copolymer, R may be any alky radical of 1 to 3 carbon atoms but it is most preferably methyl; R 1 is a perfluoroalkyl radical of 1 to 8 carbon atoms and is preferably CF 3 ; x varies from 20 to 400 as indicated above but preferably varies from 100 to 200. Generally, the two diphenylsiloxy blocks are approximately of the same siloxy unit length. It is only necessary that the diphenylsiloxy block be at least 20 units long to give the block copolymer the proper crystallinity, specifically, to give the block the desired crystallinity up to a temperature of 283° C, which is the temperature at which the fluorosilicone may degrade due to heat.
Within the above ranges for y, as indicated, y may vary from 700 to 6000 but preferably varies from 1000 to 2500; B in the above formula may be lithium or is preferably hydrogen as a result of the neutralization of the catalyst during the process of producing the block copolymer.
It should be noted at this instance that the presence of the hydroxy groups at the end of the block copolymer do not create a problem when the material is used to produce heat vulcanizable silicone rubber compositions since such hydroxy groups are present at a very small weight percent. Normally, the block copolymers of the instant invention as prepared with the foregoing process will have a viscosity of 10,000,000 to 200,000,000 centipoise at 25° C.
The presence of the perfluoroethylenesiloxy units imparts to the block copolymer the proper solvent resistance and the diphenylsiloxy units because they maintain their crystalline form up to temperatures of 283° C and imparts a stiffening effect to the block copolymer such that it facilitates the processing of the block copolymer.
The process for producing the present block copolymer is simple and economical but it must be followed carefully if a high yield of the present block copolymer is to be obtained.
Accordingly, the basic reaction for producing the block copolymer of the present case comprises taking a tricyclicsiloxane of formula (2), where R and R 1 are as previously defined and dissolve in it an excess of a solvent promoter. The solvent promoter is critical to the present invention and is preferably selected from the class consisting of tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide, trimethyl urea, and compounds of an equivalent solvent promoter nature. Optionally, at this point there may be added minor amounts of a trimethyltrivinylcyclictrisiloxane so as to introduce methylvinylsiloxy units in the polymer to facilitate the curing of the final polymer with a peroxide to produce a heat cured elastomer. Preferably, sufficient cyclictrisiloxane is added so that z can vary from 1 to 100. It must be understood that insofar as much methylvinylsiloxy units are concerned they may be interspersed with the fluorinated siloxy blocks or from a separate block depending on whether the vinyl trimer is added after the block is formed or concurrently with the addition of the fluorinated trimer to reaction vessel. To this mixture there is added the necessary catalyst which can be any dilithium compound and is specifically a dilithium aromatic containing compound. Specific types of dilithium compounds which can be utilized as catalysts in the present invention are compounds of the formula, ##STR2## and compounds of the formula, ##STR3## where R 2 and R 3 are selected from hydrogen and lower alkyl radicals of 1 to 8 carbon atoms and are preferably hydrogen, or methyl.
The reaction solution composed of the fluorinated tricyclicsiloxane, solvent promoter and catalyst are then preferably heated at the reflux temperature of the solvent promoter which is generally in the range of 55° C to 85° C. This reaction temperature range is not critical. The elevated temperature above room temperature desirably promotes the reaction and higher temperatures could be utilized, however, some of the solvent promoters specified above do have a reflux temperature above the range indicated above and it is necessary initially that the temperature not exceed 85° C. With these ingredients and the heating of the mixture the fluorosilicone block is built up. The amount of trimer that is utilized is controlled by the amount of alkylperfluoroalkylethylenesiloxy units it is desired to have in the basic block in the block copolymer. This reaction is usually carried out generally anywhere from 0.5 to 4 hours. Usually a reaction time of from 0.5 to 1 hour is sufficient for the formation of an alkylperfluoroalkylethylenesiloxy block of the desired size. At the end of that time there is then added to the reaction mixture a diphenylsiloxycyclictrisiloxane of formula (3) and the reaction is allowed to proceed in the above temperature range until the diphenylsiloxy blocks have been built up to form the block copolymer of formula (1) above. This generally takes place at an additional reaction time of anywhere from 1 to 8 hours.
It must be appreciated that during the reaction the whole system must be maintained as free of water as possible, that is, in an anhydrous state. The presence of even appreciable amounts of water will poison and neutralize the catalyst that is used as a chain propagator in the above-described process.
It must also be appreciated that only cyclictrisiloxanes should be utilized in the present reaction since they result in a high yield of polymer, that is, a yield of block copolymer in the 90 to 100% area from the above reactants. Other cyclicsiloxanes will produce a much lower yield of the desired block copolymer or will not react at all under the described conditions.
Again, the amount of diphenylcyclictrisiloxanes that are utilized in the reaction mixture will depend and is controlled by the amount or the size of the diphenylsiloxy blocks that is desired. The dilithium compound catalyst concentration may vary anywhere from 0.02 to 4.0 millimoles per mole of trimer reactants and preferably varies from 0.04 to 3.0 millimoles per mole of trimer reactants. Too little dilithium compound catalyst will not act as sufficiently as a chain propagator for the siloxy blocks to be formed and too much dilithium catalyst will result in side reactions and the formation of other copolymers other than the desired block copolymers and will result in low viscosity copolymers. After the reaction time has terminated then there may be added a neutralizing agent to the reaction solution to neutralize the lithium chain propagator ions in the block copolymer that is formed.
Such neutralizing agents may be any well known neutralizing agents for lithium ions and are most desirably acetic acid, water or aliphatic alcohols. After the utilization of the catalyst the solvent promoter may be distilled off to yield the desired ordered block copolymer of formula (1) having a viscosity of anywhere from 10,000,000 to 200,000,000 centipoise at 25° C. As such, the block copolymer will generally have anywhere from a 5 to 40 mole percent diphenylsiloxy content with the rest of the substituent groups being alkylperfluoroalkylethylenesiloxy units to give the copolymer the proper solvent resistance.
To carry out the process in two steps, the initial part of the process is carried out as described above, that is, with one of the solvent promoters indicated above, by carrying out the initial part of the reaction to form the alkylperfluoroalkylethylenesiloxy blocks by heating the reaction mixture at a temperature of 55° to 85° C for 0.5 to 4 hours. At the end of that period and after the fluorinated siloxy block has been formed, it is preferred to utilize a higher boiling solvent, that is, a solvent having a reflux temperature of anywhere from 85° to 180° C. Examples of such solvents being dichlorobenzene and the dimethoxy ether of ethylene glycol and diphenyl ether. The second solvent may be added to the reaction mixture with the diphenyl trimer of formula (3) and the solvent promoter is stripped off. The reaction mixture is then heated at temperatures of anywhere between 85° to 180° C or as high as possible within that temperature range guided by the reflux temperature of the higher boiling solvent for a period of time of anywhere from 1 to 8 hours to complete the polymerization. The amounts of the higher boiling solvent that is utilized is generally within the same range as the initial solvent promoter. Both solvents are utilized in sufficient quantities to dissolve the reaction trimers and preferably are present in excess since this tends to accelerate the reaction of the formation of the block copolymer.
The advantage of using a high boiling solvent in the second reaction period is that it facilitates the formation of an ordered diphenylsiloxy block. Although desired block copolymers are formed without this two solvent procedure, the diphenylsiloxy blocks are formed in a faster period of time when the higher boiling solvent is utilized in the second step of the reaction.
Finally, the reaction is terminated as previously stated by neutralization of the dilithium compound and then stripping off the higher boiling solvent to yield the desired ordered block copolymer of formula (1) of the present invention.
The block copolymer of the present case can be utilized in well known procedures to produce heat vulcanizable silicone rubber compositions. Thus, the block copolymer may be mixed with the appropriate amounts of reinforcing or extended fillers. Examples of reinforcing fillers are fumed silica and precipitated silica which may be untreated or treated with cyclicsiloxanes, silazanes or other well known filler treating agents. Or there may be incorporated into it an extending filler alone or with the reinforcing filler. Examples of such extending fillers being diatomaceous earth, lithopone and etc. Well known process aids for heat vulcanizable silicone rubber compositions can be utilized with the present block copolymers. In addition, flame retardant agents such as, platinum, etc.; heat stabilizing additives such as, iron oxide; compression set additives, as well as other well known additives for heat vulcanizable silicone rubber compositions can all be added to the uncured composition. The composition is then cured by incorporating into it the desired amounts of well known peroxide curing agents. Examples of such peroxide curing agents are dicumyl peroxide and benzoyl peroxide. The resulting mixture is then taken and formed into the necessary fabricated part that it is desired to utilize the composition and cured at elevated temperatures which may be in the range of anywhere from 100° to 300° C to produce a silicone elastomer with excellent solvent resistance.
As an example of the general preparation of such heat vulcanizable silicone rubber compositions in which the present ordered block copolymer may be utilized in - see, for instance, the patent of DeZuba et al., U.S. Pat. No. 3,896,123, which patent is hereby incorporated into the present case by reference.
The following examples are given for the purpose of illustrating the present invention but are not intended to define the limits or scope of the present ordered block cpolymers and the process for making them. All parts in the present specification are by weight.
EXAMPLE 1
To dry tetrahydrofuran there is added 4 moles of anhydrous 3,3,3-trifluoropropylmethylcyclictrisiloxane, the tetrahydrofuran being utilized in great excess to completely dissolve the fluorinated cyclicsiloxanes. The resulting mixture is then heated to 55° C and 1.25 millimoles of dilithio stilbene catalyst is then added. After a period of 3 hours there is formed fluorosiloxy blocks of about 2000 siloxy units long. To this mixture there is then added an anhydrous solution of 1 mole of hexaphenylcyclotrisiloxane dissolved in tetrahydrofuran where there is sufficient tetrahydrouran to completely dissolve the cyclictrisiloxane. The reaction mixture is then allowed to react for 2 hours again at 55° C. At the end of this period, the tetrahydrofuran is stripped slowly off from the reaction mixture in a period of time of about 1 hour. At the end of this time the batch temperature was 85° C, but some tetrahydrofuran was still refluxing. After two hours under these conditions, the remaining tetrahydroduran was stripped from the reaction. Then 2 drops of acetic acid are added to deactivate the catalyst. For the purpose of determining the structure of the polymer, the polymer is swelled in ethyl acetate and precipitated from ethyl acetate into methanol. No unreacted diphenyl trimer was found. The block copolymer that is formed was white in color and has the following formula, ##STR4## This copolymer has a concentration of 80 mole percent of methyltrifluoropropylsiloxy units. For comparison purposes a random block copolymer is formed. Thus, there is reacted in a typical solvent, toluene, 0.8 moles of
HO + CF.sub.3 CH.sub.2 CH.sub.2 Si(CH.sub.3)O/.sub.4.5 H
with 0.2 moles of pure diphenylsilane diol at a 160° C temperature using 800 ppm of stannous octoate catalyst for a period of time varying from 1 to 4 hours. Utilizing this procedure there is formed a clear random copolymer which had a concentration of 80 mole percent of methyltrifluoropropylsiloxy units.
The ordered block copolymer of the formula above and the random block copolymer of the formula above are then taken and per 100 parts of the polymer there is added to each polymer 40 parts of octamethylcyclictetrasiloxane treated fumed silica and 3 parts of benzoyl peroxide and the resulting mixture is then cured for 20 minutes at 300° F. The samples are cooled in the mold and then post cured for 1 hour at 400° F. The solvent swell for each rubber sample is then measured in toluene at room temperature for 24 hours. The results of the solvent swell test is as follows:
______________________________________Sample V% Solvent Swell______________________________________Block copolymer 39Random copolymer 139______________________________________
The above data indicates that for substantially the same methyltrifluoropropylsiloxy content the ordered block copolymer of the present case has substantially superior solvent resistance to hydrocarbon fluids. In addition, the uncured polymer is found to be considerably easier to handle and mix with the other ingredients than the random copolymer which did not have in it diphenylsiloxy crystalline blocks in the copolymer.
EXAMPLE 2
In an anhydrous system and to an excess of tetrahydrofuran there is added 5 moles of anhydrous 3,3,3-trifluoropropylmethylcyclictrisiloxane and 2.41 millimoles of dilithiostilbene dissolved in tetrahydrofuran is added. The resulting mixture is heated to reflux at 55° C for a period of time of about 3 hours. At the end of that time it is found that the dilithio fluorinated terminated block has 1000 siloxy units in it. Then there is added to the mixture an anhydrous solution of 11/2 moles of hexaphenylcyclotrisiloxane dissolved in an excess amount of dichlorobenzene. The resulting mixture is then heated at 95° C to strip off the tetrahydrofuran and then heated at a temperature of 150° C for 3 hours. At the end of that time, the dichlorobenzene is stripped off in about one-half hour and 2 drops of acetic acid is added to deactivate the polymer. The ordered block copolymer that is formed has the structural formula, | There is provided by the present invention a process for producing a solvent resistant block copolymer having desirable processability comprising reacting perfluoroalkylethylene substituted cyclic trisiloxane in the presence of a solvent promoter which may be tetrahydrofuran and in the presence of a dilithium compound catalyst and then adding a diphenyl cyclic trisiloxane and allowing the reaction to go to the completion. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is based on and hereby claims priority to International Application No. PCT/EP2013/003542 filed on Nov. 23, 2013 and German Application No. 10 2013 000 068.8 filed on Jan. 8, 2013, the contents of which are hereby incorporated by reference.
BACKGROUND
[0002] The invention relates to a method for synchronizing two display devices of a motor vehicle.
[0003] In general, functions have previously been triggered in the motor vehicle by operating, e.g., keys. To detect the operations, e.g. of a key, an electrical or a capacitive switch is necessary for each key. Triggering the functions requires the operation of the, e.g., mechanical pushbutton. Display devices such as, e.g., a head-up display, a display of a combined instrument or infotainment system in the motor vehicle are systems separated purely functionally. The display of information requires elaborate operation of digital menus.
[0004] DE 10 2010 056 411 A1 describes the display of information on a center display of a motor vehicle relating to a waypoint for which a reference is displayed on a predetermined other display device, namely a color display in the environment of the screen base of the front screen. To interact with the display devices, a finger tracking system can detect a wiping gesture of a user.
[0005] Transmission of a digital image which is displayed on a head-up display of a motor vehicle to another display device is known from DE 10 2005 010 843 A1. On the other display device, it is no longer information-carrying data but an icon which is displayed. Triggering of this function can take place via a hand movement of the user and be detected via an optoelectronic sensor.
[0006] DE 10 2007 035 769 A1 describes switching the representation of information of a display device to another display device, a video camera detecting a hand movement of a user.
[0007] Due to the many possible technical devices for displaying information, however, the disadvantage arises that the user cannot freely select the two display devices involved. A further problem arises if a multiplicity of data records for different thematic contexts are displayed on a universal display device, e.g. on a combined instrument with a screen, i.e., e.g., data relating to a motor speed, to the driving speed, to the tank filling level and to detected malfunctions. However, the display device of the related art to be synchronized can only be synchronized if the display device only displays data records of the same context.
SUMMARY
[0008] One possible object is to provide a method for synchronizing two arbitrary display devices.
[0009] The inventors considered on the concept of detecting an operating gesture, that is to say a movement, carried out freely in space, of a body part of the operating person, by a video camera which generates a three-dimensional image data record. In this context, the operating gesture is preferably a pointing, pulling and/or gripping gesture. This allows an elaborate installation of operating elements in the display devices to be dispensed with. In addition, it is made possible to select the involved display devices and the relevant data records.
[0010] The inventors propose a method for synchronizing a first display device of a motor vehicle with a second display device, to be synchronized, of the motor vehicle, that is to say for synchronizing, e.g., a head-up display with, e.g., a display in the center console. In this context, the first display device already displays a first data record, e.g. a picture element (e.g. a warning symbol), which comprises a first display content relating to a predefined thematic context.
[0011] An optical sensor device, e.g. a PMD camera (i.e., a photonic mixing device), detects an operating gesture of a user. The sensor device generates a signal describing the operating gesture (e.g. a video signal) on the basis of 3D image data and transmits this to a gesture detection device. On reception of the signal of the sensor device, the gesture detection device determines, by the determined operating gesture, the data record selected by the user by the operating gesture and the data record already displayed by the first display device.
[0012] A control device, e.g. a control device of the motor vehicle, receives a control signal generated by the gesture detection device which describes the first data record determined, and determines, by the control signal, the predefined thematic context of the first data record.
[0013] The control device can be, for example, also a program module of the first or of the second display device or can be implemented in a plurality of part areas, e.g. both display devices. If, for example, the control device is a program module of the first display device, it can determine, on the basis of the control signal, that is to say on the basis of a trigger of the gesture detection device, the determined predefined thematic context of the selected data record, e.g. by itself, and transmit it to the second display device.
[0014] By the predetermined thematic context determined, a further data record having a second display content of the predetermined thematic context is provided. The further data record is displayed on the second display device. Providing the further data record can be carried out, e.g., by one of the display devices or by a data processing device of the motor vehicle, possibly in interaction with a central data server on the Internet. If, e.g., the first display device transmits the predetermined thematic context of the selected data record determined to the second display device, it can thus, e.g., independently determine and display the further data record. The constellation which is selected here can depend on the technical environment in which the proposed method is implemented.
[0015] Thus, e.g., the first data record can comprise an image data record for, e.g., a warning symbol for a reference to, e.g., a critical operating state of the motor vehicle, whilst the further data record comprises, e.g., a detailed description text relating to the critical operating state of the motor vehicle. Thus, e.g., a text file supplementing the image file can be displayed on the second display device, i.e., e.g. a fault description.
[0016] Apart from the above-mentioned advantages, the advantage is obtained that the display contents are not only exchangeable, but different data records having a different amount of information content relating to a context can be output. In spite of a multiplicity of various information items on a display, the user, therefore, does not have to operate an operating element such as, e.g., a key or a digital menu for the precise selection of a data record. As a result, the user can also select when he wishes to have which volume of information displayed for which information.
[0017] In one embodiment of the method according to the method, the control device can control the transmission of the further data record from a motor-vehicle-internal data memory to the display device to be synchronized. In this case, various groups of data records are present in the data storage device, a group of data records comprising those data records which have a common thematic context.
[0018] However, the contexts are here the least of which was known before the synchronization and must be stored in at least one data storage device. Alternatively or additionally, the control device can call up the further data record from an external data server, e.g. from an Internet server of a motor vehicle manufacturer or generate, on the basis of operating parameters which are provided by a device for operating the motor vehicle, the further data record. Such data records can be provided by the control device in a group of data records of the data memory.
[0019] At least one of the display devices is preferably equipped without its own sensor. In particular, neither display device is equipped with its own sensor system. The operating gesture is preferably detected by an optical sensor device on the basis of 3D image data of a time-of-flight camera (TOF camera), PMD camera or stereocamera of the motor vehicle which is preferably a part of another device of the motor vehicle. The three-dimensional detection of the operating gesture provided enables a directional movement to be detected and increases the number of variations of operating gestures. Due to the spatially precise detection, the display devices to be synchronized become freely selectable and a multiplicity of display devices can be used for the information flow to the user. A sensor device of this type, already present in the motor vehicle, can be used for the method without the display devices having to be equipped with sensors. In addition, operating elements such as pushbuttons or touch-sensitive buttons can be omitted in the display device.
[0020] In a further preferred embodiment, the gesture detection device, by the signal of the sensor device, determines which of the display devices is the display device already displaying the data record and which of the display devices is the display device to be synchronized. This can be done, e.g., by a pulling gesture from one display device to another. The display devices thus no longer have to be selected by the elaborate operation of a menu by, e.g., keys.
[0021] In a development of this embodiment of the method, the gesture detection device, for the purposes of detecting at least a part of the operating gesture, can check a trajectory of a body part, that is to say a motion curve of a moving body part, to see whether it describes a pulling and/or gripping movement from the first display device to the second display device. In this manner, the direction of synchronization is detected.
[0022] The gesture detection device, for detecting the operating gesture, can extend the trajectory of a body part by extrapolation of the part of the operating gesture, and check whether the extended trajectory represents a pulling and/or gripping movement. This provides for faster operation. Thus, the operating gesture does not need to be completed by the user if he has to move the body part carrying out the gesture spontaneously back to, e.g., the steering wheel.
[0023] The object mentioned above is also achieved by a motor vehicle, particularly a car or a passenger vehicle, if it comprises a gesture detection device and is designed for carrying out an embodiment of the proposed method.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] These and other objects and advantages of the present invention will become more apparent and more readily appreciated from the following description of the preferred embodiments, taken in conjunction with the accompanying drawings of which:
[0025] FIG. 1 shows a block diagram for a sensor device and for a control device which can be installed in an embodiment of the proposed motor vehicle, and
[0026] FIG. 2 shows a sketch for an embodiment of the proposed method.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0027] Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout.
[0028] In FIG. 1 , a sensor device 10 of a motor vehicle, for example a passenger vehicle, is shown. In the present example, the sensor device 10 comprises an optical sensor 12 , e.g. a PMD camera, and a measuring device 14 which can detect the measurement data of the optical sensor 12 (method S 10 ) and transmit them to a gesture detection device 16 (S 20 ). The optical sensor 12 can also comprise, e.g., another 3D camera such as, e.g., a TOF camera or a stereocamera and is preferably mounted on the ceiling of the motor vehicle.
[0029] The optical sensor 12 can be designed in a manner known per se, e.g. with a luminous source 20 , e.g. an infrared lamp which illuminates a detection area 22 , for example a space above a dashboard of the motor vehicle. If this contains an object, for example a hand 24 ′ of the driver of the motor vehicle, the electromagnetic radiation radiated by the luminous source 20 is reflected back to a sensor array 26 . By the sensor array 26 , 3D image data can then be generated which specify 3 D coordinates relating to individual area elements of the hand 24 ′. Additionally or alternatively, the interior space of the motor vehicle can also be surveyed in this manner. The 3D image data are transmitted by the measuring device 14 to the gesture detection device 16 .
[0030] The gesture detection device 16 can be a gesture detection device 16 known to the expert.
[0031] By the gesture detection device 16 , extremities can be segmented from the 3D image data, by which, for example, the position of a fingertip in the detection area 22 can be determined. In this context, segmenting algorithms known per se can be used as a basis. The 3D image data of the sensor array 26 of the optical sensor 12 can also represent a sequence of successive 3D images, i.e. by the optical sensor 12 , movements of the hand 24 ′ or an extension of a lower arm can also be detected. By tracing the trajectory, for example of the fingertip in this 3D image sequence, particularly by tracing the position and the speed of the fingertip, a gesture of movement indicated by the fingertip can thus be extrapolated from the trajectory.
[0032] Depending on this evaluation, the gesture detection device 16 then generates a control signal (S 30 ). FIG. 1 also shows a control device 18 of the motor vehicle which can be, e.g., a control device for controlling two (not shown in FIG. 1 ) display devices 30 , 34 . The control device 18 receives the control signal of the gesture detection device 16 and coordinates the interaction of the display devices 30 , 34 to be synchronized.
[0033] FIG. 2 shows an embodiment of the proposed method.
[0034] As shown in the example of FIG. 2 , a data record from a group of data records can be transmitted from a data storage device 38 to the display device to be synchronized for displaying the data record during the coordination of the interaction of the display devices 30 , 34 to be synchronized. In this case, the control device 18 can thus generate, on reception of the control signal of the gesture detection device 16 , e.g. a synchronizing signal which causes the second display device 34 to call up a particular data record 40 from the data storage device 38 or which causes the data storage device 38 to transfer the data record 40 to the second display device 34 . In actuality, this can look as follows:
[0035] A user is located in the interior space of a motor vehicle. On a first display device 30 , e.g. a head-up display on a windscreen, a plurality of picture elements 32 , 32 ′, 32 ″ are displayed, e.g. warning or other symbols which signal an operating state. The picture element 32 is, e.g., an image of a warning triangle which informs the user of, e.g., the presence of important operating information. In FIG. 2 , a first position of a body part 24 of the user, e.g. a lower arm with a hand 24 ′ (dashed line), and a second position of the body part 24 (continuous line) are shown. The positions P 1 and P 2 symbolize a movement of the body part 24 from the first to the second position. In the present example, this movement with the finger position shown is an operating gesture for synchronizing, e.g., a display 34 of an infotainment system above the center console 36 with the display device 30 . The sensor device 10 which comprises, e.g., a PMD camera detects, e.g., the stretching out of the lower arm and the gripping or pointing movement of the hand 24 ′ (P 3 ).
[0036] The sensor device 10 detects the operating gesture and/or the direction into which the body part 24 of the user points in the position 28 (S 10 ). For this purpose, the sensor device 10 can detect the coordinates of the hand 24 ′ within a coordinate system of an interior space of the motor vehicle. By the coordinates, the display devices 30 , 34 involved in the synchronization are determined by the gesture detection device 16 . Similarly, the data record 32 from the group of which in the data storage device 38 a further data record is to be displayed on the display device 34 to be synchronized can thus be determined by the gesture detection device 16 .
[0037] Between the data storage device 38 and the display device 30 and between the data storage device 38 and the display device 34 , a wireless or wired communication link 42 can be present. In the present example, the data records 32 and 40 of the group of data records G 1 are present in the data storage device 38 , both of which data records 32 and 40 have a common context, e.g. a warning message, and which, as a result, form one group. A further group of data records G 2 comprises, e.g., the picture element 32 ′ already displayed on the head-up display 30 which, e.g., symbolizes a current occurring playing back of an audio file and which comprises a text file 40 ′ thematically linked to this which, e.g., comprises bibliographic data relating to the audio file 32 ′.
[0038] The detection of the operating gesture and/or of the coordinates of the operating gesture within the system of coordinates of the interior space of the motor vehicle (S 10 ), the generation of a signal describing the operating gesture and its transmission to the gesture detection device 16 (S 20 ) take place as already described in FIG. 1 .
[0039] The gesture detection device 16 can determine, e.g., by the direction, described by the signal of the sensor device 10 , of the lower arm stretching out with the hand 24 ′ (P 4 ) that, e.g., the display device 30 is the display device which already displays a data record. Analogously thereto, the gesture detection device 16 can determine by the signal of the sensor device 10 , which describes a pulling movement (P 1 , P 2 ) and/or a direction of the body part 24 with the hand 24 ′ in a second position (P 5 ), that the display device 34 is the display device 34 to be synchronized. Alternatively, e.g., a throwing gesture in the direction of the second display device 34 can also be determined as a selection gesture for, e.g., the display device 34 to be synchronized.
[0040] In addition, the gesture detection device 16 can determine by the direction (P 3 ), described by the signal of the sensor device 10 , of the lower arm stretched out with the hand 24 ′ during the execution of the gripping movement (P 4 ) that the data record 32 is the data record “selected” by the user. With the aid of the coordinates of the body part 24 within the system of coordinates of the interior space of the motor vehicle, the gesture detection device 16 can determine, e.g., the axes of the lower arm and/or the finger axes. By these axes, the position 28 of the respective limb 24 can be determined. If the forearm axes then point to the picture element 32 as in the example of FIG. 2 and the gesture detection device 16 determines a gripping movement of the hand 24 ′, the picture element 32 is selected. Alternatively, the gesture detection device 16 can detect a relative movement of the hand 24 ′ and, as a result, can control a cursor of the display device 30 , as a result of which the user can select the picture element 32 . This detected selection of the picture element 32 is followed by the selection of the data record relating to the picture element 32 . On this basis, the control device 18 can determine the predetermined thematic context and possibly, e.g., the associated group of data records.
[0041] A further possibility for determining the thematic context is if, e.g., the gesture detection device 16 generates on the basis of a determined operating gesture a control signal following which the control device 18 generates a synchronization signal and transmits the latter to the first display device ( 30 ). The first display device ( 30 ) thereupon transmits information relating to the thematic context of the first data record ( 32 ) to the control device ( 18 ).
[0042] In the present example, the control device 18 determines, e.g., the group of data records G 2 . Alternatively or additionally to the example shown in FIG. 2 , the control device 18 can call up the further data record 40 , e.g. from an Internet server, e.g., of a motor vehicle manufacturer, or generate it on the basis of, e.g., the operating data relating to an oil level.
[0043] The gesture detection device 16 generates a corresponding control signal to a control device 18 which, as already described with respect to FIG. 1 , causes the data record 40 to be displayed, e.g. in this case a text message relating to the warning, on the display device 34 (S 40 ). In the present example, the control device 18 causes the data storage device 38 to transfer the data record 40 to the display 34 of the infotainment system (S 50 ).
[0044] The gesture detection device 16 can also be designed to extrapolate a trajectory (T) of a body part, that is to say, e.g., a part of the pulling movement represented by the positions P 1 and P 2 , and to check it to see whether it will represent a pulling and/or gripping movement. Thus, the user can “nudge”, that is to say only indicate, the “displacement” of the data record (that is to say the synchronization of the display devices 30 , 34 ), e.g. in a situation in which he must unexpectedly quickly pull back his arm to the steering wheel. This means that he does not have to execute the operating gesture to its end.
[0045] The examples illustrate the principle of the proposals according to which a physically correct locatability of the passengers (e.g. by a TOF camera or a PMD camera) or of body parts of the passenger allows an approach to a surface to be detected. To displace information (contexts) from one display device to another display device, a gesture can be used. For example, a warning symbol can be displayed in a head-up display, for example. By reaching, for example, in the direction of the warning symbol and pulling it, e.g. in the direction of the center display, a detailed description of the warning can appear, for example.
[0046] This provides for a universal interaction between the displays (in addition to an enhancement of the joy-of-use factor). In addition, the interaction does not require any pushbuttons.
[0047] The invention has been described in detail with particular reference to preferred embodiments thereof and examples, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention covered by the claims which may include the phrase “at least one of A, B and C” as an alternative expression that means one or more of A, B and C may be used, contrary to the holding in Superguide v. DIRECTV, 69 USPQ2d 1865 (Fed. Cir. 2004). | A method synchronizes two display devices in a motor vehicle. The first display device already displays a first data set which comprises a first display content relating to a predetermined thematic context. A sensor device, in particular a PMD camera, detects as a control gesture of a user, a free movement in the chamber of a body part of the user. A signal which is then generated by the sensor device and which describes the control gesture, is transmitted to a gesture recognition device which generates a control signal in accordance with the determined control gesture. In accordance with the control signal, a control device determines the predetermined thematic context of the determined data set. Using the defined predetermined thematic context, an additional data set which includes a second display content of the predetermined thematic context is provided. This additional data set is displayed on the second display device. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This patent document claims priority to earlier filed U.S. Provisional Patent Application Ser. No. 62/303,535, filed Mar. 4, 2016, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to an improved method and system for the acquisition of high-resolution video images of the skin, archiving and viewing of the video images, and a way to compare acquired images. More particularly, the present invention pertains to methods of using such a system to monitor skin conditions using previous images from a patient database to perform comparisons of the acquired image data.
[0003] In the field of dermatology, it is necessary to have a way by which to capture skin conditions and a way to monitor those conditions over time. Monitoring may be performed by a skilled professional using a careful procedure to evaluate skin surfaces by eye and may include capturing a series of photographs of specific regions. This helps to track changes to the skin for better diagnosis of any problems with the skin. A carefully planned and executed procedure is important when capturing photographs of the skin, as many factors may contribute to the way a still image appears; this is of particular interest when subsequent photos are captured and used for comparison. The existing art does not capture the position where a particular image was taken.
[0004] This system improves upon the prior art by combining a camera, illumination source, and position sensor to capture an image and know the precise and absolute position and scale of the image that was captured.
[0005] In view of the foregoing, there is a demand for a system and method that can precisely determine the absolute position of where an image was taken of the skin.
[0006] There is a demand for a system and method that can determine the scale of the image that was captured.
[0007] There is a demand or a system and method that can accurately track the changes to the condition of the skin over time for medical purposes.
SUMMARY OF THE INVENTION
[0008] To accomplish the features of the present invention there is provided an apparatus for capturing high-resolution images of the skin comprising: a patient interface and a handheld exam control which may be used by dermatologists or other medical professionals interested in capturing high-resolution images of skin surfaces; said handheld exam controller combining a fixed-focus camera with a laser projector and a wired or wireless position sensor, a way to synchronize laser projector illumination with camera frame-capture, a way to determine the absolute position of the camera, and a way to determine scale.
[0009] The present invention also relates to a way to retrieve a past skin image or images based on position data in a new capture, and a way to create a new skin capture based on position data in an existing image.
[0010] Therefore, an object of the present invention is to provide system and method that can precisely determine the absolute position of where an image was taken of the skin.
[0011] A further object is to provide a system and method that can determine the scale of the image that was captured.
[0012] Yet another object of the present invention is to provide a system and method that accurately tracks the changes to the condition of the skin over time for medical purposes.
BRIEF DESCRIPTION OF THE DRAWING FIGURES
[0013] Other objects, features and advantages of the invention shall become apparent as the description thereof proceeds when considered in connection with the accompanying illustrative drawings, in which:
[0014] FIG. 1A is a system block diagram illustrating the DermaMap skin-mapping system;
[0015] FIG. 1B is a block diagram illustrating the components of the Handheld Exam Control for the present invention;
[0016] FIG. 2 is a block diagram illustrating the components of the Patient Interface for the present invention;
[0017] FIG. 3 is a flowchart illustrating an example of typical use of the DermaMap skin-mapping device;
[0018] FIG. 4 is a flowchart illustrating a typical Capture sequence for the DermaMap skin-mapping device;
[0019] FIG. 5 is a flowchart illustrating an example of the Compare process for the DermaMap skin-mapping device; and
[0020] FIG. 6 is a flowchart illustrating the View playback process for the DermaMap skin-mapping device.
DESCRIPTION OF THE INVENTION
[0021] By combining a camera, illumination source, and position sensor to capture images of the skin, the absolute position and the scale of a captured image can be determined with accuracy.
[0022] FIG. 1A shows a top-level overview of the entire DermaMap system. The handheld exam control 10 is used to capture video images (frames) of a patient's skin to create a record of the condition of the skin and make it possible to track changes that may occur over time. The exam control captures images in a manner that synchronizes frame capture and laser illumination, while the patient 13 is situated on the patient interface 12 according to the patient image capture procedure. Communication occurs between the handheld exam control and the patient interface. Requests for position data 11 are sent from the handheld to the patient interface and responses containing the position data 14 are returned from the patient interface back to the exam control. The result of this communication is that the absolute position is reported and stored for each frame. A wired or wireless network 15 is used to send acquired images with position data to an external storage device 16 . Stored images can be retrieved via a wired or wireless network 15 and position data can be accessed to capture new images of the exact same location on a patient's skin.
[0023] It should be understood that the position data collected and stored using known computer equipment that includes a microprocessor, memory, storage, I/O ports, power source and other components found in a computer device. The storage device may be a hard drive, solid state, optical drive or the like. The captured images and collected position data are accordingly stored in such storage device. The computer equipment may or may not be connected to a network, such as the Internet, to facilitate access and storage of the data therein.
[0024] The handheld exam control, shown in FIG. 1B has a position sensor 101 , display 102 , laser projector (illumination source) 103 and a camera 104 . The handheld exam control is used with the patient interface, representationally shown in FIG. 2 . The patient interface has a support surface and a position sensor interface, 201 , that communicates with the position sensor 101 on the exam control to determine the absolute position of captured images. The patient position templates 202 and 203 on a support surface of platform 200 are used to help position the patient for optimal image capture.
[0025] FIG. 3 illustrates an overview of use of the skin-mapping device and system 1 of the present invention. The patient interface is turned on at step 300 , activating the position sensor interface. At step 301 , the handheld exam controller is turned on, activating the position sensor. At 302 , the patient session begins. A patient session includes: homing the handheld exam controller at step 303 ; pressing the trigger to start capture at step 304 ; pressing the trigger a second time to end capture at step 305 ; and viewing the captured video at step 306 .
[0026] Turning now to FIG. 4 , the capture sequence is initiated when the trigger is pressed in step 400 . A laser (illumination) pattern is projected from the handheld exam control onto the patient's skin at step 401 and an odd video frame is captured at step 402 . At step 403 , an unpatterned colored light is projected from the handheld exam control onto the patient's skin and an even video frame is captured at step 404 . At step 405 , the position of the pair of captured images is recorded and save using the computer equipment. If the trigger is still pressed, the sequence will proceed and steps 401 through 405 will be repeated in sequence until the trigger on the handheld exam controller is up in the off position and the capture sequence ends at step 406 .
[0027] Next, the camera is synchronized to the laser illumination source, the illumination pattern is always displayed on the skin when odd frames are captured and the colored illumination light is always displayed on the skin when even frames are captured. Captured video frames and absolute position data allow this data to be used after it is acquired. Images may be stored for comparison using computer software. The distance, perspective or angle, and camera rotation relative to the patient are all factors that need to be accounted for. The odd video frames, captured using an illumination pattern, can be used to determine this information. The size of elements in the pattern is used to determine the scale of the video and therefore determine the size of any skin lesions in the video.
[0028] FIG. 5 illustrates the compare function of the present invention. The compare function can be used to repeat an image capture using absolute position information from a previous image capture. In step 500 , the trigger is pressed and the actual location is compared to the location in the previous image capture. In step 501 , the unpatterned colored light is projected from the handheld exam control onto the patient's skin. In step 502 , the laser pattern is projected onto a patient's skin and the actual distance between the handheld exam controller and the patient is compared to the image scale in the previous image capture. In step 503 , the actual position is compared to the position location in the previous image capture and adjustments are made. In step 504 , image capture takes place. When the trigger is pressed in step 506 , a laser (illumination) pattern is projected from the handheld exam control onto the patient's skin at step 507 and an odd video frame is captured at step 508 . At step 509 , an unpatterned colored light is projected from the handheld exam control onto the patient's skin and an even video frame is captured at step 510 . At step 511 , the position of the pair of captured images is recorded. If the trigger is still pressed, the sequence will proceed and steps 507 through 511 will be repeated in sequence until the trigger on the handheld exam controller is up in the off position and the capture sequence ends at step 512 .
[0029] FIG. 6 illustrates how captured video is played back. In step 600 , video playback is initiated. In step 601 , the even video frames are displayed in order until they have all been displayed; once the last even frame is displayed, playback stops at step 602 .
[0030] With the present invention, past skin image or images, based on position data in a new capture can be achieved. Also, a new skin capture based on position data in an existing image is possible. The system and method of the present invention can precisely determine the absolute position of where an image was taken of the skin as well as the sale of the image that was captured. As a result, changes to the condition of the skin over time for medical purposes can be tracked.
[0031] It would be appreciated by those skilled in the art that various changes and modifications can be made to the illustrated embodiments without departing from the spirit of the present invention. All such modifications and changes are intended to be covered by the appended claims. | A system for capturing, storing and comparing dermatological images includes two components, namely, a handheld exam control and a patient interface. The handheld exam control includes a camera, display screen, illuminator and a position sensor. The patient interface includes a patient position template and a position sensor interface. The system captures an image sequence and the precise location of each image. Images may be compared to previous images by a clinician. | 0 |
BACKGROUND
Posttraumatic stress disorder (PTSD) is an anxiety disorder resulting from exposure to shocking and/or distressing events. Many veterans experience PTSD because of their wartime experiences. For example, PTSD can result in persistent flashbacks, nightmares, difficulty sleeping, and significant impairment of social and occupational function.
PTSD is understood to result in neuroendocrinological changes as well, as brain morphology. As a result, some patients are known to have atypical biochemical levels associated with the sympathetic nervous system, or the system that controls the “fight or flight” response. Fear is thought to be closely associated with these neurobiological conditions.
Various attempts have been made to treat PTSD including psychotherapy, medication, and combinations of therapies. However, while medications have shown benefit in reducing PTSD symptoms, there is no clear drug treatment for PTSD. This may be because such treatment is symptom-oriented and does not necessarily cause the patient to recover from the disorder.
Alternative approaches to solving the problems presented by PTSD could desirably treat the neurobiological conditions established by the traumatic events rather than merely reducing the symptoms suffered by patients experiencing PTSD. For example, psychological and neuropsychological studies suggest a correlation with treating areas of the human brain, such as the hippocampus and amygdale, and improvement for veterans suffering with PTSD.
The foregoing examples of the related art and limitations related therewith are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent upon a reading of the specification and a study of the drawings.
SUMMARY
The following examples and aspects thereof are described and illustrated in conjunction with systems, tools, and methods that are meant to be exemplary and illustrative, not limiting in scope. In various examples, one or more of the above-described problems have been reduced or eliminated, while other examples are directed to improvements.
A technique for influencing the human brain can be applied to treat neurobiological conditions through influencing the brain to operate at a desired, therapeutic frequency by producing specific sound beats, which are converted by the inner ear into electrical signals received by the hippocampus. For example, the human brain can be stimulated with a beat in the theta (θ) frequency range to influence the brain to relax and enter into a therapeutic state. Alternatively, the human brain can be stimulated with a beat in the alpha (α) frequency range to stimulate active thinking. Over a series of treatments the brain of an individual suffering from PTSD, or other neurobiological conditions, can be influenced to operate at a normal frequency. Advantageously, as the frequency is adjusted, the symptoms of PTSD recur less often until the individual ceases to experience the symptoms or has at least experienced a decreased recurrence of the symptoms.
A system for influencing a human brain to operate at a frequency includes a fluid filled chamber having various audio reproduction devices. The audio reproduction devices are coupled to a processing device producing audio signals prepared to influence the human brain to operate at a frequency conducive to function in a particular therapeutic state. The audio reproduction devices can produce waves in both audible and inaudible frequencies. In response to the stimulation, cells within the human brain can respond to the audio frequencies by influencing cellular water action potential. In one implementation, multiple frequencies can be combined into a monaural beat, a single united resonance frequency to induce the therapeutic state. Monitoring devices can be distributed inside and/or outside the chamber to record the brainwaves emanating from the human brain.
A method for influencing a human brain of an individual to operate at a frequency includes stimulating the human brain with audio waves while the individual is floating in a fluid medium. While stimulated, the individual can be monitored for adherence to the frequency using one or more sensors to identify the frequency of operation of the individual's brain waves. In one implementation the audio waves can be projected through the fluid medium in more than one frequency where the difference between the frequencies produce a monaural beat stimulating the human brain at the desired frequency. Additionally, the audio waves can be interspersed with music to provide an engaging experience.
In one embodiment, monaural beats are produced based on the acoustical design of a chamber shaped to optimize delivery of frequencies to an individual within the chamber. In a further embodiment, the shape of the chamber is designed based on the acoustical characteristics of a musical instrument, such as the cello.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts an example of a system for influencing a human brain to operate at a frequency.
FIG. 2 depicts components of a system for influencing a human brain to operate at a frequency.
FIG. 2 a depicts an example of a chamber used for influencing a human brain to operate at a frequency.
FIG. 3 depicts a flowchart of an example of a method for influencing a human brain to operate at a frequency.
FIG. 4 depicts an example of a computing system representative of the computing systems discussed herein.
DETAILED DESCRIPTION
In the following description, several specific details are presented to provide a thorough understanding. One skilled in the relevant art will recognize, however, that the concepts and techniques disclosed herein can be practiced without one or more of the specific details, or in combination with other components. In other instances, well-known implementations or operations are not shown or described in detail to avoid obscuring aspects of various examples disclosed herein.
FIG. 1 depicts an example of a system 100 for influencing a human brain to operate at a frequency. FIG. 1 includes stimulation module 102 , individual 104 , environment 106 , and monitor 108 .
In the example of FIG. 1 , the stimulation module 102 can include devices 103 for producing audible, vibratory, magnetic or other known or convenient signals. For example, the stimulation module 102 can include devices 103 such as speakers, one or more ultrasonic transducers, or other known or convenient devices for stimulating an individual 104 while the individual 104 is within environment 106 . The stimulation provided by devices 103 can be administered at a predetermined, desired frequency, or an individual 104 can adjust the frequency to a desired level corresponding to the type of therapy that the individual 104 desires to undertake. The devices 103 can produce therapeutic effects by inducing cellular regeneration and brainwave entrainment.
In the example of FIG. 1 , environment 106 can be a chamber 216 capable of holding the individual 104 . The individual 104 is a person, such as one suffering from post traumatic stress disorder (PTSD) and having brainwave patterns that may have erratic, non-standard, or otherwise undesirable frequencies. The environment 106 can be filled with a solution, such as saline water, so that the individual 104 floats within. Alternatively, the solution may be a diamagnetic solution. The diamagnetic solution is capable of expressing a magnetic field in opposition to an externally applied electromagnetic field device 103 , such as a tensor, thus causing a repulsive effect. The environment 106 can be heated so that the solution is at a desired temperature, such as body temperature, to provide comfort to the individual 104 in the chamber 216 .
In the example of FIG. 1 , monitor 108 includes devices for collecting signals emanating from the individual 104 by, for example, an electroencephalogram (EEG) electrocardiogram (ECG/EKG), galvanic skin response sensor, heart rate variability monitor, and other known or convenient monitoring device. The monitor 108 can collect brainwaves emanating from the individual 104 and identify a transition from the original frequency to the desired frequency. In another embodiment, monitor 108 can collect infrared emanations from the individual 104 and the environment 106 , which can be used to adjust one or more modules of system 200 , discussed below.
FIG. 2 . depicts components 202 - 220 of a system 200 for influencing a human brain to operate at a desired frequency. The components depicted are logically represented as modules of various individual systems; however, one or more components 202 - 220 may be combined or divided to provide functionality to a particular solution. FIG. 2 includes user interface 202 , monitoring system 204 , processing unit 206 , storage 208 , sound generation 210 , water management 212 , sensors 214 , chamber 216 , ultra sonic transducer 218 , and heater 220 .
The chamber 216 is illustrated in greater detail in FIG. 2 a . Chamber 216 can be constructed so that it is large enough to hold an adult individual 104 while the individual 104 floats in a solution within the chamber 216 . In designing the chamber 216 , the walls can be spaced so as to provide optimal acoustics for experiencing the sound. In some embodiments, the walls of the chamber 216 are designed based on the acoustical resonance characteristics of a musical instrument. For example, in one embodiment the chamber 216 is based on a cello's design to produce acoustics optimized for delivering beats to the individual 104 within the chamber 216 . In another embodiment, the chamber 216 is based on dimensions derived using vaastu architecture. Vaastu shastra is a traditional Hindu system of building design based on directional alignments and mathematical dimensions. Vaastu-based architecture is one technique that can be used by the chamber 216 to transmit a wavelength of light and/or sound to affect cellular regeneration by stimulating cellular fluid. In humans, in response to the stimulation, cells within the brain can respond by entraining to the wavelength transmitted by the chamber 216 .
The chamber 216 can be “tuned” based on manipulating its dimensions to generate specific, desirable frequencies used in various therapeutic treatments, such as PTSD, and other applications. In one embodiment, dimensions of the chamber 216 are based on a golden ratio associated with the Fibonacci sequence, or a Fibonacci-like sequence, such as 1:2:3:5:8:5:3:2:1. By definition, the first two Fibonacci numbers are 0 and 1, and each subsequent number is the sum of the previous two. The middle number (e.g. “8” in the example above) of the sequence can represent a center point within the chamber 216 . Based on the Fibonacci ratio, concave and convex curves of the outer confines of the chamber 216 can be tuned to produce a desired wavelength of light for generating musical tonal waves.
Parabolic curves or semi-circle structures (“curves”) within the chamber 216 can be used to redirect the light back to the center point. In a particular embodiment, a curve at the center point can have golden rectangular dimension of sqrt(5)/2, and successive curves can extend from each direction of the center point to end with a maximum radius at the end of the inner golden rectangle.
Golden rectangle-based dimensions can be used within the center structure of the chamber 216 . In one embodiment, the ratio of the width of the golden rectangle to its length is 1:1.618, and the outer body of the chamber 216 has a ratio is 1:1.618. The inner and outer rectangle can have a ratio of 4:5 to create 4:5 relational tuning.
In a particular embodiment, a golden arc ratio of 1:2, 4:5, 2:3 is used to tune the chamber 216 based upon a major 3rd 4:5 ratio. The minimum width can be based on Vaastu architectural parameters. The dimension of the ratio can increase from the center point of chamber 216 to expand out to a 1:1 ratio form center point and then 1:2 ratio on both sides of center line resulting in an example sequence, 5:2:1:1:2:5.
In the example of FIG. 2 , one or more ultrasonic transducers 218 can be devices for generating vibrations to stimulate an individual 104 floating in chamber 216 . The ultrasonic transducers 218 can be coupled to the processing unit 206 to receive signals to reproduce as ultrasonic waves. In a preferred environment, the ultrasonic vibration is in a range of 0.1-10 HZ to cause micro-adjustments to the ear canal processing the vibration.
As shown in FIG. 2 a , a series of transducers 228 can be coupled to chamber 216 . In one embodiment, an ultrasonic transducer 218 has a magnetically positive first end 230 and a magnetically negative second end 232 . When positioned along opposing sides of the chamber 216 , the negative end 232 of one ultrasonic transducer 218 interacts with the positive end 504 of another ultrasonic transducer 230 to produce a magnetic field within the chamber 216 . The magnetic field can act as the tensor field to interact, in the chamber 216 , with a diamagnetic solution to produce a repulsive effect having a therapeutic effect on the individual 104 . In some embodiments, the tensor field can direct the diamagnetic solution in a constant flow around an individual floating in the diamagnetic solution. Alternatively, the chamber 216 may be filled with a saline solution.
In one embodiment, heater 220 may be a far-infrared (FIR) heater. The FIR heater 220 heats ambient air in the chamber 216 at a wavelength to facilitate FIR penetration into bone marrow, for example. The FIR heater 220 can operate at a selectable range of 4-1000 microns to provide high absorption by the human body and deep penetration of the skin.
In the example of FIG. 2 , user interface 202 can be a physical interface, a graphical interface, or another known or convenient interface for the monitoring system 204 . The user interface 202 can receive instructions from an attendant controlling the stimulation of the individual 104 . For example, the user interface 202 can be used to start and stop stimulation, select a type of music to play, control water temperature, display data about the individual, and provide any other known or convenient data about the individual receiving the stimulation.
In the example of FIG. 2 , monitoring system 204 can include devices for displaying data to an attendant monitoring stimulation of an individual in the chamber 216 . For example, a panel display, CRT (cathode ray tube) display, or other monitoring device may be used. The attendant may be a human person, an operating process within the processing unit 206 , or a combination of both.
In the example of FIG. 2 , processing unit 206 can be a system or device for analyzing biometric data from sensors. For example, processing unit 206 can be a conventional processor coupled to a memory storing instructions for execution by the processor to use in reducing the electrical signals produced by the sensors to graphs, charts, and other human interpretable representations.
In the example of FIG. 2 , storage repository 208 can include data collected from the individual 104 . As used in this paper, a repository 208 can be implemented, for example, as software embodied in a physical computer-readable medium on a general- or specific-purpose machine, in firmware, in hardware, in a combination thereof, or in any applicable known or convenient device or system. The repositories described in this paper are intended, if applicable, to include any organization of data, including trees, tables, comma-separated values (CSV) files, traditional databases (e.g., SQL), or other known or convenient organizational formats.
In an example of a system where a repository is implemented as a database, a database management system (DBMS) can be used to manage the repository. In such a case, the DBMS may be thought of as part of the repository or as part of a database server, or as a separate functional unit (not shown). A DBMS is typically implemented as an engine that controls organization, storage, management, and retrieval of data in a database. DBMSs frequently provide the ability to query, backup and replicate, enforce rules, provide security, do computation, perform change and access logging, and automate optimization. Examples of DBMSs include Alpha Five, DataEase, Oracle database, IBM DB2, Adaptive Server Enterprise, FileMaker, Firebird, Ingres, Informix, Mark Logic, Microsoft Access, InterSystems Cache, Microsoft SQL Server, Microsoft Visual FoxPro, MonetDB, MySQL, PostgreSQL, Progress, SQLite, Teradata, CSQL, OpenLink Virtuoso, Daffodil DB, and OpenOffice.org Base, to name several.
Database servers can store databases, as well as the DBMS and related engines. Any of the repositories described in this paper could presumably be implemented as database servers. It should be noted that there are two logical views of data in a database, the logical (external) view and the physical (internal) view. In this paper, the logical view is generally assumed to be data found in a report, while the physical view is the data stored in a physical storage medium and available to a specifically programmed processor. With most DBMS implementations, there is one physical view and an almost unlimited number of logical views for the same data.
In the example of FIG. 2 , sound generation unit 210 can include speakers or other devices for reproducing sound to stimulate an individual. In one embodiment, the sound generation unit 210 can operate in a range that resonates with an organ of the individual 104 , such as for example, the stomach, spleen, pancreas, lungs, kidneys, liver, heart, large intestines, small intestine, thyroid, or gallbladder. The sound generation unit 210 can be installed using waterproof speakers or transducers embedded in the chamber 216 . Alternatively, speakers could be placed above water, mobile for relocation to various positions, and otherwise installed as is known or convenient.
In the example of FIG. 2 , sensors 214 can include sensors for collecting biometric data from an individual, such as those sensors discussed in reference to monitor 108 .
In the example of FIG. 2 , water management unit 212 can include piping, tubing, or other systems for moving water and/or a solution to and from the chamber 216 . Additionally, water management unit 212 can include pumps or other devices for moving the water and/or solution to and from the chamber 216 in a continuous re-circulating slow flow.
In the example of FIG. 2 , heater 220 can be a device for altering the temperature of the fluid in the chamber 216 to the individual's 104 body temperature, or higher or lower temperatures. Heater 220 may include a sensor to determine the temperature of the fluid in the chamber 216 . In one embodiment, Heater 220 utilizes an inline water heater.
FIG. 3 depicts a flowchart of an example of a method 300 for influencing a human brain to operate at a frequency. The method is organized as a sequence of modules in the flowchart 300 . However, it should be understood that these and other modules associated with other methods described herein may be reordered for parallel execution or into different sequences of modules.
In the example of FIG. 3 , the flowchart starts at module 302 with stimulating the individual with audio waves while the individual is floating in a fluid medium, wherein the audio waves are produced as beats embedded in music. Cellular regeneration is induced by the audio waves to affect brainwave entrainment. The music can include a track that is interesting, entertaining, soothing or otherwise desirable. The beats can be embedded in this music as a second track mixed in with the music that is audible but may be barely noticeable. In this way, an individual listening to the music can be stimulated by the beat while enjoying the music. In an alternative embodiment, the beats are produced without an accompanying musical track.
In some embodiments, an audio track or audio waves is mixed with a first beat having a first frequency and a second beat having a second frequency, where the chamber 216 has a shape of a rectangle, and where sides of the rectangle have a proportion corresponding to the difference in frequency of the first frequency of the first beat and the second frequency of the second beat. Further, in some embodiments, the audio waves are projected through the aqueous solution in the chamber in a first direction at the first frequency and in a second direction at the second frequency.
One designing the music can take into account the desires of the individual to be stimulated with the beat as well as the kind of stimulation that the individual requires. For example, an individual requiring a relaxing therapeutic session can receive a beat in the theta (θ) range whereas an individual requiring a focused stimulating session can receive a beat in the alpha (α) range. Through exposure to the beat, the brain can respond to the beat and after multiple sessions the brain can begin to adopt the beat.
In the example of FIG. 3 , the flowchart continues to module 304 which monitors the biofeedback from the individual 104 for adherence to the desired frequency by utilizing one or more sensors that identify the individual's 104 operating brain frequencies. Prior to receiving the stimulation, the individual's 104 brain waves may not operate at the desired frequency. While stimulating the individual with the beat, the brain can adhere to, and begin to operate at, the desired frequency by resonating the beat's slow oscillation frequency with the hippocampus. This can induce and entrain, for example, a relaxed state or a focused state in the brain of the individual. Sensors can collect the brain waves emanating from the individual, and an attendant can monitor the brain waves for adherence to the frequency. Having monitored the individual for adherence to the frequency, the flowchart terminates.
The system 400 may be a conventional computer system that can be used as a client computer system, such as a wireless client or a workstation, or a server computer system. The system 400 includes a device 402 , I/O devices 404 , and a display device 406 . The device 402 includes a processor 408 , a communications interface 410 , memory 412 , display controller 414 , non-volatile storage 416 , I/O controller 418 , clock 422 , and radio 424 . The device 402 may be coupled to or include the I/O devices 404 and the display device 406 .
The device 402 interfaces to external systems through the communications interface 410 , which may include a modem or network interface. It will be appreciated that the communications interface 410 can be considered to be part of the system 400 or a part of the device 402 . The communications interface 410 can be an analog modem, ISDN modem or terminal adapter, cable modem, token ring IEEE 802.5 interface, Ethernet/IEEE 802.3 interface, wireless 802.11 interface, satellite transmission interface (e.g. “direct PC”), WiMAX/IEEE 802.16 interface, Bluetooth interface, cellular/mobile phone interface, third generation (3G) and fourth generation (4G) mobile phone interfaces, code division multiple access (CDMA) interface, Evolution-Data Optimized (EVDO) interface, general packet radio service (GPRS) interface, Enhanced GPRS (EDGE/EGPRS), High-Speed Downlink Packet Access (HSPDA) interface, or other interfaces for coupling a computer system to other computer systems.
The processor 408 may be, for example, a conventional microprocessor such as an Intel Pentium microprocessor or Motorola power PC microprocessor. The memory 412 is coupled to the processor 408 by a bus 420 . The memory 412 can be Dynamic Random Access Memory (DRAM) and can also include Static RAM (SRAM). The bus 420 couples the processor 408 to the memory 412 , also to the non-volatile storage 416 , to the display controller 414 , and to the I/O controller 418 .
The I/O devices 404 can include a keyboard, disk drives, printers, a scanner, and other input and output devices, including a mouse or other pointing device. The display controller 414 may control in the conventional manner a display on the display device 406 , which can be, for example, a cathode ray tube (CRT) or liquid crystal display (LCD). The display controller 414 and the I/O controller 418 can be implemented with conventional well known technology.
The non-volatile storage 416 is often a magnetic hard disk, flash memory, an optical disk, or another form of storage for large amounts of data. Some of this data is often written, by a direct memory access process, into memory 412 during execution of software in the device 402 . One of skill in the art will immediately recognize that the terms “machine-readable medium” or “computer-readable medium” includes any type of storage device that is accessible by the processor 408 .
Clock 422 can be any kind of oscillating circuit creating an electrical signal with a precise frequency. In a non-limiting example, clock 422 could be a crystal oscillator using the mechanical resonance of vibrating crystal to generate the electrical signal.
The radio 424 can include any combination of electronic components, for example, transistors, resistors and capacitors. The radio is operable to transmit and/or receive signals.
The system 400 is one example of many possible computer systems which have different architectures. For example, personal computers based on an Intel microprocessor often have multiple buses, one of which can be an I/O bus for the peripherals and one that directly connects the processor 408 and the memory 412 (often referred to as a memory bus). The buses are connected together through bridge components that perform any necessary translation due to differing bus protocols.
Network computers are another type of computer system that can be used in conjunction with the teachings provided herein. Network computers do not usually include a hard disk or other mass storage, and the executable programs are loaded from a network connection into the memory 412 for execution by the processor 408 . A Web TV system, which is known in the art, is also considered to be a computer system, but it may lack some of the features shown in FIG. 4 , such as certain input or output devices. A typical computer system will usually include at least a processor, memory, and a bus coupling the memory to the processor.
In addition, the system 400 is controlled by operating system software which includes a file management system, such as a disk operating system, which is part of the operating system software. One example of operating system software with its associated file management system software is the family of operating systems known as Windows® from Microsoft Corporation of Redmond, Wash., and their associated file management systems. Another example of operating system software with its associated file management system software is the Linux operating system and its associated file management system. The file management system is typically stored in the non-volatile storage 416 and causes the processor 408 to execute the various acts required by the operating system to input and output data and to store data in memory, including storing files on the non-volatile storage 416 .
Some portions of the detailed description are presented in terms of algorithms and symbolic representations of operations on data bits within a computer memory. These algorithmic descriptions and representations are the means used by those skilled in the data processing arts to most effectively convey the substance of their work to others skilled in the art. An algorithm is here, and generally, conceived to be a self-consistent sequence of operations leading to a desired result. The operations are those requiring physical manipulations of physical quantities. Usually, though not necessarily, these quantities take the form of electrical or magnetic signals capable of being stored, transferred, combined, compared, and otherwise manipulated. It has proven convenient at times, principally for reasons of common usage, to refer to these signals as bits, values, elements, symbols, characters, terms, numbers, or the like.
It should be borne in mind, however, that all of these and similar terms are to be associated with the appropriate physical quantities and are merely convenient labels applied to these quantities. Unless specifically stated otherwise as apparent from the following discussion, it is appreciated that throughout the description, discussions utilizing terms such as “processing” or “computing” or “calculating” or “determining” or “displaying” or the like, refer to the action and processes of a computer system, or similar electronic computing device, that manipulates and transforms data represented as physical (electronic) quantities within the computer system's registers and memories into other data similarly represented as physical quantities within the computer system memories or registers or other such information storage, transmission or display devices.
The present example also relates to apparatus for performing the operations herein. This apparatus may be specially constructed for the required purposes, or it may comprise a general purpose computer selectively activated or reconfigured by a computer program stored in the computer. Such a computer program may be stored in a computer readable storage medium, such as, but is not limited to, read-only memories (ROMs), random access memories (RAMs), EPROMs, EEPROMs, flash memory, magnetic or optical cards, any type of disk including floppy disks, optical disks, CD-ROMs, and magnetic-optical disks, or any type of media suitable for storing electronic instructions, and each coupled to a computer system bus.
The algorithms and displays presented herein are not inherently related to any particular computer or other apparatuses. Various general purpose systems may be used with programs in accordance with the teachings herein, or it may prove convenient to construct a more specialized apparatus to perform the required method steps. The required structure for a variety of these systems will appear from the description below. In addition, the present example is not described with reference to any particular programming language, and various examples may thus be implemented using a variety of programming languages.
It will be appreciated to those skilled in the art that the preceding examples are exemplary and not limiting. It is intended that all permutations, enhancements, equivalents, and improvements thereto that are apparent to those skilled in the art upon a reading of the specification and a study of the drawings are included within the true spirit and scope of the present disclosure. It is therefore intended that the following appended claims include all such modifications, permutations and equivalents as fall within the true spirit and scope of these teachings. | A technique for influencing the human brain can be applied to treat PTSD through stimulating the brain with a beat in, for example, the theta (θ) frequency to influence the brain to relax. Alternatively, the human brain can be stimulated with a beat in the alpha (α) frequency to stimulate active thinking. Over a series of treatments the brain of an individual suffering from PTSD can be influenced to operate at a normal frequency. Advantageously, as the frequency is adjusted, the symptoms of PTSD recur less often until the individual ceases to experience the symptoms or has at least experienced a decreased recurrence of the symptoms. | 0 |
BACKGROUND AND SUMMARY
The invention arose during continuing development efforts in breakaway basketball goals, including that shown in U.S. Pat. No. 4,583,732, incorporated herein by reference.
Various basketball goal assemblies are known in the art which will give or breakaway in response to a given downward threshold force on the rim such as a slam dunk. The breakaway goal protects the player by absorbing energy in order to reduce wrist, hand and arm injuries. The backboard is also protected from breaking or shattering.
The present invention provides further protection to the player by additionally enabling the rim to breakaway, or pivot, upwardly, in the event the player hits the rim with his head or another part of his body during his upward jump.
The assembly of the present invention also provides differential breakaway forces, wherein the upward threshold force causing upward pivoting of the rim is less than the downward threshold force causing downward pivoting of the rim. The greater downward threshold force before the rim pivots retains a normal rebound characteristic. There is no need for such higher threshold force before the rim will pivot upwardly. The structure of the present assembly provides a reduced upward threshold force, to in turn provide greater safety for the player.
The invention further provides breakaway in four directions for further safety. The rim can pivot rightwardly to a rightward pivoted position in each of horizontal and upwardly and downwardly pivoted positions of the rim. The rim can also pivot leftwardly to a leftward pivoted position in each of the horizontal and upwardly and downwardly pivoted positions of the rim.
In a further aspect of the invention, a backplate is provided with strength-increasing structure to prevent bowing of the backplate away from the backboard upon a slam dunk. The backplate includes a structural rib at its top in the form of a generally horizontally planar portion extending forwardly which in combination with forwardly extending sidewalls serves the additional function of covering the gap between the backplate and a forward mounting plate when the rim is pivoted downwardly, to prevent a player from pinching his fingers in such gap, without requiring the provision of a separate additional protective pinch gap shroud such as shown at 58 in incorporated U.S. Pat. No. 4,583,732.
In another aspect, the invention provides a universal basketball goal assembly selectively providing a choice between a breakaway basketball goal and a non-breakaway basketball goal, without changing the manufacturing operation producing the goal assembly. The invention enables universal parts to be produced on an assembly line, without special operations, for example coining as in incorporated U.S. Pat. No. 4,583,732, for those goals which are to be breakaway goals. Instead, a single goal assembly line is run through the factory, and designated components are merely added or deleted by the manufacturer and/or the customer for the application desired. The invention eliminates special manufacturing sequences, steps and scheduling, and achieves significant cost reduction through such universal application.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a breakaway basketball goal assembly constructed in accordance with the invention.
FIG. 2 is an exploded perspective view of portions of the structure of FIG. 1.
FIG. 3 is a side sectional view of a portion of the structure of FIG. 1.
FIG. 4 is a sectional view taken along line 4--4 of FIG. 3.
FIG. 5 is a view like FIG. 3 but showing a downwardly pivoted condition.
FIG. 6 is a view like FIG. 3 but showing an upwardly pivoted condition.
FIG. 7 is a sectional view taken along line 7--7 of FIG. 4 but showing a leftwardly pivoted position.
FIG. 8 is a view like FIG. 7 but showing a rightwardly pivoted condition.
FIG. 9 is an enlarged view of a portion of FIG. 3.
FIG. 10 is an enlarged view of a portion of FIG. 5.
FIG. 11 is like FIG. 10 but shows further downward pivoting.
FIG. 12 is like FIG. 6 but shows further upward pivoting.
DETAILED DESCRIPTION
FIG. 1 shows a breakaway basketball goal assembly 20 for mounting to a backboard 22. The assembly includes a basketball goal rim 24 having a plurality of rams 26 for holding net 28. A rear mounting plate 30, FIGS. 2 and 3, includes a generally flat planar backplate portion 32 for stationary mounting to the front of backboard 22 by bolts 34, 36, 38, 40, FIG. 4. A forward mounting plate 42, FIGS. 2 and 3, is provided by a generally inverted L-shaped member having a vertical leg 44 extending along the front of backplate portion 32 of mounting plate 30, and having a generally horizontal leg 46 extending forwardly from the top of vertical leg 44 and rigidly connected to rim 24 at weldment 48.
Compression spring 50 biases mounting plates 30 and 42 towards each other such that rim 24 is biased to a normally horizontal position, FIGS. 1 and 3. A horizontal stud 52 has its rearward end 54 formed with a T-shape or crossbar retained by mounting plate 30 and encircled by compression spring 50 bearing between vertical leg 44 of mounting plate 42 at washer 56 and a retainer nut 58 and washer 60 on the forward end of stud 52. The forward end of stud 52 is threaded and receives threaded nut 58, which provides user adjustable control of the compression of spring 50, which in turn controls the breakaway force. Spring 50 is compressed between washers 56 and 60. Washer 56 is stopped against seats 62 on vertical leg 44. A plastic bellows 64 is provided around spring 50 between washers 56 and 60 to provide a flexible expansible cover for the spring and to protect the players. Flat planar backplate portion 32 of rear mounting plate 30 has a forwardly extending humped anchor or boss portion 66 with an aperture 68 therethrough receiving stud 52 and anchoring the rearward end 54 of the stud. Spring 50 is further compressed during pivoting of front mounting plate 42 away from rear mounting plate 30, to be described. Vertical leg 44 of mounting bracket 42 has clearance holes 70, 72, 74, 76 which are larger than the heads of respective bolts 34, 36, 38, 40, to allow clearance for pivoting of vertical leg 44 toward and away from vertical backplate portion 32.
Rear mounting plate 30 has a lower guide tray portion 78 extending forwardly from the backboard. Vertical leg 44 of mounting plate 42 has a lower pivot including lower legs 80 and 82, FIG. 2, received in lower guide tray portion 78 and translatable forwardly and rearwardly therealong to provide a translational pivot. Rim 24 has a downwardly pivoted position, FIGS. 5 and 10, responsive to a downward force on the rim, wherein the lower pivot 80, 82 of vertical leg 44 of mounting plate 42 is translated rearwardly along lower guide tray portion 78 of mounting plate 30. Rim 24 has an upwardly pivoted position, FIG. 6, responsive to an upward force on the rim, wherein lower pivot 80, 82 of mounting plate 42 is translated forwardly along lower guide tray portion 78 of mounting plate 30.
Vertical leg 44 of mounting plate 42 has an upper pivot 84 pivoting about backplate portion 32 of mounting plate 30 when rim 24 is pivoted to an upwardly pivoted position, FIG. 6. Upper pivot 84 moves forwardly away from backplate portion 32 when rim 24 is pivoted to its downwardly pivoted position. Biasing spring 50 yields in response to a given downward threshold force on rim 24 to permit pivoting of the rim to its downwardly pivoted position, with upper pivot 84 moving forwardly, and lower pivot 80, 82 translated to the rear of lower guide tray portion 78. Biasing spring 50 yields in response to a given upward threshold force on rim 24 to permit pivoting of the rim to its upwardly pivoted position, with lower pivot 80, 82 translated forwardly along lower guide tray portion 78.
The noted given upward threshold force is less than the noted given downward threshold force because of the different length lever arms between spring 50 and the respective pivot points. The lever arm between upper pivot 84 and spring 50 is shorter than the lever arm between lower pivot 80, 82 and spring 50. This difference in length of lever arms provides the noted differential breakaway forces, to provide differential up and down breakaway.
Rim 24 also has a leftwardly pivoted position, FIG. 7, in each of the horizontal and upwardly and downwardly pivoted positions responsive to a leftward force on the rim. Rim 24 also has a rightwardly pivoted position, FIG. 8, in each of the horizontal and upwardly and downwardly pivoted positions responsive to a rightward force on the rim. Biasing spring 50 yields in response to a given leftward threshold force on the rim to permit pivoting of the rim about pivot 86 to its leftwardly pivoted position. Biasing spring 50 yields in response to a given rightward threshold force on the rim to permit pivoting of the rim about pivot 88 to its rightwardly pivoted position. The leftward and rightward threshold breakaway forces are the same because the length of the lever arms between spring 50 and pivots 86 and 88 are the same. The leftward and rightward breakaway force is greater than the upward breakaway force but less than the downward breakaway force because the lever arm between spring 50 and pivot 86 or 88 is longer than the lever arm between spring 50 and upper pivot 84, and is shorter than the lever arm between spring 50 and lower pivot 80, 82.
Rim 24 has a pair of support bars 90, 92 extending downwardly and rearwardly from opposite undersides of rim 24 and joined at a central support bar 94 rigidly connected to vertical leg 44 of mounting plate 42 at weldments 96, 98. Lower guide tray portion 78 of mounting plate 30 has a central upwardly turned flange 100 at the forward end thereof. Lower feet 80 and 82 are spaced along central support bar 94 on opposite right and left sides of flange 100.
Spring 50 biases rearward stud end 54 forwardly such that end 54 exerts a forward force on humped anchor portion 66. Downward pivoting of the rim further compresses spring 50 and increases the forward force exerted by stud end 54 on anchor portion 66, which in turn may cause backplate portion 32 of rear mounting plate 30 to bow forwardly away from backboard 22. Mounting plate 30 includes a generally horizontally planar upper extension portion 102 at the top of backplate portion 32 and integrally extending forwardly therefrom above horizontal leg 46 of forward mounting plate 42. Portion 102 is proximate humped portion 66 and provides a forwardly extending structural rib strengthening backplate portion 32 against bowing away from the backboard. Extension portion 102 additionally serves the function of covering the gap between backplate portion 32 and vertical leg 44 of mounting plate 42 when the rim is pivoted downwardly, to protect the fingers of the players. Mounting plate 30 further includes right and left walls 104 and 106 integrally extending forwardly from backplate portion 32 and spaced by vertical leg 44 therebetween and also covering the gap between backplate portion 32 and vertical leg 44 when the rim is pivoted downwardly. Rear mounting plate 30 thus provides all of the above noted functions and additionally provides the function of preventing a player from pinching his fingers in the noted gap, without a separate additional pinch gap shroud such as 60 in incorporated U.S. Pat. No. 4,583,732.
When rim 24 is in the downwardly pivoted position shown in FIGS. 5 and 10, feet 80, 82 are stopped against the lower end of backplate portion 32 at the rear of lower guide tray portion 78. Rim 24 has a further downwardly pivoted position as shown in FIG. 11 in which the pair of support bars 90 and 92 move downwardly past central upwardly turned flange 100 therebetween, and in which feet 80, 82 translate upwardly along backplate portion 32 of mounting plate 30.
In the upwardly pivoted position of rim 24 as shown in FIG. 6, central support bar 94 is translated partially forwardly along lower guide tray portion 78 and is spaced rearwardly of central upwardly turned flange 100. Upward pivoting of rim 24 to the position shown in FIG. 6 closes the gap 108, FIG. 3, between horizontal leg 46 of mounting plate 42 and extension portion 102 of mounting plate 30. Rim 24 has a further upwardly pivoted position as shown in FIG. 12 in which horizontal leg 46 of mounting plate 42 engages and pivots about the forward end 110 of upper extension portion 102 of mounting plate 30, and central support bar 94 translates further forwardly and is stopped against central upwardly turned flange 100, and pivot 84 translates downwardly along backplate portion 32 of mounting plate 30.
The disclosed structure also provides a universal basketball goal assembly for mounting to a backboard and selectively providing a choice between a breakaway basketball goal and a non-breakaway basketball goal without changing the manufacturing operation producing the goal assembly. Mounting plate 30 and the biasing means including spring 50 and stud 52 are omitted in applications where a non-breakaway basketball assembly is desired. In such application, vertical leg 44 of mounting plate 42 is stationarily mounted to backboard 22.
It is recognized that various equivalents, alternatives and modifications are possible within the scope of the appended claims. | A breakaway basketball goal assembly (20) includes a first mounting plate (30) for stationary mounting to the front of the backboard (22) and a second mounting plate (42) pivotally mounted to the first mounting plate and rigidly connected to the rim (24). The rim can pivot up or down in response to respective up and down forces, with the required downward force being greater, to provide differential breakaway. Left and right pivoting are also provided, to afford four way pivoting. Strength-increasing walls 102, 104, 106 are provided for the first mounting plate to prevent bowing away from the backboard and additionally serve the function of providing a protective finger pinch shroud. A universal structure selectively provides a choice between breakaway and non-breakaway applications without changing the manufacturing operation producing the goal assembly, to reduce cost. | 0 |
BACKGROUND OF THE INVENTION
[0001] Toys relate to objects, which all people use. For children toys to a big extend determine the world around them, are a powerful means of development, up-bringing and education. For adults a toy can be a pleasant souvenir that entertains, helps to relieve stress, livens up the everyday routine, or calls up memories.
[0002] Normally, toys are passive participants of interaction with the user, who using voice and imagination allots toys with speech and causes them to interact among themselves. For many years, we have known toys reacting to the activation by the user of their parts, for example, giving sounds when pressed. If toys are given an ability to interact to a certain extend independently with each other, thus, adding personality elements to each toy, letting them demonstrate emotions and respond to external actions and to other toys, the toy world will liven up, become more diverse and more instructive.
[0003] Voice-responsive “talking” toy is described in U.S. Pat. No. 4,221,927, to Dankman, et al, 1980. This invention discloses a toy, which in response to a complex sound such as human speech, generates a train of audio pulses. The pulses are psuedo-random with respect to frequency composition and to duration. The length of the pulse train is made random, too. Thus, the toy simulates syllabic speech. In this toy mouth motions are also simulated when sounds are pronounced.
[0004] This toy imitates speech interaction with a person. However, this toy can not form different sounds in reply to different effects, that is create simulation of different responses reflecting its personality.
[0005] A talking doll responsive to external signal is described in U.S. Pat. No. 4,840,602 to Rose, 1989. A remote source provides a narration and transmits a radio frequency signal providing binary coded data. The doll has a radio frequency receiver which receives encoded data from the remote signal source, a memory in which speech data is stored, a speech synthesizer and a central processing unit, which analyzes received data and accesses the memory for selected speech data to simulate the doll's response to portions of the narration from the remote signal source. Thus, either a conversation or a story told together with the doll is simulated.
[0006] U.S. Pat. No. 4,857,030 to Rose, 1987 exposes conversing dolls. Two or more dolls with speech synthesizing systems appear to intelligently converse while signaling each other via a radio frequency transmission to indicate what has been spoken, and to request a response which is intelligent with respect to the synthesized speech of the first doll. Additionally, the synthesized speech is made responsive to various positions of the doll or the actuation of certain sensors on the doll, or even the motion of the doll. The choice of a program defining the contents of conversation between dolls is every time carried out as a random selection from several programs.
[0007] The last two inventions have certain limitations. All dolls that participate in a conversation have identical programs. Every time roles are given to the dolls by a random selection. Therefore, it is not possible to give any doll a permanent role or personality. Further, the interactions among dolls will be identical if we take, for example, different combinations of two dolls out of three available. Therefore, the possibilities to diversify the game with such dolls are rather restricted.
[0008] There is also an interactive doll shown in U.S. Pat. No. 5,752,880 to Gabai et al, 1998. In this patent apparatus for a wireless computer controlled toy system is disclosed. The invention allows the user “to converse” with dolls. The phrases pronounced by the user are perceived by the device located in a doll and are broadcast to the computer, which will recognize these phrases, select answering phrases, synthesize speech and transmit it via radio back to the device inside the doll, that plays back answers. This patent also points out the possibility of interaction among dolls in such system.
[0009] However, this invention also has its limitations. The use of the computer makes the system expensive and complicated. Each doll taken separately is passive and can not reproduce any response without a link to the computer. The introduction of new dolls into the system requires execution of a series of operations with the control program on the computer, the task too difficult for the majority of users, especially for children.
OBJECTS AND SUMMARY OF THE INVENTION
[0010] It is the object of the present invention to provide interacting toys, each of which can transmit information about itself to other toys and receive information transmitted by other toys, and to respond to other toys according to the received information about other toys, so that responses of toys to each other imitate their mutual sympathy, antipathy and other interpersonal mutual relations.
[0011] Another object of the present invention is to provide interacting toys, each of which differently responds to other toys and to the activation by the user so that responses of toys imitate personalities and temperaments of characters represented by them, and mutual relations among these characters.
[0012] The further object of the present invention is to provide interacting toys, each of which will have the individuality so that even two toys of one type will have different behavior when interacting among themselves and with other toys, and also when affected by the user.
[0013] The next object of the present invention is to provide interacting toys that enable the user to add new toys to the existing toy community, thus getting new variants of behavior and mutual relations among toys.
[0014] The further object of the present invention is to provide interacting toys, the response of each of which to other toys and to the activation by the user imitates different emotional conditions of the personality represented by this toy and can have different degrees or intensities corresponding to degrees of an emotional condition.
[0015] The further object of the present invention is to provide interacting toys, the response of each of which gradually fades after the user terminates his/her activation and after other toys of the type are removed, and the time required for the response to fade can be preset differently for different toys to imitate personality features of characters represented by the toys.
[0016] The further object of the present invention is to provide interacting toys, which responses to other toys and the activation by the user to some extent depend on a random factor so that to make behavior of toys more diverse and to make playing with them more interesting.
[0017] The further object of the present invention is to provide interacting toys, which will form an open system that will give toy manufacturers a possibility to produce new toys, interacting among themselves, as well as with toys manufactured before, and add more and more new characters to the toy sets available on the market, thus, supporting interest of consumers to the product line.
[0018] The further object of the present invention is to provide interacting toys, the information exchange between which would be ensured by simple and cheap means to keep costs to the minimum.
[0019] The further object of the present invention is to provide interacting toys, in which different characters and different responses would be ensured by maximal unification of its circuits to reduce production costs of a great number of toy groups.
[0020] These and other objects of the invention are achieved in interacting toys, the description of which will be given below.
[0021] Interacting toys consist of a first toy and a second toy. The first toy contains a housing defining its shape and appearance, means for transmitting of messages containing information about this first toy, means for receiving of messages transmitted by the second toy and containing information about the second toy, means for reproduction of responses of the first toy to the second toy and to the activation by the user, storage means containing data about responses of the first toy to different second toys and to different types of the activation by the user. The second toy has the similar structure.
[0022] The first toy periodically sends messages about itself to the second toy and receives messages from the second toy. If the first toy detects the presence of the second toy, it responds to this fact, for example, by producing sounds that characterize the response of the first toy to the second toy. A type of response and degree of its intensity are determined by the information received from the second toy. The second toy operates similarly. Thus, simulation of different mutual relations between toys and the range of toys behavior models are provided.
[0023] Other objects, features and advantages of the invention shall become apparent as the description thereof proceeds when considered in connection with accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] [0024]FIG. 1 shows two interacting toys and the structure of each of them;
[0025] [0025]FIG. 2 shows an electrical structural circuit of a toy;
[0026] [0026]FIG. 3 shows areas of data in a read-only memory (ROM);
[0027] [0027]FIG. 4 shows a structure of Sound Responses area in ROM;
[0028] [0028]FIG. 5 shows a parameter table Id-LUT for determination of a response to the presence of the known toy;
[0029] [0029]FIG. 6 shows a parameter table OP-LUT for determination of a response to the presence of an unknown toy;
[0030] [0030]FIG. 7 shows a parameter table Eff-LUT for determination of a response to an external action;
[0031] [0031]FIG. 8 shows a flowchart of a program executed by the controller in a toy;
[0032] [0032]FIG. 9 shows a flowchart of a subroutine of sensors interrogation;
[0033] [0033]FIG. 10 shows a flowchart of a receiver interrogation subroutine;
[0034] [0034]FIG. 11 shows a flowchart of a response determination subroutine;
[0035] [0035]FIG. 12 shows a flowchart of a subroutine of determination of a response to the presence of another toy;
[0036] [0036]FIG. 13 shows a flowchart of a subroutine of determination of a response to an external action;
[0037] [0037]FIG. 14 shows a flowchart of a subroutine of determination of a response in the absence of other toys and external actions;
[0038] [0038]FIG. 15 shows a flowchart of a subroutine of testing a condition for the beginning of response forming;
[0039] [0039]FIG. 16 shows a flowchart of a subroutine of testing a condition for transition to Power Down mode.
DETAILED DESCRIPTION OF THE INVENTION
[0040] In the beginning we will provide the general principles of interacting toys structure and operation.
[0041] [0041]FIG. 1 shows the first toy 1 and the second toy 2 , that interact with one another. Each of toys 1 , 2 can have appearance of a doll, fantastic character, real or fantastic animal, or an object. Each of toys 1 , 2 has housing 3 . Inside housing 3 of each toy there are electronic block 4 , photoreceptor 5 , and light-emitting diode 6 . In different parts of toys 1 and 2 sensors 7 and 8 are placed. In appropriate places of housing 3 there are speaker 9 and supply unit 10 .
[0042] Photoreceptor 5 is a regular photodiode of a short-wave infrared (IR) range. Light-emitting diode 6 also radiates in a short-wave IR range. Mini switches can be used as sensors 7 and 8 . The switches are locked when pressed and are unlocked when the pressure is terminated. Supply unit 10 can contain one or several batteries. In the preferred embodiment of the present invention,
[0043] [0043]FIG. 7 shows a parameter table Eff-LUT for determination of a response to an external action;
[0044] [0044]FIG. 8 shows a flowchart of a program executed by the controller in a toy;
[0045] [0045]FIG. 9 shows a flowchart of a subroutine of sensors interrogation;
[0046] [0046]FIG. 10 shows a flowchart of a receiver interrogation subroutine;
[0047] [0047]FIG. 11 shows a flowchart of a response determination subroutine;
[0048] [0048]FIG. 12 shows a flowchart of a subroutine of determination of a response to the presence of another toy;
[0049] [0049]FIG. 13 shows a flowchart of a subroutine of determination of a response to an external action;
[0050] [0050]FIG. 14 shows a flowchart of a subroutine of determination of a response in the absence of other toys and external actions;
[0051] [0051]FIG. 15 shows a flowchart of a subroutine of testing a condition for the beginning of response forming;
[0052] [0052]FIG. 16 shows a flowchart of a subroutine of testing a condition for transition to Power Down mode.
DETAILED DESCRIPTION OF THE INVENTION
[0053] In the beginning we will provide the general principles of interacting toys structure and operation,
[0054] [0054]FIG. 1 shows the first toy 1 and the second toy 2 , that interact with one another. Each of toys 1 , 2 can have appearance of a doll, fantastic character, real or fantastic animal, or an object. Each of toys 1 , 2 has housing 3 . Inside housing 3 of each toy there are electronic block 4 , photoreceptor 5 , and light-emitting diode 6 . In different parts of toys 1 and 2 sensors 7 and 8 are placed. In appropriate places of housing 3 there are speaker 9 and supply unit 10 .
[0055] Photoreceptor 5 is a regular photodiode of a short-wave infrared (IR) range. Light-emitting diode 6 also radiates in a short-wave IR range. Mini switches can be used as sensors 7 and 8 . The switches are locked when pressed and are unlocked when the pressure is terminated. Supply unit 10 can contain one or several batteries. In the preferred embodiment of the present invention, each of toys 1 and 2 taken separately responds to the user activation realized as pressing sensors 7 and 8 . Responses of each of toys 1 , 2 are sounds synthesized in electronic block 4 and played back through speaker 9 .
[0056] The first toy 1 sends message 11 , which contains information about the first toy 1 . The second toy 2 sends message 12 , which contains information about the second toy 2 . In each toy the sent message is generated in the form of an electrical signal by electronic block 4 and is radiated in the form of modulated IR radiation by light-emitting diode 6 . Each of toys 1 , 2 receives messages transmitted by another toy with the help of photoreceptor 5 . The received message is decoded in electronic block 4 .
[0057] Having received message 12 from the second toy 2 and having selected information about the second toy 2 from message 12 , the first toy 1 reacts to the presence of the second toy 2 by reproduction of a sound response, which imitates an emotional response of the first toy 1 when meeting the second toy 2 . Similarly, the second toy 2 , having received message 11 from the first toy 1 and having selected information about the first toy 1 from message 11 , reacts to the presence of toy 1 by reproduction of a corresponding sound response.
[0058] Sound responses played back by each of toys 1 , 2 correspond to the appearance of the toy. For example, bears can growl, cats can mew and purr, a fantastic animal can give extraordinary fantastic sounds. It is also possible to synthesize sounds that would resemble elements of human speech-simple words and interjections.
[0059] Each of toys 1 , 2 has several types of responses corresponding to different emotional conditions of the character represented by this toy. The type of response is further denoted as RType. In the preferred embodiment of the present invention RType can receive four values: 3-Joy, 2-Sadness, 1-Anger, and 0-Fear. There is a reference sound that corresponds to each condition. For example, a toy dog can express its joy by sounds imitating cheerful barking, its sadness-by whining, its anger-by roaring or angry barking; it expresses its fear by growling that goes into whining. Common notions can serve a base for selecting sounds or voice messages that characterize different emotional states of any toy.
[0060] Each type of response has several degrees. The value of response degree is further designated RDeg. In the preferred embodiment of the present invention, RDeg can receive four values: 0, 1, 2, 3. RDeg=0 corresponds to a neutral state, which is identical for all emotional conditions. RDeg=1 corresponds to minimal level of an emotion, RDeg=2 corresponds to a medium level, and RDeg=3-to a maximal emotion level. Synthesized sounds depend on a degree of response. For different toys these dependencies can be expressed as a change of volume level, of content frequency, of intervals between repetitions of synthesized sound patterns, etc. The character of the sound can also change, for example from growling to loud barking when expressing anger in case of the above-mentioned toy dog.
[0061] The response of toy 1 or 2 taken separately to the activation by the user is determined by the character represented by this toy, and by which of sensors 7 and 8 the user has activated. During the interaction of two toys 1 and 2 responses of each of them depend on the fact, what toy exactly is its partner. In all cases the type and degree of response can have a random component. For example, when Winnie-the-Pooh meets Mickey Mouse, both toys can express mutual moderate joy. But when Mickey Mouse meets Cat Basilio, Mickey will be slightly frightened and the Cat will react by demonstrating anger.
[0062] The response of each of interacting toys 1 , 2 gradually fades after removal of the other toy, that is value RDeg gradually decreases. The response of toy 1 or 2 taken separately gradually fades after the user stops activation of sensor 7 or 8 . The rate of response fading depends on properties of the toy, that imitate temperament of the character represented by this toy. Later, after complete fading of a response, that is after value RDeg becomes equal to zero, electronic block 4 goes to Power Down Mode, when power consumption from power supply 10 becomes very low. To activate the toy the user has to press sensors 7 and 8 simultaneously.
[0063] Further, we will procede to the detailed description of the preferred embodiment of the present invention.
[0064] As shown in FIG. 2, electronic block 4 contains controller 21 comprising Read-Only Memory (ROM) 22 , Random Access Memory (RAM) 23 and timer 24 . One of the outputs of controller 21 is coupled with transmitting circuit 25 , to the outputs of which light-emitting diode 6 is attached. One of the inputs of controller 21 is connected to the output of receiving circuit 26 , to inputs of which photoreceptor 5 is attached. Another output of controller 21 is connected with sound reproducing circuit 27 , an output of which is connected to speaker 9 . Sensors 7 and 8 are attached to other inputs of controller 21 . Sensors 7 and 8 are also attached to inputs of logic gate AND 28 , the output of which is connected with Reset input of controller 21 . Power is supplied from supply unit 10 to electronic block 4 .
[0065] Microprocessor AT89C52 by Atmel Inc., USA, that has 8 Kbytes ROM 22 , 256 bytes RAM 23 and programmed timer 24 can be used as controller 21 . Timer 24 can serve to interrupt the running of the program. The particular bits of input/output ports of controller 21 fulfill the functions of its inputs and outputs in the described embodiment of the invention. Controller 21 realized on the above-mentioned microprocessor has Power Down Mode, wherein power consumption is minimum. Controller 21 exits Power Down Mode, when signals simultaneously from both sensors 7 , 8 are sent through logic gate AND 28 to Reset input of controller 21 .
[0066] Transmitting circuit 25 contains a transistor switch and a resistor for forming current pulses through light-emitting diode 6 . Receiving circuit 26 contains a preamplifier, a filter and a comparator. Such circuits are well known in the art. Sound reproducing circuit 27 contains a digital-to-analog converter (DAC) and an amplifier, which can be implemented on any appropriate integrated circuit.
[0067] Controller 21 executes the program recorded in ROM 22 . To do so, it interrogates sensors 7 , 8 and receiving circuit 26 , sends data to sound reproducing circuit 27 for forming sound responses depending on the type of the activation by the user and on signals received from other toys, and sends data to transmitting circuit 25 for a message transmission. The program run on controller 21 will be described in detail later. During operation of the device, data received through receiving circuit 26 and variables used by the program are stored in RAM 23 . Timer 24 periodically interrupts execution of the main program to run a subroutine of transmitting a message through transmitting circuit 25 and light-emitting diode 6 .
[0068] Each message 11 transmitted by the first toy 1 contains a starting part, which allows electronic block 4 in the second toy 2 to detect the beginning of the message and to begin its reception, and parameters identifying the first toy 1 . Each message 12 transmitted by the second toy 2 has the same structure. Messages format and method of transmitted parameters coding can be the same as in the widely known IR remote-control units. For example, different duration of pulse-to-pulse spacings of IR radiation can correspond to logic zeros and logic unites.
[0069] As it is shown in FIG. 3, ROM 22 consists of some areas, each of which has a special assignment. The program run by controller 21 is stored in control program area 31 . This program is identical for all toys made according to the present invention.
[0070] As shown in FIG. 4, Sound Responses area 32 contains Address map 41 and Sound Programs area 42 . Address map 41 contains starting addresses of sound response reproduction programs for all the possible couples of values of response type RType and response degree RDeg. As in the preferred embodiment of the present invention the number of such possible couples is equal to twelve, address table 41 contains twelve addresses of programs Adr 1 . . . Adrl 2 . Sound Programs area 42 contains sound responses reproduction programs. The amount of memory occupied by different programs can be different. Sound Program I is disposed in ROM 22 starting with address Adrl, Sound Program 2 is disposed in ROM 22 starting with address Adr 2 , etc.
[0071] Sound response reproduction programs are different for different types of toys. In each toy there are different sound response reproduction programs for different values of response type RType and response degree RDeg. Different RType and RDeg result in playing back sounds of different types, volume levels, timbres, etc.
[0072] Constants area 33 contains parameters describing the given toy during the interaction with other toys. The first of these parameters is ID identifier, which is unique for each type of toys according to the present invention. In the preferred embodiment, ID is a three-digit decimal number. ID is a part of each message transmitted by each toy for reception by another toy. As it will be described below, each toy “knows” beforehand identifiers of several other toys, that thus are familiar to it.
[0073] Further, Constants area 33 contains permanent parameters describing the given toy when it is interacting with other toys that “do not know” it in the above-mentioned sense. There are two such parameters in the considered embodiment: Size, describing dimensions or sizes, and Appearance, describing appearance. Parameter Size can have values 0-small, 1-it is smaller than medium, 2-medium, 3-large. Parameter Appearance can have values 0-terrible, 1-unpleasant, 2-pleasant, 3-beautiful. Parameters Size and Appearance are given to each type of toys and are a part of each message transmitted by the given toy for the reception by another toy.
[0074] Besides, Constants area 33 contains other parameters that define features of sound responses of the given toys type. Information about these parameters will be provided later when the programs are discussed.
[0075] Identificators Look-Up Table (Id-LUT) 34 contains identifiers ID of toys known to the first toy 1 , and parameters that determine a response of the first toy 1 to every toy, known to it. Object Parameters Look-Up Table (OP-LUT) 35 contains parameters that define a response of the first toy 1 to a toy unknown to it, that is a toy, ID of which is not in Id-LUT 34 , but this toy has sent its parameters of Size and Appearance to the first toy 1 . Effect Look-Up Table (Eff-LUT) 36 contains parameters defining the response of the first toy 1 to the activation by the user.
[0076] Each of Id-LUT 34 , OP-LUT 35 , Eff-LUT 36 contains the values of four parameters: Rb-base value of the response type, Db-base value of a response degree, WR-bandwidth of random component values of the response type, WD-bandwidth of random component values of a response degree.
[0077] The response type is found by the following equation:
RType Round ( Rb+ (Random ( WR )− WR/ 2)/100), (1)
[0078] where Random (X) is a function returning a random integer from interval ( 0 , X), X is a positive integer, Round (Y) is a function returning an integer proximate to real argument Y. If in the result of calculation of equation (1), RType<0, then RType is assigned the value of 0, and if RType>3, then RType is assigned the value of 3.
[0079] The response degree is found by the following equation:
RDeg=Round ( Db+ (Random ( WD )− WD/ 2)/100). (2)
[0080] If in the result of calculation of equation (2), RDeg<0, then RDeg is assigned the value of 0, and if RDeg>3, then RDeg is assigned the value of 3.
[0081] [0081]FIG. 5 shows an example of table Id-LUT 34 in ROM 22 for the first toy 1 . The Id-LUT 34 in the second toy 2 has the same structure, but its parameter values can be different. ID values of toys familiar to the first toy 1 are given in column ID. The number of rows in Id-LUT 34 can be different for different types of toys depending on the number of other toys types familiar for the toys of the given type. In columns Rb, Db, WR, WD the values of corresponding parameters are given. These values are used in equations (1) and (2) to compute the values of response type RType and response degree RDeg of the first toy 1 , when the first toy 1 has received a message from the second toy 2 , ID value of which is present in ID column.
[0082] [0082]FIG. 6 shows an example of table OP-LUT 35 in ROM 22 for the first toy 1 . OP-LUT 35 in the second toy 2 has the same structure, but its parameter values can be different. In columns Size and Appearance there are Size and Appearance values accordingly. In the preferred embodiment of the present invention, the number of rows in table OP-LUT 35 is equal to 16 . In columns Rb, Db, WR, WD parameter values Rb, Db, WR, WD accordingly are given. These values are used in equations (1) and (2) to compute the values of response type RType and response degree RDeg of the first toy 1 , when it has received a message from the second toy 2 , ID value of which is not given in ID column of Id-LUT 34 of the first toy 1 .
[0083] [0083]FIG. 7 shows an example of table Eff-LUT 36 in ROM 22 for the first toy 1 . Eff-LUT 36 in the second toy 2 has the same structure, but its parameter values can be different. In NSens column values of activation number are given. In the preferred embodiment of the present invention, NSens= 1 corresponds to activation of sensor 7 , and NSens=2 corresponds to activation of sensor 8 . In columns Rb, Db, WR, WD values of the corresponding parameters are given. These values are used in equations (1) and (2) to compute values of response type RType and response degree RDeg of the first toy 1 , when the user activates one of sensors 7 , 8 .
[0084] Further, the detailed description of the program run on controller 21 in the first toys 1 is considered. The program in the second toy 2 is the same as in the first toy 1 , but the numerical parameters can be different. The following global variables will be used in the description of the main program and subroutines:
[0085] N is a counter of the main program cycle runs;
[0086] NM is a number of the main program cycle runs, without response reproduction between two reproductions of response;
[0087] NR is a counter of fulfilled reproductions of a sound response;
[0088] NRM is a number indicating how many times sound response reproduction is executed, before response degree decreases by a unity, when there is no interaction with another toy or the user;
[0089] NSens is a variable, that shows what sensor is activated by the user;
[0090] FR is a logic variable, which shows if there is a message received from the second toy 2 (FR=True), or there is no message from the second toy 2 (FR=False).
[0091] As shown in FIG. 8, running of the program starts in block 51 , when power is switched on or when signals are received simultaneously from both sensors 7 , 8 via logic gate AND 28 to controller 21 Reset input. In block 52 the initialization of global variables is fulfilled: N=0, NM=0, NR=0, NRM=0, NSens=0, FR=False. In the same block, interruptions of the main program by timer 24 are enabled, and a value of the period of these interruptions is installed by loading of the corresponding number into timer 24 .
[0092] Then, sensors interrogation subroutine 53 , which determines value NSens, and receiver interrogation subroutine 54 , which determines a value of logic variable FR are executed. After that response determination subroutine 55 is executed, that in accordance with found values NSens and FR determines a response type RType and a response degree RDeg for the response to be formed. Three above-mentioned subroutines will be described in detail below.
[0093] In logic block 56 , the program determines, whether it is necessary to reproduce a sound response in the current run of the cycle. If the answer is positive, response forming subroutine 57 is executed. This subroutine finds out in Sound Responses area 32 in ROM 22 (FIG. 4) the address of the sound response reproducing program in accordance with the found values RType and RDeg and calls this subroutine. Programs of reproducing of sound responses are well known in the art, so there is no need to describe them.
[0094] In the opposite case, the program continues to logic block 58 , in which it determines, whether it is time to go into Power Down Mode. This is done, if during a certain number of the main program cycles there was neither the user activation, nor reception of a message from the second toy 2 . If in logic block 58 the answer “True” is obtained, in block 59 the program prohibits interruptions by timer 24 , after this controller 21 goes to Power Down Mode, in which it will remain until the user activates both sensors 7 , 8 simultaneously. If in logic block 58 the answer “False” is obtained, the program returns to the beginning of the cycle in block 53 .
[0095] Parallel to the described main program, the subroutine caused by interruptions from timer 24 is executed. The flowchart of this subroutine is shown on the right side of FIG. 8. This subroutine begins, when an interrupt signal from timer 24 is received (block 60 ). Then parameter transmitting subroutine 61 is executed. Controller 21 according to the predetermined transfer protocol sends to transmitting circuit 25 starting bits of a message, then ID value of the first toy 1 , then Size and Appearance values of the first toy 1 . After that, the interruption subroutine terminates (block 62 ). Thus, the first toy 1 transmits periodically with period TInt its parameters, so that the second toy 2 could receive them.
[0096] Further, we will describe flowcharts of subroutines called from the main program. As shown in FIG. 9, after entering subroutine of sensors interrogation 53 (block 71 ), controller 21 interrogates the first sensor 7 checking, if the user is activating this sensor (block 72 ). If the user is activating the first sensor 7 , variable NSens gets the value of 1 (block 73 ), then subroutine 53 terminates in block 77 . If the user does not activate the first sensor 7 , controller 21 interrogates the second sensor 8 (block 74 ). If the second sensor 8 is activated, variable NSens gets the value of 2 (block 75 ), then subroutine 53 terminates in block 77 . If the second sensor 8 is not activated, variable NSens gets the value of 0 (block 76 ), and subroutine 53 terminates in block 77 .
[0097] Thus, as a result of execution of subroutine 53 , variable NSens receives the value of 1 or 2 , if the user is pressing sensor 7 or sensor 8 accordingly, or the value of 0 , if the user does not press one of sensors 7 , 8 .
[0098] [0098]FIG. 10 shows the flowchart of receiver interrogation subroutine 54 , which interrogates receiving circuit 26 . In this flowchart the following designation are used: K is a counter of loops of waiting for an output signal of receiving circuit 26 ; KM is a maximal number of loops of waiting for an output signal of receiving circuit 26 .
[0099] After entering subroutine 54 (block 81 ) variable K gets the value of 0 (block 82 ). Then in logic block 83 , the program checks if there are impulses on the output of receiving circuit 26 . To do this, the program can, for example, check, if the voltage level on the output of receiving circuit 26 has changed during a given time interval. The detailed description of this procedure is not required, as such operations are well known, for example, they are used in remote control devices for signal reception. If impulses are not detected on the output of receiving circuit 26 , it is concluded, that no message is received from the second toy 2 , and the program continues to block 84 , where value K increases by a unit.
[0100] Further, the program checks in logic block 85 , whether the maximal number KM of loops of waiting for the output signal at receiving circuit 26 is reached. If this number is not reached yet, that is K<KM, the program returns to the beginning of the cycle of waiting to block 83 . If K=KM, the cycle of waiting is terminated, logic variable FR gets value “False” (block 86 ), and subroutine 54 completes in block 91 .
[0101] If checking in block 83 determines, that there are impulses on the output of receiving circuit 26 , the program continues to logic block 87 , in which it checks value K. If K =0, it means that the execution of receiver interrogation subroutine 54 started, when the message transmission by the second toy 2 has already began. In this case, the program continues to logic block 88 , in which it waits for the message transmission to end, that is the absence of impulses at the output of receiving circuit 26 . When the transmission of a current message is completed, the program returns to logic block 83 to begin the cycle of waiting for the transmission of the next message by the second toy 2 . The waiting loop has already been described.
[0102] If checking in logic block 87 determines, that K>0, it means, that the message transmission by the second toy 2 has just began, as by the time impulses are detected, several loops of waiting cycle have been fulfilled. In this case the program continues to data reception subroutine 89 . In duration of this subroutine, controller 21 reads data from the output of receiving circuit 26 , selects from the received data the values of ID, Size and Appearance of the second toy 2 , and saves these values in the corresponding variables in RAM 23 . The detailed description of data reception subroutine 89 is not required, as such subroutines are well known, for example, in IR remote control devices.
[0103] Then, in block 90 logic variable FR receives value “True” that displays availability of the second toy 2 and successful reception of parameters transmitted by the second toy 2 . Then, subroutine 54 terminates in block 91 .
[0104] [0104]FIG. 11 depicts the flowchart of response determining subroutine 55 . After entering this subroutine in block 111 , controller 21 checks logic variable FR (block 112 ). If FR is true, that is in subroutine 54 parameters of the second toy 2 were received, variable NR gets the value of 0 (block 113 ), then subroutine of determining response to another toy 114 is carried out, in which response type RType and response degree RDeg are determined. Then subroutine 55 terminates in block 119 .
[0105] If FR is false, that is the second toy 2 is not present, the program continues to block 115 , in which controller 21 checks value NSens. If NSens>0, that is the activation by the user of one of sensors 7 , 8 is detected, then variable NR gets the value of 0 (block 1116 ). After that, subroutine of determining response to an external action 117 is fulfilled, in which response type RType and response degree RDeg are determined. Then subroutine 55 terminates in block 119 .
[0106] If NSens=0, that is the user is not activating sensors 7 , 8 , subroutine of determining a fading response 118 is carried out, in which response type RType and response degree RDeg for the fading response are determined. Then subroutine 55 terminates in block 119 .
[0107] As it follows from the description of subroutine 55 , the availability of the second toy 2 has the priority over the activation by the user of sensors 7 , 8 . If there is the second toy 2 available, that is FR is true, the type and degree of response are determined in subroutine 114 , and the activation by the user of sensors 7 or 8 is ignored. The variable NR, as it will be shown later, will be used for determination of the response fading when there is no other toy available and the user does not interact with the given toy. If there is the second toy 2 or the user activation, variable NR is set to zero in blocks 113 or 116 accordingly.
[0108] [0108]FIG. 12 shows the flowchart of subroutine of determining a response to another toy 114 . After entering this subroutine in block 121 , controller 21 checks in logic block 122 , whether the second toy 2 is known to the first toy 1 . To do so, controller 21 sequentially compares ID value received from the second toy 2 with values of all identifiers in ID column in Id-LUT 34 in ROM 22 . If there is a value of identifier coinciding with the received ID value in Id-LUT 34 , logic block 122 gives the answer “True”, that is the second toy 2 is familiar to the first toy 1 . In this case, the program continues to block 123 , in which controller 21 reads parameters Rb, Db, WR and WD (their meaning was explained above) from Id-LUT 34 row containing a required identifier.
[0109] If in Id-LUT 34 there is no identifier value coinciding with the received ID value, logic block 122 gives the answer “False”, that is the second toy 2 is not familiar. In this case, the program continues to block 124 , in which controller 21 finds in OP-LUT 35 in ROM 22 a row corresponding to received Size and Appearance parameters of the second toy 2 , and reads parameters Rb, Db, WR and WD from the row found in OP-LUT 35 .
[0110] Then, in both mentioned cases, controller 21 , in accordance with read values Rb, Db, WR and WD, using equation (1) calculates the value of response type RType (block 125 ) and using equation (2) calculates the value of response degree RDeg (block 126 ). The operations executed in blocks 125 and 126 were fully explained when equations (1) and (2) were considered.
[0111] Next, controller 21 in block 127 computes value NRM, that, as it was explained earlier, displays the number of sound responses before lowering response degree by a unit, when there is no interaction either with the second toy 2 or with the user. In the preferred embodiment of the present invention, value NRM is calculated by the following equation:
NRM=NRMb+ Random ( WNRM ), (3)
[0112] where NRMb is a base value of NRM; WNRM is a bandwidth of a random component of NRM. Values NRMb and WNRM characterize fading rate of the toy response. The process of response fading will be described later in detail. Values NRMb and WNRM for the first toy 1 are stored in Constants area 33 in ROM 22 of the first toy 1 .
[0113] After calculation of NRM, the subroutine terminates in block 128 .
[0114] [0114]FIG. 13 shows the flowchart of subroutine of determining response to external effect 117 . After entering this subroutine in block 131 , controller 21 finds out in Eff-LUT 36 in ROM 22 the row corresponding to NSens value calculated before, that is corresponding to a sensor activated by the user, and reads from this row parameters Rb, Db, WR and WD (block 132 ). Then, controller 21 with the help of read values Rb, Db, WR and WD, using the equation (1) calculates the value of response type RType (block 133 ), using equation (2) calculates the value of response degree RDeg (block 134 ) and using equation (3) calculates values NRM (block 135 ). All these calculations are done in the same way as in subroutine 114 described before. Then, subroutine 117 terminates in block 136 .
[0115] [0115]FIG. 14 shows the flowchart of response fading determining subroutine 118 . After entering this subroutine in block 141 , controller 21 checks a current value of response degree RDeg (block 142 ). If RDeg=0, subroutine 118 immediately terminates in block 147 . In this case, the response degree of the toy is already equal to zero, and its further reduction is impossible.
[0116] If in block 142 it is found out, that RDeg>0, the program continues to block 143 , in which it checks, whether variable NR has reached value NRM. If the answer to this question is negative, that is NR<NRM, subroutine 118 terminates in block 147 . In this case response degree RDeg of the toy does not change, as NRM of response reproductions has not been fulfilled yet.
[0117] If in block 143 it is found out, that NR=NRM, block 144 is executed, in which controller 21 using equation (3) calculates a new value NRM. Then, the value of response degree RDeg decreases by a unit (block 145 ), variable NR gets the value of 0 (block 146 ), and subroutine 118 terminates in block 147 .
[0118] Thus, if the first toy 1 in the result of receiving data from the second toy 2 or in the result of the activation by the user has transferred into the condition characterized by response type RType and response degree RDeg, and then there are no messages transmitted by the second toy 2 or no activation by the user for a sufficiently long time, the degree of response RDeg gradually decreases, until it becomes equal to zero. As it was explained, when equation ( 3 ) was described, parameters NRMb and WNRM are set for each toy by recording in Constants area 33 in ROM 22 . There can be toys with a response fading fast and with a response fading slowly that allows to imitate different temperaments of the characters represented by the toys. Availability of a random component in equation (3) diversifies behavior of the toy.
[0119] [0119]FIG. 15 shows the flowchart of subroutine 56 that defines whether it is necessary to reproduce a response in the current loop of the main program cycle. After entering this subroutine in block 151 , controller 21 checks a current value of response degree RDeg. If checking in logic block 152 gives the negative answer, that is RDeg=0, the program continues to block 154 , in which value N is increased by a unit. Then, in block 155 , subroutine 56 returns the logic value “False” and terminates.
[0120] If checking in block 152 gives the positive answer, that is RDeg>0, the program continues to block 153 , in which it compares a current value N with value NM, which reflects a number of the main program cycles executed without response reproduction. If in block 153 it is found out, that N<NM, that is it is early to play back the response, the program continues to block 154 , in which value N increases by a unit. Then, in block 155 , subroutine 56 returns the logic value “False” and terminates.
[0121] If it was found out that N=NM, then the program continues to block 156 , in which variable N gets the value of 0. Then in block 157 , controller 21 calculates a new value NM, then subroutine 56 returns the logic value “True” and terminates in block 158 . After that, subroutine 57 of response reproducing is executed, in which value NR is increased by a unit.
[0122] In the preferred embodiment of the present invention, value NM is found according to the following equation:
NM= ( NMb+ Random ( WNM )) * (4−RDeg), (4)
[0123] where NMb is base value NM; WNM is a bandwidth of a random component of NM. Values NMb and WNM characterize frequency of repetitions of response reproduction by the first toy 1 to the presence of the second toy 2 and to the activation by the user. Values NMb and WNM for the first toy 1 are stored in Constants area 33 in ROM 22 . The factor (4−RDeg) reflects the influence of the current value of response degree RDeg on the frequency of repetitions of response reproductions. The higher the value RDeg, that is the higher the intensity of the response, the less the above-mentioned factor and, therefore, the less the value NM, that is responses are played back more often. Thus, the frequency of response reproductions is one of characteristics of this response intensity.
[0124] The availability of a random component in equation (4) provides additional diversity of the toy behavior, as value NM is computed separately for each interval between response reproductions, and these intervals can change randomly.
[0125] [0125]FIG. 16 shows the flowchart of subroutine 58 , which determines, whether it is necessary to pass to Power Down Mode. In this subroutine constant NPD will be used to define how many runs of the main program should be fulfilled starting with setting during response fading to RDeg=0 and till transition to Power Down Mode. Value NPD is stored in Constants area 33 in ROM 22 .
[0126] After entering subroutine 58 in block 161 , controller 21 checks the current value of response degree RDeg (block 162 ). If RDeg>0, then the subroutine returns logic value “False” and terminates in block 165 , because if the toy has a nonzero response degree, transition to Power Down Mode cannot take place.
[0127] If checking in block 162 shows, that RDeg=0, controller 21 in block 163 compares the current value N with constant NPD. If this checking determines that N<NPD, that is it is still early to pass to Power Down Mode, the program continues to block 165 , in which it returns logic value “False” and terminates. If it is found out in block 163 , that N=NPD, that is it is time to pass to Power Down Mode, the subroutine passes to block 164 , in which it returns the logic value “True” and terminates.
[0128] As it follows from the explanation of the last two subroutines, the counter of cycle runs N is first used for control of reproducing of the toy response, and when the response has faded to zero, it is used to determine a moment of transition to Power Down Mode.
[0129] Herein we have described the program for the first toy 1 . It is clear, that the program for any other interacting toy according to the present invention is created in the similar way, but numerical parameters can be different.
[0130] Thus, in devices according to the preferred embodiment of the present invention the possibility is ensured to change both, sound responses and time intervals between separate responses reproductions, that makes behavior of toys manifold and more interesting to the user.
CONCLUSION, RAMIFICATIONS AND SCOPE
[0131] As it is clear from the description of the preferred embodiment of the present invention, this invention provides new possibilities and advantages over toys reacting to external activation known before. These new possibilities and advantages are possible because the toys according to the present invention can recognize one another and react to each other in different ways.
[0132] Each toy according to the present invention periodically transmits messages containing information about this toy. Another toy receives these messages and reacts to them according to the information received. Different types of responses imitate personalities of characters represented by toys, their mutual sympathies and antipathies. Each toy can have individuality and its own way to react to other toys. If there are more than two toys, different pairs of toys establish different variants of reciprocal reactions. In result, there will be a community of interacting toys, that creates absolutely new possibilities of cognitive, pedagogic and entertainment impact on children. This community can be enlarged by introducing new toys, and thus getting new variants of behavior and mutual relations among toys.
[0133] The responses of the present invention toys to other toys of the kind and to the activation by the user differ in types and in intensity degrees. It creates vast possibilities to vary individuality of toys and variants of their behavior when they meet. The gradual fading of the toy response after removal of another toy or after the termination of the user interaction with the toy makes toys behavior more natural.
[0134] Another advantage of toys according to the given invention is that the response of one toy to another or to the activation by the user is only partially determined. The influence of a random factor on selection of a response type and on its intensity degree brings in more diversity in toys behavior and makes playing with them even more interesting and instructive.
[0135] Toys with different responses sets imitating different characters and personalities can have identical electronic blocks and differ only by data recorded during programming. The unification of electronic blocks allows to reduce toys production costs.
[0136] Another advantage of the toys according to the present invention is that the consumer can extend a community of toys available for him/her, introducing new members into it, or purchasing such toys by subject sets, for example, sets of characters of any popular fairy tale, or sets of tropical animals. At the same time, manufacturers of toys can produce new toys, that will interact among themselves, as well as with toys manufactured earlier. Due to this, the interest of consumers to interacting toys and, therefore, the demand for such toys will be permanently supported.
[0137] Although the description above contains many specificities, these should not be construed as limiting the scope of the invention but as merely providing illustrations of the presently preferred embodiment of this invention. Many other embodiments are possible. Some of these variants are discussed below.
[0138] Message transmission from one toy to another using IR rays was described above as an example. Radio communication can be used as an alternative message transmission method. In this case, it is possible to make use of any known technique, for example, as in cordless telephones. Messages can also be transmitted by the way of audible tones or ultrasonic signals. For each message transmission method any suitable message format and antijamming coding method can be used.
[0139] The amount of sensors in the toy according to the present invention can be different. Their layout can be different, too. Sensors can react not only to pressing by the user, but also to sounds (claps, whistles etc.), to turning the light on and off, to approaching of a person and other external events. Sensors of different types of external actions are well known in the art.
[0140] Response types and response degrees are given in the description of the invention as examples. The number of response types and response degrees and the characteristics of these parameters can be different. Besides, they can be different for different toys. There can be responses such as, for example, curiosity, invitation to play together, giving in to a partner or the demand to take control over a partner, etc.
[0141] Other variants of dependencies of responses on time are also possible. For example, if the presence of another toy is detected, the response degree can first rise with time and then fade. Furthermore, the dependence of the response degree on time can be different depending on what other toy is detected. The type of dependence of the response degree on time can be selected randomly to make behavior of the toy more manifold and interesting.
[0142] Messages transmitted by the toy, can contain not only its ID identifier and Size and Appearance parameters, as it is described in the preferred embodiment of the present invention, but also other data, which can affect interaction among toys, for example, color, presence and type of coat, presence of a tail and its length, etc. The principles of determining the toy response to these parameters will be the same, as described in the preferred embodiment of the present invention. It is only necessary to increase the size of OP-LUT table and include additional toy parameters in it.
[0143] Data transmitted by each toy, can include not only its static parameters, such as Size and Appearance, but also values of response type RType and response degree RDeg, that describe the current emotional condition of the toy. In this case, the response of the toy, which has received a message can depend on the current condition of the toy, which has transmitted this message. For this purpose, it is necessary to enter appropriate data into Id-LUT and OP-LUT tables. Cross-influence of conditions of interacting toys in combination with different condition dependencies on time and with random components in equations (1) and (2) will make a huge range of variants of development in time of toys responses to each other.
[0144] Responses of the toy to the presence of another toy and to the activation by the user can be expressed not only by sounds, but also by motions of any parts of the toy, for example, hands, by light signals, for example, luminescence of an eye, by displaying of text or digits on LCD, and by other possible ways.
[0145] The transition of controller 21 into Power Down Mode available in the preferred embodiment of the present invention is optional. The variants are possible, in which the toy is in active state and can perceive messages from other toys all the time, while the power supply is switched on. In such variants, sensors sensing the activation by the user, can be excluded, and, for example a power switch can be used instead. The toys of such embodiment will respond only to the presence of the other toy. Thus, among toys available for consumers, there can be both, toys with sensors of the activation by the user, and toys without such sensors, and all these toys will interact among themselves.
[0146] Thus, the present invention provides ample possibilities for creation of manifold and interesting interactions between toys, for creation of community of toys living a life independent of the person.
[0147] Having described the preferred embodiment of the invention with reference to the accompanying drawings, it is to be understood that the invention is not limited to this precise embodiment, and that various changes and modifications may be effected therein by one skilled in the art without departing from the scope or spirit of the invention as defined in the appended claims. | Each of interacting toys comprises a housing defining its form and outward appearance, means for transmitting messages with information about the first toy, means for receiving messages transmitted by the other toy with information about the second toy, means for reproducing reaction of the first toy to the second toy and to the user interaction, storage means containing data about reactions of the first toy to various other toys and to various user actions.
Each of interacting toys periodically sends messages about itself to another toy and receives messages from it. If the first toy detects the presence of the second toy, it reacts to this fact for example by making a sound characterizing the reaction of the first toy to the second toy. Type of reaction and its intensity level depend on the information received from the second toy. The seconds toy operates in the same way. Thus, the imitation of various relationships between toys and the variety of toys' behavior is provided. | 0 |
FIELD OF THE INVENTION
This invention relates to an apparatus for crimping the ends of banding straps and to the resulting crimp.
BACKGROUND OF THE INVENTION
In the manufacture of heat exchangers such as automotive radiators and air conditioner evaporators many elements are assembled to form a core and are held together by steel bands for subsequent processing. The banded cores are subject to wash, flux, and brazing processes. It is critical that the band strap does not loosen from the core after it has been banded, especially in the brazing process, where the core is subjected to temperatures in excess of 1000° F. Failure in any of these stages would result in damage to the core and could also cause damage to the processing equipment. It is also essential that the strap itself or the application of the strap does not damage the core.
Apparatus for applying straps to such cores, known as band heads, typically employ a four step process for banding: feed, tension, crimp, and cut. In the feed cycle, strap is fed from stock material through a track which encloses the core. When the feeding is complete, the end of the strap is clamped and the tensioning step begins. The tensioning comprises pulling the strap from the opposite direction from which it was fed, thereby pulling the strap out of the track and around the core such that the strap overlaps its end. When the desired tension is reached, the strap is fastened or crimped at the overlap region to create a seal around the core. Then the strap is cut to separate the sealed loop portion of the strap from the stock material.
A number of techniques are known for securing the ends of the straps together. One band head requires an external clip to hold the strap ends, thereby mandating that a supply of the clips be maintained. Another known band head uses a key-hole notching approach which produces a strong seal but has short tool life.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to provide a crimp configuration which is reliable in hot environments and which requires no separate clip.
It is another object to provide crimping apparatus which has long tool life and yields a strong seal.
The invention is carried out by a strap crimp for securing the ends of a banding strap comprising: a pair of overlapping strap ends meeting at an interface plane; first and second pairs of tabs spaced along the overlapping strap ends, each pair comprising tabs on opposite side edges of the overlapping strap ends; each tab comprising juxtaposed narrow tab portions of both of the strap ends bent in the same direction out of the plane of the strap to form a notch in each strap end such that the tab portion of one strap end extends through the notch of the other strap end to hold the strap ends against separating.
The invention is further carried out by a tool for crimping together the overlapping ends of a strap comprising: means for holding the strap in a crimping station; anvil means mounted for movement against a first side of the strap; blade means mounted for movement against a second side of the strap in cooperation with the anvil means for cutting crimp tabs from the overlapping strap ends and bending the tabs normal to the strap; the anvil means and the blade means having a rest position on the same side of the strap; and linear actuator means movable between a rest position and a work position and coupled directly to the anvil means for moving the anvil means from its rest position to its work position against the said first side of the strap; and a motion transfer mechanism coupling the linear actuator means to the blade means for moving the blade means from its rest position to its work position at the second side of the strap.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other advantages of the invention will become more apparent from the following description taken in conjunction with the accompanying drawings wherein like references refer to like parts and wherein:
FIG. 1 is a top view of a strap crimp according to the invention;
FIG. 2 is a sectional view along lines 2--2 of FIG. 1;
FIG. 3 is a schematic front view of strap crimping apparatus employing a band head according to the invention;
FIG. 4 is a cross-sectional view of a band head according to the invention;
FIG. 5 is a cross-sectional view taken along lines 5--5 of FIG. 4 and showing clamp elements and cutter elements;
FIG. 6 is an isometric view of an anvil assembly of the band head of FIG. 3;
FIG. 7 is a cross-sectional view taken along line 7--7 of FIG. 4 and showing crimping blades in cooperation with the anvil assembly and with the tooling in down position;
FIG. 8 is a partial view of the FIG. 7 section with the tooling in up position; and
FIG. 9 is a detail view of the crimp forming region of FIG. 7 showing the crimp formation.
DESCRIPTION OF THE INVENTION
The crimp and the apparatus for making the crimp were specifically developed for a steel strap having a thickness of 0.015 inch and a width of 3/8 inch, but it should be evident that the invention is adaptable to other materials and dimensions. Referring to FIGS. 1 and 2, a banding strap is 10 is joined at a region of overlap of a lower end 12 and upper end 14. The ends are notched at two places along each side of the strap to produce two longitudinally spaced pairs of tabs 16, each tab being double layered. That is, a tab portion 19 of each strap end is bent upwardly to form a notch in the side edges of the strap ends so that the tab portion of the lower strap end extends through the notch in the upper strap end. Each notch 18 extends into the strap 10 about one third of the strap width, and the tabs extend at an angle of 90° to the surface of the strap with the tab portions 19 juxtaposed. The width of the tabs 16 and of the corresponding notches 18 is typically 0.094 inch and the longitudinal spacing of the tabs is 0.156 inch. This configuration gives good strength in tension and compression as well in torsion. During development smaller angles of tab bending as well as shorter tabs were tested and were deficient in torsional strength, the ends tending to break apart when twisted. Thus the preferred configuration as depicted in the drawings is the one with the greatest strength
FIG. 3 is a front view of the banding apparatus. An oval track 20, surrounding or enclosing the core 22 or other object to be banded, is attached to the band head 24. The band head 24 contains the tooling for notching the strap ®nds and cutting off the strap from the supply. Tandem cylinders 26 on the band head 24 actuate the tooling. By using tandem cylinders, a first cylinder can be actuated to move the tooling partially through a prescribed path, and the second cylinder can be separately actuated to complete the tooling action. A feed device 28 meters strap stock 10' from a supply coil into the track 20 and retracts the stock during a tensioning step. The track is designed to release the strap when tension is applied. The oval track 20 and the feeding apparatus 28 are similar to those already known in the art and are not described herein in detail. An electrical controller 29 connected to the band head 24, the cylinders 26 and the feeding apparatus 28 initiates and coordinates the action of each one. Under the commands of the controller 29 the strap is fed by the device 28 into the oval track and when the end of the strap completes the path around the track and reaches the band head 24 so that the end overlaps the strap portion just newly fed in, the strap is gripped near the end by a clamp on the band head. Then the feed device pulls back on the strap until it is pulled from the track and the strap is tightened around the core 22. Then the band head is actuated to crimp the overlapping portions of the strap and cut off the crimped strap from the supply. Finally the crimped strap is released from the band head and the strap snaps against the core.
Housing and Guides. As shown in FIGS. 4 and 5, the band head 24 has a housing comprising a side wall portion 30 having three walls 32 and a cover 34 which serves as a fourth wall to complete the sides of the housing. A base 36 covers a portion of the housing bottom and has an upwardly inclined surface 38 at its inboard end. A retractable cooperating element 40 spaced below the base 36 has a downwardly inclined surface 42 which, with the surface 38, defines a funnel-like opening for receiving the end of a strap as it is being fed into the track 20. A guide element 44 fastened to the cover 34 has an inclined upper flange 46, and an outer stationary member 48 and an inner stationary member 50 spaced from the flange 46 to form a funnel-like slot for receiving the strap being fed from the feed device 28 to the band head. As will be seen below, the inner member 50 has an inboard end 52 serving as a cutting edge and a lower surface 54 serving as a clamp jaw. A second retractable member 56 spaced below the inner and outer members 48 and 50 has an outward and downward inclined upper surface 58 to define another funnel-like slot which receives the strap end as it exits the track 20 to enter the band head where it overlaps the incoming strap from the feed device.
Drive Mechanism. Within the housing, a guide insert 60 supported on the base 36 and in contact with the wall 32 opposite the cover has a vertical channel 62 and the inside wall of the cover has a corresponding vertical channel 64. A ram 66 operated by the cylinder 26 slides vertically within the housing and has two depending ears 68 which hold a horizontal main drive pin 70, the pin 70 having ends 72 which are slidably retained in the channels 62 and 64. A pair of secondary drive pins 74 above and to either side of the main drive pin are also held by the ears 68 of the ram 66. The pins 74 each pass through a pair of drive links 76 between the ears 68, the links being pivotally journaled at one end on the pins 74. The other end of each link 76 engages a rod 78 which extends across the housing and has one slidably engaged in an L-shaped slot 80 in the guide insert 60 and the other end in a similar slot in the cover 34.
Clamp. A pocket defined by vertical side walls 82 on the inside of the cover 34 contains a pair of spaced sliding blocks 84 which are journaled at their upper ends to the drive pins 74. A compression spring 86 between the blocks urge them toward the side walls 82. Each sliding block 84 contains a cam slot 88 which has an upper vertical section and a contiguous lower section inclined downwardly and toward the other block 84. A pair of rods 90 below the lowest position of each block 84 are rotatably journaled in the insert 60 and the cover 34 and carry clamp arms 92 which are generally vertically elongated and have an inboard finger or clamp jaw 94 movable into opposition with the clamp surface 54 of the stationary member 50 for holding the strap 10 and movable to a release position upon pivoting about the axis of the respective rod 90. The upper end of each clamp arm 92 carries a short pin which rides in the cam slot 88 of a block 84 such that as the ram 66 and the blocks 84 move up the clamp arms 92 move to release position and conversely, when the ram descends the clamps jaws close against the strap 10. Due to the shape of the cam slots 88 the clamping movement occurs during the first half of the ram descent which is caused by actuation of the first tandem cylinder 26. The clamp position is maintained during the second half of the ram descent which is caused by actuation of the second tandem cylinder 26. This allows the clamp to be closed early in the ram cycle so that strap tensioning can occur before crimping.
Cutter Mechanism. A second pair of inner side walls 96 of the cover 34 are closely spaced to define a narrow vertical channel which receives a knife 98 of a cutter assembly 99. The lower end of the knife 98 has a sharp edge 100 which cooperates with the cutting edge on the inboard end 52 of the stationary member 50 to sever the strap 10 from the supply strap 10'. The upper end of the knife has a concave surface 102 which is engaged by the main drive pin 70 during its downward stroke to actuate the knife. The remainder of the cutter assembly 99 comprises a block 104 which resides between the blocks 84 and below the spring 86, and an outboard plate 106 having a slot 108 encompassing an end 72 of the drive pin 70. A bolt 110 and pins 112 secure the assembly. When the ram 66 moves up, the drive pin 70 engages the end of the slot and pulls the cutter assembly up. When the ram descends, the drive pin 70 engages the concave surface 102 of the knife 98 and pushes the assembly 99 down.
Crimp Tooling. FIGS. 4 and 6 show a laminate anvil assembly 114 comprising two anvil blades 116 sandwiched between three plates 118, and all secured to the three driving pins 70 and 74 for reciprocating movement with the ram 66. Each anvil blade 116 is T-shaped for attachment to the driving pins at the top and center, and terminates at the bottom in a narrow nose 120 having a flat bottom 121 for contacting the top surface of the strap 10 and vertical sides 122 which help shape the crimp tabs 16 and define their angle normal to the strap surface. The plates 118 have vertically extending slots 124 for accommodating transverse rods in the band head and permitting vertical plate movement relative to the rods. The bottom center of each plate 118 has a cutting edge 126 flush with the bottom of the nose 120 for contact with the strap and somewhat wider than the nose. The cutting edge 126 has sharp corner edges and cut the tabs 16 from the strap when crimp blades 128 aligned with the anvil blades 116 push up on the strap 10 in the regions between the cutting edges. The plates 118 serve to guide and space the crimp blades 128, and thus the spacing of the crimp blades and of the tabs 16 is established by the width of the center plate 118. It is preferred that the three plates 118 be identical. The width of each tab 18 is the same as the anvil blade 116 width.
FIGS. 7 and 8 show the crimp blades 128 and the anvil assembly 114 in the ram down position and the ram up position, respectively. Each crimp blade 128 is elongated generally vertically and has a claw 130 on its lower end which is turned toward the other crimp blade. The blade is shaped to curve around and avoid interference with the transverse rod 90. The top of each blade 128 is apertured for receiving the rod 78 and the center of each blade is similarly apertured to receive a rod 132 which is supported at its ends in vertical slots 134 in the insert 60 and the cover 34. The rods 78 and 132 and the driving links 76 provide the support and driving force for the blades 128 and the slots 80 and 134 govern the path of the blades in response to ram 66 movement. The crimping blades receive lateral support and guidance from the plates 118 which bound the blades 128 on either side, the blades being slightly thinner than the spacing between the plates 118 to allow sliding movement. When in the upper position of FIG. 8 the pins 78 and 132 are at the upper ends of their respective slots 80 and 134. Then the drive links 76 are oriented at a substantial angle to the horizontal so that a downward ram movement causes the links to push down on the blade 128 and urge the rods 78 against the outboard side of the slots 80. In the lower range of the ram movement, the pins 78 move through the longitudinal portions of the slots 88 and finally the drive links assume a horizontal position as shown in FIG. 7.
In operation, starting with the upper position of FIG. 8, when the ram descends the links 76 push the blades 128 straight down as guided by the vertical portion of the slot 80, and the anvil assembly 114 descends as well, so that the relative positions of the anvil assembly and the crimp blades are unchanged. The claws 130, however move from a position above the strap 10 to a position below the level of the strap as shown in phantom lines in FIG. 7. Then, as the ram descent continues, the anvil assembly reaches the strap as the outward movement of the rods 78 in the horizontal portion of the slot 80 causes the blades to pivot about the rods 132 which reach the bottoms of the slots 134. The claws 130 then move inward and upward, pushing the strap against the anvil assembly 114 and forming the tabs 16. The place in the band head where the crimping tooling meets the strap is the crimping station and is immediately adjacent the stationary member 50 which is used for cut off and clamp functions.
As best seen in FIG. 9, the inboard end of each claw 130 has a cutter tip comprising an upper horizontal edge 136 which contacts the bottom of the overlapping straps in the extreme ram down position, and an adjacent vertical edge 138 which, during final descent of the ram, presses up on the straps, causing them to cut on the cutting edge 126 to form a tab 16, and finally presses the tab against the sides 122 of the anvil blade 116.
Operation: In summary of the overall operation which is under the controller 29, strap stock 10, is fed into a crimping station in the band head 24 and is guided by a track 20 surrounding the core 22. When the strap end passes into the crimping station for the second time in overlapping relation with stock which just entered the station, the first cylinder 26 is actuated by the admission of air pressure to push the ram down half way, causing the clamp jaws 94 to clamp the strap end against the clamping surface 54. The ram is held at the half way position while the strap stock 10' is retracted to tightly wrap around the core 22. The tension on the strap is inferred from the current drawn by a servomotor in the feeding apparatus 28 which is monitored by the controller 29. The strap tightening process may require three seconds or more. When the desired tension is achieved, the second cylinder is actuated to complete the ram travel. Then the anvil assembly 114 descends into contact with the strap and the claws 130 move beneath the strap and then upward to form the tabs 16 and push them up between the cutting edges 126 and against the sides 122 of the anvil blades 116. During the final down motion of the ram the knife 98 cuts off the strap 10 from the stock Upon upward movement of the ram the crimp claws 130 and the clamp jaws 54 retract and the retractable elements 40 and 56 are also withdrawn to release the strap. When the strap 10 is released it snaps against the core 22. The sharp tabs 16 on the strap point away from the core so that they do not damage the core when the strap engages the core. The entire cycle time including feeding the strap into the track 20 is accomplished in 8 or 9 seconds. | A banding strap for holding together the parts of a heat exchanger core during a brazing operation is crimped at its overlapping ends by forming two longitudinally spaced pairs of tabs, each pair being on opposite side edges of the strap. The tabs are bent from the strap ends at an angle normal to the strap surface so that corresponding notches are formed in the strap. The crimping apparatus includes a clamp for holding one end of the strap, a knife for cutting off the strap from stock, a laminated anvil which descends onto one side the strap, and crimping blades which move around to the opposite side of the strap to push portions of the strap ends against the sharp edges of the anvil to form the tabs. A powered ram is coupled to each of the clamp, knife, anvil, and crimping elements to operate each element in proper sequence during ram motion. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to storage mechanisms for flexible conduits and cables, and more particularly, to a vehicle mounted system for winding a flexible conduit or cable in a horizontal coil and automatically extending and retrieving cable responsive to vehicle movement.
2. Description of the Prior Art
Vehicles which are electrically powered through a multi-conductor umbilical chord are commonly used in underground mines. These vehicles are generally load-haul and dump type mining machines. One problem with such vehicles is the need to extend the cable as the vehicle moves forwardly and retract cable as the vehicle moves rearwardly. This function has generally been accomplished in the past by winding the cable on a reel or drum which is rotatably mounted on a transverse horizontal axis. The power is transferred from the cable to the vehicle drive motor through slip rings such as utilized by conventional AC motors. The slip rings must be custom designed to fit within the relatively small available volume. The reel is generally powered by an electric or hydraulic motor. The hydraulically powered varieties are generally either dual pressure systems or constant tension systems.
The dual pressure system continuously applies a torque to the reel, but the torque is lower for cable extension or a stationary condition than for cable retrieval. For proper functioning of the system the low torque setting must be large enough to keep excessive cable sag or slack from developing. The minimum cable tension is 100 pounds.
The constant tension system applies a constant torque to the reel. The value of the torque is not critical, but again it must be large enough to keep slack or sag from developing in the cable. The minimum cable tension for the constant tension system is 150 pounds. These conventional reel systems exhibit many problems which are alleviated by the inventive cable winding system. A principal problem with the prior art technique is the need to employ slip rings which quickly deteriorate in the severe environmental conditions of a mine. Additionally, the high inertia of the reel and particularly the cable wound thereon reduces the transient response of the cable retracting and extending system. Good transient response can only be maintained, then, by providing a fairly high cable tension. Yet, a relatively high cable tension in itself causes problems. As the cable is wound on the reel with a tension, the inward force exerted by the cable on the reel continues to build up thereby preventing the cable from being adequately cooled and excessively compressing the underlying cable. Also, the cable often catches on irregular contours in a mine, and the cable tension causes violent whipping of the cable as the cable is released, thereby posing a serious safety hazard. Cable whipping also occurs when the vehicle stops or reverses direction suddenly, although this problem is less severe with the constant tension system than the dual pressure system.
Another problem with conventional reel systems is that they must receive cable from the rear so that the cable is often severely damaged by backing over the cable with the vehicle. For these reasons, conventional vehicle mounted cable storage devices have not been entirely satisfactory.
Another approach to the problem of extending, retracting and storing umbilical cable in a mining vehicle is described in U.S. Pat. No. 3,990,551 issued to Jamison et al. The Jamison et al device includes a pair of selectively driven rollers engaging the cable therebetween. The rollers convey the cable to and from a rectangular storage box through a slot without guiding the cable in a specific arrangement. A constant torque is applied to the rollers thereby maintaining the tension in the cable constant. Thus the Jamison et al devices does not solve most of the above mentioned problems.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a cable winding system which is capable of retracting and extending cable from a vehicle without maintaining a significant tension on the cable.
It is another object of the invention to provide a system for winding a cable in a cylindrical configuration in a manner which allows the end of the cable to be connected to a vehicle without the use of slip rings.
It is still another object of the invention to provide a cable winding system having a relatively good transient response so that the cable winding mechanism is capable of responding to sudden changes in vehicle velocity.
It is a further object of the invention to provide a system for winding cable in a cylindrical configuration without placing the cable under tension in order to facilitate convection cooling of the cable and to preserve cable life.
These and other objects of the invention are accomplished by a powered drive mechanism for applying either a constant axial force to a cable or flexible conduit or an axial force having a magnitude and direction determined by a conduit control signal. A generally cylindrical conduit container receives the conduit from the drive mechanism through a guide arm which arranges the conduit in a generally cylindrical coil. The guide arm has a first end positioned adjacent a conduit port of the drive mechanism and a second end facing radially outwardly and circumferentially within the conduit container. The guide arm is rotatably mounted about an axis extending through the centers of both the conduit coil and the conduit port of the drive mechanism so that as cable is drawn through the drive mechanism the first end of the guide arm remains adjacent the conduit port while the second end of the guide arm moves circumferentially within the conduit container to arrange the conduit in a coil. The conduit extends from a point external of the vehicle to the drive mechanism through a fairlead which may pivot about a horizontal axis responsive to vehicle movement. The angle of the fairlead may be measured and utilized to actuate the drive mechanism to either retract or extend conduit responsive to vehicle movement. In order to provide good transient response without allowing excessive movement of the fairlead a feedback signal indicative of fairlead angle may be summed with the output of a tachometer to bias the control system in a conduit winding or unwinding condition responsive to vehicle movement. Alternatively, the drive mechanism may apply a constant tension to the conduit. The drive mechanism, which is preferably a powered sheave, may be pivotally mounted about a vertical axis extending through both the conduit port of the drive mechanism and the rotational axis of the guide arm in order to allow conduit to extend to the vehicle from a variety of directions.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of a mining vehicle with the inventive cable or conduit winding system installed thereon.
FIG. 2 is a top plan view of the conduit winding system.
FIG. 3 is a cross-sectional view of the conduit winding system taken along the line 3--3 of FIG. 1.
FIG. 4 is a schematic of the control circuitry for the conduit winding system.
FIG. 5 is a schematic of the hydraulic mechanisms for the conduit winding system.
FIG. 6 is a cross-sectional view of the conduit drive mechanism take along the line 6--6 of FIG. 3.
FIG. 7 is a cross-sectional view of an alternative embodiment of a conduit drive mechanism allowing the drive mechanism to exert a greater force on the cable.
DETAILED DESCRIPTION OF THE INVENTION
The conduit winding system 10, as illustrated in FIGS. 1 and 2 installed on a conventional mining vehicle 12, is adapted to extend and retract a length of electrical conduit or cable 14 responsive to vehicle movement. Although the system 10 is described herein for use with cable, it may also be used with conduits for fluid as well as electricity. Consequently, the term "conduit" as used herein is intended to apply to all flexible, elongated members including cables and pipelines. The winding system 10 includes a generally cylindrical or oval cable storage area 16, a drive mechanism 18 for selectively applying an axial force to the cable 14, a fair-lead 20 for guiding and supporting the cable 14 between the drive mechanism 18 and a power source external of the vehicle 12, and a guide arm 22 for guiding the cable 14 between the drive mechanism 18 and cable storage area 16 and positioning the cable 14 in a cylindrical coil. The fairlead 20 is pivotally secured to a cylindrical cable guide 24 so that as the vehicle 12 moves away from the cable, the fairlead 20 pivots upwardly toward the deployed cable and away from the vehicle causing cable to be extended. Similarly, as the vehicle 12 moves toward the deployed cable, the fairlead 20 pivots through a vertical position toward the cable and vehicle casing cable to be retracted. Thus, as illustrated in FIG. 1, forward movement of the vehicle 12 causes the fairlead 20 to pivot rearwardly to extend cable, and rearward movement of the vehicle 12 causes the fairlead 20 to pivot forwardly to retract cable. It will be understood, however, that the cable 14 may extend from a point forwardly or to one side of the vehicle so that forward movement of the vehicle 12 may cause cable to be retracted and rearward movement of the vehicle 12 may cause cable to be extended.
As explained hereinafter, the angle of the fairlead 20 is measured and applied to control circuitry for selectively actuating the drive mechanism 18 to retract or extend cable 14. The drive mechanism 18 is powered by a conventional hydraulic motor 26 connected to a hydraulic servo valve 27 through conduits 28. The end of the cable 14 is anchored at 30 to the cylindrical sidewalls of the cable storage area 16. Since the cable 14 is fixedly anchored to the vehicle 12, conventional slip rings or similar devices are not required. Since the cable 14 is not wound on a reel, the inertia effect of the cable 14 is minimal, thus insuring good transient response.
The drive mechanism 18 is rotatably supported through a hinge 32 allowing the drive mechanism 18 to rotate about a vertical axis in order to receive cable 14 from a variety of points around the vehicle 12 in order to position the cable 14 away from the wheels of the vehicle thereby reducing cable damage. The guide arm 22 is rotatably supported about a vertical axis so that the guide arm 22 rotates as cable is retracted or extended by the drive mechanism 18. The rotational axes of the hinge 32 and the guide arm 22 are common to each other so that the position of the opening of the guide arm 22 with respect to a cable port for the drive mechanism 18 remains fixed as the drive mechanism 18 and guide arm 22 rotate.
The internal structure of the inventive cable winding mechanism is illustrated in further detail in FIG. 3. Cable 14 enters the fairlead 20 where it is supported by forward, rear and transverse rollers 40, 42, 44, respectively. As explained above, the fairlead 20 is pivotally secured to a cylindrical cable guide 24 by conventional bearings 46. A potentiometer 50 rotates with the fairlead 20 to provide an electrical indication of the fairlead position in order to control the drive mechanism as explained in greater detail hereinafter. The cable guide 24 is composed of two sections, a lower cable guide section 24a and an upper cable guide section 24b. The lower section 24a is rotatably secured to the upper cable guide section 24b by a conventional bearing mechanism 48 which allows the lower cable guide section 24a to rotate with respect to the upper cable guide section 24b about a vertical axis. The bearing mechanism 48 allows the cable 14 to extend from the fairlead 20 at a variety of azimuths even when the rotational position of the drive mechanism 18 is fixed. In the normal stationary condition the cable 14 assumes a natural catenary configuration as it extends to the ground with the fairlead 20 assuming an offset angle from the vertical that corresponds to the desired catenary of the cable at rest. Any forward or reverse movement of the vehicle changes the position of the fairlead 20 to produce a positive or negative error signal depending upon whether the movement tends to increase or decrease the angle of the catenary of the cable passing through the fairlead 20.
The cable 14 extends through the upper cable guide 24b and engages a rotatably mounted sheave 52 having an axle 54 connected to the hydraulic motor 26 (FIGS. 1 and 2). The periphery of the sheave 52 may have a variety of cross-sectional shapes, but the embodiment illustrated in FIGS. 3 and 6 utilizes a peripheral edge having a substantially rectangular shape. The cable 14 is positioned between the sheave 52 and a plurality of freely rotatable guide rollers 56. The rollers 56 loosely engage the cable 14 since they are not pressure rollers but are provided to prevent the cable 14 from bowing outwardly when the sheave 52 rotates counterclockwise as illustrated in FIG. 3. The cable 14 extends along the periphery of the sheave 52 to a pair of pressure rollers 58 which resiliently bias the cable 14 against the sheave 52. The rollers 58 are carried by hydraulic rams 60 which, as explained hereinafter, apply a constant force to the cable 14 but allow the rollers 58 to move away from the sheave 52 to accommodate splices in the cable 14 having a relatively large diameter.
Under some conditions the friction between the cable 14 and sheave 52 may be insufficient for optimum performance thereby allowing the cable 14 to slide or slip on the periphery of the sheave 52. Under these circumstances the alternative embodiment 18' of the conduit drive mechanism illustrated in FIG. 7 may be employed. In this embodiment 18' the cable 14 is gripped between a fixed flange 300 integral with a sheave 302 and a movable flange 304. The movable flange 304 is mounted on a hub 306 which is, in turn, mounted on a drive shaft 308 through a bearing 310. The bearing 310 allows the flange 304 to freely pivot about the axis of the shaft 308 so that the flange 304 can contact the cable 14 along the upper periphery of the sheave 302. The upper periphery of the sheave 302 is biased against the cable 14 by a pressure shoe 312 containing a roller 314 for allowing circumferential movement of the movable flange 304 with respect to the pressure shoe 312. The pressure shoe 312 is biased against the flange 304 by a conventional hydraulic ram 316. A plurality of circumferentially spaced guides 318 carried by the sheave 302 extend through apertures in the flange 304 to insure that the flange 304 rotates with the sheave 302. In operation the hydraulic motor 26 selectively rotates the shaft 308 in either direction which in turn rotates the sheave 302 through a hub 320 and the flange 304 through the beaming 310. The ram 316 continuously urges the pressure shoe 312 against the flange 304 through the roller 314 so that the cable is gripped between the flanges 300, 304.
Cable 14 is guided from a cable port 61 of the sheave 52 to the cable storage area 16 through the guide arm 22. The guide arm 22 is formed in a generally S-shaped configuration when viewed from both the top, as illustrated in FIG. 2, and the side, as illustrated in FIG. 3. The guide arm 22 is mounted on a cylindrical support 62 having an annular flange which is bolted to a circular plate 64. The plate 64 is mounted on a shaft 66 which is rotatably supported in a frustoconically shaped base 68 by bearings 70. The upper end of the guide arm 22 is tangent to the periphery of the sheave 52 and the axis of rotation of the arm 22 is tangent to the periphery of the sheave 52. Consequently, the upper end of the support arm 22 remains fixed with respect th the cable port 61 and the periphery of the sheave 52 as the guide arm 22 rotates. Similarly, the hinge 32, which includes a pin 72 extending through apertures in drive mechanism flanges 74 and support flanges 76, has an axis of rotation which is common to the rotational axis of the guide arm 22. Consequently, the upper end of the guide arm 22 remains fixed with respect to the sheave 52 as the drive mechanism 18 pivots. The position of the drive mechanism 18 is normally fixed by a locking bolt 78 extending through the flange 76 into flange 74.
In operation, when the vehicle moves away from the cable, the increased tension on cable 14 causes the fairlead 20 to pivot toward the direction from which the cable extends. As explained hereinafter, pivotal movement of the fairlead 20 actuates the hydraulic motor 26 thereby causing the sheave 52 to rotate counterclockwise in order to extend cable from the fairlead 20. The fairlead 20 then pivots downwardly to the desired offset for a neutral position. As the sheave 52 rotates counterclockwise, the guide rollers 56 (FIG. 6) prevent the cable 14 from buckling while the pressure rollers 58 cause the cable 14 to frictionally engage the periphery of the sheave 52. As cable 14 is drawn from the guide arm 22 the guide arm 22 rotates counterclockwise thereby removing cable 14 from the cable storage area 16. Alternately, as illustrated in FIG. 7, as the vehicle moves toward the cable, the fairlead 20 pivots away from the direction from which the cable extends thereby actuating the hydraulic motor 26 to rotate the sheave 52 clockwise. Cable 14 is then drawn inwardly through the fairlead 20 causing the fairlead 20 to pivot rearwardly toward its neutral position. As the sheave 52 continues to rotate clockwise, the guide arm 22 rotates counterclockwise thereby winding cable 14 in the cable storage area 16. The cable 14 is relatively loosely wound in the cable storage area 16 thereby allowing good convection cooling of the cable 14 and freeing the cable from damaging forces exerted on each other. When a cable splice having a relatively large dimension is encountered, the pressure rollers 58 are permitted to move away from the sheave 52 while the splice passes therebetween.
Alternatively, the hydraulic motor 26 may apply a constant torque to the sheave 52 in a cable retracting direction to impart a constant tension to the cable. In this configuration, the fairlead 20 is not instrumented, and the cable is extended and retracted responsive to vehicle movement as in the conventional drum mounted system. Even this simplified alternative system is a great improvement over prior art systems since it eliminates slip rings, high reel inertial and high cable storage tension of conventional reel systems.
One advantageous property of the inventive cable winding mechanism is its adaptability to various size cables. The system may be modified to handle a differeing cable diameter by simply unbolting the lower cable guide 24a and fairlead 20 from the upper cable guide 24b at the bearing mechanism 46, replacing the sheave 52 with one having a different transverse dimension, and replacing the guide arm 22 by unbolting the guide arm support 62 from the support plate 66.
The circuitry for controlling the operation of the cable winding system is illustrated in FIG. 4. The circuitry includes sheave control circuitry 89 receiving the output of the potentiometer 50 connected to the fairlead support pin 48. The potentiometer 50 is connected to plus and minus supply voltages through variable resistors 90, 92 which may be adjusted to control the magnitude of the signal on the wiper of the potentiometer 50 for a given movement of the fairlead 20. Thus, by decreasing the value of resistor 90 and increasing the value of resistor 92, the voltage at the wiper of potentiometer 50 will be larger for a given upward movement of the wiper than for the same movement of the wiper downwardly. Since the wiper of the potentiometer 50 is grounded, the voltage on the wiper is always zero for a neutral fairlead position. The wiper of potentiometer 50 is connected to an operational amplifier 94 arranged as a voltage follower. The output of the amplifier 94 is amplified by operational amplifier 96 having a gain which is proportional to the ratio of the resistance of potentiometer 98 to the resistance of resistor 100. In accordance with good design practice, the resistance of resistor 102 is approximately equal to the parallel combination of resistances 98, 100. The output of amplifier 96 is thus a positive or negative voltage proportional to the rearward or forward pivotal movement of the fairlead 20.
In accordance with an optional, unessential feature of the invention, the fairlead positon signal may be combined with a vehicle speed signal to control the hydraulic motor 26.
The speed of the vehicle 12 may be measured by a conventional tachometer 104 and applied to a voltage follower operational amplifier 106 through potentiometer 108. The voltage on the wiper of potentiometer 108 is filtered by capacitor 110. The voltage at the output of amplifier 106 which is proportional to vehicle speed, and the voltage at the output of amplifier 96 which is proportional to fairlead position, are applied to summing amplifier 112 through resistors 114, 116, respectively. Amplifier 112 produces a voltage across a current sensing resistor 118 which is proportional to the sum of the vehicle speed voltage at the output of the amplifier 106 and the fairlead position voltage at the output of the amplifier 96. The magnitude of the voltage across current sensing resistor 118 for a given vehicle speed voltage or fairlead position voltage is determined by the ratio of the resistance of potentiometer 120 to the resistance 114 or 116, respectively. The value of resistor 122 is approximately equal to the resistance of the parallel combination of resistors 114, 116, 120. The voltage across current sensing resistor 118 is proportional to the current therethrough. All of the current flowing through resistor 118 essentially flows through resistor 124 and solenoid coil 126 when the switch 128 is in either the test or operate modes as explained hereinafter. The servo coil 126 controls the operation of the hydraulic motor 26 as explained hereinafter. The magnitude and direction of the current flowing through the servo coil 126 is thus proportional to the fairlead position voltage at the output of amplifier 94 or, where the vehicle speed option is employed, the sum of the fairlead position voltage, and the vehicle speed signal at the output of amplifier 106. At high vehicle speeds the voltage at the output of amplifier 112 must be relatively large. Without a signal proportional to vehicle speed, a larger pivotal movement of the fairlead 20 would be required to generate a sufficiently large signal at the output of amplifier 94. Alternatively, the loop gain of the system could be greatly increased, but this could introduce instability problems. The vehicle speed signal thus serves as a rough approximation of the required current through the coil 126 while slight corrective movements of the fairlead 20 produce a small corrective signal at the output of the amplifier 94. In most applications, however, the vehicle speed feedback option is not required.
The control system for the inventive cable winding system also includes failsafe circuitry 129 for applying the brakes of the vehicle when either the sheave 52 is unable to rotate as the vehicle moves or the supply of cable 14 in the storage area 16 falls to a predetermined value. The rotational velocity of the sheave 52 is measured by a speed sensor as illustrated in FIG. 6. The sensor 130 includes a hub 132 secured to the shaft of the hydraulic motor by a bolt 134. The hub 132 has integrally formed therein a flange 136 containing a plurality of circumferentially space apertures. The flange 136 extends between a sensing head 138 having an optical source such as a photodiode 140 and an optical sensor such as a phototransistor 142. Thus, as the sheave 52 rotates, light is alternately received by the phototransistor 142 from the photodiode 140 through the apertures in flange 136.
With reference, once again, to FIG. 4, current flows through the photodiode 140 through current limiting resistor 144, and current flow through phototransistor 142 and resistor 146 when light from photodiode 140 reaches phototransistor 142 through the apertures in flange 136. Thus, when the sheave 52 is rotating, a plurality of pulses are sequentially applied to NAND gate 148. NAND gate 148, in combination with NAND gate 150, capacitor 152 and resistor 154, form a one-shot which produces a pulse having a duration determined by the RC time constant of resistor 154 and capacitor 152 at the end of each pulse at the input of NAND gate 148. The sequentially generated pulses from NAND gate 150 are applied to the reset terminal of a counter 156 through NAND gate 158 when NAND gate 158 is enabled as explained hereinafter. When NAND gate 158 is disabled, a logic "1" at the output of NAND gate 158 holds the counter 156 in its reset condition. The counter 156 is normally incremented by clock pulses received from a conventional oscillator 160. One of the outputs of the clock 156 is applied to NAND gate 162 through switches 164 to apply the brakes of the vehicle as explained hereinafter.
NAND gate 158 is disabled to allow the clock 156 to increment by the output of threshold circuitry 166. Basically, the threshold circuitry 166 receives the hydraulic motor command signal from the output of amplifier 96 and determines whether the command signal exceeds a predetermined value in either the clockwise or counterclockwise direction. The command signal is applied to comparators 168, 170 which also receive positive or negative reference voltages from resistor dividers 172, 174 and 176, 178, respectively. The amplifier 168 thus detects a positive command signal while the amplifier 170 detects a negative command signal. The output of comparator 168 is applied to NAND gate 180 through resistor 182. The output of comparator 170 is applied to NAND gate 180 through NAND gate 184 and resistor 186. When the command signal is close to zero volts the output of comparator 168 is positive and the output of comparator 170 is negative. The positive voltage at the output of comparator 168 represents a logic "1" applied to NAND gate 180, and the negative output of comparator 170 is divided through resistor 186, diode 190, resistor 192 connected to ground and resistor 194 connected to positive voltage supply so that the input to NAND gate 184 is logic "0" thereby producing a "1" at its output. Consequently, the output of NAND gate 180 is logic "0" which disables NAND gate 158 and continuously applies a "1" to the reset terminal of counter 156 in order to prevent the counter 156 from incrementing. When the hydraulic motor command signal at the output of amplifier 96 exceeds a predetermined positive threshold the output of amplifier 168 goes negative thereby producing a "0" to its input to NAND gate 180 so that NAND gate 158 is enabled by the "1" at the output of NAND gate 180. Counter 156 is then allowed to increment between pulses from NAND gate 150, and if the sheave 52 has not rotated at a predetermined velocity, one of the outputs of the counter 156 will go high before the counter 156 is reset at the trailing edge of light transmitted from the photodiode 140 to the phototransistor 142. When the hydraulic motor command signal from amplifier 96 goes negative above a predetermined value, the output of amplifier 170 goes positive until the input to NAND gate 184 is at logic "1" at which point the "0" at the output of NAND gate 184 produces a "1" at the output of NAND gate 180 which enables NAND gate 158 to allow counter 156 to begin incrementing.
In either the test or operate modes, the input to NAND gate 200 is connected to ground through resistor 202 thereby producing a "1" at the output of NAND gate 200 which continuously enables NAND gate 162 and NAND gate 204. When one of the outputs of counter 156 as selected by switches 164 goes high responsive to the sheave 52 being unable to rotate a sufficient distance responsive to a command signal above a predetermined value, the "0" at the output of NAND gate 162 is twice inverted by NAND gates 206, 208 and applied to enabled NAND gate 204 to produce a "0" at the output of inverter 210 which actuates a solid-state relay 212. The solid-state relay 212 applies a signal through a coil 214 of the vehicle emergency brake. In the standby mode, a logic "1" is applied to NAND gate 200 through resistor 218 thereby producing a "0" at the output of NAND gate 200 which also applies the emergency brake through solid-state relay 212.
In the operate mode, as selected by mode select switch 226, the left side of a 25 foot limit switch 230 and a ten foot limit switch 232 are grounded. The limit switches 230, 232 are adapted to close when 25 feet and 10 feet, respectively, of cable remain in the cable storage area 16. When the 25 foot limit switch 230 is closed, a "1" at the output of NAND gate 234 is inverted by inverter 236 to produce a "0" which actuates the coil 238 of an alarm through solid state relay 240. The output of NAND gate 234 is normally held at "0" by the logic "1" voltage level at its input produced by resistor divider 242, 244. Capacitor 246 is provided to delay actuation of the horn for a short period after switch 230 is closed. When the cable remaining in the cable storage area 16 reaches the 10 foot limit, switch 232 is actuated thereby producing a "1" at the output of NAND gate 206 which actuates the emergency brake through a solid-state relay 212 in the same manner that the brake is actuated by NAND gate 162. The input to NAND gate 206 is normally held at a logic "1" voltage level by voltage divider resistors 248, 250 with capacitor 252 delaying the actuation of the brakes for a predetermined period after the 10 foot limit switch 232 closes. In the test mode, the left side of test switches 254, 256 are grounded so that manual actuation of the switches 254, 256 apply the alarm and emergency brake, respectively.
The threshold circuit 166 also relieves the load on the hydraulic pump driving the hydraulic motor 26 when the sheave 52 is stationary as indicated by a logic "0" at the output of NAND gate 180. The "0" at the output of NAND gate 180 is applied to a solid state relay 266 causing current to flow through the coil 268 of a solenoid valve to connect the output of the hydraulic pump to the return line.
A schematic of the hydraulic system for the hydraulic motor 26 and pressure roller rams 60 is illustrated in FIG. 5. Hydraulic fluid stored in a reservoir 270 is pressurized by conventional hydraulic pump 272 and applied to a servo valve 274 having its control coil 126 connected to the hydraulic motor control circuitry illustrated in FIG. 4. The hydraulic motor 26 is connected to the output of the servo valve 274 so that the direction and magnitude of fluid flow through the hydraulic motor 26 is proportional to the magnitude and direction of the current through the servo valve control coil 126. The hydraulic cylinders 60 connected to the pressure rollers 58 (FIG. 3) also receive pressurized hydraulic fluid from the hydraulic pump 272 and are connected to the reservoir 270 through a pressure reducing valve with built-in relief 276 which allows the pressure rollers to retract and accommodate a splice while retaining a relatively constant force against the cable 14 and sheave 52. When the sheave 52 is stationary, current flows through a solenoid valve coil 268 as explained above. The coil 268 actuates a valve 280 to connect the output line of the pump 272 to the return line to prevent the pump 272 from laboring.
In the constant tension alternative system the hydraulic motor 26 is coupled directly to the hydraulic pump 272 so that the motor 26 applies a constant torque to the sheave 52. | A cable winding system carried by a vehicle for extending and retracting cable responsive to vehicle movement. The cable frictionally engages a controllably powered sheave and is guided into a horizontally disposed coil by a cylindrical guide arm having a vertically directed opening adjacent the sheave and a downwardly, radially and circumferentially directed opening adjacent the coil. The guide arm is freely rotatable about a vertical axis so that as cable is extended and retracted the guide arm rotates to guide the cable between the coil and sheave. The powered sheave directs cable from the vehicle through an instrumented fairlead which, through a control system, controls the operation of the sheave. The fairlead is pivotally mounted about a horizontal pivot axis so that the head pivots in one direction as the cable is tensioned and in the opposite direction as the cable tension is relieved. The control system measures the angle of the fairlead and may also measure the vehicle speed to cause the sheave to extend cable as the fairlead moves rearwardly and/or the velocity of the forward vehicle is increased and to retract cable as the fairlead moves forwardly and/or the forward velocity of the vehicle is reduced. Also included is a failsafe system for applying the brakes of the vehicle when the supply of cable in the coil falls to a predetermined value or when the fairlead pivots to a point indicative of excessive cable tension and the rotational velocity of the powered sheave is below a predetermined value. | 1 |
BACKGROUND OF THE INVENTION
[0001] The present invention includes a method of feeding livestock and in particular feeding swine. It also involves a novel composition of a gel feed and a method of manufacturing such a gel feed.
[0002] There are many situations in which a feed and a supply of water are both needed but are difficult to provide or providing both results in extra expense. For example, when livestock are being transported it is difficult and expensive to maintain a supply of water for such livestock. In addition, there are situations in the life of an animal where the animal has not much interest in consuming feed but has particular nutritional needs. For example, transitional stages such as weaning pose nutritional problems since the young animal has to learn how to consume solid food. It is sometimes difficult for the young animal to get accustomed to nourishment other than by suckling. Early weaning provides advantages relating to avoidance of diseases and increased weight gain. However, care is needed in early weaning to ensure that the young animal consumes sufficient nutrients.
[0003] Sows also require special nutritional needs just prior to and after farrowing. Proper nutrient intake is needed by the sow for the growth of developing fetuses, the sow's own body needs (body maintenance), for lactation and minimizing any feed intake depression by the sow after farrowing.
[0004] Growing and finishing pigs on occasion also have special nutrient requirements which may be due to any number of factors such as diseases and environmental factors. Diseases and environmental factors may affect nutritional intake which in turn have an affect on profitability for the swine farmer.
SUMMARY OF THE INVENTION
[0005] The present invention includes a method of making a gel-type feed for livestock. The method includes initially forming a feed mixture by mixing feed nutrient components, water, alginate, a calcium component insoluble in water or a sequestrate to inhibit the calcium component from reacting with the alginate. Once the feed mixture is formed, the calcium component is solubilized or the sequestrate's affect on the reactivity between the alginate and the calcium component is removed such that a gel feed is formed that includes a gel matrix containing the feed nutrient components.
[0006] The present invention also includes a method of feeding the gel feed to livestock made according to the method of this invention.
[0007] In another aspect of the present invention, piglets are weaned by feeding the gel feed containing the nutrients for at least seven days directly after weaning.
[0008] In yet another aspect of the present invention, the gel livestock feed includes an alginate based gel matrix in which water is the major component and protein derived from blood, such as plasma or serum. In another aspect, egg protein may be substituted or combined with the blood derived protein.
[0009] The present invention also includes a method of providing water to confined livestock by providing to the confined livestock its daily requirements of water by feeding the confined livestock a gel feed wherein water is the major component.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] The present invention provides a nutrient containing palatable shelf stable feed in a gel matrix whose major component is water. The gel feed provides livestock with both a feed component and a water component to an extent that no additional water external of the feed is needed for the livestock's sustenance. By livestock is meant agricultural or farm animals such as swine, horses, cattle, sheep or goats raised in a farm, ranch or agricultural setting or animals kept in zoos or zoological settings.
[0011] Alternatively, the gel may be used along without any nutrients solely as a water source. Providing water to swine that are confined such as being transported individually in pens or in a truck trailer without pens is difficult at best. Providing water in solid form eliminates spillage due to vehicle movement or animal collisions.
[0012] In addition, the gel feed of the present invention may be used as a delivery system for medication such as antibiotics and chemotherapeutics or for microbial supplements such as probiotics and nutraceuticals. When used as a delivery system for medication, the medication may be the sole constituent in the gel. Examples of antibiotics approved for swine include apramycin, bacitracin methylene disacylate, bacitracic zinc, bambermycins, chlortetracycline, lincomycin, neomycin, oxytetracycline, penicillin, tiamulin, tylosin, and virginiamycin. Chemotherapeutics approved for swine include arsanilic acid, carbodox, roxarsone, sulfamethazine and sulfathiazole. Other medication for swine are well known and are within the scope of the present invention.
[0013] The consistency of the gel-type feed of the present invention may range from a soft gel having the consistency of pudding to a harder gel having the consistency of a gel candy such as Gummy Bears®. The gel can be described as a hydrogel that is a colloidal gel in which water is a dispersion medium. One consideration in the consistency of the gel is that the gel not stick to the feeding animal. Gel that sticks to the swine poses two problems. The first problem relates to the cleanliness of the animal and to the pen in which the animal is contained. The other problem is waste of feed, since the animal cannot consume the feed that sticks to its face and other parts of the body that are not reachable by the animal's mouth. It is not very important as to how hard the gel is and in most situations, preferably the major component will be water. By major component is meant that the weight percent of water is higher than any other component in the gel feed.
[0014] The composition of the gel feed of the present invention is as follows:
[0000]
TABLE 1
Approximate Weight Percent
Component
On a Wet Basis
Protein
2-25
Carbohydrate
3-40
Fat
0-10
Fiber
Less than 2
Water
25-90
[0015] Suitable sources for protein useful in the composition of the present invention include both animal and plant based protein. A non-exhaustive list of animal based protein includes meat meal, meat and bone meal, blood meal, red blood cells, dried porcine solubles, hydrolyzed feather meal, fish meal, dried milk, plasma and serum protein, poultry by-product meal, dried whey, whey protein concentrate and eggs. Suitable concentration of plasma and/or a serum protein in gel feed is about 0-25 wt. % and a suitable concentration of egg is about 0-15%. A non-exhaustive list of plant based protein includes alfalfa meal, canola seed meal, rice protein, coconut meal (copra), wheat gluten, potato protein, cotton seed meal, linseed meal (flax), peanut meal, safflower meal, sesame meal, soybean meal, soybean proteins and sunflower meal and other oil seed meals.
[0016] Sources for carbohydrates useful in the present invention include sorgum flour, ground rice, rice flour, ground corn, oat products, wheat, ground sorgum, or starch from any suitable grain such as wheat, oats, barley, and triticale, or tubers such as tapioca, and potato. Lactose, dextrin, sucrose, fructose and other simple sugars are also suitable carbohydrates.
[0017] Fat useful in the present invention may come from both plant or animal sources. Some fat may be the result of inclusion in the protein or carbohydrate source. However, additional fat may be added and is typically a rendered product such as a blended fat (animal and vegetable blends), or may be a poultry fat or tallow or a vegetable source such as soybean oil, corn oil, canola oil, coconut oil, olive oil and the like. Fat is necessary as a source of energy and also in the assimilation of certain vitamins that may be added to the feed of the present invention.
[0018] Fiber useful in the present invention is dietary fiber. Principal sources of dietary fiber are the same plant sources that provide protein and/or carbohydrates. If additional dietary fiber is needed, it may be obtained from such typical sources as soybean hulls or psyllium.
[0019] In addition to the nutrients discussed above, it may be desirable to provide additional supplementation of vitamins and minerals depending on the needs of the particular animal.
[0020] One gelling agent used in the present invention is a gum which binds with water and is capable of forming a matrix in which the feed components (nutrients discussed previously) are retained. Examples of suitable gums include agar, alginate, carrageenan, gum Arabic, ghatti, tragacanth, pectin, guar, Gelan, Carboxy Methylcellulose and locus bean. In the case of alginate, about 0.25 to 1.5 weight percent alginate of the feed components (excluding water) is necessary to form the gel. Other types of gels are also includable within the present invention, including those based on carbohydrates other than gums such as the starches including sorghum flour, ground rice, rice flour, ground extruded corn, ground sorghum, wheat and sugars including dextrin and sucrose. Other gelling agents that may be useful in the present invention include pectin, chitin, and gelatin based on animal protein.
[0021] The gel of the present invention is preferably a cold set gel, however, a gel made by heating the gum in water such as described in U.S. Pat. No. 5,217,740 which is hereby incorporated by reference is included within the present invention. In the specific embodiment discussed herein, the gel feed is not made through the use of an external heat source. Initially, the protein, carbohydrate, fat and fiber components and any other nutrients, vitamins, minerals or other supplements along with the gum and a source of calcium are mixed in water according to selected portions within the ranges of Table 1. The portions chosen are engineered for the particular animal and the particular period in the lifecycle of the animal. For example, piglets during and after weaning would require different portions of the components listed in Table 1 as compared to a sow during gestation.
[0022] Preferably, the source of calcium is insoluble with water or includes a sequestrant that inhibits the calcium from reacting with the alginate so that an immediate gel does not form. Gels formed through the reaction between calcium and alginate are well known. The propensity for alginate to form a gel and the difficulty of forming an appropriate gel are also well known. The method of the present invention in forming the gel provides for a controlled formation of alginate gel. The use of sequestrants or the use of acids to control alginate gel formation in the presence of calcium for use in human food is known.
[0023] Preferably, the source of calcium is a calcium salt which is initially insoluble but may be made soluble. One calcium salt suitable in the present invention is dicalcium phosphate. Dicalcium phosphate is virtually insoluble in water at a pH of 6 or above. Other calcium salts suitable for use include calcium carbonate, calcium gluconate, calcium iodate, calcium oxide, calcium sulfate.
[0024] Once the mixture is mixed, the pH is lowered. Preferably citric, fumaric, or propionic acid are used alone or in combination with other organic acids. Other organic or mineral acids or acidulents suitable in lowering the pH are included within the present invention. Once the pH is lowered below about pH 4.5, the gel of the present invention forms.
[0025] The strength of an alginate based gel depends on a number of factors including calcium levels, pH and the type of alginate used. Varying the calcium content, or varying the type of alginate used or adjusting the pH can create gels of different gel strength. Low calcium availability, either due to pH or low calcium concentration, may form a soft gel. A low pH may result in a harder gel. Water hardness may also have an effect on the formation of the alginate gel depending on the calcium carbonate content of the water.
[0026] The alginate based gel of the present invention may be made in either a batch or continuous manner. If made in a batch, the nutrients, alginate, dicalcium phosphate and water are mixed together. An organic acid is then added to lower pH to a selected level upon which the gel forms. However, mineral acids are also suitable for addition. For production in a continuous fashion, again a batch of nutrients with alginate, dicalcium phosphate and water are mixed initially in a tank. In a second tank, water and the acids are mixed. These two mixtures are then pumped through an outlet line and mixed via an in line static mixer to continuously form the gel.
[0027] One particularly useful situation for the present invention includes providing nutrients to piglets during weaning. Weaning presents many challenges to the young pig. These challenges include an abrupt change from a liquid to a solid diet that contains ingredients that may not initially be easily digestible to the young pig. In addition, the young pig is presented with a new social structure. Combined, these effects disrupt nutrient intake that is necessary to maintain gut integrity. Such disruptions affect growth performance and are further exacerbated by an immature immune system which creates susceptibility to digestive upsets or diarrhea or both.
[0028] Research has shown that only 50% of the piglets drink water during the first 24 hours postweaning (Varley and Stockill, 2001).
[0029] During the first five days after weaning, water intake by the young pig fluctuates independently of apparent physiological need and water intake does not seem to be related to growth, feed intake or severity of diarrhea. (McLeese et al. 1992). After the fifth day, however, it seems that water intake follows a more consistent pattern that parallels growth and feed intake. It has been speculated that during the first few days after weaning, water consumption may be high as a consequence of a need for gut fill to obtain a sense of satiety in the absence of feed intake. Voluntary feed of early-weaned pigs fed dry diets during the first few days after weaning is often limited. Evidence suggests that growth rate of early-weaned pigs is largely limited by feed intake rather than growth potential. Pluske (1993) reported that the weanling pig does not meet the maintenance requirements until the 5 th day after weaning at 21 days of age.
[0030] The gel product of the present invention provides the young piglet not only with the required nutrient intake but also with the appropriate water requirement. Utilizing the gel feed of the present invention, piglets surprisingly started eating the gel feed of the present invention almost immediately after weaning. Preferably, a gel-type feed for young piglets includes a high quality protein source such as spray dried plasma protein. It has been shown that spray dried plasma protein helps to improve performance during the first 7 to 14 days after weaning and during periods of stress for young pigs. It appears that plasma protein has biological functions beyond its nutritional qualities.
[0031] The present invention is more particularly described in the following examples that are intended as illustrations only since numerous modifications and variations within the scope of the present invention will be apparent to those skilled in the art.
EXAMPLE 1
[0032] A total of 57 weaning pigs averaging 13.3 lb body weight were used in a 35-day growth trial. Some of the piglets were fed a gel based feed in which the gel matrix was a starch (Soft Set™ starch obtained from Staley Mfg. Co., of Decatur, Ill.). A control (no gel) feed along with two gel feeds, each gel feed containing a different protein source (Solutein™ or Appetein™ obtained from American Protein Corp of Ames, Iowa) were used in the trial. Appetein™ is a plasma based protein while Solutein™ is a serum based protein. The formulation for the gel containing Solutein™ is listed in Table 2 below while the gel containing Appetein™ is listed in Table 3 below.
[0000]
TABLE 2
Ingredient
Dry wt. %
Lbs.
Solutein ™
14.4000
1.44
Sucrose
19.6388
1.96
Sodium Chloride
0.4000
0.04
Citric Acid Anhydrous
2.0000
0.20
Fumaric Acid
4.0000
0.40
Potassium Sorbate
4.0000
0.40
Propionic Acid
2.0000
0.20
Dicalcium Phosphate
3.2000
0.32
Choline Chloride 60%
0.3897
0.04
Luctarom LS 1
1.2000
0.12
Soft Set Starch
40.0000
4.00
Mineral Pmx 2 2
2.3120
0.23
Vit Pmx 1 2
3.3796
0.34
Copper Sulfate
0.0799
0.01
Animal Fat
3.0000
0.30
1 Lucta, S.A., Spain
2 Land O'Lakes, Inc., Arden Hills, MN
[0000]
TABLE 3
Ingredient
Dry wt. %
Lbs.
Plasma Protein
14.4000
1.44
(Appetein ™)
Sucrose
19.6388
1.96
Sodium Chloride
0.4000
0.04
Citric Acid Anhydrous
2.0000
0.20
Fumaric Acid
4.0000
0.40
Potassium Sorbate
4.0000
0.40
Propionic Acid
2.0000
0.20
Dicalcium Phosphate
3.2000
0.32
Choline Chloride 60%
0.3897
0.04
Luctarom LS 1
1.2000
0.12
Soft Set Starch
40.0000
4.00
Mineral Pmx 2 2
2.3120
0.23
Vit Pmx 1 2
3.3796
0.34
Copper Sulfate
0.0799
0.01
Animal Fat
3.0000
0.30
1 Lucta, S.A., Spain
2 Land O'Lakes, Inc., Arden Hills, MN
[0033] The dry ingredients in the formulations listed in Tables 2 and 3 were blended in a 5-quart KitchenAid Mixer. Propionic acid and water (3 parts water to 1 part of the listed ingredients in Tables 2 and 3) were blended in five gallon buckets utilizing a Myers Mixer mixing the liquid contents for 30 seconds. After 30 seconds, the dry mix was added and the dry and liquid ingredient mixture were blended for an additional three minutes. Five batches of each formulation (Solutein™ and Appetein™) were made.
[0034] At weaning, pigs were sorted by weight, and divided into six weight groups (blocks). Dietary treatments were randomly assigned to pens (3-4 pigs per pen) within each of the weight groups (blocks, 6 replication/treatment). Pens within a block had the same number of pigs. Three dietary treatments were evaluated and consisted of the following:
[0000]
TABLE 4
TRT
3
2
Starch based gel
1
Starch based gel
with Appetein ™
Control (no gel)
with Solutein ™
(plasma protein)
Days 0-4
Pellet diet
Team Lean 10-15
Team Lean 10-15
Team Lean 10-15
Gel type
None
Solutein ™
Appetein ™
Days 4-7
Pellet diet
Team Lean 10-15
Team Lean 10-15
Team Lean 10-15
Gel type
None
50:50 mix
50:50 mix
(gel with
(gel with
Solutein ™:Team
Appetein ™:Team
Lean 10-15)
Lean 10-15)
Days 7-21
Pellet diet
Team Lean 14-20
Team Lean 14-20
Team Lean 14-20
Days 21-35
Pellet diet
Team Lean 25-50
Team Lean 25-50
Team Lean 25-50
Team Lean 10-15 is a dry pelleted feed formulation from Purina Mills of St. Louis, MO.
Team Lean 14-20 is a dry pelleted feed formulation from Purina Mills of St. Louis, MO.
Team Lean 25-50 is a dry pelleted feed formulation from Purina Mills of St. Louis, MO.
[0035] Team Lean 10-15 pellets were fed for 7 days, Team Lean 14-20 pellets and Team Lean 25-50 pellets were fed for 14 days each. All pellets were fed in metal feeders attached to pen gates. Gel feeds were fed from days 0 to 4 postweaning in creep feeders, and a mix (50:50) of gel and dry feed (Team Lean 10-15 pellets) was fed from days 4 to 7 postweaning in creep feeders.
[0036] Pigs were housed in a conventional nursery facility in pens with a nipple waterer, four-hole feeder, and plastic grate flooring. Pigs had ad libitum access to feed and water. Pig body weight and feed intake (both gel feed and pellet) were determined at days 0, 4, 7, 14, 21, and 35 postweaning to evaluate average daily gain (ADG), average daily feed intake (ADFI), and feed:gain ratio. Gel feed intake was measured during the first week postweaning. In addition, fecal color and consistency scores were taken twice a week.
[0037] Data were analyzed as a randomized complete block design with pen as the experimental unit and blocks based on initial body weight. Mean separation for significant treatment effects was accomplished by least significant difference (LSD) procedures.
[0000]
TABLE 5
TRT 2
TRT 3
TRT 1
with
with
Gel Feed
None
Solutein ™
Appetein ™
SE
(1)
(2)
(3)
ADG Day 0-7
0.390
0.450
0.434
0.0988
—
—
—
ADG Day 7-14
0.718
0.719
0.880
0.0709
—
—
.14
ADG Day 14-21
1.02 a
1.17 b
1.12 b
0.0288
.01
.01
—
ADG Day 21-35
1.26
1.34
1.34
0.0335
—
.10
—
ADG 0-Final
0.930
1.003
1.022
0.0388
—
.11
—
Dry gel intake
Day 0 to 4, lb/hd/d
0
0.169
0.154
0.0569
—
.03
—
Day 4 to 7, lb/hd/d
0
0.090
0.071
0.0073
.13
.03
—
Day 0 to 7, lb/hd/d
0
0.135
0.119
0.0055
.09
.03
Pellets lb/hd/d, Day 0-7
0.43 a
0.647 b
0.627 ab
0.0636
.07
.03
ADFI Day 7-14 lb
0.864
0.948
1.016
0.0819
—
—
—
ADFI Day 14-21 lb
1.22 a
1.38 b
1.39 b
0.0414
.03
.01
—
ADFI Day 21-35 lb
1.80
1.96
1.91
0.0585
.20
.09
—
ADFI Day 0-35 lb
1.22 a
1.40 b
1.40 b
0.0563
.08
.03
Gain/Feed Day 0-7 lb
0.879
0.677
0.615
0.0883
.14
.06
—
Gain/Feed Day 7-14 lb
0.822
0.762
0.871
0.0582
—
—
—
Gain/Feed Day 14-21 lb
0.822
0.840
0.796
0.0148
.17
—
.07
Gain/Feed Day 21-35 lb
0.706
0.685
0.700
0.0147
—
—
—
Gain/Feed Day 0-35 lb
0.759
0.729
0.738
0.0121
.20
.10
—
Initial Weight lb
13.3
13.3
13.3
0.019
—
—
—
4 Day Weight lb
14.4
14.7
14.9
0.369
—
—
—
7 Day Weight lb
16.0
16.4
16.3
0.692
—
—
—
14 Day Weight lb
21.0
21.5
22.5
1.00
—
—
—
21 Day Weight lb
28.1
29.6
30.3
1.14
—
—
—
35 Day Weight lb
45.8
48.4
49.1
1.37
—
.11
—
PR > F if <.10 for (1) Geltype (2) Standard vs Gel (3) Solutein ™ vs Plasma
Values in treatment columns are simple arithmetic mean values and mean values in the same row not followed by a common letter differ (P < .05) using LSD procedure.
[0038] No significant differences (P≧0.1) were observed in ADG among treatment groups during days 0 to 7 and 7 to 14 postweaning (Table 5). Pigs fed gel feeds, however, had numerically greater ADG than pigs not fed gel feed. During days 14 to 21 and 21 to 35 postweaning, pigs fed the gel feeds continued to have greater (P<0.1) ADG than pigs receiving no gel feed. Similarly, during the overall 35 day trial period, pigs fed the gel feed tended to have greater (P<0.11) ADG than those not receiving the gel feeds. By day 35 postweaning, pigs fed the Solutein™ and Appetein™ containing gel were 2.6 and 3.3 lb heavier, respectively than those not receiving the gel feed.
[0039] Gel feed also containing Solutein™ intake was similar to gel feed containing Appetein™ intake during days 0 to 4, 4 to 7, and 0 to 7 postweaning. During days 0 to 7, ADFI of pellets was greater (P<0.03) in pigs fed the gel feed than in those not receiving the gel feed. This is probably an indication of some dry feed wastage when the pellets were mixed with the gel feed. During days 7 to 14, pigs fed the gel feed had numerically greater ADFI than those receiving no gel feed. During days 14 to 21, 21 to 35 and 0 to 35, pigs receiving the gel feed continued to have greater (P<0.1) ADFI.
[0040] During days 0 to 7 postweaning, pigs fed the gel feeds had lower (P<0.06) gain:feed ratio than those not receiving the gel feed. This is probably an indication of some dry feed wastage when the pellets were mixed with the gel feed. No significant differences were observed in gain:feed ratio among treatment groups during days 7 to 14, 14 to 21 and 21 to 35 postweaning.
[0041] No significant differences in fecal color score and consistency were observed among treatment groups.
[0042] The results of this trial indicate that feeding a gel feed containing Solutein™ or Appetein™ (plasma protein) during the first week after weaning improved performance of nursery pigs. Improvements in gain were more evident in later phases which may suggest that gel feed intake during the first week after weaning may have a carry-over effect through the rest of the nursery period. By the end of the trial, pigs fed the gel feed containing Solutein™ and plasma protein were 2.6 and 3.3 lb heavier, respectively, than those not receiving the gel feed.
EXAMPLE 2
[0043] A total of 270 weaning pigs averaging 10.5 lb body weight were used in a 35-day growth trial. At weaning, pigs were sorted by weight, and divided into eleven weight groups (blocks). Each weight block had 20 or 25 piglets of as equal weight as possible. Five different dietary treatments were randomly assigned to each of the pens in each weight block. Each pen contained four or five piglets. The schedule of the dietary treatments is shown in Table 6 below:
[0000]
TABLE 6
Treatment
1
2
3
4
5
Gel Type (day 0-7)
None
Alginate Based
Alginate Based
Alginate Based
Gel Based on
Gel with
Gel with
Gel with
2 Alginate
Solutein ™
Plasma
Plasma protein
Types with
and egg
Solutein ™
Dry Feed (pellets)
Lean Metrics Infant 1
I
I
I
I
I
(I) (Day 0-7)
Lean Metrics Junior 1
J
J
J
J
J
(J) (Day 7-21)
Lean Metrics Senior 1
S
S
S
S
S
(S) (Day 21-35)
1 Dry feed pellets were produced at local feed mill and composition of pellets was according to Lean Metrics Starter Program of Purina Mills LLC. of St. Louis, MO.
[0044] The gel feeds for the four treatments in Table 6 above were mixed using a batch process. The composition of each of the treatments is indicated in Table 7 below. Initially, water, tetrasodium pyrophosphate, xanthan gum, alginate dicalcium phosphate and potassium sorbate were mixed together for about 2½ minutes in the proportions listed in Table 7 below. Treatment 5 (Table 6) utilized two alginate-types to form the gel. Then fat, vitamins and minerals, Luctarom®, and sucrose were mixed along with either dried animal plasma, Solutein™, or dried animal plasma and dried whole egg. The mixture was then mixed for one minute.
[0045] Each treatment was poured into five gallon buckets. While stirring the mixture in each of the five gallon buckets using a lab Myers mixer, fumaric acid, propionic acid and citric acid in the proportions listed in Table 7 were added until the mixture started to gel (about 15 seconds). Gel formation occurred in about five minutes.
[0000]
TABLE 7
Gel with 2
Alginate
Gel with
Gel with
Gel with
types with
Ingredient
Solutein ™
Plasma
Plasma Egg
Solutein ™
LOL STARTER MINERAL PX 1
0.0525
0.0525
0.0525
0.0525
LOL STARTER VITAMIN PX 1
0.0175
0.0175
0.0175
0.0175
DRY LUCTAROM (FLAVOR) 2
0.075
0.075
0.075
0.075
KELTROL-XANTHAN GUM 3
0.2
0.2
0.2
0.2
CITRIC ACID ANHYDROUS
0.5
0.5
0.5
0.5
FUMARIC ACID
1
1
1
1
PROPIONIC ACID
0.5
0.5
0.5
0.5
MANUGEL GMB-ALGINATE 4
1
1
1
0.5
MANUCOL DH-ALGINATE 4
—
—
—
0.5
OATMEAL
10.84
9.4525
9.4525
10.84
ANIMAL PLASMA-DRIED
—
4.5
3
—
DRIED WHOLE EGG
—
—
1.5
—
SOLUTEIN ™
4
—
—
4
DICALCIUM PHOSPHATE
0.17
0.17
0.17
0.17
SALT
0.1
0.1
0.1
0.1
SUCROSE
4.7
5.5875
5.5875
4.7
ANIMAL FAT
0.75
0.75
0.75
0.75
WATER
75
75
75
75
CHOLINE CHLORIDE 60%
0.025
0.025
0.025
0.025
COPPER SULFATE
0.02
0.02
0.02
0.02
POTASSIUM SORBATE
1
1
1
1
TETRASODIUM
0.05
0.05
0.05
0.05
PYROHOSPHATE
1 Land O'Lakes, Inc., Arden Hills, MN
2 Lucta, S.A., Spain
3 Monsanto Company, St. Louis, MO
4 International Specialty Products, Wayne, New Jersey
[0046] Pigs had ad libitum access to pelleted diets in metal feeders which were located on pen gates in each pen. Gel feeds for treatments 2, 3, 4 and 5 were fed in round pan type creep feeders added to each pen in which the piglets were to be subjected to a gel-type feed. The gel feed was fed ad libitum and gel feed was added later each day if all the gel feed in that pen was consumed. The piglets also had unlimited access to water. In treatments 2, 3, 4 and 5, dry feed (pellets) was added to the gel feed on days 3-7. On day 3, 0.1 pounds of dry feed was added per pound of gel feed. On day 4, 0.5 pounds of dry feed was added per pound of gel feed. On days 5, 6 and 7, 1 pound of dry feed was added per 1 pound of gel feed. Gel feed intake ended in all treatments after Day 7.
[0047] Pig body weight and feed intake (gel feed and pellet) were determined at initiation and days 7, 14, 21, and 35 postweaning to evaluate average daily gain (ADG), average daily feed intake (ADFI), and feed:gain ratio. In addition, fecal color and consistency scores were taken twice a week.
[0048] Data were analyzed as a randomized complete block design with pen as the experimental unit and blocks based on initial body weight. (See Table 8) The effects of initial weight (less than 10 lb and greater than 10 lb), gel type, and initial weight×gel type were evaluated.
[0000]
TABLE 8
P > F if <.20
Gel
Less than 10 lb Body Weight
Greater than 10 lb Body Weight
Feed
Plasma
Solutein
Plasma
Solutein
Size
v. No
and
and 2
and
and 2
Treat-
v. treat-
Gel
Gel Type
None
Solutein
Plasma
egg
alginates
None
Solutein
Plasma
egg
alginates
SE
ments 1
ment 2
Feed 3
Week 1
ADG, lb
0.202
0.285
0.201
0.318
0.235
0.391
0.360
0.338
0.388
0.325
0.020
0.04
—
—
ADFI
0.214
0.162
0.093
0.201
0.194
0.423
0.251
0.200
0.303
0.240
0.023
0.01
0.19
0.01
(pellet)
only)
Dry gel, lb
—
0.170
0.200
0.184
0.146
—
0.188
0.233
0.183
0.179
0.017
0.05
—
0.01
Wet gel, lb
—
0.679
0.798
0.735
0.583
—
0.752
0.932
0.733
0.717
0.068
0.05
—
0.01
Pellet in
—
0.294
0.315
0.306
0.241
—
0.303
0.318
0.299
0.299
0.0126
0.09
—
0.01
mix, lb
Week 2
ADG, lb
0.321
0.318
0.322
0.358
0.391
0.582
0.567
0.509
0.587
0.508
0.0203
—
0.11
—
ADFI
0.403
0.412
0.394
0.408
0.448
0.607
0.543
0.535
0.563
0.537
0.018
—
—
—
(pellet)
Feed:
1.274
1.298
1.279
1.162
1.153
1.045
0.971
1.066
0.973
1.076
0.038
—
—
—
gain
Week 3
ADG, lb
0.594
0.809
0.712
0.798
0.847
0.937
0.975
0.968
0.950
0.900
0.0357
0.12
0.07
0.01
ADFI
0.742
0.914
0.821
0.897
0.954
1.173
1.171
1.086
1.101
1.079
0.029
0.18
0.02
0.18
(pellet)
Feed:
1.252
1.134
1.175
1.123
1.154
1.255
1.205
1.157
1.152
1.200
0.0423
—
—
0.06
gain
Weeks 3-5
ADG, lb
0.844
0.941
0.902
0.938
0.963
1.201
1.197
1.266
1.227
1.095
0.0342
—
0.13
—
ADFI
1.091
1.261
1.175
1.237
1.257
1.624
1.587
1.664
1.626
1.439
0.036
—
0.01
—
(pellet)
Feed:
1.292
1.339
1.302
1.319
1.307
1.352
1.328
1.312
1.325
1.319
0.015
—
—
—
gain
Weeks 0-5
ADG, lb
0.561
0.659
0.608
0.670
0.680
0.863
0.859
0.869
0.876
0.784
0.0187
0.19
0.01
0.07
ADFI
0.708
0.802
0.732
0.796
0.822
1.09
1.028
1.030
1.044
0.947
0.0201
—
0.01
—
(pellet)
Feed:
1.260
1.290
1.300
1.267
1.267
1.264
1.257
1.257
1.248
1.272
0.0131
—
—
—
gain
Pig Weight,
lb
Initial
8.51
8.52
8.51
8.52
8.52
12.13
12.14
12.14
12.13
12.14
0.002
Week 1
9.93
10.52
9.92
10.74
10.16
14.86
14.65
14.51
14.85
14.41
0.144
0.05
—
—
Week 2
12.17
12.74
12.17
13.25
12.90
18.94
18.62
18.07
18.95
17.97
0.218
0.04
0.13
—
Week 3
16.33
18.40
17.16
18.84
18.83
25.50
25.45
24.84
25.60
24.27
0.329
0.03
0.01
0.05
Week 5
28.14
31.58
29.78
31.97
32.31
42.32
42.20
42.56
42.78
39.59
0.654
0.19
0.01
0.07
1 Treatment effect
2 Initial weight (greater than 10 lb versus less than 10 lb) × treatment interaction effect.
3 No gel versus gel during the first week of treatment
[0049] During the first week postweaning, numeric improvements in ADG were observed in pigs weighing initially less than 10 lb and fed a gel feed during the first week. No improvements in ADG, however, were observed in pigs weighing greater than 10 lb. During week 2, no significant differences were observed in ADG among treatment groups. During week 3, weeks 3-5, and during the overall 5-week trial period, a gel feed improved ADG of nursery pigs initially weighing less than 10 lb, but had little effect on pigs initially weighing greater than 10 lb at (initial wt×gel interaction, P=0.07, P=0.13, and P=0.01, respectively). Gel intake during the first week after weaning had a carry-over effect through the rest of the nursery period. By the end of the trial, pigs weighing less than 10 lb and receiving the gel feed of treatments 2, 3, 4 and 5 were 3.44, 1.64, 3.83, and 4.17 lb, respectively heavier than pigs receiving no gel.
[0050] During the first week postweaning, pigs given gel feed consumed less (P<0.01) dry feed (pellets) than those not receiving the gel feed. Pigs receiving the gel feed with plasma consumed more gel feed but consumed less dry feed (pellets). Pigs receiving the 2 alginate-type gel feed with Solutein™ consumed less gel feed. No significant differences (P>0.1) were observed in ADFI among treatment groups during week 2.
[0051] A significant initial weight x gel type interaction (P<0.05) was observed in ADFI during week 3, weeks 3-5, and weeks 0-5. During week 3, pigs weighing <10 lb at weaning and receiving the gel containing Solutein™, plasma and egg, or the Solutein™ plus 2 alginates consumed more (P<0.05) dry feed (pellets) than those not receiving the gel feed. During weeks 3-5, pigs weighing<10 lb at weaning and receiving the Solutein™ or the Solutein™ plus 2 alginates gel consumed greater amounts (P<0.05) of dry feed than those receiving no gel. Pigs weighing>10 lb at weaning and receiving the Solutein™ plus 2 alginates gel consumed less (P<0.05) dry feed than those not receiving the gel. Similarly, during weeks 0-5, pigs weighing<10 lb at weaning and consuming the Solutein™, plasma plus egg or the Solutein™ plus 2 alginates gel consumed more dry feed (P<0.05) than those not receiving the gel. Pigs weighing>10 lb at weaning and fed the Solutein™ plus 2 alginates gel consumed less dry feed (P<0.05) than those fed the other treatments.
[0052] No significant differences were observed in feed:gain ratio among treatments during week 2, week 3, week 3-5, or weeks 0-5. During week 3, however, pigs fed gel feed during week 1 (treatments 2, 3, 4 and 5) had improved feed:gain compared to those receiving no gel feed (P<0.1).
[0053] The results of this trial indicate that feeding any of the gel feeds (treatments 2, 3, 4 and 5) during the first week after weaning improved performance of nursery pigs weighing less than 10 lb at weaning, but had little effect on performance of nursery pigs weighing greater than 10 lb at weaning. By the end of the trial (week 5), pigs weighing less than 10 lb at weaning and receiving gel feeds (treatments 2, 3, 4 and 5) were heavier than pigs receiving no gel feed. Pigs receiving the gel feed with plasma and egg had numerically greater gains than those fed treatments 2 and 3.
EXAMPLE 3
[0054] One hundred-ninety weanling barrows (MCG GPK 35 maternal) averaging 12.2 lb body weight were used in a 35-day growth trial to evaluate the effect on performance of nursery pigs receiving a standard nursery program by feeding a gel feed during the first week after weaning. At weaning, pigs were sorted by weight, and divided into eight weight groups (blocks) of twenty or twenty five pigs per weight group. Four weight groups averaged 10.6 lb (small reps) and four weight groups averaged 13.8 lb (large reps). Pigs within each weight block were allotted into five equal subgroups (pens) of five or four pigs per pen (8 pens/treatment; 4 small reps and 4 large reps/treatment). The number of pigs per pen within each block was kept constant. Dietary treatments were randomly assigned to pens (subgroups) within each of the weight groups (blocks). Five dietary treatments were evaluated during Phase 1 (day 1 to day 7 postweaning). Gels evaluated are described in the following table:
[0000]
TABLE 9
Gel Type
Gel A
Gel B
Gel C
1% Algin,
0.5% Algin,
0.5% Algin,
Ingredient
75% H 2 0
75% H 2 O
62% H 2 O
LOL Starter Mineral PX 1
0.0525
0.0525
0.0525
LOL Starter Vitamin PX 1
0.0175
0.0175
0.0175
Dry Luctarom 2
0.075
0.075
0.075
Keltrol-Xanthan Gum 3
0.2
0.2
0.0
Citric Acid Anhydrous
0.5
0.5
0.5
Manugel GMB-Alginate 4
1
0.5
0.5
Sodium Hexametaphosphate
0.25
0.25
0.25
Feeding Oatmeal
9.2525
9.7525
14.09
Animal Plasma-Dried
3
3
4.5
Dried Whole Egg
1.5
1.5
2.25
Fructose
0
5.5875
5.6
Dicalcium Phosphate
0.17
0.17
0.17
Salt
0.1
0.1
0.1
Sucrose
5.5875
0
5.6
Animal Fat
0.75
0.75
1.25
Water
75
75
62.5
Choline Chloride 60%
0.025
0.025
0.025
Copper Sulfate
0.02
0.02
0.02
Fumaric Acid
1
1
1
Potassium Sorbate
1
1
1
Propionic Acid
0.5
0.5
0.5
1 Land O'Lakes, Inc., Arden Hills, MN
2 Lucta, S.A., Spain
3 Monsanto Company, St. Louis, MO
4 International Specialty Products, Wayne, New Jersey
[0055] The gel feeds described in Table 9 were mixed using the batch process as described in Example 2. The dry pelleted feeds, Lean Metrics Infant, Lean Metrics Junior, and Lean Metrics Senior are commercially available pelleted feed formulated for feeding to pigs according to their ages (days of treatment) described in Table 10.
[0000]
TABLE 10
Treatment Description a
Treatment 2
Treatment 3
Treatment 4
Treatment 5
Gel A (75% H 2 O)
Gel B (75% H 2 O)
Gel C (62% H 2 O)
Gel A (75% H 2 O)
Treatment 1
Plasma + egg
Plasma + egg
Plasma + egg
Plasma + egg
Control
1% Algin
0.5% Algin
0.5% Algin
1% Algin
No Gel
(7 days)
(7 days)
(7 days)
(3 days)
Days 1-7
Pellets: Lean
I
I
I
I
I
Metrics Infant (I)
Days 7-21
Pellets: Lean
J
J
J
J
J
Metrics Junior (J)
Days 21-35
Pellets: Lean
S
S
S
S
S
Metrics Senior (S)
a Lean Metrics Infant, Lean Metrics Junior, and Lean Metrics Senior are dry pelleted feed formulations from Purina Mills, LLC of St. Louis, MO.
[0056] Pigs had ad libitum access to pelleted diets in metal feeders which were located on pen gates on treatments 1 to 4. Gel diets were fed in round creep feeders (added to each pen) to pigs on treatments 2, 3 and 4 on days 1 to 3 post weaning. On days 4-7, a combination of gel plus dry feed was offered in creep feeders to pigs in treatments 2-4. 0.1, 0.5, 1 and 1 lb of dry feed per lb of gel was added to the creep feeders on days 4, 5, 6, and 7, respectively. Pigs on treatment 5 were fed gel only in the metal feeders on the pen gates on days 1 to 2. On day 3, 1 lb of dry feed per lb of gel was added and offered in the metal feeder on the pen gate. On day 4 through the remainder of the study only dry feed was offered in the metal feeder on the pen gate.
[0057] Pig body weight and feed intake (pellet) were determined at initiation, days 7, 14, 21, and 35 post weaning to evaluate average daily gain (ADG), average daily feed intake (ADFI), and feed:gain ratio. Gel intake was measured during the first week post weaning. In addition, fecal color and consistency scores were taken twice a week.
[0058] Data was analyzed as a randomized complete block design with the pen as the experimental unit and block based on initial body weight. The effects of initial weight (small and large), rep (size), gel type, and initial weight×gel type were evaluated.
[0059] During the first week postweaning, no signinficant differences (P>0.10) were observed in ADG among treatment groups. Numeric improvements, however, were observed in ADG by supplementing the gel to weanling pigs. The greatest effect was observed with the smallest pigs. Pigs weighing less than 10.6 lb on average (9 to12 lb) and fed the gel containing 75% water and 0.5% alginate (treatment 3) had numerically greater ADG than pigs fed the gel containing 62% water and 0.5% algin (treatment 4). The biggest pigs (weighing 13.8 lb on average, 12 to 17 lb), however, grew better when fed the gel containing 62% water than when fed the gel containing 75% water. In addition, pigs offered the gel in the regular feeders for the first three days after weaning had numerically greater ADG than those offered the gel in the creep feeders. This was probably due to greater consumption of dry feed by pigs offered the gel in the regular feeder for only three days and then followed by just dry feed in the regular feeders.
[0060] During week 2, week 3, and overall, the smallest pigs supplemented with the gel continued to have numerically greater ADG than those not supplemented with the gel. By day 35 postweaning, the smallest pigs on treatment 2, 3, 4, and 5 were 0.86, 1.53, 2.01, and 3.43 lb heavier, respectively than those no receiving the gel (treatment 1).
[0061] As expected, during week 1, pigs on treatment 5 (received gel for only 3 days) consumed less gel (P<0.05) but consumed more dry feed from the regular feeder (P<0.05) than pigs on treatment 2, 3, and 4. Pigs on treatment 5 consumed similar amounts of dry feed as those on treatment 1 (control). Pigs on treatment 2, 3, and 4 had greater pellet intake per day than those in treatment 1 or treatment 5. This may be a reflection of some feed wastage when pellets were mixed with the gel since pellet intake per day from the regular feeder was lower (P<0.05) in pigs fed treatment 2, 3, and 4 compared with pellet intake of pigs on treatment 1 and 5. During week 2, the smallest pigs receiving the gel had numerically greater (no statistically significant) pellet intake than those not receiving the gel.
[0062] During the first week postweaning, pigs on treatment 2, 3, and 4 had greater (P<0.05) feed:gain ratio than pigs on treatment 1 or treatment 5. This is probably an indication of feed wastage when the pellets were mixed with gel. During week 2, pigs in treatment 5 utilized feed more efficiently than those in treatment 2. No significant differences (P>0.1) were observed in feed:gain ratio during week 3 or week 3 to 5 among treatment groups.
[0063] The results of this study indicate that feeding a gel containing plasma and egg during the first week after weaning improved performance of nursery pigs weighing between 9 to 12 lb at weaning, but had little effect on performance of nursery pigs weighing between 12 to 17 lb at weaning. Similar to previous experiments, gel supplementation during the first week after weaning had a carry-over effect through the rest of the nursery period and had the greatest effect in the smallest reps of pigs. By day 35 postweaning, the smallest reps of pigs on treatment 2 (plasma:egg gel with 75% water and 1% alginate), treatment 3 (plasma:egg gel with 75% water and 0.5% algin), treatment 4 (plasma:egg gel with 62% water and 0.5% alginate), and treatment 5 (as treatment 2, but gel was offered in regular feeder for only 3 day) were 0.86, 1.53, 2.01, and 3.43 lb heavier, respectively than those no receiving the gel (treatment 1).
EXAMPLE 4
[0064] Fifty four weanling pigs (MCG) averaging 7.5 lb body weight were used in a 40-day growth trial to evaluate the effect of feeding a gel with or without flavor on performance of nursery pigs receiving a standard nursery feeding program. At weaning, pigs were sorted by weight, and divided into six weight groups (blocks) of nine pigs per weight group. Dietary treatments were randomly assigned to pens (subgroups) within each of the weight groups (blocks). Three dietary treatments were evaluated during Phase 1 (day 1 to day 7 postweaning): 1) control (no gel), 2) a gel containing flavor, and 3) a gel without flavor.
[0065] The gel feeds (plasma and egg) were mixed using the batch process as described in Example 2. The dry pelleted feeds, Lean Metrics Premier, Lean Metrics Infant, Lean Metrics Junior, and Lean Metrics Senior are commercially available pelleted feed formulated for feeding to pigs according to their ages (days of treatment) described in Table 11.
[0000]
TABLE 11
Treatment Description a
Treatment 1
Control
Treatment 2
Treatment 3
No Gel
Gel with flavor
Gel without flavor
Days 1-7
Pellets: Lean
P
P
P
Metrics Premier (P)
Days 7-14
Pellets: Lean
I
I
I
Metrics Infant (I)
Days 14-28
Pellets: Lean
J
J
J
Metrics Junior (J)
Days 28-40
Pellets: Lean
S
S
S
Metrics Senior (S)
a Lean Metrics Premier, Lean Metrics Infant, Lean Metrics Junior, and Lean Metrics Senior are dry pelleted feed formulations from Purina Mills, LLC of St. Louis, MO.
[0066] Pigs had ad libitum access to pelleted diets in metal feeders which were located on pen gates. Gel diets were fed in round creep feeders (added to each pen) to pigs on treatments 2 and 3 on days 1 to 3 post weaning. On days 4-7, a combination of gel plus dry feed was offered in creep feeders to pigs in treatments 2 and 3. 0.1, 0.5, 1 and 1 lb of dry feed per lb of gel was added to the creep feeders on days 4, 5, 6, and 7 respectively. Pig body weight and feed intake (pellet) were determined at initiation, days 7, 14, 28, and 40 post weaning to evaluate average daily gain (ADG), average daily feed intake (ADFI), and feed:gain ratio. Gel intake was measured during the first week post weaning.
[0067] Data was analyzed as a randomized complete block design with the pen as the experimental unit and block based on initial body weight.
[0068] During the first week postweaning, pigs fed the gel with or without flavor had greater (P<0.05) ADG than pigs not receiving gel, and pigs fed the gel with flavor had greater ADG than those fed the gel without flavor. Pigs fed the gel with flavor consumed greater amounts of gel than those fed the gel without flavor. Similarly, pigs fed the gels had numerically greater pellet intake than those not receiving the gel. By day 40 postweaning, pigs on treatment 2 (gel with flavor) and treatment 3 (gel without flavor) were 2.1 and 1.8 lb heavier, respectively than those not receiving the gel (treatment 1; Table 12).
[0000]
TABLE 12
Performance of pigs fed a gel with our without flavor a
Gel with
Gel without
Day 0 to 40
Control
Flav
Flav
SEM
ADG, lb
0.857
0.906
0.898
0.026
Pellet intake, lb per day
1.07
1.10
1.15
0.034
Gel intake, lb per day
0
0.328
0.185
0.043
Initial Weight
7.54
7.55
7.54
0.01
Weight day 40
41.7
43.8
43.5
1.06
a Six pens per treatment and 3 pigs per pen (5.8-9.7 lb beginning weight, 9 to 14 day of age).
EXAMPLE 5
[0069] A trial was conducted to evaluate the effect of feeding a gel (plasma and egg) three days prior to weaning and seven days postweaning on performance of nursery pigs. Ten litters received the gel in the farrowing crate on creep feeders or in a matt for 3 days prior to weaning. At weaning, ⅓ of each litter received the feeding program described in Table 13 for treatment 1, ⅓ received the feeding program described for treatment 2, and ⅓ received the feeding program described for treatment 3. A total of 90 weanling pigs averaging 10.9 lb were used. Only pigs in treatment 3 received gel in the nursery and were fed in round pan type creep feeders added to each pen. On day 4, 0.5 pounds of dry feed per pound of gel was added. On days 5, 6, and 7, 1 pound of dry feed per pound of gel was added.
[0070] The gel feeds (plasma and egg) were mixed using the batch process as described in Example 2. The dry pellet feeds are commercially available pellet feed formulated for feeding to pigs according to their ages (days of treatment) as described in Table 13.
[0000]
TABLE 13
(Ration Use) a
Treatment
1
2
3
Gel in Farrowing
Gel (plasma + egg)
Gel (plasma + egg)
Gel (plasma + egg)
Gel in Nursery (day 1-7)
No gel
No gel
Gel (plasma + egg)
Dry Diets
TW Program
UC Program
UC Program
Day 1-7
UWP
UC200
UC200
Day 7-14
LWT
UC240
UC240
Day 14-28
TWPH2
UC400
UC400
Day 28-39
TWPH3
UC500
UC500
a Ultra Wean Plus (UWP), Litter Wean Transition (LWT), Top Wean Phase 2 (TWPH2), Top Wean Phase 3 (TWPH3), Ultra Care 200 (UC200), Ultra Care 240 (UC240), Ultra Care 400 (UC400), and Ultra Care 500 (UC500) are dry pelleted feed formulations from Land O'Lakes Farmland Feed, LLC.
[0071] Data was analyzed as a randomized complete block design with the pen as the experimental unit and block based on initial body weight.
[0072] During the first week postweaning, pigs fed the gel three days prior to weaning (farrowing crates) and in the nursery (treatment 3) had greater (P<0.05) ADG than pigs receiving the gel only in the farrowing crate (no gel in the nursery, treatment 1 and treatment 2). During day 0 to 28 postweaning, pigs receiving treatment 3 continued to have greater ADG (P<0.10) and ADFI (P<0.05) than pigs receiving dietary treatment 2 (Table 14). During the overall 39-day trial, pigs receiving treatment 3 had greater ADFI (P<0.05) than those receiving treatment 2.
[0000]
TABLE 14
Performance per day 0 to 39 Postweaning a
Ultra
Top Wean
Ultra Care
Care + gel
SEM
Day 0 to 28
ADG, lb per day
0.894 de
0.866 d
0.912 e
0.015
ADFI, lb per day
1.05 bc
0.98 d
1.13 c
0.02
Day 0 to 39
ADG, lb per day
1.02
1.03
1.06
0.018
ADFI, lb per day
1.29 b
1.27 b
1.38 c
0.015
Pig weight, lb
Initial
11.03
10.94
10.95
0.05
Day 7
13.73 b
13.56 b
14.28 c
0.16
Day 28
36.00 de
35.2 d
36.5 e
0.44
Day 39
50.8
51.3
52.1
0.71
a Six pens per treatment and 5 pigs per pen (10.9 lb beginning weight).
bc Means in the same row with different superscript differ (P < 0.05)
dc Means in the same row with different superscript differ (P < 0.10) | A method of making a gel-type livestock feed includes initially forming a feed mixture by mixing feed nutrient components, water, alginate, and a calcium component insoluble in water or a sequestrate to inhibit the calcium component from reacting with the alginate. Once the feed mixture is formed, the calcium component is solubilized or the sequestrates affecting the reactivity between the alginate and the calcium component is removed such that a gel feed is formed that includes a gel matrix containing the feed nutrient components. The gel feed may then be fed to the livestock. In another aspect of the present invention, piglets are weaned by feeding the gel feed for at least seven days directly after weaning. The gel feed may also include protein derived from blood with or without egg protein. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to new 3-methyl oxetanemethanol derivatives and their use as fragrance chemicals suitable for incorporation in fine fragrances, cosmetics, toiletries and related applications.
BACKGROUND OF THE INVENTION
[0002] There is an ongoing need in the fragrance industry to provide new chemicals to give perfumers and other persons ability to create new fragrances for perfumes, colognes and personal care products. Those with skill in the art appreciate how differences in the chemical structure of the molecule can result in significant differences in the odor, notes and characteristics of a molecule. These variations and the ongoing need to discover and use the new chemicals in the development of new fragrances allows perfumers to apply the new compounds in creating new fragrances. The preparation of the compound 3-methyl oxetanemethanol is disclosed by Pattison (J. Amer. Chem. Soc., 79, p3455, 1957).
SUMMARY OF THE INVENTION
[0003] The present invention provides novel chemicals, and the use of the chemicals to enhance the fragrance of perfumes, toilet waters, colognes, personal products and the like. More specifically, the present invention is directed to the novel compounds represented by the general structure of the Formula I set forth below:
wherein R is selected from the group consisting of straight, branched, cyclic or aromatic hydrocarbon moieties containing single and/or double bonds; carbonyls and carboxy compounds.
[0004] In another embodiment, the present invention is directed to a method for enhancing a perfume by incorporating an olfactory acceptable amount of compounds represented by the general structure of the Formula II set forth below:
wherein R is selected from the group consisting of straight, branched, cyclic or aromatic hydrocarbon moieties containing single and/or double bonds; carbonyls and carboxy compounds.
[0005] These and other embodiments of the present invention will be apparent by reading the following specification.
DETAILED DESCRIPTION OF THE INVENTION
[0006] In the Formulae I and II above R is selected from the group consisting of straight, branched, cyclic or aromatic hydrocarbon moieties containing single and/or double bonds; carbonyls and carboxy compounds.
[0007] Suitable straight hydrocarbon moieties include ethyl, propyl, butyl, cyclopentyl, cyclohexyl, and the like. Suitable branched hydrocarbon moieties include isopropyl, sec-butyl, tert-butyl, 2-ethyl-propyl, and the like. Suitable hydrocarbon moieties containing double and triple bonds include ethene, propene, 1-butene, 2-butene, penta-1-3-deine, hepta-1,3,5-triene, butyne, hex-1-yne and the like. Suitable cyclic hydrocarbon moieties include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Suitable aromatic moieties include phenyl, benzyl, phenylethyl and the like. Suitable carbonyls include derivatives of aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benxaldehyde and the like; derivatives of ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone and the like.
[0008] In the preferred embodiment of the invention, the novel compounds of the present invention are represented by the following structures:
[0009] Those with the skill in the art will appreciate that the compound of Formula III is 3-methyl-3-[(2-propenyloxy)methyl] oxetane, the compound of Formula IV is 3-methyl-3-[(3-methylbutyl)oxy]methyl oxetane, the compound of Formula V is 3,7-dimethyl-1-[(3-methyloxetane-3yl)methyloxy]octa-2,6-diene.
[0010] The table below lists additional compounds derived from Formula I that are described in the present invention:
R Compound C(CH 3 )C 3 H 7 3-methyl-3-(3-methyl-hex-2- ethyloxymethyl)oxetane C(CH 3 )C 4 H 9 3-methyl-3-(3-methyl-hept-2- ethyloxymethyl)oxetane C(CH 3 )C 4 H 8 3-methyl-3-(3-methyl-hepta-2,6- dienyloxymethyl)oxetane C(CH 3 )C 2 H 4 CHC 2 H 4 3-(5-Cyclopropyl-3-methyl-pent-2- enyloxymethyl)-3-methyl-oxetane C(CH 3 )Phenyl 3-(3-cyclohexyl-but-2-enyloxymethyl)-3- methyl-oxetane C(CH 3 )CN 2-methyl-4-(3-methyl-oxetan-3-ylmethoxy)- but-2-enenitrile C(CH 3 )COCH 3 3-methyl-5-(3-methyl-oxetan-3-ylmethoxy)- pent-3-en-2-one C(CH 3 )COC 3 H 7 3-methyl-1-(3-methyl-oxetan-3-ylmethoxy)- hept-2-en-4-one C(CH 3 )COC 3 H 6 5-methyl-7-(3-methyl-oxetan-3-ylmethoxy)- hepta-1,5-dien-4-one C(CH 3 )COCH 2 CHC 2 H 4 1-cyclopropyl-3-methyl-5-(3-methyl-oxetan- 3-ylmethoxy)-pent-3-en-2-one
[0011] With reference to the compounds of our invention, the synthesis is effected by means of the reaction of 3-methyl oxetanemethanol with methyl ether under sodium methoxide catalysis to furnish the desired compound according to the scheme below:
base is added to a mixture of the 3-methyl oxetanemethanol and an ester which is then heated at a temperature ranging from 60° C. to 150° C., most preferably from 90° C. to 120° C. Methanol is distilled overhead and removed from the reaction. The mixture is cooled to 25° C. and neutralized with acetic acid. The reaction mass is given a 10% aqueous sodium chloride solution wash and the crude product is purified by distillation. The reaction occurs in 70-90% mole yield based on ester, methyl benzoate. The preparation of the compound 3-methyl oxetanemethanol is disclosed by Pattison (J. Amer. Chem. Soc., 79, p3455, 1957).
[0012] In another embodiment, the present invention is directed to a method for enhancing a perfume by incorporating an olfactory acceptable amount of compounds represented by the general structure of the Formula II set forth below:
wherein R is selected from the group consisting of straight, branched, cyclic or aromatic hydrocarbon moieties containing single and/or double bonds; carbonyls and carboxy compounds.
[0013] Suitable straight hydrocarbon moieties include ethyl, propyl, butyl, cyclopentyl, cyclohexyl, and the like. Suitable branched hydrocarbon moieties include isopropyl, sec-butyl, tert-butyl, 2-ethyl-propyl, and the like. Suitable hydrocarbon moieties containing double and triple bonds include ethene, propene, 1-butene, 2-butene, penta-1-3-deine, hepta-1,3,5-triene, butyne, hex-1-yne and the like. Suitable cyclic hydrocarbon moieties include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Suitable aromatic moieties include phenyl, benzyl, phenylethyl and the like. Suitable carbonyls include derivatives of aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, benxaldehyde and the like; derivatives of ketones such as acetone, methyl ethyl ketone, methyl n-propyl ketone, diethyl ketone, 2-hexanone, 3-hexanone and the like.
[0014] The table below lists some of the compounds derived from Formula II that are described in the present invention:
R Compound C 2 H 5 3-Ethoxymethyl-3-methyl-oxetane C 2 H 4 3-methyl-3-vinyloxymethyl-oxetane CH 2 CH(CH 3 ) 2 3-isobutoxymethyl-3-methyl-oxetane COCH 3 (3-methyloxetan-3-yl)methyl 2 methylacetate COCH 2 CH 2 CH 3 (3-methyloxetan-3-yl)methyl 2 methylpropanoate COCH 2 CH 2 CH 2 CH 3 (3-methyloxetan-3-yl)methyl 2 methylbutanoate COCH 2 CH 2 CH 2 CH 2 CH 3 (3-methyloxetan-3-yl)methyl 2 methylpentanoate COOCH 3 Ethyl 2-(3-methyloxetane-3-yloxy)acetate COOCH 2 CH 2 CH 3 Ethyl 2-(3-methyloxetane-3- yloxy)propanoate COO(CH 2 ) 6 CH 3 Ethyl 2-(3-methyloxetane-3- yloxy)heptanoate
[0015] The synthesis of these compounds is described in the examples below.
[0016] The use of this compound is widely applicable in current perfumery products, including the preparation of perfumes and colognes, the perfuming of personal care products such as soaps, shower gels, and hair care products as well as air fresheners, candles and cosmetic products. The compound can also be used to perfume candles and cleaning agents, such as, but not limited to soaps, detergents, dishwashing materials, scrubbing compositions, window cleaners, and the like.
[0017] In these preparations, the compound of the present invention can be used alone or in combination with other fragrance compositions, solvents, adjuvants and the like. Those with skill in the art will appreciate the nature and variety of the other ingredients that can be used in combination with the compound of the present invention.
[0018] Many types of fragrances can be employed in the present invention, the only limitation being the compatibility with the other components being employed. Suitable fragrances include but are not limited to fruits such as almond, apple, cherry, grape, pear, pineapple, orange, strawberry,. raspberry; musk, flower scents such as lavender-like, rose-like, iris-like, and carnation-like. Other pleasant scents include herbal and woodland scents derived from pine, spruce and other forest smells. Fragrances may also be derived from various oils, such as essential oils, or from plant materials such as peppermint, spearmint and the like.
[0019] A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891, the contents of which are incorporated by reference as if set forth in its entirety. Another source of suitable fragrances is found in Perfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher, 1959. Among the fragrances provided in this treatise are acacia, cassie, chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle, hyacinth, jasmine, lilac,, lily, magnolia, mimosa, narcissus, freshly-cut hay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose, vanilla, violet, wallflower, and the like.
[0020] As used herein olfactory effective amount is understood to mean the amount of compound in perfume compositions the individual component will contribute to its particular olfactory characteristics, but the olfactory effect of the perfume composition will be the sum of the effects of each of the perfume or fragrance ingredients. Thus the compounds of the invention can be used to alter the aroma characteristics of the perfume composition by modifying the olfactory reaction contributed by another ingredient in the composition. The amount will vary depending on many factors including other ingredients, their relative amounts and the effect that is desired.
[0021] The level of compound of the invention employed in the perfumed article varies from about 0.005 to about 10 weight percent, preferably from about 0.1 to about 8 and most preferably from about 0.5 to about 5 weight percent. In addition to the compounds, other agents can be used in conjunction with the fragrance. Well known materials such as surfactants, emulsifiers, and polymers to encapsulate the fragrance can also be employed without departing from the scope of the present invention.
[0022] Another method of reporting the level of the compound of the invention in the perfumed composition, i.e., the compounds as a weight percentage of the materials added to impart the desired fragrance. The compounds of the invention can range widely from 0.005 to about 10 weight percent of the perfumed composition, and preferably from about 0.1 to about 5 weight percent. Those with skill in-the art will be able to employ the desired level of the compound of the invention to provide the desired fragrance and intensity.
[0023] The following are provided as specific embodiments of the present invention. Other modifications of this invention will be readily apparent to those skilled in the art; without departing from the scope of this invention. As used herein all percentages are weight percent. IFF is meant to be understood as International Flavors & Fragrances Inc.
EXAMPLE 1 PREPARATION OF ESTERS OF THE PRESENT INVENTION
[0024] The following reaction sequence was used to prepare the specific compounds described by the NMR data set forth below:
[0025] The 3-methyl oxetanemethanol (1.3 mole) and ester (1 mole) are combined to which sodium methoxide (0.2 mole) is added. The resulting mixture is heated to 90° C. to 120° C., and methanol is removed from the reaction via a Dean-Stark trap. The reaction is aged until methanol is no longer produced and GC analysis of the reaction indicates less than 10% starting ester is present. The reaction mass is cooled to room temperature and neutralized with acetic acid (0.5 mole). The reaction is washed with 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation affording the product ester.
[0026] The esters are synthesized according to the general scheme above with the following specific examples. Equivalents set out are mole equivalents based on starting esters, yields are distilled chemical yields based on starting ester.
[0000] (3-methyloxetan-3-yl)methyl 2-methylpropanoate
[0000] 3-methyloxetane methanol 1.3eq, methyl 2-methylpropanoate 1eq, sodium methoxide 0.2eq, quench, acetic acid 0.5eq, with 10% sodium chloride solution, yield=88%. Odor: fruity.
[0000] 1.20 ppm (d, 6H, J=7.01 Hz) 1.34 ppm (s, 3H) 2.61 ppm (septet, 1H, J=6.99 Hz) 4.16 ppm (s, 2H, d) 4.38 ppm (d, 2H, J=5.93 Hz) 4.53 ppm (d, 2H, J=5.93 Hz)
[0000] (3-methyloxetan-3-yl)methyl 2-methylpentanoate
[0000] 3-methyloxetane methanol 1.3eq, methyl. 2-methylpentanoate 1eq, sodium methoxide 0.2eq, quench, acetic acid 0.5eq, with 10% sodium chloride solution, yield=80%. Odor: fruity apple like.
[0000] 0.91 ppm (t, 3H, J=7.21 Hz) 1.17 ppm (d, 3H, J=7.00 Hz) 1.32 ppm (m, 1H) 1.34 ppm (s, 3H) 1.36 ppm (m, 2H) 1.66 ppm (m, 1H) 2.51 ppm (sextet, 1H, J=6.95 Hz) 4.16 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.94 Hz) 4.53 ppm (d, 2H, J=5.92 Hz)
[0000] (3-methyloxetan-3-yl)methyl 3-methylbutanoate
[0000] 3-methyloxetane methanol 1.3eq, methyl 3-methylbutanoate 1eq, sodium methoxide 0.2eq, quench, acetic acid 0.5eq, with 10% sodium chloride solution, yield=90%. Odor: fruity tropical like.
[0000] 0.97 ppm (d, 6H, J=6.62 Hz) 1.34 ppm (s, 3H) 2.12 ppm (m, 1H) 2.25 ppm (d, 2H, J=7.30 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.95 Hz) 4.52 ppm (d, 2H, J=5.95 Hz)
[0000] (3-methyloxetan-3-yl)methyl (6E)-3,7-dimethyloct-6-enoate
[0000] 3-methyloxetane methanol 1.3eq, methyl (6E)-3,7-dimethyloct-6-enoate 1eq, sodium methoxide 0.2eq, quench, acetic acid 0.5eq, with 10% sodium chloride solution, yield=86%. Odor: weak fruity.
[0027] 0.96 ppm (d, 3H, J=6.64 Hz) 1.09-1.31 ppm (m, 1H) 1.34 ppm (s, 4H) 1.60 ppm (s, 3H) 1.68 ppm (s, 3H) 1.93-2.07 ppm (m, 3H) 2.18 ppm (d, 1H, J=14.69 Hz, of d, J=8.13 Hz) 2.37 ppm (d, 1H, J=14.69 Hz, of d, J=6.00 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.94 Hz) 4.52 ppm (d, 2H, J=5.94 Hz) 5.08 ppm (t, 1H, J=7.10 Hz)
[0000] (3-methyloxetan-3-yl)methyl octanoate
[0000] 3-methyloxetane methanol 1.3eq, methyl octanoate 1eq, sodium methoxide 0.2eq, quench, acetic acid 0.5eq, with 10% sodium chloride solution, yield =90%. Odor: weak woody like.
[0000] 0.88 ppm (t, 3H, J=6.85 Hz) 1.27-1.32 ppm (m, 8H) 1.34 ppm (s, 3H) 1.64 ppm (pentet, 2H, J=7.38 Hz) 2.36 ppm (t, 2H, J=7.54 Hz) 4.16 ppm (s, 2H) 4.39 ppm (d, 2H, J=5.94 Hz) 4.52 ppm (d, 2H, J=5.93 Hz)
[0000] The following 3-methyl oxetanremethanol esters are prepared as cited in references provided.
[0000] Kanoh, S; Naka, M; Nishimura, T; Motoi, M, Tetrahedron 58, 7049-64, 2002.
[0000] Rakus, K; Verevkin, S; Peng, W; Beckhous, H; Ruchardt, C, Liebigs Ann. Org. Bioorg. Chem. 12, 2059-68, 1995.
[0000] Dale, J; Fredriksen, S, Acta Chemica Scandinavica 45, 82-91, 1991.
[0000] Corey, E; Natarajan, R, Tetrahedron Lett. P5571-5574, 1983.
[0000] (3-methyloxetan-3-yl)methyl hexanoate
[0000] Odor: sour acidic.
[0000] 0.90 ppm (t, 3H, J=6.95 Hz) 1.31-1.33 ppm (m, 4H) 1.34 ppm (s, 3H) 1.65 ppm (pentet, 2H, J=7.44 Hz) 2.36 ppm (t, 2H, J=7.54 Hz) 4.16 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.92 Hz) 4.52 ppm (d, 2H, J=5.91 Hz)
[0000] (3-methyloxetan-3-yl)methyl benzoate
[0000] Odor: non descript.
[0000] 1.42 ppm (s, 3H) 4.39 ppm (s, 2H) 4.45 ppm (d, 2H, J=5.93 Hz) 4.64 ppm (d, 2H, J=5.93 Hz) 7.46 ppm (t, 2H, J=7.82 Hz) 7.56 ppm (t, 1H, J=7.42 Hz) 8.07 ppm (d, 2H, J=7.77 Hz)
[0000] (3-methyloxetan-3-yl)methyl acetate
[0000] Odor: fruity strawberry like.
[0000] 1.34 ppm (s, 3H) 2.10 ppm (s, 3H) 4.16 ppm (s, 2H,) 4.37 ppm (d, 2H, J=5.94 Hz) 4.51 ppm (d, 2H, J=5.94 Hz)
[0000] (3-methyloxetan-3-yl)methyl propanoate
[0000] Odor: fruity like.
[0000] 1.17 ppm (t, 3H, J=7.57 Hz). 1.34 ppm (s, 3H) 2.39 ppm (q, 1H, J=7.58 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.94 Hz) 4.52 ppm (d, 2H, J=5.94 Hz)
[0000] (3-methyloxetan-3-yl)methyl heptanoate
[0000] Odor: fruity pineapple like.
[0000] 0.89 ppm (t, 3H, J=6.79 Hz) 1.30 ppm (s, 3H) 1.34 ppm (s, 6H) 1.64 ppm (m, 2H) 2.36 ppm (t, 2H, J=7.52 Hz) 4.16 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.94 Hz) 4.52 ppm (d, 2H, .J=5.94 Hz)
[0000] (3-methyloxetan-3-yl)methyl butyrate
[0000] Odor: fruity like.
[0000] 0.97 ppm (t, 3H, J=7.42 Hz) 1.34 ppm (s, 3H) 1.68 ppm (sextet, 2H, J=7.32 Hz) 2.34 ppm (t, 2H, J=7.41 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.95 Hz) 4.52 ppm (d, 2H, J=5.96 Hz)
[0000] 3-methyl-but-2-enoic acid 3-methyloxetan-3-yl methyl ester
[0000] Odor: green metallic like.
[0000] 1.35 ppm (s, 3H) 1.92 ppm (d, 3H, J=1.32 Hz) 2.18 ppm (d, 3H, J=1.26 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.92 Hz) 4.54 ppm (d, 2H, J=5.93 Hz) 5.73 ppm (t, 1H, J=l.32 Hz)
EXAMPLE 2 PREPARATION OF ETHERS OF THE PRESENT INVENTION
[0028] The following reaction sequence was used to prepare the specific compounds described by the NMR data set forth below:
[0029] The 3-methyl oxetanemethanol (1 mole) is dissolved in THF (500 mL) and fed into 60% sodium hydride dispersion (1.1 mole) in THF (500 mL) at 0° C. Following evolution of hydrogen gas the chloride (1.1 mole) is added to the reaction at room temperature. The reaction is aged for 2-4 hrs. The reaction is quenched when GC analysis indicates less than 10% starting alcohol is present. The reaction mass is washed with 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation affording the product.
[0030] The ethers are synthesized according to the general scheme above with the following specific examples. Equivalents set out are mole equivalents based on starting alcohol, yields are distilled chemical yields based on starting alcohol.
[0000] Preparation of Formula III
[0031] The 3-methyl oxetanemethanol (1 mole) is dissolved in THF (500 mL) and fed into 60% sodium hydride dispersion (1.1 mole) in THF (500 mL) at 0° C. Following evolution of hydrogen gas the ally chloride (1.1 mole) is added to the reaction at room temperature. The reaction is aged for 2-4 hrs. The reaction is quenched when GC analysis indicates less than 10% starting alcohol is present. The reaction mass is washed with 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation affording 114 g of 3-allyloxymethyl-3-methyl-oxetane.
[0000] Odor: waxy mushroom like.
[0032] 1.32 ppm (s, 3H) 3.50 ppm (s, 2H) 4.03 ppm (d, 2H, J=5.58 Hz, of t, J=1.43 Hz) 4.36 ppm (d, 2H, J=5.74 Hz) 4.51 ppm (d, 2H, J=5.74 Hz)5.19 ppm (d, 1H, J=10.41 Hz, of d, J=1.70 Hz 5.28 ppm (d, 1H, J=17.25 Hz, of d, J=1.70 Hz) 5.91 ppm (d, 1H, J=17.24 Hz, of d, J=10.40 Hz, of t, J=5.553 Hz)
[0000] Preparation of Formula IV
[0033] The 3-methyl oxetanemethanol (1 mole) is dissolved in THF (500 mL) and fed into 60% sodium hydride dispersion (1.1 mole) in THF (500 mL) at 0° C. Following evolution of hydrogen gas the prenyl chloride (1.1 mole) is added to the reaction at room temperature. The reaction is aged for 2-4 hrs. The reaction is quenched when GC analysis indicates less than 10% starting alcohol is present. The reaction mass is washed with 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation affording 136 g of 3-methyl-3-{[3-methylbut-2-en-1-yloxy]methyl}oxetane.
[0000] Odor: floral muguet like.
[0000] 1.32 ppm (s, 3H) 1.68 ppm (s, 3H) 1.76 ppm (s, 3H) 3.49 ppm (s, 2H) 4.01 ppm (d, 2H, J=6.83 Hz) 4.36 ppm (d, 2H, J=5.74 Hz) 4.49 ppm (d, 2H, J=5.96 Hz) 5.35 ppm (t, 1H, J=6.83 Hz)
[0000] Preparation of Formula V
[0034] The 3-methyl oxetanemethanol (1 mole) is dissolved in THF (500 mL) and fed into 60% sodium hydride dispersion (1.1 mole) in THF (500 mL) at 0° C. Following evolution of hydrogen gas the prenyl chloride (1.1 mole) is added to the reaction at room temperature. The reaction is aged for 2-4 hrs. The reaction is quenched when GC analysis indicates less than 10% starting alcohol is present. The reaction mass is washed with 10% aqueous sodium chloride solution. The crude reaction mass is purified by fractional distillation affording 190g of (2E,6E)-3,7-dimethyl-1-[(3-methyloxetan-3-yl)methyloxy]octa-2,6-diene.
[0000] Odor: sweet lemon like.
[0035] 1.32 ppm (s, 3H) 1.61 ppm (s, 3H) 1.68 ppm (2s, 6H) 2.05-2.10 ppm (m, 4H) 3.49 ppm (s, 2H) 4.04 ppm (d, 2H, J=6.70 Hz) 4.36 ppm (d, 2H, J=5.73 Hz) 4.50 ppm (d, 2H, J=5.71 Hz) 5.09 ppm (t, 1H, J=6.81 Hz, of t, J=1.33 Hz) 5.34 ppm (t, 1H, J=6.67 Hz, of d, J=1.19 Hz)
[0000] 3-{[(2E)-but-2-en-1-yloxy]methyl}-3-methyloxetane
[0000] Odor: harsh green octenecarbonate like.
[0000] 1.32 ppm (s, 3H) 1.8 ppm (s, 2H) 3.48 ppm (s, 2H) 3.96 ppm (d, 2H, J=6.13 Hz) 4.36 ppm (d, 2H, J=5.74 Hz) 4.50 ppm (d, 2H, J=5.73 Hz) 5.54-5.77 ppm (m, 2H)
[0000] The following 3-methyl oxetanemethanol ethers are prepared as cited in references provided.
[0000] Blaskovich, M; Lajoie, G., J. Amer. Chem. Soc. 115,. p5021-30, 1993.
[0000] Gorin et al., J. Appl. Chem.USSR, 42, p1095, 1969.
[0000] 3 -methoxymethyl-3-methyl-oxetane
[0000] Odor: solvent glue like.
[0000] 1.31 ppm (s, 3H) 3.40 ppm (s, 3H) 3.45 ppm (s, 2H) 4.35 ppm (d, 2H, J=5.74 Hz) 4.50 ppm (d, 2H, J=5.75 Hz)
[0000] 3-methyl-3-{[(2-methylprop-2-en-lyl)oxy]methyl}oxetane
[0000] Odor: Strong, Green solvent like
[0000] 1.35 ppm (s, 3H) 1.92 ppm (d, 3H, J=1.32 Hz) 2.18 ppm (d, 3H, J=1.26 Hz) 4.17 ppm (s, 2H) 4.38 ppm (d, 2H, J=5.92 Hz) 4.54 ppm (d, 2H, J=5.93 Hz) 5.73 ppm (t, 1H, J=1.32 Hz)
EXAMPLE 3 PREPARATION OF CARBONATE MATERIALS OF THE PRESENT INVENTION
[0036] The following reaction sequence was used to prepare the specific compounds described by the NMR data set forth below:
[0037] The 3-methyloxetane methanol (1 mole) and dimethylcarbonate (1.5 mole) are combined to which sodium methoxide (0.2 mole) is added. The resulting mixture is heated to 90° C. to 120° C., and methanol is removed from the reaction via a Dean-Stark trap. The reaction is aged until methanol is no longer produced and GC analysis of the reaction indicates less than 10% starting alcohol is present. The reaction mass is cooled to room temperature and neutralized with acetic acid (0.5 mole). The reaction is washed with 10% sodium chloride solution.
[0038] The crude reaction mass is purified by fractional distillation affording the product carbonate.
[0039] The carbonates are synthesized according to the general scheme above with the following specific examples. Equivalents set out are mole equivalents based on starting alcohol, yields are distilled chemical yields based on starting alcohol.
[0000] Ethyl 2-(3-methyloxetane-3-yloxy)acetate
[0000] 3-methyloxetane methanol 1eq, diethylcarbonate 1.5eq, sodium ethoxide 0.2eq, quench, acetic acid 0.5eq, with 10% sodium chloride solution, yield=85%.
[0000] Odor: weak floral.
[0000] 1.30 ppm (t, 3H, J=7.18 Hz) 1.34 ppm (s, 3H) 4.14 ppm (q, 2H, J=7.14 Hz) 4.17 ppm (s, 2H) 4.25 ppm (d, 2H, J=5.65 Hz) 4.38 ppm (d, 2H, J=5.65 Hz)
[0000] Incorporation of 3-methyl-3-{[3-methylbut-2-en-1-yloxy]methyl}oxetane into a fragrance formulation.
[0040] A fragrance was prepared according to the following formulation:
Material Parts TRIPLAL ® (IFF) 0.8 Allyl cyclohexyl propionate 0.5 BORNAFIX ® (IFF) 10.4 CYCLABUTE ® (IFF) 9.0 APHERMATE ® (IFF) 15 Ethyl methyl phenyl glycidate 1.0 CYCLOGALBANIFF (IFF) 0.5 Isoamylbutyrate 1.0 ISOCYCLOCITRAL ® (IFF) 0.5 JASMAL ® (IFF) 3.0 Menthone 0.3 Peach aldehyde 12.0 3-methyl-3-{[3-methylbut-2-en- 5.0 1-yloxy] methyl}oxetane Phenyl acetate 4.0 HC VERDOX ® (IFF) 28 FRUCTONE ® (IFF) 4.0 | The present invention relates to new 3-methyl oxetanemethanol derivatives and their use as fragrance chemicals suitable for incorporation in fine fragrances, cosmetics, toiletries and related applications. | 2 |
BACKGROUND OF THE INVENTION
This application is a continuation of U.S. patent application Ser. No. 13/204,889 filed on Aug. 8, 2011, now abandoned which claims priority under 35 U.S.C. §119 to U.S. Provisional Patent Application Ser. No. 61/371,882 filed on Aug. 9, 2010.
The present invention relates to an illuminated surgical instrument, such as a vitrectomy probe or other illuminated ophthalmic surgical instrument, and more particularly to an illuminated surgical instrument having a molded optical light sleeve designed to provide illumination over a specific area at the working end of an instrument, for example, the cutting port of a vitrectomy probe.
Anatomically, the eye is divided into two distinct parts—the anterior segment and the posterior segment. The anterior segment includes the lens and extends from the outermost layer of the cornea (the corneal endothelium) to the posterior of the lens capsule. The posterior segment includes the portion of the eye behind the lens capsule. The posterior segment extends from the anterior hyaloid face to the retina, with which the posterior hyaloid face of the vitreous body is in direct contact. The posterior segment is much larger than the anterior segment.
The posterior segment includes the vitreous body—a clear, colorless, gel-like substance. It makes up approximately two-thirds of the eye's volume, giving it form and shape before birth. It is composed of 1% collagen and sodium hyaluronate and 99% water. The anterior boundary of the vitreous body is the anterior hyaloid face, which touches the posterior capsule of the lens, while the posterior hyaloid face forms its posterior boundary, and is in contact with the retina. The vitreous body is not free-flowing like the aqueous humor and has normal anatomic attachment sites. One of these sites is the vitreous base, which is a 3-4 mm wide band that overlies the ora serrata. The optic nerve head, macula lutea, and vascular arcade are also sites of attachment. The vitreous body's major functions are to hold the retina in place, maintain the integrity and shape of the globe, absorb shock due to movement, and to give support for the lens posteriorly. In contrast to aqueous humor, the vitreous body is not continuously replaced. The vitreous body becomes more fluid with age in a process known as syneresis. Syneresis results in shrinkage of the vitreous body, which can exert pressure or traction on its normal attachment sites. If enough traction is applied, the vitreous body may pull itself from its retinal attachment and create a retinal tear or hole.
Various surgical procedures, called vitreo-retinal procedures, are commonly performed in the posterior segment of the eye. Vitreo-retinal procedures are appropriate to treat many serious conditions of the posterior segment. Vitreo-retinal procedures treat conditions such as age-related macular degeneration (AMD), diabetic retinopathy and diabetic vitreous hemorrhage, macular hole, retinal detachment, epiretinal membrane, CMV retinitis, and many other ophthalmic conditions.
A surgeon performs vitreo-retinal procedures with a microscope and special lenses designed to provide a clear image of the posterior segment. Several tiny incisions just a millimeter or so in length are made on the sclera at the pars plana. The surgeon inserts microsurgical instruments through the incisions, such as a fiber optic light source to illuminate inside the eye, an infusion line to maintain the eye's shape during surgery, and instruments to cut and remove the vitreous body (such as a vitrectomy probe—which has a cutting end that is inserted into the eye. A vitrectomy probe has a small gauge needle or cannula with a cutting mechanism on the end that is inserted into the eye).
During such surgical procedures, proper illumination of the inside of the eye is important. Typically, a thin optical fiber is inserted into the eye to provide the illumination. A light source, such as a metal halide lamp, a halogen lamp, a xenon lamp, or a mercury vapor lamp, is often used to produce the light carried by the optical fiber into the eye. The light passes through several optical elements (typically lenses, mirrors, and attenuators) and is launched at an optical fiber that carries the light into the eye.
To reduce the number of required incisions during vitrectomy surgery and improve the delivery of light to the surgical site, an effort has been made to integrate a light source (typically one or more optical fibers) with a vitrectomy probe. These efforts have been difficult because of the small diameters of vitrectomy probes. It is desirable to make the diameter of the cutting end of the vitrectomy probe as small as possible so that it can be inserted through very small incisions into the eye.
Traditionally, however, illumination designs consist of many thin diameter round fibers either inserted between an inner and an outer stiff mechanical part or bonded to a tubing component of the surgical instrument. The possible packing density of the optical fibers is limited and it is difficult to handle the thin optical fibers without damage to at least some of them, reducing quality and manufacturing efficiencies. The optical fibers must also have been formed prior to assembly of the surgical instrument. Furthermore, the ends of the optical fibers, which are typically borosilicate glass, must be grinded or polished, which can lead to dust and burrs during manufacture. Manufacturing can thus be time-consuming and expensive.
For example, one prior art illumination system comprises a ring of optical fibers disposed around a vitrectomy probe, or other ophthalmic instrument, and held in place by a sleeve. This illuminated vitrectomy sleeve consists of a bundle of small diameter optical fibers fed into a hub region and then distributed in a ring pattern. The illuminated vitrectomy sleeve is designed to be a stand-alone device into which the vitrectomy probe or other surgical instrument is inserted. As such, it must have its own structural strength that is provided by a sandwiching the array of optical fibers between two metal or plastic cylindrical cannulas. Since it is preferable to make the total diameter of the surgical instrument and sleeve as small as possible, very little cross-sectional area is left to house the optical fibers. Accordingly, very little light is transmitted into the eye.
In another case, a single fiber may be attached to a cannula of a surgical instrument, such as a vitrectomy needle, and held in place with a plastic sleeve. For example, Synergetics, Inc. manufactures a 25-gauge vitrectomy needle with a single optical fiber that is held in place with a plastic sleeve. The plastic sleeve can then fit into a 20-gauge cannula that is inserted into the eye. Very little cross-sectional area is available between the 25 gauge vitrectomy needle and the inner surface of the plastic sleeve (which is typically one or two mils thick). In addition, a larger incision must be made to accommodate the 20-gauge cannula through which the plastic sleeve must fit. Today, it is preferable to keep the incision size small so as to accommodate a probe with a diameter of 23 gauge or smaller. What is needed is an improved illumination system for ophthalmic surgical instruments that can deliver sufficient light into the eye while accommodating these smaller incision sizes.
The same size constraints that apply to the vitrectomy probes of the above examples also restrict the feasible size of other ophthalmic surgical instruments. For example, scissors, forceps, aspiration probes, retinal picks, delamination spatulas, various cannulas, and the like may also benefit from targeted illumination. These instruments are designed to fit through small gauge cannulas that are inserted through the sclera during surgery. The same principles used to design an improved illuminated vitrectomy probe can also be used to provide targeted illumination for these other surgical instruments.
SUMMARY OF THE INVENTION
One embodiment of the present invention is an illuminated surgical instrument comprising: a cannula and an injection-molded light-sleeve adjacent to and encircling at least a portion of the cannula. The surgical instrument can be a vitrectomy probe having a cutting port disposed at a distal end of the cannula. The light-sleeve can terminate near a distal end of the cannula, for example, near the cutting port of the vitrectomy probe. The light-sleeve is optically coupled to a light source. The light-sleeve can be injection-molded during manufacture using the cannula as an insert for the injection molding. The light-sleeve is oriented for providing illumination in a direction along a longitudinal axis of the instrument.
In another embodiment consistent with the principles of the present invention, the present invention is an illuminated surgical instrument. The instrument has a working area located near an end of the instrument. An injection-molded light sleeve terminates near the end of the instrument. The light-sleeve is located adjacent to the instrument. The light-sleeve is optically coupled to a light source. The light-sleeve can be injection-molded during manufacture using a portion of the surgical instrument an insert for the injection molding. The light-sleeve is oriented for providing illumination in a direction along a longitudinal axis of the instrument.
In another embodiment consistent with the principles of the present invention, the present invention is an illuminated surgical instrument. The instrument has a working area located near an end of the instrument. The working area has an orientation with respect to the end of the instrument. An injection-molded light sleeve terminates near the end of the instrument. The light-sleeve is located adjacent to the instrument. The light-sleeve is optically coupled to a light source. The light-sleeve can be injection-molded during manufacture using a portion of the surgical instrument an insert for the injection molding. The light-sleeve is oriented for providing illumination in a direction configured for the orientation of the working area.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the invention as claimed. The following description, as well as the practice of the invention, set forth and suggest additional advantages and purposes of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate several embodiments of the invention and together with the description, serve to explain the principles of the invention.
FIG. 1 is an unfolded view of an ophthalmic endoilluminator according to an embodiment of the present invention.
FIGS. 2A and 2B are perspective views of a vitrectomy probe according to an embodiment of the present invention.
FIG. 3 is a perspective view of an illustrative embodiment of a distal tip portion of an embodiment of an illuminated surgical instrument in accordance with the teachings of the present invention.
FIG. 4 is a diagrammatical representation of an illustrative embodiment of an illuminated surgical instrument in accordance with the teachings of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference is now made in detail to the exemplary embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used throughout the drawings to refer to the same or like parts.
FIG. 1 is an unfolded view of an exemplary illuminated surgical instrument, such as an ophthalmic endoilluminator as used with an illuminated vitrectomy probe, according to an embodiment of the present invention. In FIG. 1 , the endoilluminator includes light source 105 , collimating lens 110 , optional cold mirror 115 , optional hot mirror 116 , attenuator 120 , condensing lens 125 , connector 150 , optical fiber 155 , hand piece 160 , and vitrectomy probe 165 .
The light from light source 105 is collimated by collimating lens 110 . The collimated light is reflected and filtered by optional cold mirror 115 and/or transmitted and filtered by optional hot mirror 116 . The resulting beam is attenuated by attenuator 120 and focused by condensing lens 125 . The focused beam is directed through connector 150 and optical fiber 155 to vitrectomy probe 165 where it illuminates the inside of the eye as described below.
Light source 105 is typically a lamp, such as a mercury vapor lamp, a xenon lamp, a metal halide lamp, or a halogen lamp. Light source 105 is operated at or near full power to produce a relatively stable and constant light output. In one embodiment of the present invention, light source 105 is a xenon lamp with an arc length of about 0.18 mm. Other embodiments of the present invention utilize other light sources such as light emitting diodes (LEDs). One or more LEDs can be operated to produce a constant and stable light output. As is known, there are many types of LEDs with different power ratings and light output that can be selected as light source 105 .
Collimating lens 110 is configured to collimate the light produced by light source 105 . As is commonly known, collimation of light involves lining up light rays. Collimated light is light whose rays are parallel with a planar wave front.
Optional cold mirror 115 is a dichroic reflector that reflects visible wavelength light and only transmits infrared and ultraviolet light to produce a beam filtered of harmful infrared and ultraviolet rays. Optional hot mirror 116 reflects long wavelength infrared light and short wavelength ultraviolet light while transmitting visible light. The eye's natural lens filters the light that enters the eye. In particular, the natural lens absorbs blue and ultraviolet light which can damage the retina. Providing light of the proper range of visible light wavelengths while filtering out harmful short and long wavelengths can greatly reduce the risk of damage to the retina through aphakic hazard, blue light photochemical retinal damage and infrared heating damage, and similar light toxicity hazards. Typically, a light in the range of about 430 to 700 nanometers is preferable for reducing the risks of these hazards. Optional cold mirror 115 and optional hot mirror 116 are selected to allow light of a suitable wavelength to be emitted into an eye. Other filters and/or dichroic beam splitters may also be employed to produce a light in this suitable wavelength range. For example, holographic mirrors may also be used to filter light.
Attenuator 120 attenuates or decreases the intensity of the light beam. Any number of different attenuators may be used. For example, mechanical louvers, camera variable aperture mechanisms, or neutral density filters may be used. A variable-wedge rotating disk attenuator may also be used.
Condensing lens 125 focuses the attenuated light beam so that it can be launched into a small diameter optical fiber. Condensing lens 125 is a lens of suitable configuration for the system. Condensing lens 125 is typically designed so that the resulting focused beam of light can be suitably launched into and transmitted by an optical fiber. As is commonly known, a condensing lens may be a biconvex or plano-convex spherical or aspheric lens. In a plano-convex aspheric lens, one surface is planar and the other surface is convex with a precise aspheric surface in order to focus the light to a minimum diameter spot.
The endoilluminator that is handled by the ophthalmic surgeon includes connector 150 , optical fiber 155 , hand piece 160 , and illuminated vitrectomy probe (or other ophthalmic surgical instrument) 165 . Connector 150 is designed to connect the optical fiber 155 to a main console (not shown) containing light source 105 . Connector 150 properly aligns optical fiber 155 with the beam of light that is to be transmitted into the eye. Optical fiber 155 is typically a small diameter fiber that may or may not be tapered. Hand piece 160 is held by the surgeon and allows for the manipulation of illuminated vitrectomy probe 165 in the eye.
Similarly, a laser light source, such as shown in FIG. 15A , can be optically connected to provide laser light to an endolaser fiber in those embodiments of the illuminated surgical instrument of the present invention that comprise an endolaser fiber to provide laser light to, for example, the retina.
FIGS. 2A and 2B are perspective views of a vitrectomy probe according to an embodiment of the present invention. In a typical vitrectomy probe, an outer cannula 205 includes port 210 . An inner piston 215 reciprocates in cannula 205 . One end of piston 215 is configured so that it can cut vitreous when as it enters port 210 . As shown in FIGS. 2A and 2B , piston 215 moves up and down in cannula 205 to produce a cutting action. Vitreous enters port 210 when the vitrectomy probe is in the position shown in FIG. 2A . The vitreous is cut as piston 215 moves upward closing off port 210 as shown in FIG. 2B . While most of the details of a vitrectomy probe are omitted, it is important to note that the cutting of the vitreous takes place at port 210 . Accordingly, it would be desirable to concentrate illumination around port 210 , so that a surgeon can see the vitreous being cut (as well as other eye structures near the cutting mechanism).
FIG. 3 is a perspective view of an illustrative embodiment of a distal tip portion 300 of an embodiment of an illuminated surgical instrument in accordance with the teachings of the present invention. FIG. 3 shows a tube 310 , which can be, for example, a hollow cannula associated with a number of ophthalmic surgical instruments. Tube 310 can be made of various bio-compatible materials, such as surgical steel, and has a molded light fiber/lightsleeve 320 adjacent to and encircling the outer lateral area of the tube 310 . Lightsleeve 320 can be polished at its distal end to provide high light transmission (output) from the lightsleeve 320 . Lightsleeve proximal end 330 is optically connected to a light source via, for example, mounting into a ferule and can likewise be polished to provide for high light transmission. Such an arrangement is shown in FIG. 4 . Lightsleeve 320 can be injection molded around tube 310 by, for example, injection die-casting. As part of the manufacturing and assembly of an ophthalmic surgical instrument in accordance with the teachings of the present invention, tube 310 can be used as an insert in the injection mold to injection-mold lightsleeve 320 around tube (insert) 310 . Lightsleeve 320 can be made from any suitable optically transmissive material capable of being injection-molded, such as polymethylmethacrylate (PMMA).
FIG. 4 is a diagrammatical representation of an illustrative embodiment of an illuminated surgical instrument in accordance with the teachings of the present invention. Illuminated surgical instrument 400 comprises tube 310 around which has been injection-molded lightsleeve 320 . Tube 310 and lightsleeve 320 are coupled to distal cap 470 of surgical instrument 400 . Distal cap 470 can comprise, for example, the distal cap of a probe handle for holding and manipulating surgical instrument 400 , as will be known to those having skill in the art. The proximal end of lightsleeve 320 is optically coupled to a ferule 430 for optically coupling lightsleeve 320 to optical fiber 440 . Optical fiber 440 can be a connection cable for coupling the output of light source 460 , via an optical coupler 450 , to the surgical instrument 400 body (e.g., a probe body). Optical coupler 450 can be standard optical connector and can have identifying technology, such as RFID identification capability, for identifying a particular surgical instrument 400 and configuring surgical instrument 400 for use.
Embodiments of the illuminated surgical instrument of the present invention also include a method of manufacturing a lightsleeve for a surgical instrument, such as lightsleeve 320 , using injection-molding techniques. Injection molding of a lightsleeve 320 using the cannula of a surgical instrument as an insert for injection-molding has the advantage over prior art illuminated surgical instruments that the lightsleeve does not have to be formed prior to assembling nor mounted to the cannula in separate processes. The cannula can instead be used as an insert and the lightsleeve injection-molded in an appropriate die.
Other advantages of the various embodiments of the illuminated surgical instrument of the present invention over the prior art include: elimination of the potential risk of uncured adhesives or adhesive inside the cannula as the injection-molding method does not use adhesives to couple the lightsleeve to the cannula; the capability of an inexpensive, simple and fully-automated production process; short production cycle times; highly repeatable production accuracy; the ability to bend a formed cannula and lightsleeve combination to a desired shape without risk of broken light fibers; easy and safe handling of semi-finished instruments; and the ability to define the surgical instrument cannula outer diameter by the design of the injection-molding tooling.
While examples provided herein describe an illuminated vitrectomy probe or other illuminated surgical instrument that can fit through a 23-gauge cannula, it will be appreciated that the same arrangement of a vitrectomy probe and optical fiber array can be applied to cannulas of other sizes. For example, an optical lightsleeve can be arranged around a vitrectomy probe in the same way described herein to fit through a 20-gauge cannula, or even through cannulas smaller than 23-gauge. For example, as the diameter of a vitrectomy probe decreases, more cross section area is available for illumination. An illuminated surgical instrument that fits through a 25-gauge cannula can have the same optical lightsleeve configuration described herein.
More generally, the same principles described with respect to the illuminated vitrectomy probe of the preceding figures can be applied to any surgical instrument designed to fit through a small gauge cannula. For example, in ophthalmic surgery, scissors, forceps, aspiration probes, retinal picks, delamination spatulas, various cannulas, and the like may also benefit from targeted illumination. These instruments are designed to fit through small gauge cannulas that are inserted through the sclera during ophthalmic surgery. For each of these instruments, targeted illumination around the working end of the instrument is beneficial.
The same lightsleeve arrangement can be applied to any surgical instrument with a generally circular, elliptical, rectangular or other cross-section. In this manner, illumination can be targeted to a certain area (typically the working end of the instrument considering the orientation of the instrument in the eye) to provide light where it is needed. For example, in ophthalmic surgery, scissors, forceps, aspiration probes, retinal picks, delamination spatulas, various cannulas, and the like may benefit from targeted illumination. Providing light to the working area of the instrument or to the eye structure with which the instrument interfaces allows the surgeon to better see during surgery.
The same principles can be applied to an instrument of any cross section. In addition, instruments may be approximated by geometrical shapes. For example, an instrument that has an oblong cross section can be approximated by an ellipse. Of course, the location of the targeted illumination corresponds to the location of the distal end of the lightsleeve 320 . While the lightsleeve 320 is generally selected to maximize light throughput, its location can be adjusted for a given instrument.
From the above, it may be appreciated that the present invention provides an improved illuminated surgical instrument. Arranging a lightsleeve distal end near the working area of a surgical instrument provides light that is usable by the surgeon during surgery. In addition, the present invention provides a method for effectively injection-molding a lightsleeve around a cannula of an ophthalmic surgical instrument for coupling to a light source and providing illumination to a surgical site. The present invention is illustrated herein by example, and various modifications may be made by a person of ordinary skill in the art.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims. | An illuminated surgical instrument is disclosed. One embodiment of the illuminated surgical instrument comprises a cannula and an injection-molded light-sleeve adjacent to and encircling at least a portion of the cannula. The surgical instrument can be a vitrectomy probe having a cutting port disposed at a distal end of the cannula. The light-sleeve can terminate near a distal end of the cannula, for example, near the cutting port of the vitrectomy probe. The light-sleeve is optically coupled to a light source. The light-sleeve can be injection-molded during manufacture using the cannula as an insert for the injection molding. The light-sleeve can be oriented for providing illumination in a direction along a longitudinal axis of the instrument. | 0 |
BACKGROUND OF THE INVENTION
This invention relates to fluid sampling devices and more particularly to blood collection containers for drawing blood samples.
Evacuated containers or tubes having needle pierceable stoppers are used extensively in drawing blood samples for the purpose of conducting laboratory tests on the patient's blood. A conventional method of obtaining a sample is to employ a blood collection tube and a tube and needle holder having a double-ended needle cannula. After the distal end of the cannula is placed in the vein of the patient, the air evacuated blood collection tube is moved in the holder with the tube stopper being guided onto the proximal end of the cannula. The cannula pierces the stopper and the negative pressure in the container facilitates the drawing of blood from the vein of the patient.
In many cases, a number of evacuated containers are filled with blood samples while using the same tube holder and while the cannula remains in the vein of the patient. For example, containers provided with different chemicals may be used to draw a number of blood samples for the purpose of conducting different clinical tests on the patient's blood. Care must be taken to avoid the flowback of drawn blood to the patient since these chemicals may be harmful to the patient. Also, non-sterile tubes are usually used.
When employing conventional tube and needle holders and evacuated collection tubes, faulty techniques in drawing blood can cause withdrawn blood to be returned to the patient. For example, if the contents of the tube is allowed to contact the proximal end of the needle and an employed tourniquet is not removed soon after blood begins to flow or if the arm of the patient is raised, a drop in venous pressure may cause the flowback of blood from the tube to the patient. Also, if a force is applied to the tube in a manner to compress the stopper against the holder while the tube contains blood, a pumping effect may be produced causing withdrawn blood to flow back into the patient.
Valves have been provided in the needle assembly of sampling devices to prevent the backflow of drawn blood from the container or tube to the patient. U.S. Pat. No. 3,874,367, for example, shows a valve disposed in a chamber constructed in a needle assembly between distal and proximal needles for preventing withdrawn blood from returning to the patient. This construction, however, is relatively expensive not only because of the new tooling required in the manufacture of such needle assemblies but because of the additional parts required. Such devices require two needles, two hubs, and the steps of securing each needle to its hub. Such parts and steps result in relatively high manufacturing costs.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a fluid collection device which prevents backflow of fluid from the collection chamber of the device to the source of the fluid and which is relatively economical. A more specific object of the present invention is to provide a blood collection device which prevents backflow of blood from the collection chamber of the device to the patient, is relatively economical, and wherein it can be employed with conventional needle assemblies and tube holders.
In accordance with one form of the present invention, a collection device is provided that includes an evacuated container closed at one end and having a needle-pierceable stopper closing the opposite end, and a fluid flow one-way valve disposed within the container which allows fluid to flow from the needle to the collection chamber but prevents fluid flow from the collection chamber to the needle.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation partly in section of a fluid collection device in accordance with a preferred embodiment of the prevent invention with the device shown disposed in a tube and needle holder;
FIG. 2 is an enlarged elevational cross-sectional view of the stopper and fluid pressure responsive valve of FIG. 1;
FIG. 3 is a side elevational view partly in section of the valve of FIG. 2, rotated 30°;
FIG. 4 is a bottom end view of the upper member of the valve of FIG. 2; and
FIG. 5 is a cross-sectional elevational view of a valve in accordance with a modified embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, and particularly to FIG. 1, a fluid collection device 10 is shown disposed in a conventional tube and needle holder 12. The holder 12 includes a cylindrical barrel 14 having an open lower end 16 for receiving the collection device 10 and an upper closed end 18 carrying a needle assembly 20 having a double-ended needle cannula or hypodermic needle 21. Needle 21 is fixed to a threaded hub 22 that is threadedly connected to the holder 12. The needle 21 extends longitudinally along the axis of the holder and has a distal portion 23 exterior to the holder and a proximal portion 24 extending proximally within the barrel 14.
Collection device 10 includes a blood collection container or tube 26 having an integrally closed bottom end 28 and an upper open end 30 in which is disposed a needle-pierceable stopper 32. The tube 26 is preferably of glass and the stopper 32 is of a suitable elastomeric or rubber material that will maintain a negative pressure within the tube 26. Tube 26 provides a blood collection chamber 34 within the tube below the stopper 32. Stopper 32 is self-sealing after the needle 21 has pierced the stopper and is subsequently removed. In FIG. 2, the stopper 32 is shown provided with a relatively hard needle guide insert 36 which serves to guide the needle into the central portion 38 of the stopper even if it is somewhat off center. The stopper 32 has a lower cylindrical portion 40 which extends into the tube 26 and which is provided with a bottom, central cylindrical recess 42 which is directly below central portion 38.
Disposed within the collection tube 26 below the stopper 32 is a one-way fluid flow valve indicated generally at 44. Valve 44 is received in the recess 42 of the stopper. The valve 44 includes an upper cylindrical body member 46 having an annular ridge 48 which extends outwardly and downwardly from the upper end of the body member and has an outer annular sharp edge which frictionally holds the valve to the underside of stopper 32 within recess 42. The body member 46 has a valve chamber 50 extending through it which is in the series flow path between the needle 21 and collection chamber 34.
Valve 44 has a movable member 52 shown in the form of a resilient rubber diaphragm closing the lower end of the valve chamber 50. Diaphragm 52 is normally held in the valve closed position as shown in FIG. 2, by a lower end cap 54 which is frictionally connected to the lower end portion of the body member 46. Cap 54 is circular and has an upwardly extending central abutment 56 engaging the central portion of the diaphragm to cause the upper marginal surface of the diaphragm 52 to resiliently engage the bottom open end of the body member 46 and sealingly close the bottom end of valve chamber 50. Diaphragm 52 is disc-shaped and preferably formed of a suitable elastomeric or rubber material. The cap 54 is cup-shaped and may be formed of a suitable plastic. Also, the body member 46 can be formed of a suitable plastic material or of metal if desired.
As also seen in FIGS. 3 and 4, the upper body member 46 is provided with a plurality of circumferentially spaced flat portions 58 with a plurality of circumferentially spaced arcuate relatively small portions 60 alternating with the flat portions 58. The cap 54 has an inner diameter such that when the lower portion of the body member 46 is inserted into the cap as shown in FIG. 3, the inner walls of the cap frictionally engage the arcuate portions 60 to frictionally hold the cap on the lower end of body 46. The flat portions 58 are spaced from the cap 54 to permit blood to flow between them to collection chamber 34 when the valve is open during the filling of the collection tube.
The stopper 32 and valve 44 may be inserted into the tube 26 while in an air evacuated chamber during assembly of the device 10. The valve chamber 50 and collection chamber 34 are provided with a negative pressure in accordance with the desired amount of blood to be drawn into the collection chamber. With the pressures on opposite sides of the diaphragm 52 equal, the abutment 56 of cap 54 normally maintains the diaphragm 52 in the closed condition as seen in FIG. 2. When a fluid pressure differential exists across the diaphragm 52 such that the pressure in valve chamber 50 is positive with respect to the pressure in collection chamber 34, the peripheral or marginal portions of the diaphragm are moved away from the bottom end of valve member 46 to allow fluid to pass from the valve chamber 50 into cap 54 and then into collection chamber 34.
In use, after the needle assembly 20 is attached to the barrel 14, the distal end 23 of the needle may be inserted into a vein 66 of a patient from whom a blood sample is to be collected. The collection device 10 is then inserted into and guided by the holder 12 toward the proximal end portion 24 of needle 21. When needle portion 24 has fully penetrated the stopper, it enters the valve chamber 50 and fluid communication between the blood in vein 66 and the air evacuated collection chamber 34 is effected. Since the fluid pressure in valve chamber 50 is now positive with respect to the pressure in collection chamber 34, the valve 44 will be opened and blood flows from valve chamber 50 past the diaphragm 52, upwardly into the spaces between the flat portions 58 of the body 46 and the inner walls of the cap 54, downwardly between the inner walls of the tube 26 and the outer walls of the cap, and then into the collection chamber 34. As the collection chamber fills, the pressure differential across the diaphragm 52 will decrease until the pressure is small or substantially equalized, and then the resiliency of the diaphragm will again close against the bottom end of body 46 to close the valve. When valve 44 is closed, no blood can flow from the collection chamber 34 back through the valve and into the patient. Thus, where chemicals or other materials are disposed in the tube 26 by the manufacturer, the blood mixing with such chemicals cannot be inadvertently returned to the patient since the valve 44 is closed to such flow.
FIG. 5 shows a one-way valve 70 of modified construction connected to a needle-pierceable rubber stopper shown in phantom at 72 and which is disposed in a blood collection tube which is partially shown in phantom at 74. Valve 70 includes a cylindrical body 76 having a valve chamber 78 and an integral, diametrically extending rod 80. The rod 80 has an axial stem 82 fixed to it which extends axially below the bottom end of body 76. A generally circular or disc-like diaphragm 84 is disposed on the extending lower end of the stem 82. The diaphragm 84 has a central hole of smaller diameter than that of the stem so that the diaphragm can be readily pushed onto the stem to the desired position shown in FIG. 5. The diaphragm 84 is shown resiliently urged against the lower end of the body member to close the bottom of chamber 78. Diaphragm 84 may be formed of any suitable, resilient rubber or other elastomeric material.
Valve 70 of FIG. 5 operates in a manner similar to that of valve 44 of FIG. 1. When a blood collection needle pierces the stopper 72, blood from the patient's vein flows into valve chamber 78 and through the valve to the collection portion of the tube below the stopper and valve. The valve is open to pass this flow of blood since the upper side of the diaphragm will be positive with respect to the negative pressure on the bottom side of the valve.
As a collection tube 74 fills, the original relatively high negative pressure decreases with the pressure differential across the diaphragm 84 also decreasing. When the pressure differential across the valve is relatively low or approaching or reaching zero, the resiliency of the diaphragm causes the marginal surfaces of the upper side of the diaphragm to again sealingly engage the annular bottom end of the body 76 to thereby close the valve 70. Under these conditions, blood in the collection chamber of tube 74 cannot flow past the diaphragm 84 so that this blood cannot be returned to the patient.
In some cases, after the filled collection tube is removed from the holder 12, it is inserted in a centrifuge to separate the serum from the cellular phase for performing laboratory tests on the separated serum. Where serum tests are run in this manner, the embodiment shown in FIGS. 1-4 has the advantage of tending to trap a blood clot in the one-way valve. For example, a blood clot which forms before or during centrifugation in the blood that may remain in the valve chamber 50, would tend to be wedged and trapped in the spaces between the facing inner walls of the cap 54 and the inclined surfaces 58 of the body member 46. Such a clot would be removed from the tube 26 with the stopper 32 as it is removed to open the tube for extracting the separated serum.
Both of the pressure responsive valves 44 and 70 are disposed in series in the blood flow path from the patient to the container and are responsive to predetermined pressure differentials across their movable valve members, such as the diaphragms, for allowing blood flow in one direction through them, that is, from the valve chamber to the collection chambers. The valves are open only when fluid flows from the valve chamber to the collection chamber. In the closed condition of the two valves, the condition shown in the drawing, the valve chambers 50 and 78 provide closed, fluid or airtight, chambers since one end of each chamber is sealingly closed by the stopper and the opposite end by the movable valve member or diaphragm. With the valve chamber closed in this manner, blood from the valve chamber cannot be returned to the patient since air or blood from the collection chamber could not enter the valve chamber to replace such blood flow. Thus, blood cannot flow back from the collection or valve chamber so that economical non-sterile blood collection devices can be employed.
The stopper and valve are readily assembled together by simply inserting the valve into the stopper recess. This provides a stopper and valve assembly which is readily inserted into the collection tube.
The size or length of the upper valve member or chamber and size of the proximal portion of the needle cannula are so related that when the collection tube is inserted fully into the holder, the lower tip of the needle cannula is within the valve chamber between the stopper and diaphragm.
As various changes could be made in the above construction without departing from the scope of the invention, it is intended that all matter contained in the above description or shown in the accompanying drawing shall be interpreted as illustrative and not in a limiting sense. | A blood collection tube is provided with a stopper adapted to be pierced by a needle cannula for introducing a sample of blood into the collection tube, and a valve disposed within the tube which allows blood to flow from the proximal end of the needle into the blood collection chamber of the tube but prevents the reflux of blood from the collection chamber to the patient. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the field of medical surgical tools, and more particularly, to retractors for chest surgery.
2. Art Background
In open chest surgery, and particularly for cardiac surgery, the sternum is split with chest saw and is held open by a retractor. The sternum is a short bone in the middle of the chest to which all of the ribs are attached either directly, or indirectly. The ribs attached to the top of the sternum are shorter than the ribs attached to the bottom of the sternum. Accordingly, when the chest is opened using the retractor, more stress is placed on the shorter upper ribs than the longer lower ribs, as explained in more detail below. Such stress causes various problems including broken ribs.
Typical prior art retractors, also termed sternal spreading or chest spreading retractors, comprise two elongated metal members, termed arms, with blades disposed thereon to capture the sternum, the arms being parallel to each other, and a rack or bar with teeth on which the arms are disposed. One of the arms is fixed in position for moving the other arm along the rack. The prior art retractors opened so that the arms remain parallel with respect to each other throughout their range of motion. Accordingly, in use, the sternum was displaced an equal amount along the entire length of the retractor. Prior art retractors include those devices which have long blades, short blades, multiple short blades or bent arms. Also, for pediatric and small patients, a small sized retractor of the same general configuration as described above may be used.
One recent prior art device comprises a pair of blades which are pivotable through the plane defined by the blades and the bar connecting them. This device is intended to provide pressure evenly along the entire sternum and it opens in a generally triangular configuration as opposed to the generally rectangular configuration. However, the device does not provide positive control of the movement of the sternum as it is opened and does not necessarily open the sternum to a desired position. The device is described in U.S. Pat. No. 4,627,421 issued to Symbas et al.
Another prior art device described in Chaux et al., U.S. Pat. No. 4,852,552 comprises a sternal retractor with blades which rotate in two different axes to permit one portion of the split sternum to be raised above the other portion in order to provide access to particular portions of the chest cavity.
It has been observed that as a result of the use of such prior art devices, that following the surgery, a substantial percentage of patients develop a neuropathy in which numbness occurs in their left or right hand, and specifically, in the fourth and/or fifth digits (the ring finger and little finger). This numbness usually disappears after a while, but it has been known to occur for a substantial period of time, and in any event, such numbness is at best annoying to the surgical patients. The apparent cause of this numbness is that in opening the chest, the opening of the ribs puts substantial pressure on the lower branch of the brachial plexus. The lower ribs are longer and also have more cartilage which permits them to be spread more easily and with less risk than the upper ribs. Also, the lower ribs are not connected to any neurologically important portion of the plexus.
One method of overcoming this problem of applying excessive pressure to the upper ribs and the adjacent portion of the plexus has been for the surgeon to attempt to position the retractor as low as possible so that there is minimal pressure on the upper, shorter ribs. However, this approach is not particularly desirable because the surgeon is not able to position the retractor in the most advantageous position for retraction of the chest. The present invention overcomes the foregoing deficiencies of the prior art devices and methods.
SUMMARY OF THE INVENTION
The present invention is a retractor of the general type found in the prior art with certain improvements therein which eliminate the problem which occurs during cardiac or other open chest surgery wherein numbness of the fourth and fifth digits of the right and/or left hand is caused when the chest is opened and held open with the prior art retractors and methods. The present invention also minimizes the risk of breaking ribs, particularly the shorter ribs, during such surgery.
The present invention comprises a retractor, a specifically a sternal spreader, having two arms with blades disposed on each arm, said arms being disposed on a cross bar, sometimes referred to as a rack. The invention specifically comprises the cross bar being curved rather than straight, as is provided in the prior art. The arms remain generally perpendicular to the cross bar as they moved along the cross bar closer to and away from each other, but in view of the curvature of the cross bar, one end of the arms is always closer to each other than the other end of the arms.
Preferably, for an adult sternal spreader, when the end of the arms adjacent with the short ribs is approximately 4 inches apart, the end of the arms adjacent the long ribs is approximately 8 inches apart. Also preferably, the curvature of the cross bar is approximately 40 degrees. Of course the curvature of the cross bar can be varied considerably, the important feature being that the arms spread apart to form a generally triangularly-shaped opening in the chest as the sternum is spread apart. Any form of attachment means for attaching the arms to the cross bar and moving the arms along the cross bar may be employed, the preferred system comprising a rack and pinion.
In accordance with one aspect of the invention, a surgical sternal retractor is provided, including a bar, and a pair of arms mounted on the bar. At least one of the arms is mounted to slide along the bar and to be locked in place on the bar. Each of the arms includes a blade extending downward along the arm from a proximal end of the blade to a distal end of the blade at a distal end of the arm. At least one of the arms includes a proximal portion mounted on the bar and a distal portion mounted by a hinge to pivot on the proximal portion between the proximal end of the blade and the bar.
Preferably, the bar is curved so that proximal and distal ends of the blades of the pair of arms are additionally separated by different distances as the arms are moved apart, with the arms being configured for mounting to extend from the bar in a first direction or opposite the first direction. Preferably, the bar includes gear teeth extending along a first side and a side opposite the first side, with at least one of the arms including a rotatably mounted pinion engaging the teeth extending along the first side of the bar with the arms mounted to extend from the bar opposite the first direction, and engaging the teeth extending along the side of the bar opposite the first side with the arms mounted to extend from the bar opposite the first direction.
In accordance with another aspect of the invention, a method for sternal retraction is provided, including: inserting blades extending downward from arms within a sternal retractor into a split within the sternum; spreading the arms within the sternal retractor through a short distance to begin sternal retraction; rotating a distal portion of one of the arms, including one of the blades; about a pivot point attaching the distal portion of the arm to a proximal portion of the arm; locking the distal portion in place on a proximal portion of the arm including the distal portion; and spreading the arms within the sternal retractor further to complete sternal retraction. For example, the distal portion is rotated toward the other arm with the bar located near the abdomen of the patient, and with the bar being curved so that, as the arms are spread apart, the distal ends of the blades are spread apart through a first distance, and the proximal ends of the blades are spread apart through a distance greater than the first distance.
It is an object of the present invention to provide a retractor which is structurally simple and which does not obstruct the surgeon's view of the chest cavity, and particularly which does creates the largest possible viewing area with a minimal amount of trauma to the ribs.
It is another object of the present invention to provide a retractor which minimizes injury to the brachial plexus during open chest surgery.
It is another object of the present invention to provide a retractor which minimizes the risk of broken ribs, particularly the shorter ribs.
It is another object of the present invention to provide a retractor which can be used in a plurality of configurations with the cross bar being disposed either above or below the surgical area.
It is yet another object of the present invention to provide a retractor which can be provided a variety of sizes and curvatures and with a variety in the number of blades, as required.
These and other objects of the present invention are achieved by providing a retractor which is shown in several presently preferred embodiments in the drawings which are described briefly below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a retractor built in accordance with a preferred embodiment of the present invention assembled in a first configuration.
FIG. 2 is a perspective view of the retractor of FIG. 1 assembled in a second configuration.
FIG. 3 is a perspective exploded view of the retractor of FIG. 1 .
FIG. 4 is a side view of a first arm within the retractor shown in FIG. 2 .
FIG. 5 is a plan view of the retractor assembled as shown in FIG. 2 .
FIG. 6 is a side view of the a second arm within the retractor shown in FIG. 1 .
FIG. 7 is a plan view of the retractor assembled as shown in FIG. 1 .
DETAILED DESCRIPTION OF THE INVENTION
As shown in FIGS. 1 , 3 , 4 , 6 , and 7 , a retractor 23 of the present invention comprises generally a cross bar or rack 22 , a first arm 24 , comprising a proximal portion 24 A and a distal portion 24 B, and second arm 26 . FIG. 1 is a perspective view of the retractor 23 , while FIG. 3 is an exploded perspective view thereof. FIGS. 4 and 6 are side views of the first arm 24 and the second arm 26 , respectively. FIG. 7 is a plan view of the retractor 23 assembled as shown in FIG. 1 . The distal portion 24 B of the first arm 24 is pivotally connected to the proximal portion 24 A thereof by a hinge 59 and is further held in position by a locking mechanism 60 . When the locking mechanism 60 is released, the distal portion 24 B may be rotated about the hinge 59 to be locked in a new position. For example, the distal portion 24 B can be rotated between a medial position, in which it is shown in FIG. 1 , and an inward position, indicated by dashed lines 24 C. The cross bar 22 has, in the preferred embodiment, teeth on two opposing surfaces 25 and 27 for reasons that will be explained below. The cross bar 22 is curved so that the arms 24 and 26 are not parallel to each other when the arms are opened or spread apart, but are angled outward away from each other as shown in FIG. 1 . The distal portion 24 B of the first arm 24 includes a downwardly extending blade 32 , and the second arm 26 includes a downwardly extending blade 33 .
When the arms are closed to be adjacent to each other with the distal portion 24 B of the of the first arm 24 held in the inward position, in which it is shown with dashed lines in FIG. 1 , by the locking mechanism 60 , the distal portion 24 B of the first arm 24 and the second arm 26 are substantially parallel to each other, facilitating the insertion of the blades 32 , 33 into an open sternum. One, or possibly both, of the arms 24 , 26 may be moved along the bar 22 preferably by a moving means comprising a pinion 28 driven by a handle 30 . This arrangement allows the present invention to be installed and to force the severed portions of the sternum apart. The arms have disposed thereon blades 32 and 33 , which are common to prior art chest separators, and which are adapted to secure the sternum after it is severed. The present invention includes the use of blades which are longer than those depicted as well as multiple blades on a single arm, and angled arm blades, all of which is well known in the art, and after a short distance opening the fixed arm will be moved to straight (neutral) position and held in place by pin spring 60 and, continued to the desired opening.
FIGS. 1 and 7 are views of the retractor 23 assembled in a first configuration, for use with the bar 22 disposed closer to the head of a patient than to the abdomen. FIG. 1 is a perspective view of the retractor 23 so assembled, while FIG. 7 is a plan view thereof. with the distal end 39 of the blade 32 and the distal end 40 of blade 33 being further apart than their proximal ends 41 , 42 . Accordingly, as used in the configuration of FIG. 1 , the retractor 23 positively forces the sternum into a specific angled position dictated by the curvature of the bar 22 and the distance between the arms 24 . 26 . In this way the chest opening can be small at area adjacent the short ribs and larger at the area adjacent the longer ribs.
FIGS. 2 and 5 are views of the retractor 23 assembled in a second configuration, for use with the bar 22 near the abdomen. FIG. 2 is a perspective view of the retractor 23 so assembled, while FIG. 5 is a plan view thereof. It will be appreciated in this connection that the reversible nature of the preferred embodiment of the present invention is not a requirement of the invention but is the preferred embodiment for purpose of obtaining multiple uses for a single device. The positioning of the bar 22 can be chosen to provide the best view for the surgeon in a manner which is well known in the art. When the retractor 23 is used in the second orientation of FIG. 2 , the blades 32 , 33 are first placed into the severed sternum with the locking mechanism 60 holding the distal portion 24 B of the first arm 24 in the inward position, as indicated by dashed lines 24 C in FIG. 2 to have the blades together for initial positioning. After the arms 24 , 26 are moved apart through a short distance, the distal portion 24 B of the first arm 24 is moved to the medial position, in which it is shown in FIG. 2 , to be subsequently held in place by the locking mechanism 59 .
As is further shown in FIGS. 1 , 3 , 6 and 7 , the bar 22 comprises teeth on sides 25 and 27 , and arms 24 and 26 have blades 32 and 33 , respectively. Arm 26 has a pinion 28 , rotatably mounted within a hole 29 , a crank 30 , attached to the pinion 28 , and a locking pin 31 , which screws into hole 51 to secure the arm in a desired position. The proximal portion 24 A has a locking pin 29 which secures it in place as well by screwing into hole 50 and impinging on the bar 22 . Pinion 28 comprises individual teeth 44 adapted to mate with the teeth on bar 22 so that the arm 26 can be cranked open to spread open the chest. The locking pin 29 the arm with means for disconnecting said arm 24 from said bar 22 so that the arms can be reversed if desired to change the retractor 23 between the first configuration of FIG. 1 and the second configuration of FIG. 2 , reversing the direction of curvature of the bar 22 relative to the arms 24 , 26 to locate the bar either above or below the surgical area. Similarly, arm 26 can be removed from bar 22 so that it can be reversed between the first configuration of FIG. 1 and the second configuration of FIG. 2 Bar 22 is provided with a flattened area 43 onto which arm 24 may be secured. Arms 24 and 26 have slots 49 and 46 , respectively, in which the bar 22 may be disposed in use.
As particularly shown in FIG. 3 , the distal portion 24 B of the first arm 24 is pivotally attached to the proximal portion 24 A thereof by a hinge 59 , including a pin 55 extending through a hole 61 in the proximal portion 24 A and through a pivot hole 63 in the distal portion 24 B. A locking pin or screw 60 extends through one of a plurality of holes 58 within the distal portion 24 B of the first arm 24 and through holes 56 within the proximal portion 24 A of the first arm 24 . When the locking screw 60 extends through a central hole 53 within the plurality of holes 58 , the distal portion 24 B of the first arm 24 is held in the medial position, in which it is shown in FIGS. 1 and 2 . When the locking screw 55 extends through a first lateral hole 64 , the distal portion 24 B is held in the inward position indicated by dashed lines 24 C in FIGS. 2 , 7 . When the locking screw 60 extends through a second lateral hole 57 , the distal portion 24 B is held in an outward position (not shown).
In the preferred embodiment, the bar 23 is approximately 8 inches long, for adult sternal retractors and has a curvature of 40 degrees. The curvature of the bar 23 may be regular, that is, with a single radius of curvature or it may have multiple radii of curvature along its length to provide variation in the angle of the blades with respect to each other. The curvature of the bar can be of any desired radius, the preferred curvature providing an opening of 8 inches at the bottom of the sternum and an opening of 4 inches at the top of the sternum. The blades can be short, long, multiple or slightly angled to provide the desired secure opening of the sternum.
It will be obvious to a person of ordinary skill in the art that a number of modifications and changes can be made to the subject invention without departing from the spirit and scope of the present invention, which is defined by the claims appended hereto and all equivalents thereof. | The invention is a sternal retractor comprising a pair of arms each of which includes a downward extending blade, and one of which includes a proximal portion and a distal portion pivotally mounted on the proximal portion, a curved cross bar on which said arms are disposed so that in use the retractor can open the bottom of the sternum wider than the top of the sternum to minimize damage to the upper ribs and numbness, which sometimes occurs in the hands of open chest surgery patients. The retractor also has applications within other surgical procedures, as well, for the same general purpose of providing an opening of varying size along the length of an incision. | 0 |
TECHNICAL FIELD
[0001] The invention pertains to a device to support cardiac function. In particular, the device according to the invention serves to support a pumping function of a heart.
BACKGROUND
[0002] Due to illness, the pumping function of a heart can be reduced, which is also called cardiac insufficiency. Cardiac insufficiency is from the medical as well as from the economical standpoint of great and increasing importance. In the second decade of this century, 23 million people worldwide will suffer from cardiac insufficiency; the annual rate of new cases will be about 2 million people. In the US alone, 5 million people are currently suffering from cardiac insufficiency. Here, the annual rate of new cases is approximately 550,000 people. Already in this decade, the number of incidences in people over 50 years of age will double to more than 10 million. The same applies to the European continent.
[0003] Causes for cardiac insufficiency can be impaired contractility or reduced filling of the cardiac chambers due to damage to the myocardium. Hypertension can lead to an increased pumping resistance, which can also negatively affect the pumping function of the heart. The pumping function of a heart can also be reduced by leaking valves (e.g., a leaking aortic valve or mitral valve). Impairments of the cardiac conduction system generate arrhythmias, which can also lead to a reduced pumping function of the heart. If the movement of the heart is restricted from the outside, e.g., due to an accumulation of fluid in the pericardium, this can result in a reduced pumping function as well. Cardiac insufficiency often leads to shortness of breath (especially in the case of left ventricular insufficiency), or to water retention in the lungs or in the abdomen (in particular in the case of right ventricular insufficiency).
[0004] Different types of cardiac insufficiencies are treatable with medication or surgery. In some cases of arrhythmias, normal cardiac rhythm can be restored with a pacemaker. A leaking valve can be replaced surgically with a cardiac valvular prosthesis. A reduced pumping function can be assisted by an implanted heart pump. A treatment approach addressing the various causes of heart insufficiency is to assist the pumping function of the heart by means of an implant, which exerts mechanical pressure onto the heart and therefore improves its pumping performance.
[0005] Some known mechanical ventricular assist devices have been disclosed in U.S. Pat. No. 5,749,839 B1 and U.S. Pat. No. 6,626,821 B1, and in WO application 00/25842. These documents disclose mechanical ventricular assist devices that require open-chest surgery. Many cardiac assist systems are complex and can only be implanted by means of an elaborate surgical procedure. All cardiac assist systems are integrated into the blood circulation of the patients. Improved centrifugal or magnetically supported impeller systems carry blood continuously. The contact of the blood with the surface of the implanted systems poses a great engineering and medical challenge. Common complications of cardiac assist systems are strokes, hemorrhage and septicemia. They often lead to long-term hospitalization and frequent re-admissions of patients already released from the hospital.
SUMMARY
[0006] Various aspects of the invention feature methods of implanting a cardiac device, and systems for performing such a method. According to one aspect of the invention, the method includes inserting an inner seal member through an opening in a pericardium about a living human heart. The inner seal member has a first sealing lip disposed inside the pericardium and surrounding an aperture through the inner seal member. An outer seal member is aligned with the inner seal member. The outer seal member has a second sealing lip disposed outside the pericardium and surrounding an aperture through the outer seal member. The inner seal member is secured to the outer seal member, with the firsts sealing lip engaged against an inner surface of the pericardium and the second sealing lip engaged against an outer surface of the pericardium. A cardiac device is inserted into the pericardium through the apertures of the inner and outer seal members.
[0007] In various aspects of the invention a device for the support of the cardiac function includes a sheath configured to transition from a non-expanded state into an expanded state, with the sheath being self-expanding and being configured to be inserted into a delivery system, and which in the expanded state can at least partially enclose a heart. One potential advantage of the device is that it may be implanted using minimally invasive procedures.
[0008] In some implementations, the sheath can be made of a wire mesh, which can have diamond-shaped cells. Preferably, the mesh is made of a shape memory alloy. The crossing points of the wires of the wire mesh can be permanently attached to each other, thus increasing the stability of the sheath. The crossing points may also be separable, which increases the flexibility of the sheath and thereby can make the sheath easier to compress. Or some of the crossing points may be permanently interconnected while other crossing points are not permanently interconnected. By selecting suitable crossing points to be permanently interconnected, and crossing points that are not permanently interconnected, the stability and flexibility of the sheath can be adjusted.
[0009] According to one aspect of the invention, the sheath can also consist of a lattice structure, with the lattice structure consisting of links, and multiple links defining one cell. The lattice structure exhibits a diamond-shaped lattice structure. The links and the intersections of the links exhibit enforcements in order to increase the stability of the sheath. The effect of the enforcements is similar to the effect of the interconnected crossing points in embodiments of the sheath in the form of a wire mesh. The links and the intersections can also be made of a thinner or weaker material in order to increase the flexibility of the sheath. The effect of a thinner or weaker material at intersections is similar to the effect of the non-interconnected intersections in embodiments of the sheath in the form of a wire mesh.
[0010] The sheath can also be made of a solid material, from which parts have been removed. For example, the sheath can be made of a tube or an individually shaped sheath sleeve, into which holes have been formed or cut. The holes can be formed such that the sheath exhibits increased stability in some areas, and increased flexibility in other areas.
[0011] Generally, areas of increased stability are desired in situations, in which the sheath acts as an abutment. Areas of greater flexibility can enable the natural motion of the heart. Increased flexibility is also advantageous for compressing the sheath into a delivery system.
[0012] The sheath generally exhibits openings being created by the wires of the wire mesh, the links of the lattice structure, or by the holes formed in the sheath sleeve. The openings can be rectangular, diamond-shaped or round. The cells or holes can have a pin opening of 1 mm to 50 mm. A pin opening is defined as the largest diameter of a pin, which can be pushed through a cell or a hole. Using the holes, the stability and flexibility of the sheath can be adjusted individually. The holes also allow the exchange of substances from the inside of the sheath with the outer environment of the sheath.
[0013] The sheath can be covered with a membrane; the membrane may, in particular, be made of polyurethane, silicon or polytetrafluorethylene (PTFE). The membrane can reduce the mechanical stress exerted by the sheath onto the pericardium or the myocardium. The membrane can also increase the biocompatibility of the sheath. A coating of the membrane with an active substance is also conceivable.
[0014] Another aspect of the present invention features a method of manufacturing a cardiac assist device. The method includes using a virtual or real image of a heart and forming a sheath based on the shape of the heart image.
[0015] The method can be used to manufacture a custom-made sheath. The shape of the sheath can match the form of the 3D-image of the surface of the heart, spatially stretched by a factor. In particular, the stretch factor can range from 1.01 to 1.2. A sheath applied to a true-to-scale real or virtual 3D image of the heart should exhibit a distance to the 3D image of 1 to 10 mm, in particular 2 to 8 mm, in particular 3 to 5 mm.
[0016] Additional features and advantages of the invention will be apparent from the description and drawings, and from the claims.
DESCRIPTION OF DRAWINGS
[0017] FIG. 1 shows a human torso with an implanted device and an extracorporeal supply unit.
[0018] FIG. 2 shows a human torso with an implanted device and a partially implanted supply unit.
[0019] FIG. 3 shows a human heart with the device.
[0020] FIGS. 4 a and 4 b show a cross-section through the heart with the device along line A-A in FIG. 3 .
[0021] FIG. 5 shows a step of the implantation of the device.
[0022] FIG. 6 shows a step of the implantation, in which a pericardium seal has not yet been screwed shut.
[0023] FIG. 7 shows a step of the implantation, in which a pericardium seal is screwed shut.
[0024] FIG. 8 shows a partially expanded sheath with a sleeve.
[0025] FIGS. 9 a - c show different views of a closed pericardium seal.
[0026] FIG. 10 shows a tool for the closing of a pericardium seal.
[0027] FIG. 11 shows a plug connector system of the device.
[0028] FIG. 12 a shows a heart with anatomical points of reference.
[0029] FIG. 12 b shows a cross-section of the heart from FIG. 12 a.
[0030] FIG. 13 a shows a 3D view of part of a heart with a system of coordinates.
[0031] FIG. 13 b shows a 2D-rollout of the 3D view from FIG. 13 a with a system of coordinates.
[0032] FIG. 14 a shows a 3D view of a sleeve with augmentation and positioning units.
[0033] FIG. 14 b shows a 2D rollout of a sleeve with augmentation and positioning units from FIG. 14 a.
[0034] FIGS. 15 a - b show one compressed and one expanded augmentation unit in the form of a chamber with a bellows-type section.
[0035] FIG. 16 a shows a 3D view of a sleeve with sensors and/or electrodes.
[0036] FIG. 16 b shows a 2D rollout of the sleeve with sensors and/or electrodes from FIG. 16 a.
[0037] FIG. 17 shows a sample embodiment for a sleeve with augmentation and positioning units.
[0038] FIG. 18 shows a sample embodiment for a sleeve with sensors and electrodes.
DETAILED DESCRIPTION
[0039] FIG. 1 shows an embodiment ( 10 ) of a device in the implanted state. In this example, the device is implanted into a human body. The device, however, can also be implanted into an animal body, in particular into the body of a mammal like a dog, a cat, a rodent, a primate, an even-toed ungulates or an odd-toed ungulate. Depending on the species, the form and the mode of operation of the device is adjusted, in order to accommodate anatomical and/or physiological needs of the individual species.
[0040] FIG. 1 shows a human torso with the device. The device includes a sheath ( 2 ), which can at least partially enclose the heart ( 61 ). Multiple components inserted in the sheath ( 2 ) support the cardiac function ( 61 ). The device also includes a supply unit ( 30 ).
[0041] The sheath ( 2 ), which can at least partially enclose the heart ( 61 ), is configured to transition from a non-expanded state into an expanded state. Preferably, the sheath ( 2 ) is self-expanding and can be inserted into a delivery system in the non-expanded state. The sheath ( 2 ) can be a mesh, in particular a wire mesh, whereby the wire mesh can be at least partially made of a shape memory alloy.
[0042] The sheath ( 2 ) at least partially encloses the heart ( 61 ) in the implanted state and is located inside the pericardium ( 6 ). Embodiments in which the sheath ( 2 ) is placed outside of the pericardium ( 6 ) are possible as well. These embodiments are not described separately; rather, the description for embodiments for implantation inside and outside the pericardium ( 6 ) (with the exception of the not-required pericardial seal ( 5 ) in embodiments of the sheath ( 2 ) for implantation outside the pericardium ( 6 )) is applicable. The architecture of the sheath ( 2 ) is explained in greater detail in a later section of the description.
[0043] Located inside the expandable sheath ( 2 ) is at least one expandable unit, which can be used to apply pressure to the heart ( 61 ). The expandable unit can be a mechanical unit, configured to transition between an expanded and a non-expanded state. Such a mechanical unit can include spring elements, which can be tensioned and released, or lever elements, which can be folded and unfolded. Preferably, the expandable units are chambers, which can be filled with a fluid. Suitable fluids for the filling of a chamber include liquids, gases, or solids (like nanoparticle mixtures, for example), or mixtures of fluids and/or gases and/or solids. The expandable unit can be secured inside the sheath ( 2 ). Preferably, the expandable unit is attached to a sleeve, which can be inserted into the sheath ( 2 ). The at least one expandable unit is described in greater detail with reference to FIG. 8 .
[0044] The sheath ( 2 ) can furthermore include at least one sensor and/or one electrode, which can be used to detect at least one parameter of the heart ( 61 ). The sensor can be configured to determine the heart rate, the ventricular pressure, the contact force between the heart wall and the expandable unit, the systolic blood pressure, the diastolic blood pressure, the pressure applied to a surface of the heart, the fluid presence, the acidity, the electrical resistance, the osmolarity, the oxygen saturation or the flow through a vessel. The sensor can also be configured to measure the pressure applied by an expandable unit onto a surface, the pH-value, the electrical resistance, the osmolarity of a solution, the oxygen saturation of tissue or blood or the flow through a vessel. The sensor can be attached inside or on the sheath ( 2 ). Preferably, the sensor is secured on a sleeve configured to be inserted into the sheath ( 2 ). In addition to the at least one sensor or in place of the sensor, the sheath ( 2 ) can also include at least one electrode configured to measure a parameter, like e.g. the action potential at the myocardium during the excitation process, or to stimulate a tissue with currents. The sensor can also be an electrode. The sensor and the electrode are explained in greater detail in a later section of the description.
[0045] FIG. 1 shows a supply unit ( 30 ), which can be worn outside the body. The supply unit can also be partially or completely implanted into the body, which will be explained in the following sections in greater detail. If the supply unit ( 30 ) is worn outside the body, it may be attached to a chest belt, to a hip belt, or to an abdominal belt. The supply unit ( 30 ) is equipped with an energy storage device allowing the expandable unit to be powered. The energy storage device can be available in the form of a rechargeable battery providing electrical energy to expand the expandable unit. The rechargeable battery is exchangeable. The supply unit ( 30 ) can also include a pressure storage device supplying a compressed gas, to inflate an inflatable chamber. Suitable gases are, among others, compressed air, CO 2 , or inert gases. The housing of the supply unit ( 30 ) itself can serve as a pressure storage housing. The supply unit ( 30 ) can furthermore contain pumps, valves, sensors and displays. The supply unit ( 30 ) can furthermore include a microprocessor configured to receive and process data from the at least one sensor. If the supply unit ( 30 ) is worn outside the body, the required energy can be transferred by direct connection via a cable ( 4 ) or connectionless via electromagnetic induction, for example. The data from the at least one sensor can also be transmitted directly via a cable ( 4 ) or connectionless via wireless technology like bluetooth, for example.
[0046] The device can furthermore include a cable ( 4 ) connecting the expandable unit and/or the sensor or the electrode to the supply unit ( 30 ). If the supply unit ( 30 ) is connected directly to the expandable unit and/or to the sensor, or the electrode, a cable ( 4 ) is not required. If the expandable unit is a mechanical unit which, using electrical energy, is configured to transition from a non-expanded state into an expanded state, or from an expanded state into a non-expanded state, the cable ( 4 ) includes lines configured to transfer the required energy from the supply unit ( 30 ) to the expandable unit. The sleeve can include internal chambers, configured to enable hydraulic alteration of the volume of at least one of the internal chambers of the sleeve. If the expandable unit is a chamber that can be filled by means of a fluid, the cable ( 4 ) includes at least one line allowing the flow of fluid from the supply unit ( 30 ) into the chamber. In some implementations, the cable ( 4 ) includes at least one pneumatic or hydraulic line. If the device includes one sensor or one electrode at, in or on the sheath, then the line leading to the sensor or the electrode can also be in the cable ( 4 ). Embodiments can also exhibit separate cables for providing energy for the expandable unit and for the sensor, or the electrode.
[0047] The cable ( 4 ) connecting the supply unit ( 30 ) to the expandable unit and/or the sensor, or the electrode, can be a single continuous cable or a multi-part cable. In the case of a continuous cable connection, the cable ( 4 ) can be attached to the expandable unit and/or the sensor or one electrode. A connector ( 90 ) can be attached to the end of the cable ( 4 ). The connector ( 90 ) can be connected to the supply unit ( 30 ) via the matching connector ( 91 ). Alternatively, a cable with a connector is only attached to the supply unit ( 30 ). In this case, the matching connector is installed on the sheath ( 2 ), on the expandable unit and/or on the sensor or electrode. In case of a multi-part cable, a cable ( 4 ) with a connector ( 91 ) can be attached to the expandable unit and/or at the sensor or the electrode, and a cable can also be attached to the supply unit ( 30 ), at the end of which can be a connector. The cable ( 4 ) and the connector ( 90 ) are described in greater detail in a later section of the description.
[0048] FIG. 2 shows an embodiment ( 11 ) of the device in the implanted state, where the supply unit ( 31 ) is implanted into the body. Preferred locations for the implantation of the supply unit ( 31 ) are the chest (thoracic) cavity and the abdominal (peritoneal) cavity, which are separated from each other by the diaphragm ( 63 ).
[0049] The sheath ( 2 ) shown in FIG. 2 , the pericardium seal ( 5 ), and the cable ( 4 ) of the device are essentially identical to the components shown in FIG. 1 . The supply unit ( 31 ) can include an energy storage device, which can be used to power the expandable unit located inside the sheath ( 2 ). The energy storage device can be provided in the form of a rechargeable battery, which supplies electrical energy in order to expand the expandable unit. The supply unit ( 31 ) can furthermore contain sensors and one or more microprocessors. If the expandable unit includes at least one chamber, which can be filled with a fluid, then the supply unit ( 31 ) can include pumps, valves, and a pressure reservoir. The pressure reservoir can provide a compressed gas in order to inflate an inflatable chamber. Suitable gases are, among others, compressed air, CO 2 , or inert gases. The housing of the supply unit ( 31 ) itself can represent the housing of the pressure reservoir. A preferred place for the implantation of the supply unit ( 31 ) is inside the right lateral chest cavity above the liver ( 62 ) and above the diaphragm ( 63 ). Alternatively, or in addition to the pressure reservoir ( 32 ) in the supply unit ( 31 ), the pressure reservoir ( 32 ) can be preferably implanted inside the right lateral abdominal cavity below the diaphragm ( 63 ) and above the liver ( 62 ).
[0050] The pressure reservoir ( 32 ) can be connected to the supply unit ( 31 ) with a tube ( 33 ), which penetrates the diaphragm ( 63 ). The opening in the diaphragm required for the tube ( 33 ) to pass through can be sealed with a seal. The seal can be designed similar to the pericardium seal, as previously described. The supply unit can be connected via a cable ( 4 ) directly with the expandable unit and/or the sensor, or the electrode. Alternatively, at the end of the cable ( 4 ) can also be a connector configured to connect via a matching connector to the supply unit ( 31 ) or to the expandable unit and/or to the sensor or the electrode.
[0051] The cable ( 4 ) runs preferably in the chest cavity above the diaphragm ( 63 ). In the case of a multi-part cable, a cable with a connector can be attached to the expandable unit and/or the sensor or one electrode, and a cable with a matching connector can be attached to the supply unit ( 31 ).
[0052] Alternatively or in addition to a rechargeable battery in the supply unit ( 31 ), a rechargeable battery ( 34 ) can be implanted subcutaneously, into the abdominal wall. The energy required in the supply unit ( 31 ) can be transferred, for example, by electromagnetic induction from an extracorporeal controller ( 35 ) transcutaneously to the rechargeable battery ( 34 ) and be transmitted by an electric cable ( 36 ) from the rechargeable battery ( 34 ) to the supply unit ( 31 ). The extra-corporeal controller ( 35 ) can include an exchangeable rechargeable battery and/or a charging device. The extracorporeal controller ( 34 ) can contain, among others, microprocessors and displays, which can be used for system monitoring of the device and for a display of the operating status. The data from the sensor can be transmitted connectionless via a wireless technology like bluetooth, for example, to and between the supply unit ( 31 ) and the controller ( 34 ).
[0053] FIG. 3 shows an example of a human heart ( 61 ), as well as a sheath ( 2 ), a sleeve ( 7 ) with expandable units ( 71 , 72 ), a sleeve ( 80 ) with sensors ( 81 ) and/or electrodes a cable ( 4 ) with a connector ( 90 ), a catheter ( 103 ) of a delivery system, and a pericardium seal ( 5 ) of the device.
[0054] In this embodiment, the sheath ( 2 ) is shown in the form of a wire mesh. Instead of a wire mesh, the sheath ( 2 ) can alternatively be formed as a lattice consisting of links. In this case, the links create a lattice structure with openings. The sheath ( 2 ) can also consist of a continuous material, from which parts have been removed; for example, the sheath ( 2 ) can consist of a tube and an individually shaped sheath sleeve, into which holes have been formed or cut.
[0055] The sheath ( 2 ) represented in FIG. 3 consists of a mesh made of wires. The wires form crossing points (intersections), which can be permanently interconnected. The wires could, for example, be welded together at their crossing points. Connecting the wires at crossing points increases the stability of the sheath ( 2 ). The crossing points can be free from each other, increasing the flexibility of the sheath ( 2 ) and therefore leading to an easier compressibility of the sheath ( 2 ). In some embodiments, the sheath includes wires that do not cross each other, forming longitudinally oriented struts. Increased sheath flexibility is especially helpful if the sheath ( 2 ) is to be inserted into a delivery system with a smaller diameter catheter ( 103 ). Some of the crossing points of the sheath ( 2 ) can also be permanently interconnected and others not. Through appropriate selection of crossing points that are permanently interconnected and crossing points that are separable, the stability and flexibility of the sheath ( 2 ) can be customized. Areas requiring increased stability in the implanted state can be stabilized by connecting the wires at the crossing points. These can be areas serving as bearing surfaces or abutments for expandable units ( 71 , 72 ). Such abutments can be located directly under an expandable unit ( 71 , 72 ) or next to areas with expandable units ( 71 , 72 ). Areas requiring increased flexibility can be areas which during insertion into a delivery system must be compressed more than other areas. Areas requiring increased flexibility can also be areas, in which an increased flexibility supports the natural movement of the heart. If the sheath ( 2 ) is not made of a wire mesh but of a latticework or a sheath sleeve with holes, the stability and/or the flexibility of selected areas of the sheath ( 2 ) can be adjusted as well. In these cases, adjustments can be brought about by choosing the width of the links and/or the thickness of the links, through the choice of the material to be used, through modifications of the material in certain areas through application of energetic radiation, like heat, for example. Preferably, the sheath ( 2 ) exhibits openings being formed by the wires of a wire mesh, the links of a latticework, or the holes in a sheath sleeve. These openings enable compression of the sheath ( 2 ); they allow the exchange of substances from inside the sheath ( 2 ) with areas outside the sheath ( 2 ) and vice versa; they reduce the amount of material being used for the sheath ( 2 ), and they allow an increased flexibility of the sheath ( 2 ). Shapes which are difficult to realize with solid materials are easier to achieve with mesh-type or lattice-type structures. The openings can be rectangular, round or oval. The openings defined by the wires, the links or the holes in a sheath sleeve have a diameter of approximately 1 to 50 mm, preferably 4 mm to 10 mm. The diameter of an opening is defined as pin opening, meaning that the diameter of the opening represents the largest diameter of a cylindrical pin that can pass through an opening (e.g., a cell or a hole).
[0056] The sheath ( 2 ) is preferably made of a material allowing expansion. Preferably, the sheath ( 2 ) is formed from a material selected from the group consisting of nitinol, titanium and titanium alloys, tantalum and tantalum alloys, stainless steel, polyamide (PA), polyurethane (PUR), polyether ether ketone (PEEK), polyethylene (PE), polypropylene (PP), polycarbonate (PC), polyethylene terephthalate (PET), polymer fiber materials, carbon fiber materials, aramide fiber materials, glass fiber materials and combinations thereof A material suitable for forming a self-expanding sheath ( 2 ) is at least partially made of a shape memory alloy. Examples of shape memory alloys include NiTi (nickel-titanium; nitinol), NiTiCu (nickel-titanium-copper), CuZn (copper-zinc), CuZnAl (copper-zinc-aluminum), CuAlNi (copper-aluminum-nickel), FeNiAl (iron-nickel-aluminum) and FeMnSi (iron-manganese-silicon).
[0057] The sheath ( 2 ) preferably exhibits a form adapted to the individual shape of the patient's heart, or a cup-shaped form. The individual shape of the patient's heart can be reconstructed from CT or MRI image data. The sheath ( 2 ) is open at the top. The upper rim of the sheath ( 2 ) preferably exhibits loops of a wire or straps, which are formed by links. The loops or straps can serve as anchoring points for a sleeve ( 80 ) with at least one sensor ( 81 ) or one electrode, and/or for a sleeve ( 7 ) with at least one expandable unit ( 71 , 72 ). Positioned at the lower end of the cup-shaped sheath is preferably an opening, through which one or multiple leads of the sensor ( 81 ) or of the electrode, and/or of the expandable unit ( 71 , 72 ) can be passed. The shape of the sheath ( 2 ) at least partially represents the anatomical shape of a heart ( 61 ), in particular the lower part of a heart ( 61 ). Details regarding the shape of the sheath ( 2 ) are explained in greater detail in a later section of the description.
[0058] The sheath ( 2 ) can be covered by a membrane ( 21 ), in particular by a membrane ( 21 ) made of polyurethane or silicon. The membrane ( 21 ) is configured to reduce the mechanical stress applied by the sheath ( 2 ) onto the pericardium ( 6 ) or the myocardium ( 61 ). The membrane ( 21 ) can also increase the biocompatibility of the sheath ( 2 ). The membrane ( 21 ) can be attached to the inner surface or to the outer surface of the sheath ( 2 ). The membrane ( 21 ) can also be manufactured by dipping the mesh- or lattice-type sheath ( 2 ) into an elastomer-containing liquid, which subsequently envelops the latticework or the mesh. The membrane ( 21 ) can then stretch across the openings of the mesh or the lattice. A membrane ( 21 ) on the mesh or the lattice can also improve the abutment properties of an expandable unit ( 71 , 72 ). If an expandable unit ( 71 , 72 ) is, for example, an inflatable chamber, then a membrane ( 21 ) across, at or on the mesh or the lattice can prevent parts of the chambers being pressed through the mesh or the lattice while the chamber is expanding. The membrane ( 21 ) can furthermore prevent excessive widening of the sheath ( 2 ), in particular during inflation of an inflatable chamber. A membrane ( 21 ) on a mesh or a lattice can ensure that an expandable unit positioned on the lattice or the mesh expands into a direction from the mesh or lattice towards the inside only. The membrane ( 21 ) does not interfere with the compressibility of the sheath ( 2 ) while being inserted into a delivery system.
[0059] The sheath ( 2 ) and/or the membrane ( 21 ) can also include an active pharmaceutical ingredient, for example, an anti-thrombotic ingredient, an anti-proliferative ingredient, an anti-inflammatory ingredient, an anti-neoplastic ingredient, an anti-mitotic ingredient, an anti-microbial ingredient, a biofilm synthesis inhibitor, an antibiotics ingredient, an antibody, an anti-coagulating ingredient, a cholesterol-lowering ingredient, a beta blocker, or a combination thereof. Preferably, the ingredient is in the form of a coating on the sheath ( 2 ) and/or the membrane ( 21 ). The sheath ( 2 ) and/or the membrane ( 21 ) can also be coated with extra-cellular matrix proteins, in particular fibronectin or collagen. Bio-compatible coating can be advantageous if ingrowth of the sheath ( 2 ) is desired.
[0060] The expandable unit ( 71 , 72 ) is located inside the sheath ( 2 ). FIG. 3 shows a sheath ( 2 ), into which a sleeve ( 7 ) with expandable units ( 71 , 72 ) in the form of inflatable chambers is inserted. The expandable unit ( 71 , 72 ) is being supplied by a line ( 41 ) inside the cable ( 4 ). The expandable unit ( 71 , 72 ) can be a hydraulic or a pneumatic chamber. The expandable unit ( 71 , 72 ) can be attached directly to the sheath ( 2 ) without a sleeve ( 7 ). The expandable unit ( 71 , 72 ) can also be attached to a sleeve ( 7 ), and the sleeve ( 7 ) can be attached inside the sheath ( 2 ). The expandable unit ( 71 , 72 ) can be designed to apply pressure to the heart ( 61 ). The applied pressure can be a permanent pressure, or it can be a periodically recurring pressure. The device can include different types of expandable units ( 71 , 72 ). The device can include at least one augmentation unit ( 71 ). The device can include at least one positioning unit ( 72 ). The augmentation unit ( 71 ) and/or the positioning unit ( 72 ) can be attached directly to the sheath ( 2 ) or onto a sleeve ( 7 ), which is inserted into the sheath ( 2 ).
[0061] An augmentation unit ( 71 ) is a unit that can be periodically expanded and relaxed, and thereby applies a rhythmical pressure to the heart ( 61 ). The pressure is preferably applied in the areas of the heart muscle, under which a ventricle is located. By applying pressure on a ventricle by means of the augmentation unit ( 71 ) the natural pumping motion of the heart ( 61 ) is being amplified or substituted, and the blood inside the heart ( 61 ) is pumped from the ventricle into the discharging artery. A pressure applied by an augmentation unit ( 71 ) to a right ventricle assists the ejection of the blood from the right ventricular chamber into the pulmonary artery. A pressure applied by an augmentation unit ( 71 ) to a left ventricle assists the ejection of the blood from the left ventricular chamber into the aorta. The positioning of the augmentation unit ( 71 ) inside the sheath ( 2 ) is explained in greater detail in a later section of the description.
[0062] A positioning unit is preferably expanded during the operation of the device in support of the heart function more statically than periodically. The positioning unit ( 72 ) can be expanded in order to fix the device to the heart and to ensure proper fitting of the device. A positioning device ( 72 ) can also be used to respond to changes in the myocardium (e.g., shrinking of the myocardium due to lack of fluids or enlargement of the myocardium due to the absorption of fluids). If the size of the myocardium decreases or increases within a particular period of time, a positioning unit can be expanded or relaxed further in order to ensure a perfect fit. The positioning unit ( 72 ) may, for example, also be used to ensure that the device does not lose contact to the heart wall over the span of a heartbeat. Loss of contact can lead to impact stress between the myocardium and the device, and/or cause malfunction of the sensors ( 81 ) and/or electrodes. In some implementations, the positioning unit ( 72 ) can counteract the pathological, progressive expansion of the damaged myocardium in heart failure patients. The positioning of the positioning unit ( 72 ) inside the sheath ( 2 ) is explained in greater detail in a later section of the description.
[0063] Located at the lower end of the sheath ( 2 ) can be an opening, through which the lead ( 83 ) from the sensor ( 81 ) or the electrode and/or the line ( 41 ) of the expandable unit ( 71 , 72 ) can be passed. The opening can be installed at the lower distal end of the sheath ( 2 ). Alternatively, the opening can also be installed on one side of the sheath ( 2 ). Shown in FIG. 3 is an opening at the lower distal end of the sheath ( 2 ), through which one cable ( 4 ), which includes all leads ( 41 , 83 ), has been routed. Instead of one cable ( 4 ), there can be multiple separate cables. The cables can be routed through one opening of the sheath ( 2 ) or through multiple openings of the sheath ( 2 ). Attached to the end of the cable ( 4 ) is a connector ( 90 ), which is used to connect the sensor ( 81 ) or the electrode, and/or the expandable unit ( 71 , 72 ) to a supply unit. The sheath ( 2 ) is preferably brought inside the pericardium ( 6 ). The cable ( 4 ) is then passed through the pericardium ( 6 ). The device can include a pericardium seal ( 5 ). The seal can seal the opening of the pericardium, which is required for the cables to pass through. The pericardium ( 6 ) is a connective-tissue-type sac surrounding the heart ( 61 ), and which, due to a narrow lubricant layer, gives the heart ( 61 ) the ability to move freely. As a lubricant, it contains a serous fluid, also called liquor pericardii. In order to prevent this lubricant from escaping from the pericardium ( 6 ) through the cable opening, and to prevent any other fluids or solids (like, for example, cells, proteins, foreign matter, etc.) from entering the pericardium ( 6 ), a pericardium seal ( 5 ) can be installed around the cable ( 4 ). The pericardium seal ( 5 ) seals the opening of the pericardium ( 6 ) to the cable ( 4 ). The pericardium seal ( 5 ) can include a first sealing component with a first sealing lip, and a second sealing component with a second sealing lip. A cable ( 4 ) can be routed through a central lumen of the seal. The first sealing lip and/or the second sealing lip can seal the pericardium opening. Located inside the central lumen can be an additional sealing component, which seals the cable ( 4 ) against the pericardium seal ( 5 ) and, if necessary, fixes it as well. The first and the second sealing component can be combined. Preferably, the first and the second sealing component can be secured with a mechanism. Possible mechanisms to secure the sealing components are screw mechanisms, clamping mechanisms, or a bayonet mechanism. The first sealing component and/or the second sealing component can be expandable, or even self-expanding. The pericardium seal ( 5 ) is explained in greater detail in a later section of the description.
[0064] FIGS. 4 a and 4 b show a cross-section of the heart ( 61 ) and part of the device for the support of the cardiac function ( 61 ) along line A-A in FIG. 3 . Starting from the outside to the inside, the following layers are represented: The sheath ( 2 ) with a membrane ( 21 ), a sleeve ( 7 ) with at least one expandable unit ( 71 , 72 ), a sleeve ( 80 ) with at least one sensor ( 81 ) or one electrode ( 82 ), and a transverse cross-section of the heart ( 60 ). Three augmentation units ( 71 ) and three positioning units ( 72 ) are illustrated as examples. In FIG. 4 a , the expandable units ( 71 , 72 ) have been drawn in the non-expanded state. In FIG. 4 b , the augmentation units ( 71 ) have been drawn in the expanded state. The expandable unit ( 71 , 72 ) is located in an area adjacent to a ventricle. An expansion of the expandable unit ( 71 , 72 ) can reduce the volume of the ventricle and cause blood to be ejected from the ventricular chamber. The sensor ( 81 ) or the electrode ( 82 ) is installed in a particular location, where at least one parameter of the heart ( 61 ) can be measured. An electrode ( 82 ) can be installed in a particular location, where the myocardium can be stimulated. In FIGS. 4 a and 4 b , four sensors ( 81 ) in the sleeve ( 80 ) and three electrodes ( 82 ) at the inside of the sleeve ( 80 ) are illustrated as examples.
[0065] FIG. 5 shows a delivery system ( 100 ), which can be used to implant the device to support the cardiac function. The delivery system ( 100 ) includes a catheter ( 103 ), which has a lumen. Preferably, the catheter ( 103 ) is an elongated, tubular component, into which the device for the support of the cardiac function can be inserted in its compressed state. The cross-section of the catheter ( 103 ) and/or of the lumen can be circular, oval or polygonal. The delivery system ( 100 ) can further include a guide wire ( 101 ) and/or a dilatation component. The dilatation component can be soft cone-shaped tip ( 102 ) with a shaft. The guide wire ( 101 ) can be passed through a puncture of the chest wall ( 65 ) between the ribs ( 64 ) and of the pericardium ( 6 ). The soft, cone-shaped tip ( 102 ) can have at the center a circular, oval or polygonal lumen. The soft, cone-shaped tip ( 102 ) can be pushed over the guide wire ( 101 ) and the puncture can be dilated without injury to the epicardium. The distal section of the catheter ( 103 ) of the delivery system ( 100 ) can be passed through the dilated opening. At the distal end of the catheter ( 103 ), a first sealing component ( 51 , 52 ) of the pericardium seal can be snapped on or otherwise attached. The catheter ( 103 ) may, for example, be pushed onto a cone ( 55 ) located at the end of the first sealing component ( 51 , 52 ). Not shown is another embodiment, where a cone is located at the side of the catheter, onto which the first sealing component can be pushed. The catheter ( 103 ) with the attached first sealing component ( 51 , 52 ) of the pericardium seal can be guided via the shaft of the soft tip ( 102 ) and inserted into the pericardium ( 6 ).
[0066] Alternatively, the catheter ( 103 ) and the first sealing component ( 51 , 52 ) of the pericardium seal can be parts that are not interconnected to each other. In this case, the catheter ( 103 ) is initially inserted into the pericardium ( 6 ), and the first sealing component ( 51 , 52 ) can then be pushed into the pericardium via the catheter or withdrawn from the pericardium ( 6 ) through the lumen of the catheter ( 103 ). The first sealing component ( 51 , 52 ) can be a self-expanding sealing component, and is configured to unfold inside the pericardium ( 6 ). Alternatively, a non-expandable part ( 51 ) of the first sealing component contains a self-expanding sealing lip ( 52 ) or a sealing lip ( 52 ), which is configured to fold down while the first seal component ( 51 , 52 ) is being inserted, and which opens up inside the pericardium ( 6 ). The first sealing component ( 51 , 52 ) can expand into a mushroom or umbrella-like shape.
[0067] A second sealing component ( 53 , 54 ) can be inserted along the catheter ( 103 ) or through the catheter ( 103 ). For example, the second sealing component ( 53 , 54 ) can be moved via the catheter ( 103 ) of the delivery system ( 100 ) to the distal end of the delivery system ( 100 ), and then coupled with the first sealing component ( 51 , 52 ). The second sealing component ( 53 , 54 ) can be expandable or non-expandable. The second sealing component ( 53 , 54 ) can be coupled to the first sealing component ( 51 , 52 ). The second sealing component ( 51 , 52 ) is preferably self-expanding, and can in its expanded form assume the shape of a mushroom or an umbrella. The second sealing component ( 53 , 54 ) can be secured with the first sealing component ( 51 , 52 ). Shown in FIG. 5 is a screw mechanism. Other mechanisms to secure the sealing components ( 51 , 52 , 53 , 54 ) include a clamping mechanism or a bayonet seal. After securing the sealing components ( 51 , 52 , 53 , 54 ), the catheter ( 103 ) of the delivery system ( 100 ) can remain on the cone ( 55 ) of the first sealing component ( 51 ) or remain in the lumen of the sealing component ( 51 , 52 ). After the guide wire ( 101 ) and the shaft of the soft tip ( 102 ) have been pulled out of the catheter, the shell with the sensor or the electrode and/or with the expandable unit can be inserted through the lumen of the catheter ( 103 ). The sheath is preferably self-expanding and at least partially encloses the heart ( 61 ) after expansion. Located at the lower end of the sheath can be a connector or a cable with a connector. The supply unit can be directly attached to the sheath, or be connected to the sheath via a cable. After the sheath has been delivered, the delivery system ( 100 ) can be removed. The delivery system ( 100 ) is detached from the sheath by using a pre-weakened breaking point ( 104 ) of the delivery system ( 100 ) and/or on the catheter ( 103 ). Preferably, there are one or multiple pre-weakened breaking points ( 104 ) along a longitudinal axis of the delivery system ( 100 ). The pre-weakened breaking point ( 104 ) can be represented by a breaking line. When the delivery system ( 100 ) is broken open along a pre-weakened breaking point ( 104 ), the delivery system ( 100 ) can be split, unrolled and removed. The delivery system ( 100 ) can also include grasping components ( 105 ), which can be used to apply a force to the delivery system ( 100 ). Preferably, the grasping components ( 105 ) can be used to apply a force directed sideways from the catheter ( 103 ) onto the delivery system ( 100 ) suitable to break open the pre-weakened breaking point ( 104 ).
[0068] The delivery system ( 100 ) can further include a sensor ( 107 ). The sensor can be a temperature sensor ( 107 ) to measure the temperature within the catheter before and during the implantation of the sheath. The temperature sensor ( 107 ) can include a thermocouple, a crystal oscillator or an infrared camera. Alternatively, the sensor can be a sensor to measure at least one of the temperature, pH-value, osmolarity and oxygen saturation of a fluid within the catheter. The wall of the catheter ( 103 ) can further contain heating elements ( 108 ).
[0069] The heating elements ( 108 ) can be used to heat the catheter ( 103 ) and its content before or during implantation. The delivery system ( 100 ) can contain one, two, three, four or more heating elements ( 108 ). The heating elements ( 108 ) can be arranged along the circumference of the catheter wall ( 103 ) equidistantly or irregularly. The heating elements ( 108 ) can span the whole length of the catheter ( 103 ) or cover the length of the catheter only partially. The heating elements ( 108 ) can be adjacent to the catheter wall ( 103 ) at the inside or the outside or they can be within the catheter wall.
[0070] The heating elements ( 108 ) can include heating filaments, heating coils or heating wires, which produce heat via an electrical current. The heating elements ( 108 ) can further consist of ducts within the catheter wall that are perfused by a tempered fluid. The catheter can be heated by using a perfusion fluid whose temperature is higher than the ambient temperature. The ducts can also be perfused by a fluid whose temperature is lower than the ambient temperature, in this way the ducts are utilized to cool down the catheter and its content to a lower temperature. With a temperature sensor and the heating elements, the temperature within the catheter can be maintained at a specific level between −5° C. and +40° C.
[0071] FIG. 6 shows a step of the implantation of the device. After the first sealing component ( 51 , 52 ) in the pericardium ( 6 ) has assumed the expanded form, the sheath ( 2 ), which is preferably self-expanding, can be passed through the lumen of the catheter ( 103 ) of the delivery system and lumen of the first sealing component ( 51 ). After entering through the pericardium seal, the sheath ( 2 ) with the sensor or the electrode and/or the expandable unit expands inside the pericardium ( 6 ).
[0072] Shown in FIG. 6 is also the second sealing component ( 58 , 59 ) before being coupled with the first sealing component ( 51 , 52 ). In this embodiment, the second sealing component ( 58 , 59 ) is a ring-shaped component ( 58 ), e.g., a nut, on which a sealing disk ( 59 ) can be attached to its distal side. The second sealing component ( 58 , 59 ) can be expandable or non-expandable. The second sealing component ( 58 , 59 ) can be moved on the catheter ( 103 ). In this embodiment, the first sealing component ( 51 , 52 ) the sheath with the sensor or the electrode and/or with the expandable unit can be inserted through the lumen and the second sealing component ( 58 , 59 ) exhibit thread sections, which can be screwed together.
[0073] FIG. 7 shows a step of the implantation of the device. In this embodiment, the first sealing component ( 51 , 52 ) is coupled with the second sealing component ( 53 ). The pericardium ( 6 ) can thereby be sealed. The expandable sheath ( 2 ) is partially located inside the pericardium ( 6 ) and can be expanded. FIG. 7 shows markings ( 22 , 23 , 24 ) applied to the sheath ( 2 ). The device generally contains at least one marking ( 22 , 23 , 24 ), which can facilitate the correct placement of the sheath ( 2 ). The marking ( 22 , 23 , 24 ) can be a visual mark, in particular a color marking. The marking ( 22 , 23 , 24 ) can be a phosphorescent or fluorescent marking, making it easier to see in dark environment. Such environments can be present in the operating room itself, and can also be caused by the casting of shadows. Such environments can also be inside the body of a patient. The marking ( 22 , 23 , 24 ) can be made of a material able to be represented by imaging techniques. Suitable imaging techniques include X-rays, CT-methods, and MRI-methods. For example, the marking ( 22 , 23 , 24 ) can be formed of a more radiopaque material than the material of adjacent regions. The marking ( 22 , 23 , 24 ) can have the form of a point, a circle, an oval, a polygon, or the form of a letter. Other forms can be areas created by the connecting of dots. The form can be, for example, a half-moon or a star. The marking ( 22 , 23 , 24 ) can be applied to the sheath ( 2 ) or applied to a sleeve. The marking can be applied in the form of a line. The line can start at the upper edge of the sheath ( 2 ). The line can run from an upper edge of the sheath ( 2 ) to a point at the lower tip of the sheath ( 2 ). The line can run from the upper edge of the sheath perpendicular to the lower tip of the sheath ( 2 ). The starting point of the line at the upper edge of the sheath ( 2 ) can be located at a place, which in the implanted state is close to an area, or at an area, which is level with the cardiac septum. The marking ( 22 , 23 , 24 ) can be located at crossing points of the mesh or the lattice. If the sheath ( 2 ) includes a sheath sleeve, into which holes were formed, the marking ( 22 , 23 , 24 ) can be worked into the sheath sleeve. For example, a hole can be manufactured with a predefined form, which then serves as marking ( 22 , 23 , 24 ).
[0074] The delivery system and/or the catheter ( 103 ) of the delivery system can include one or multiple markings ( 106 ). A marking ( 106 ) on a delivery system can be formed like a marking on a sheath. The marking ( 106 ) can have the form of a dot or the form of a line. A marking ( 106 ) in the form of a line can be a line, which at least partially describes a circumference of the delivery system. A marking ( 106 ) in the form of a line can be a longitudinal line along an axis of the delivery system. A marking ( 106 ) in the form of line can be a straight line or a meandering line. A marking ( 106 ) in the form of a line can be a line running diagonally on a catheter ( 103 ) of a delivery system. A marking ( 106 ) can facilitate the orientation of the delivery system during implantation. A marking ( 106 ) at or on the delivery system can be in alignment with a line at or on a medical implant. For example, the medical implant can be a device for the support of the cardiac function, which can be compressed. In a compressed state, the device can be inserted into a delivery system. One or multiple markings ( 22 , 23 , 24 ) on or at the device can be aligned with one or multiple markings ( 106 ) on or at the delivery system. Such markings ( 22 , 23 , 24 , 106 ) facilitate the orientation of a medical implant. Markings ( 22 , 23 , 24 ) can also be located along an axis of a medical implant. Such markings ( 22 , 23 , 24 ) can be helpful in tracking the progress of the discharge of a medical implant out of the delivery system. The delivery system and/or a catheter ( 103 ) can be made of a transparent material, which allows the medical implant to be visually traceable during insertion.
[0075] FIG. 8 shows a step of the implantation of the device. In this example, the first sealing component ( 51 , 52 ) and the second sealing component ( 53 ) of the pericardium seal are interconnected. The device for the support of the cardiac function has already been partially discharged from the delivery system. Shown is a self-expanding sheath ( 2 ). In this embodiment, the sheath ( 2 ) is formed from a wire mesh exhibiting loops ( 26 , 28 ) at the upper edge and/or at the lower edge of the sheath ( 2 ). The sheath ( 2 ) can also be formed of a lattice structure and can exhibit links in the form of straps at the upper edge and/or at the lower edge of the sheath ( 2 ). If the sheath ( 2 ) is formed from a sheath sleeve, into which holes have been formed, the upper edge and/or the lower edge of the sheath ( 2 ) can be designed such that at least one strap is located at the upper and/or lower edge of the sheath ( 2 ). The sheath ( 2 ) represented in FIG. 8 includes a sleeve ( 80 ), which is inserted into the sheath ( 2 ). Another sleeve including at least one expandable unit can be located between the sleeve ( 80 ) and the sheath ( 2 ).
[0076] One or both sleeves can be fastened to the loops ( 26 , 28 ) or straps of the sheath ( 2 ). A sleeve can, in particular, be hooked onto the loops ( 26 , 28 ) or the straps of the sheath ( 2 ). In such case, the sleeve ( 80 ) can exhibit at least one pocket ( 27 ), which can be pulled over at least one loop ( 26 , 28 ) or at least one strap. Another embodiment can include a sleeve ( 80 ), which is turned inside out at its upper edge and/or at its lower edge. This inversion can form a pocket ( 27 ) around the entire sleeve ( 80 ) or around a part thereof, which can be hooked into the upper edge and/or the lower edge of the sheath ( 2 ). In FIG. 8 , the sheath ( 2 ) exhibits multiple markings ( 22 , 23 , 24 , 25 ). As previously described, these markings ( 22 , 23 , 24 , 25 ) can assume different forms or positions. In this case, the markings ( 22 , 23 , 24 , 25 ) are attached to the upper edge and the lower tip of the sheath ( 2 ).
[0077] FIGS. 9 a - c show different views of a pericardium seal ( 5 ). The pericardium seal ( 5 ) serves to prevent the loss of pericardium fluid or also as an option to apply artificial pericardium fluid, medications or other therapeutics. The prevention of loss of pericardium fluid also serves to prevent adhesions of the system with the epicardium. The pericardium seal ( 5 ) generally includes a first sealing component ( 51 ) and a second sealing component ( 52 ). The first sealing component ( 51 ) has a central lumen, and the second sealing component ( 53 ) has a central lumen. The first sealing component ( 51 ) can be coupled with the second sealing component ( 53 ). After coupling the first sealing component ( 51 ) to the second sealing component ( 52 ), the pericardium seal ( 5 ) exhibits a lumen running through the pericardium seal ( 5 ). The lumen can be formed exclusively by the central lumen of the first sealing component ( 51 ), or the lumen can be formed exclusively by the central lumen of the second sealing component ( 53 ). In another embodiment, the lumen can also be formed from both lumens of the two coupled sealing components ( 51 , 53 ). Located in the lumen can be a sealing gasket, an O-ring, a labyrinth seal or another sealing component ( 56 ). A sealing component ( 56 ) in the lumen of the pericardium seal can seal the pericardium seal ( 5 ) against an object protruding through the pericardium seal ( 5 ). For example, a cable can be passed through the pericardium seal ( 5 ), which is then sealed against the pericardium seal ( 5 ). A sealing component ( 56 ) in the lumen can serve not only to seal but also to fix an object protruding through the lumen of the pericardium seal. The sealing component ( 56 ) can be attached to both sealing components ( 51 , 53 ) or to one of both sealing components ( 51 , 53 ) only.
[0078] Using a mechanism, the first sealing component ( 51 ) can be secured with the second sealing component ( 53 ). A mechanism to secure a first sealing component ( 51 ) with a second sealing component ( 53 ) can include a screw mechanism or clamping mechanism. A mechanism to secure a first sealing component ( 51 ) with a second sealing component ( 53 ) can also include a bayonet catch. The first sealing component ( 51 ) and the second sealing component ( 53 ) can be made of the same material or made of different materials. Suitable materials for the first sealing component ( 51 ) and/or the second sealing component ( 53 ) include synthetic materials, metals, ceramics or combinations thereof.
[0079] Attached to the first sealing component ( 51 ) can be a first sealing lip ( 52 ). The first sealing lip ( 52 ) can be part of the first sealing component ( 51 ) or can be attached to the first sealing component ( 51 ). Attached to the second sealing component ( 53 ) can be a second sealing lip ( 54 ). The second sealing lip ( 54 ) can be part of the second sealing component ( 53 ) or can be attached to the second sealing component ( 53 ). The first sealing lip ( 52 ) and the second sealing lip ( 54 ) can be formed of the same material or of different materials. One or both sealing lips ( 52 , 54 ) can be part of the respective sealing component ( 51 , 53 ) and can be formed from the same material as the associated sealing component ( 51 , 53 ). The first sealing lip ( 52 ) and/or the second sealing lip ( 54 ) can be formed of a synthetic material (preferably of an elastomer), natural rubber, rubber, silicon, latex or a combination thereof. The first sealing lip ( 52 ) and/or the second sealing lip ( 54 ) can be disk-shaped. The first sealing lip ( 52 ) and/or the second sealing lip ( 54 ) can exhibit a concave or a convex curvature. Curved sealing lips ( 52 , 54 ) can better adapt to anatomic conditions. The pericardium exhibits a convex form in the area of the cardiac apex. With the sealing lips ( 52 , 54 ) exhibiting a curvature in the shape of the anatomically available form, an improved anatomic fit of the pericardium seal ( 5 ) can be achieved.
[0080] Curved sealing lips ( 52 , 54 ) can also be used to achieve better sealing properties. The first sealing lip ( 52 ) and/or the second sealing lip ( 54 ) can have reinforcements. With increasing radial distance from the lumen of the pericardium seal towards the outside, the first sealing lip ( 52 ) and/or the second sealing lip ( 54 ) can exhibit increased flexibility. Increased flexibility at the edges of sealing lip ( 52 , 54 ) can strengthen the sealing properties of the sealing lip ( 52 , 54 ) and can also support the anatomically correct positioning of the sealing lip ( 52 , 54 ). Increased flexibility at the edges of the sealing lip ( 52 , 54 ) can be achieved through the choice of material. Each sealing lip ( 52 , 54 ) can be made of one material or of multiple materials. Reinforcements of a sealing lip ( 52 , 54 ) can be concentric reinforcements or radial reinforcements. Reinforcements can be achieved by means of variable material thicknesses or by introduction of a reinforcing material. The reinforcing material can be the same material as the base material of the sealing lip ( 52 , 54 ), having been converted into a different form of the material. Alternatively, regions, that are not to be reinforced can be weakened by converting the material of the sealing lip ( 52 , 54 ) into a weaker form of the material. A weakening of the material can be induced by exposure to energetic radiation (e.g., heat). Reinforcements of the material can also be achieved by application of material, whereby the applied material can be the same material as the base material of the sealing lip ( 52 , 54 ), or whereby the applied material can be a material different from the base material of the sealing lip ( 52 , 54 ). Suitable materials for the reinforcement of sections of a sealing lip ( 52 , 54 ) are metals, ceramics, rubber, or a combination thereof.
[0081] One of the two sealing components ( 51 , 53 ) can exhibit a coupling mechanism, allowing the coupling of a sealing component ( 51 , 53 ) with the delivery system or a catheter of the delivery system. The coupling mechanism can consist, for example, of a cone ( 55 ) located at the first sealing component ( 51 ), onto which the delivery system or a catheter of a delivery system can be clamped. The clamping effect can be achieved by the diameter of the cone ( 55 ) being larger than the luminal diameter of the delivery system, for example. The coupling mechanism to couple the pericardium seal ( 5 ) to the delivery system can also be available at the second sealing component ( 53 ). The coupling mechanism can also be provided as a separate part in addition to the sealing components ( 51 , 53 ), and can link the delivery system to one of the two sealing components ( 51 , 53 ) of the pericardium seal ( 5 ). Other embodiments of the coupling mechanism may include, among others, a non-conical (e.g., cylindrical) extension on one of the sealing components ( 51 , 53 ), onto which the delivery system can be placed or glued. In some embodiments, the catheter of the delivery system and a sealing component form a single integrated part. In some embodiments, the catheter can after successful insertion and securing of the pericardium seal ( 5 ) be disconnected from the sealing component ( 51 , 53 ) or the pericardium seal ( 5 ) by means of a pre-weakened breaking point.
[0082] One or both sealing components ( 51 , 53 ) can exhibit engaging components ( 57 ). These engaging components ( 57 ) can be used to apply a force to one or both sealing components ( 51 , 53 ) appropriate to couple and/or secure the sealing components ( 51 , 53 ). Engaging components ( 57 ) on one or on both sealing components ( 51 , 53 ) can be holes, indentations or elevations. The engaging components ( 57 ) can be installed around the circumference of the sealing component ( 51 , 53 ) at an equal distance from each other. The circumferential distance between the engaging components ( 57 ) can also vary. FIGS. 9 a - c illustrate six engaging components ( 57 ) equidistantly disposed around the circumference. On the ring-shaped sealing component ( 53 ), the six engaging components ( 57 ) are installed at an angular distance of approximately 60°. In the case of two, three, four, five, six, eight or more evenly distributed engaging components ( 57 ), the angular distance is 180°, 120°, 90°, 72°, 60°, 45° or less, respectively. The engaging components ( 57 ) can also be installed in an unevenly spaced configuration.
[0083] FIG. 10 shows a pericardium seal ( 5 ) and a tool ( 11 ) to secure a pericardium seal ( 5 ). The pericardium seal ( 5 ) shown in FIG. 10 is essentially identical to the seal shown in FIG. 9 . As an example, the tool ( 11 ) is represented as an elongated tubular tool. Located at the distal end of the tool ( 11 ) are components ( 111 ), which can be at least partially engaged with the engaging components ( 57 ) of a sealing component ( 53 ). In the embodiment shown in FIG. 10 , the inside of the tubular tool ( 11 ) exhibits at the distal end six elevations ( 111 ) pointing to the inside, which can engage with the six engaging components ( 57 ) of the sealing component ( 53 ), for example, with six indentations on the sealing component ( 53 ). The tool ( 11 ) essentially exhibits the same number of components ( 11 ), which are complementary to the engaging components ( 57 ) of the sealing component ( 53 ). The tool ( 11 ) shown in FIG. 10 is a tubular tool, consisting of a complete tube. The tubular component of the tool ( 11 ) can also be half a tube, a quarter tube, or a third of a tube. In the extreme case, instead of the tube, only one shaft or multiple shafts can be attached to a distal, ring-shaped tool. A shaft can extend from the ring-shaped tool in longitudinal direction. A shaft can also extend laterally away from a longitudinal axis of the tool. Other embodiments of the tool ( 11 ) (not shown) can be provided in the form of a modified box wrench or a modified open-end wrench.
[0084] FIG. 11 shows a connector system consisting of two connectors ( 90 , 92 ). The device for the support of the cardiac function includes a sheath with at least one sensor or at least one electrode and/or at least one expandable unit, whereby the sensor or electrode and/or the expandable unit are connected to a supply unit. The sensor or the electrode and/or the expandable unit can be directly connected to the supply unit. The sensor or the electrode and/or the expandable unit can be connected to the supply unit via a cable ( 4 ). The sensor or the electrode and/or the expandable unit can be directly linked to the supply unit via the cable ( 4 ), or the sensor or the electrode and/or the expandable unit can be connected to the supply unit. The supply unit can include a connector ( 92 ). The connector ( 92 ) can be attached directly to the supply unit. The connector ( 92 ) can be connected to the supply unit via a cable ( 4 ). The sensor or the electrode and/or the expandable unit can include a cable ( 4 ). At the end of the cable ( 4 ) can be a connector ( 90 ). The connector ( 90 ) at the end of the cable of the sensor or of the expandable unit matches the connector ( 92 ) at the supply unit. The connector ( 90 ) of the sensor or of the electrode and/or the expandable unit can be a male or a female connector. A female connector on the side of the sensor or the electrode and/or the expandable unit can be advantageous, since the female connector in contrast to the male connector does not include any pins ( 951 ) or any other terminals, which can protrude and therefore could break. If an exchange of the supply unit is required, the connector system is disconnected, and a new supply unit is connected to the connector ( 90 ) of the sensor or the electrode and/or the at least expandable unit. The reconnection of the connector ( 90 ) with a supply unit might cause pins ( 951 ) or other terminals to break. If the pins ( 951 ) or terminals are located in a male connector on the side of the sheath with the sensor or the at last one electrode and/or the expandable unit, an exchange of the sheath may be required. A female connector on the side of the sheath with the sensor or the electrode and/or the expandable unit can be advantageous, since the breaking of pins ( 951 ) or other terminals cannot occur at a female connector. The connector system ( 90 , 92 ) usually includes two connectors. The device can consist of a connector system ( 90 , 92 ) for the sensor or the electrode and/or the expandable unit, or of multiple connector systems. If multiple connector systems are used, a connector system for electrical leads and a connector system for hydraulic and/or pneumatic lines can be provided. The connector system ( 90 , 92 ) represented in FIG. 11 is a connector system consisting of connections to supply the sensor or the electrode and the expandable unit. The number of connections depends on how many sensors or electrodes and how many expandable units are being used. In some implementations, the number does not necessarily have to correlate directly with the number of sensors or electrodes and/or the number of expandable units. Split leads/lines on both sides of the connector system ( 90 , 92 ) are possible, and a pneumatic or hydraulic line is configured to supply one, two, three, four, five, six or more fillable chambers. The filling of the multiple chambers by one line does not have to occur simultaneously; it can also occur individually by means of individually controllable valves. Likewise, one electrical lead inside the cable can be used for multiple sensors or electrodes, and switches can individually energize circuits. The connector system ( 90 , 92 ) represented in FIG. 11 includes four hydraulic or pneumatic connection ports ( 93 , 94 ) and one connection for electrical leads ( 95 , 96 ). The connecting port for electrical leads ( 95 , 96 ) shown in FIG. 11 exhibits 16 connecting components in the form of pins ( 951 ) and pin sockets ( 961 ). More or fewer connections for electrical leads ( 95 , 96 ) and/or pneumatic or hydraulic lines ( 93 , 94 ) can exist in one connector system. The pneumatic or hydraulic lines ( 93 , 94 ) can include one, two, three, four, five, six, seven, eight, nine or ten connections.
[0085] The electric leads ( 95 , 96 ) can include one, two, three, four, five, six, seven, eight, nine, ten, twelve, fourteen, sixteen, twenty or more connections. One electrical connector for electric leads ( 95 , 96 ) can have one, two, three, four, five, six, seven, eight, nine, ten, twelve, fourteen, sixteen, twenty or more connecting components in the form of pins ( 951 ) and pin sockets ( 961 ). The number of connecting components in the form of pins ( 951 ) and pin sockets ( 961 ), however, is identical for the respective pair of connections for electricals leads ( 95 , 96 ). Each of the connections ( 93 , 94 , 95 , 96 ) in one or in both of the connectors of the connector systems ( 90 , 92 ) can have its own seal ( 931 , 952 ). The seal ( 931 , 952 ) of the individual connections ( 93 , 94 , 95 , 96 ) can be a sealing tape or a sealing gasket. The connector system ( 90 , 92 ) can in addition or only one seal inside the connector system ( 973 ) or around the connector system. A seal via the connector system can be a sealing tape or a sealing gasket. The connector parts ( 90 , 92 ) can be interconnected in order to create the connector system ( 90 , 92 ). The connector parts ( 90 , 92 ) can have a guide peg ( 972 ) and a guide slot ( 974 ). The guide peg ( 972 ) and the guide slot ( 974 ) can prevent wrong connection of the two connector parts and/or turning the connector parts the wrong way during connection. The connector parts ( 90 , 92 ) can also include two, three, or more guide pegs ( 972 ) and guide slots ( 974 ). In the case of two or more guide pegs ( 972 ) and guide slots ( 974 ), unequal distances between the individual guide pegs ( 972 ) and guide slots ( 974 ) can be used. The interconnected connector parts ( 90 , 92 ) can also be secured with a mechanism ( 971 ). Such mechanism ( 971 ) can be a screwing mechanism or a clamping mechanism or a bayonet catch. A mechanism to secure the interconnected connector system ( 90 , 92 ) can also be a retainer nut, a clamp, a latch or a snap-lock mechanism. Securing the connector system ( 90 , 92 ) is advantageous, since any accidental partial or complete disconnection of the connector system ( 90 , 92 ) can interrupt the supply of the sensor or the at least one electrode and/or the expandable unit.
[0086] FIG. 12 shows a model for the preparation of a system of coordinates. The development of a system of coordinates can facilitate the manufacture of a device for the support of the cardiac function, since the position for the sensor or one electrode and/or the expandable unit and/or the marking can be exactly defined. FIG. 12 a shows a heart ( 61 ) with anatomical points of reference. The example illustrates the heart ( 61 ) with the aortic arch (AO) originating at the left ventricle (LV) (with head arteries, neck arteries, and subclavian arteries (TR, CL, SCL) branching off), and the pulmonary artery (PU) originating at the right ventricle (RV). Also shown are sections of the inferior vena cava (IVC) and the superior vena cava (SVC). The broken line ( 601 ) represents the height of the valve plane. The point ( 604 ) of the cardiac apex is defined by letting a perpendicular ( 603 ) fall from this plane ( 601 ) through the most distal point of the cardiac apex. The device includes a sheath, into which a sleeve with at least one sensor or one electrode and/or a sleeve with at least one expandable unit can be inserted. The dimension of the sheath and/or the sleeve can be designed such that the upper edge of the sleeve ( 602 ) runs parallel to the valve plane with a downward offset in the direction of the cardiac apex at a distance from the valve plane of 1 mm to 30 mm, 3 mm to 20 mm, 5 mm to 10 mm, preferably 5 mm. The upper edge of the sheath is shown by the line ( 602 ) in FIG. 12 a . The lower edge of the sheath ( 605 ) and/or the sleeve can be parallel to the valve plane with a distance to the most distal point ( 604 ) of 1 mm to 30 mm, 3 mm to 20 mm, 5 mm to 10 mm, preferably 5 mm. FIG. 12 b shows a cutting plane B-B along the line ( 602 ) shown in FIG. 12 a , i.e., along the line corresponding to the upper edge of the sheath.
[0087] FIG. 12 b shows the right ventricular chamber (RV) and the left ventricular chamber (LV), the heart wall and the septal wall separating the cardiac chambers. The points ( 608 ) and ( 609 ) are defined as the points of intersection of the centerlines of the heart wall with the septal wall. The point ( 608 ) is also called the anterior intersecting point of the centerlines of the heart wall with the septal wall. The point ( 609 ) is also called the posterior intersecting point of the centerlines of the heart wall with the septal wall. The center point on a line connecting points ( 608 ) and ( 609 ) is defined as point ( 607 ). These points can be used to define a system of polar coordinates. The z-axis ( 606 ) of the polar coordinate system is defined as the line connecting the most distal point ( 604 ) to the center point ( 607 ) of the line connecting points ( 608 ) and ( 609 ). The circumferential direction of the coordinate system is suggested by the reference numeral ( 610 ) and defined as angle measure φ, whereby a line radially running from the z-axis ( 606 ) through the anterior point of intersection ( 608 ) is defined as φ=0°.
[0088] FIG. 13 shows a sheath and/or sleeve with the coordinate system described above in conjunction with FIG. 12 . FIG. 13 a shows a 3D-model ( 611 ) of a sheath or sleeve with the z-axis ( 606 ) extending through the most distal point ( 604 ) and the center point ( 607 ) of the line connecting points ( 608 ) with ( 609 ). The points ( 608 ) and ( 609 ) are the anterior and the posterior point of intersection of the center lines of the heart wall with the septal wall, whereby the φ=0° line is drawn through the point ( 608 ). The broken line connecting the points ( 608 ) and ( 609 ) along an outer circumference of the sheath or the sleeve, represents the position of the septal wall of the heart as projected onto the sheath/sleeve. At the upper edge of the sheath or the sleeve, the angle measures starting at φ=0° are shown in 30° increments, whereby—viewed from above—the angles increase counterclockwise. Longitudinal lines ( 613 ) projected onto the sheath/sleeve respectively extend along these angles up to the cardiac apex ( 604 ). The angle measure of φ=360° then again corresponds to the angle measure of φ=0°. Contour lines ( 614 ) are indicated at distances of 15 mm increments. The contour lines ( 614 ) and planes are running perpendicular to the z-axis ( 606 ). The broken-dotted line ( 615 ) constitutes a cutting line, where the 3D shape ( 611 ) can be cut open and rolled out. FIG. 13 b shows a rolled-out sheath or sleeve ( 612 ), which has been cut along the line ( 615 ) in FIG. 13 a and then rolled out. The positions ( 608 , 609 ) and lines ( 613 , 614 , 615 , 616 ) shown in FIG. 13 b represent the same positions and lines that are shown in FIG. 13 a.
[0089] FIG. 14 shows a sleeve ( 7 ) with at least one expandable unit ( 71 , 72 ). The 3D-shape of the sleeve ( 7 ) in FIG. 14 a is comparable to the 3D-model explained in conjunction with FIG. 13 a and shows a coordinate system as described above. The sleeve ( 7 ) can at least partially enclose a heart. The sleeve ( 7 ) can at least partially have the shape of a heart. The sleeve ( 7 ) can have a shape similar to the sheath. The sleeve can be inserted into the sheath. The sleeve can be made of synthetic material, polymer, natural rubber, rubber, latex, silicon or polyurethane.
[0090] In FIG. 14 a , the sleeve ( 7 ) with at least one expandable unit ( 71 , 72 ) is shown as a sleeve ( 7 ) with a multiplicity of chambers. FIG. 14 b shows a 2D-rollout of the 3D-model from FIG. 14 a . The rollout represented in FIG. 14 b is essentially identical to the rollout of a 3D-model explained in conjunction with FIG. 13 b . Unlike in FIG. 13 a , the 3D-model in FIG. 14 a is rotated such that a view from above into the sleeve ( 7 ) is possible. In FIGS. 14 a and 14 b , four expandable units ( 71 , 72 ) are shown as examples, three of which are augmentation units ( 71 ) and one is a positioning unit ( 72 ). The expandable units ( 71 , 72 ) can be structurally similar but can serve different purposes, as described above.
[0091] Generally, an augmentation unit ( 71 ) can be periodically expanded and relaxed in order to be configured to apply pressure to the heart. This pressure is preferably applied in ventricular areas. By applying pressure to a ventricle via the augmentation unit ( 71 ) the natural pumping motion of the heart is supported or substituted, and the blood inside the ventricular chamber is pumped into the corresponding artery. A pressure applied by an augmentation unit ( 71 ) to a right ventricle leads to the blood being ejected from the right ventricle into the pulmonary artery. A pressure applied by an augmentation unit ( 71 ) to a left ventricle leads to the blood being ejected from the left ventricle into the aorta.
[0092] FIG. 14 shows three augmentation units ( 71 ), which are located at the upper edge of the sleeve ( 7 ). In this example, each of the augmentation units ( 71 ) is supplied by its own line ( 41 ).
[0093] In the case of augmentation units ( 71 ) in the form of inflatable chamber, the lines ( 41 ) are preferably pneumatic or hydraulic lines. Other embodiments include one, two, three, four, five, six or more augmentation units ( 71 ), which are supplied by one, two, three, four, five, six or more lines ( 41 ). The line ( 41 ) can be made of synthetic material, polymer, natural rubber, rubber, latex, silicon, or polyurethane. The line ( 41 ) can run above, adjacent to or below the augmentation unit ( 71 ). The line ( 41 ) can preferably run below a positioning unit ( 72 ), so that no pressure points result between the line ( 41 ) and the heart wall. The line ( 41 ) can also run above or adjacent to a positioning unit ( 72 ).
[0094] The augmentation units ( 71 ) A1, A2, and A3 shown in FIG. 14 are located in an area at the upper edge of the sleeve ( 7 ) and are each supplied by their own respective line ( 41 ). The augmentation units ( 71 ) A1 and A2 can—as illustrated in FIG. 14 —be positioned such that they can assist a left ventricle. Augmentation unit ( 71 ) A3 is positioned to assist a right ventricle. The individual augmentation units ( 71 ) A1, A2 and A3 can be expanded individually. Augmentation units ( 71 ) A1 and A2 can assist cardiac function for a heart with left ventricular insufficiency. Augmentation unit ( 71 ) A3 can serve to support a right ventricular insufficiency.
[0095] Augmentation units ( 71 ) A1, A2 and A3 can be used for support of a bilateral heart insufficiency. The augmentation units ( 71 ) can be expanded synchronously or asynchronously. Preferably, the expansion of the augmentation units ( 71 ) can be coordinated such that a natural pumping function of the heart is supported.
[0096] A positioning unit ( 72 ) is a unit, which can also be expanded. Preferably, a positioning unit is expanded during operation of the device for the support of the cardiac function more statically than periodically. The positioning unit ( 72 ) can be expanded in order to fix the device to the heart and to optimize the accuracy of the fit of the device. A positioning unit ( 72 ) can also help to respond to changes of the myocardium. If the size of the myocardium decreases or increases, a positioning unit can be expanded or relaxed further in order to ensure a perfect fit.
[0097] FIG. 14 illustrates a positioning unit ( 72 ), which essentially fills the spaces between the three augmentation units ( 71 ) on the sleeve ( 7 ). The positioning unit ( 72 ) can have a distance from one or multiple augmentation units ( 71 ) of 1 mm, 3 mm, 5 mm, 10 mm, 20 mm, 30 mm, 40 mm or more. The positioning unit ( 72 ) can be supplied by its own line ( 41 ), in the case of a chamber fillable with a fluid, by a pneumatic or hydraulic line. Other embodiments include one, two, three, four, five, six or more positioning units ( 72 ), which are supplied by one, two, three, four, five, six or more pneumatic or hydraulic lines ( 41 ). The line ( 41 ) can consist of a synthetic material, polymer, natural rubber, rubber, latex, silicon or polyurethane. The line ( 41 ) for the supplying of the positioning unit ( 72 ) can run below the positioning unit ( 72 ). The positioning unit ( 72 ), shown in FIG. 14 , fills the spaces between the augmentation units ( 71 ). The depicted positioning unit ( 72 ) has extensions that protrude into the spaces between the augmentation units ( 71 ).
[0098] FIG. 15 shows an expandable unit ( 71 , 72 ) in the form of a chamber ( 710 ). The depicted chamber is a bellows-shaped chamber ( 710 ). A bellows-shaped chamber ( 710 ) has at least one section in the form of bellows. Preferably, chamber 710 is a folding bellows consisting of one, two, three, four, five, six, seven or more folds. An outwardly bent edge ( 711 ) can be defined as a fold. An inwardly bent edge ( 712 ) can be defined as a fold. In some embodiments, the regions of the chamber wall between the folds are less stable than the folds. One, multiple or all bent edges ( 711 , 712 ) can be reinforced. A reinforcement of a bent edge ( 711 , 712 ) is advantageous, since the bent edge ( 711 , 712 ) can be exposed to increased stress due to the expanding and relaxing of the chamber ( 710 ). A reinforcement of one or multiple bent edges ( 711 , 712 ) can reduce or prevent material fatigue along the bent edge ( 711 , 712 ). Reinforcement of a bent edge ( 711 , 712 ) can be achieved through a greater wall thickness of the material at the bent edge ( 711 , 712 ). A bent edge ( 711 , 712 ) can also be reinforced through application of additional material, wherein the applied material can be the same material as the underlying material, or wherein the applied material can be a different material than the underlying material. A chamber ( 710 ) can exhibit a top side ( 713 ), a bottom side and a side surface, whereby the side surface is preferably designed in the shape of a bellows. The top ( 713 ) and/or the bottom side can be oval, circular, elliptical, or polygonal. The top side ( 713 ) can have a different shape than the bottom side.
[0099] A bellows-shaped chamber ( 710 ) can be inserted into a sheath of the type described above. The chamber ( 710 ) can be directly attached or fixed inside the sheath. The chamber ( 710 ) can be attached to structural components of the sheath, like, for example, a wire of a wire mesh, a strap of a latticework, or a structure on a sheath sleeve.
[0100] The chamber ( 710 ) can be attached to crossing points of a mesh or latticework. The sheath can be covered by a membrane, as described above. In these cases, the chamber ( 710 ) can also be attached to the membrane. The membrane can also be a bottom side of the chamber ( 710 ).
[0101] The bellows-shaped chamber ( 710 ) can also be fastened to a sleeve ( 7 ). Multiple bellows-shaped chambers ( 710 ) can be fastened to a sleeve ( 7 ). The sleeve ( 7 ) can at least partially have the shape of a heart. The sleeve ( 7 ) can have a shape similar to that of the sheath. The sleeve ( 7 ) can be inserted into the sheath. The sheath ( 7 ) can be fastened and/or fixed inside the sheath. The sleeve ( 7 ) can, in addition to one or multiple augmentation units like, for example, one or multiple bellows-shaped chambers ( 710 ), also exhibit one or multiple positioning units. The bottom side of the chamber ( 710 ) can be made of the same material as the sleeve ( 7 ). The sleeve ( 7 ) can be part of the chamber ( 710 ). The sleeve ( 7 ) can form the bottom side of the chamber. In those cases, only the lateral surfaces, which can be bellows-shaped, are applied to a sleeve ( 7 ). In addition, a top side ( 713 ) can be attached as well. The top side ( 713 ) can be a sleeve as well. Embodiments consist of two sleeves ( 7 ), whereby the sleeves ( 7 ) create the top side and the bottom side of the chambers, and lateral surfaces are formed between the sleeves. In this case, lateral surfaces can also be formed by joining, in particular by welding or gluing together of the two sleeves. The sleeves ( 7 ) can be joined together, in particular, welded or glued together, such that a chamber is formed. In some embodiments, the sleeves are connected to each other in a common edge region. In some embodiments, the chamber defines a gap of 0.1 mm to 5 mm. The line supplying the chamber can be formed similar to the chamber at least partially by joining the two sleeves ( 7 ), in particular by welding or gluing together of the two sleeves ( 7 ). Located on one of the two sleeves ( 7 ) or on both sleeves ( 7 ) can be one or multiple sensors or one or multiple electrodes.
[0102] The sleeve ( 7 ) with the expandable unit can at the upper edge and/or at the lower edge exhibit at least one pocket. The pocket can be at least partially pulled over a structural shape of a sheath. The pocket can, for example, be at least partially pulled over a loop of a wire mesh or a strap of a latticework.
[0103] The sleeve ( 7 ) with the expandable unit can contain an active agent. The sleeve ( 7 ) may, for example, contain an anti-thrombotic agent, an anti-proliferative agent, an anti-inflammatory agent, an anti-neoplastic agent, an anti-mitotic agent, an anti-microbial agent, a biofilm synthesis inhibitor, an antibiotic agent, an antibody, an anticoagulative agent, a cholesterol-lowering agent, a beta blocker, or a combination thereof. The agent is preferably provided in the form of a coating on the sleeve ( 7 ). The sleeve ( 7 ) can also be coated with extra-cellular matrix proteins, in particular, fibronectin or collagen.
[0104] FIG. 16 shows a sleeve ( 80 ) with at least one sensor ( 81 ) and/or at least one electrode ( 82 ). The 3D-shape of the sleeve ( 80 ) in FIG. 16 a is comparable to the 3D-model described in FIG. 13 a and shows a coordinate system as described above. The sleeve ( 80 ) can at least partially enclose a heart. The sleeve ( 80 ) can at least partially have the shape of a heart. The sleeve ( 80 ) can have a shape similar to that of the sheath. The sleeve ( 80 ) can be inserted into the sheath. The sleeve ( 80 ) can be made of a synthetic material, polymer, natural rubber, rubber, latex, silicon or polyurethane. The sleeve ( 80 ) can exhibit a thickness of 0.1 mm to 1 mm, preferably 0.2 mm to 0.5 mm. The sleeve ( 80 ) with the sensor ( 81 ) and/or the electrode ( 82 ) can be pressed against the myocardium by the sleeve with the expandable units. The sleeve ( 80 ) can be coated, in particular, with a lubricant, which reduces the friction between the myocardium and the sleeve ( 80 ) with the sensor ( 81 ) and/or the electrode ( 82 ). A coating, in particular, a coating with a lubricant can also be provided between the sleeve ( 80 ) with the sensor ( 81 ) and/or the electrode ( 82 ) and the sleeve with the expandable unit. The sensor ( 81 ) and/or the electrode ( 82 ) can be worked, molded or welded into the sleeve ( 80 ) or attached, glued onto or sewn onto the sleeve ( 80 ). The sensor ( 81 ) and/or the electrode ( 82 ) can be equipped with reinforcements configured to prevent bending during the compression of the device.
[0105] In FIG. 16 a , the sleeve ( 80 ) is depicted with at least one sensor ( 81 ) and/or at least one electrode ( 82 ) as a sleeve ( 80 ) with a multiplicity of sensors ( 81 ) and electrodes ( 82 ). FIG. 16 b shows a 2D-rollout of the 3D-model from FIG. 16 a . The rollout depicted in FIG. 16 b essentially matches the rollout of a 3D-model explained in conjunction with FIG. 13 b . Unlike in FIG. 13 a , the 3D-model in FIG. 16 a is rotated to allow a view from above into the sleeve ( 80 ). In FIGS. 16 a and 16 b , eight sensors ( 81 ) or electrodes ( 82 ) are shown as examples. Other embodiments can include one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or more sensors ( 81 ) and/or electrodes ( 82 ). The sleeve ( 80 ) with the sensor ( 81 ) or at least one electrode ( 82 ) can be a net of sensors ( 81 ) or electrodes ( 82 ). The net of sensors ( 81 ) or electrodes ( 82 ) can at least partially enclose the heart. The sensors ( 81 ) or electrodes ( 82 ) in the net of sensors ( 81 ) or electrodes ( 82 ) can be interconnected. The sleeve ( 80 ) can function as the carrier of the net of sensors ( 81 ) or electrodes ( 82 ). The net of sensors ( 81 ) or electrodes ( 82 ) can also be only partially attached to a sleeve ( 80 ). The net of sensors ( 81 ) or electrodes ( 82 ) can also be inserted without a sleeve ( 80 ) into a sheath as the one described above.
[0106] The sensor ( 81 ) or the electrode ( 82 ) can determine a physical or a chemical property of its environment. The property can be detected qualitatively or quantitatively. The sensor ( 81 ) can be an active sensor or a passive sensor. The sensor ( 81 ) can detect at least one parameter of the heart. The sensor ( 81 ) can be configured to determine the heart rate, the ventricular pressure, the systolic blood pressure, the diastolic blood pressure, pressure applied to a surface of the heart, fluid presence, acidity, electrical resistance, osmolarity, oxygen saturation or flow through a vessel. The sensor ( 81 ) can be configured to measure the pressure applied by an expandable unit onto a surface, the pH-value, the electric resistance, the osmolarity of a solution, or the flow through a vessel. The sensor can also be used as an electrode.
[0107] The electrode ( 82 ) can be configured to electrically stimulate areas of the heart and/or to measure the electrical activity at the epicardium during the excitation process. The electrode ( 82 ) can be configured to stimulate the myocardium with the use of electrical impulses. An electrical stimulation can induce a myocardium to contract. The electrode ( 82 ) can be a pacemaker electrode. The electrode ( 82 ) can be an extra-cardial stimulation electrode. With an electrode ( 82 ), the myocardium can be stimulated before, during or after a support of the pumping function of the heart by a sheath with at least one expandable unit. The expansion of an expandable unit can occur before, during or after stimulation with an electrode ( 82 ). The device for the support of the cardiac function can be operated only with at least one expandable unit or only through stimulation with at least one electrode ( 82 ). Simultaneous operation of the expandable unit and the electrode ( 82 ) can be synchronous or asynchronous. The electrode can also be used a sensor.
[0108] The sensor ( 81 ) or the electrode ( 82 ) can be fastened to the sleeve ( 80 ). The sensor ( 81 ) or the at least one electrode ( 82 ) can be glued, sewed or welded to the sleeve ( 80 ). The sensor ( 81 ) or the electrode ( 82 ) can be attached to the inside of the sleeve ( 80 ), preferably welded in. The sensor ( 81 ) or the electrode ( 82 ) can be connected via a lead ( 84 ) to a supply unit. The data detected by the sensor ( 81 ) or the electrode ( 82 ) can be transmitted connectionless via wireless technology, like bluetooth, for example.
[0109] The contacts of the electrodes or sensors or the entire sleeve can be coated with a substance, which increases or improves conductivity. A graphite coating on the contacts, for example, can increase their conductivity.
Example #1
[0110] FIG. 17 shows an embodiment of a sleeve ( 7 ) with at least one expandable unit ( 71 , 72 ). FIG. 17 depicts a 2D-rollout of a 3D-model described in conjunction with FIG. 13 . The illustrated sheath includes three augmentation units ( 71 ) (A1, A2, A3) and a positioning unit ( 72 ) (P). In some embodiments, the augmentation units A1 and A2 each occupy an area of 28.6 cm 2 on the sleeve. The area occupied by augmentation unit A3 in this example is 34.5 cm 2 . The positioning unit ( 72 ) (P) occupies an area 114.5 cm 2 . Under normal conditions, the nominal expansion of the positioning unit (P) is 5 mm (e.g., the positioning unit is partially expanded and exhibits a thickness of 5 mm). The positioning unit can be a chamber, which can be filled and unfilled with a fluid. The thickness of the positioning unit can therefore be between 1 mm and 10 mm, preferably between 3 mm and 7 mm. By changing the thickness of the positioning unit ( 72 ) (P) an increase or decrease of the size of the heart can be compensated, and the correct fit of the sleeve ( 7 ) and/or the sheath essentially remains guaranteed.
[0111] In this example, the thicknesses of augmentation units A1 and A2 can be expanded by about 1.9 cm in order to build up a pressure onto a ventricle (here, the left ventricle). The effective volume expansion of the augmentation units A1 and A2 in this example is 40 ml. The effective volume expansion of the augmentation unit A3 in this example is 50 ml and leads to an effective expansion of the thickness by 1.45 cm. Every corner of an augmentation unit can be described by the coordinates of the corner points (vertices). The coordinate system has been explained in conjunction with FIG. 13 .
[0112] In this example, augmentation unit A1 extends from vertex 1 (φ=359°; z=100) via vertex 2 (φ=48°; z=85) and vertex 3 (φ=48°; z=40) to vertex 4 (φ=328°; z=56), and, in the implanted state, lies flat against the left ventricle. The connection of vertex 1 to vertex 2 essentially extends parallel to the upper edge of the sleeve ( 7 ) at a distance (d) of about 5 mm. The connection of vertex 2 to vertex 3 essentially extends along the φ=48° line. The connection of vertex 3 to vertex 4 essentially extends parallel to the upper edge of the sleeve ( 7 ) shown in the 3D-model. The connection of vertex 4 to vertex 1 essentially extends along the septal line ( 616 ). The corners of the augmentation unit A1 are rounded and describe a circular arc with a diameter of 4 mm.
[0113] In this example, augmentation unit A2 extends from vertex 1 (φ=116°; z=69) via vertex 2 (φ=182°; z=74) and vertex 3 (φ=212°; z=37) to vertex 4 (φ=116°; z=26) and, in the implanted state, lies flat against the left ventricle. The connection of vertex 1 to vertex 2 essentially extends parallel to the upper edge of the sleeve ( 7 ) at a distance (d) of about 5 mm. The connection of vertex 2 to vertex 3 essentially extends along the septal line ( 616 ). The connection of vertex 3 to vertex 4 essentially extends parallel to the upper edge of the sleeve ( 7 ) shown in the 3D-model.
[0114] The connection of vertex 4 to vertex 1 essentially extends along the φ=116° line. The corners of the augmentation unit A2 are rounded and describe a circular arc with a diameter of 4 mm.
[0115] In this example, the augmentation unit A3 extends from vertex 1 (φ=235°; z=92) via vertex 2 (φ=303°; z=108) and vertex 3 (φ=303°; z=64) to vertex 4 (φ=235°; z=48) and, in the implanted state, lies flat against the right ventricle. The connection of vertex 1 to vertex 2 essentially extends parallel to the upper edge of the sleeve ( 7 ) at a distance (d) of about 5 mm. The connection of vertex 2 to vertex 3 essentially extends along the φ=303° line. The connection of vertex 3 to vertex 4 essentially extends parallel to the upper edge of the sleeve ( 7 ) shown in the 3D-model. The connection of vertex 4 to vertex 1 essentially extends along the φ=235° line. The corners of augmentation unit A3 are rounded and describe a circular arc with a diameter of 4 mm.
[0116] The positioning unit P in the example of FIG. 17 is designed to essentially fill the spaces between the augmentation units ( 71 ) on the sleeve ( 7 ). The positioning unit ( 72 ) can also be described as a positioning unit ( 72 ) with extensions, which fill in the areas of the sleeve ( 7 ) that are not filled by the augmentation units. In this embodiment, the positioning unit P is essentially located at a lateral distance (d) from the augmentation units ( 71 ) and the upper edge of the sleeve ( 7 ) of about 5 mm. The positioning unit ( 72 ) is also located at a distance from the cutting line ( 615 ), which can be advantageous during manufacturing. If the sleeve ( 7 ) with the expandable unit is formed in a two-dimensional state, all augmentation units ( 71 ) and positioning units ( 72 ) can be attached to the sleeve ( 7 ) before the sleeve ( 7 ) is rolled into a three-dimensional form.
[0117] In the example of FIG. 17 , the lines ( 41 ) supplying the expandable units ( 71 , 72 ) are hydraulic or pneumatic lines ( 41 ) extending radially from the lower edge of the sheath to the augmentation units. The line ( 41 ) for the augmentation unit A2 extends along the line φ=15° and ends at the height of z=54. The line ( 41 ) for augmentation unit A2 extends along the line φ=165° and ends at the height of z=31. The line ( 41 ) for augmentation unit A3 extends along the line φ=270° and ends at the height of z=65. The line ( 41 ) for the positioning unit P extends along the line φ=330° and ends at a height of z=25.
Example #2
[0118] FIG. 18 shows an embodiment for a sleeve ( 80 ) with at least one sensor ( 81 ) and/or an electrode ( 82 ). Shown in FIG. 18 is a rollout as described in conjunction with FIG. 13 . The sleeve ( 80 ) of this embodiment includes eight sensors ( 81 ) or electrodes ( 82 ), whereby four of these are pressure sensors (force sensor FS1, FS2, FS3, FS4) ( 81 ), and four are electrocardiogram electrodes (e.g., ECG1, ECG2, ECG3, ECG4) ( 82 ). The sleeve ( 80 ) can be made of a synthetic material, polymer, natural rubber, rubber, latex, silicon or polyurethane. The sleeve ( 80 ) can have a thickness of 0.1 to 1 mm, preferably 0.2 mm to 0.5 mm. The four pressure sensors ( 81 ) can be integrated into the sleeve ( 80 ), for example, molded or welded to the inside surface of the sheath. The pressure sensors ( 81 ) can be equipped with reinforcements, which can prevent bending during the compression of the device. The ECG electrodes ( 82 ) can be attached at the side of sleeve ( 80 ) facing the heart. In the embodiment in FIG. 18 , a system of coordinates is depicted as described in conjunction with FIG. 13 . Using the coordinate system, the positions of the sensors ( 81 ) and electrodes ( 82 ) can be determined as follows: pressure sensor FS1 is located at coordinate (φ=17°; z=71), pressure sensor FS2 is located at coordinate (φ=158°; z=48), pressure sensor FS3 is located at coordinate (φ=268°; z=78), pressure sensor FS4 is located at coordinate (φ=67°; z=61). ECG electrode ECG1 is located at coordinate (φ=76°; z=54), ECG electrode ECG2 is located at coordinate (φ=352°; z=39), ECG electrode ECG3 is located at coordinate (φ=312°; z=93) and ECG electrode ECG4 is located at coordinate (φ=187°; z=18). For smaller or larger hearts, the angular coordinates for the sensors ( 81 ) and/or electrodes ( 82 ) essentially remain the same; while the z-value is scaled by a factor. For example, for smaller hearts, the scaling factor can be between 0.85 and 0.95, and for larger hearts, the scaling factor can be between 1.05 and 1.15. | A method of implanting a cardiac device featuring the insertion of an inner seal member through an opening in a pericardium about a living human heart. The inner seal member has a first sealing lip disposed inside the pericardium and surrounding an aperture through the inner seal member. An outer seal member is aligned with the inner seal member. The outer seal member has a second sealing lip disposed outside the pericardium, surrounding an aperture through the outer seal member. The inner seal member is secured to the outer seal member. The firsts sealing lip is engaged against an inner surface of the pericardium. The second sealing lip is engaged against an outer surface of the pericardium. A cardiac device is inserted into the pericardium through the apertures of the inner and outer seal members. | 0 |
BACKGROUND OF THE INVENTION
The problem of pet waste control in the large cities is becoming particularly acute. Canine waste deposited on lawns of homes, in parks and on sidewalks is both unsightly and unhealthy. In the past, proposals have been made that dog owners carry devices for scooping up and removing the dog waste from the surface on which it falls. The problem with most of these devices is that they are fairly large and the dog owner does not wish to carry the device with him when he is walking the dog. In addition, some dogs are allowed to run loose so that no dog owner is with them to clean up after them. Oftentimes pet owners wish to prevent their pets from soiling furniture or carpeting while the pets are indoors. At the present time, if the pet is not housebroken, this is often difficult.
Therefore, what is needed, is a canine refuse container which the dog carries himself. The canine waste container should be light and easy to place on the dog for wearing. At the same time, the container should present a minimum of interference with the animal's natural movement. The refuse container should also be disposable or have a disposable portion to promote hygiene.
SUMMARY OF THE INVENTION
An animal refuse container is herein disclosed. The animal refuse container includes a substantially cylindrical jacket, having a zipper closure. The substantially cylindrical jacket is connected to a flexible disposable receptacle. The flexible disposable receptacle is approximately pyramidal in shape. A receptacle cover is connected to the substantially cylindrical jacket adjacent the flexible disposable receptacle and surrounds the flexible disposable receptacle.
In use, the substantially cylindrical jacket is positioned snugly around a torso of an animal. The flexible disposable receptacle and receptacle cover are positioned between a pair of hindquarters of the animal and connected to the flexible cylindrical jacket at a back portion. Thus, the flexible disposable receptacle is positioned below a urinary and an anal termini of the animal to receive waste material from the animal. The animal is then exercised while wearing the animal refuse container. After the animal has urinated or defecated, the jacket is removed from the animal and the flexible disposable receptacle is removed from the jacket, thrown away and a new flexible disposable receptacle replaced in its stead.
It is therefore, a principal object of the present invention to provide an animal refuse container which can be worn by an animal without impeding the animal's natural movement.
It is another object of the present invention to provide an animal refuse container for use as a housebreaking aid for young dogs.
It is another object of the instant invention to provide an animal refuse container having a disposable receptacle portion which may be quickly and easily replaced.
It is a still further object of the present invention to provide an animal refuse container which is economical, aesthetically pleasing, and simple to use.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective view of a dog wearing an animal refuse container embodying the instant invention, portions of the animal refuse container being shown in phantom view;
FIG. 2 is a top view of the animal refuse container of FIG. 1;
FIG. 3 is a view taken along line 3--3 of FIG. 2 of the animal refuse container;
FIG. 4 is a top view of a portion of the animal refuse container shown in FIG. 2, with portions broken away showing details of the attachment of a flexible disposable receptacle to other portions of the animal refuse container; and
FIG. 5 is a perspective view of the flexible disposable receptacle.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawing, and especially to FIGS. 1, 3 and 4, an animal refuse container generally indicated by numeral 10 and embodying the instant invention is shown therein. Animal refuse container 10 has a substantially cylindrical jacket 12. Substantially cylindrical jacket 12 has a flexible disposable receptacle 14 connected to it. A receptacle cover 15 is connected to the substantially cylindrical jacket 12 and substantially covers flexible disposable receptacle 14.
Substantially cylindrical jacket 12 has approximately the same diameter as a thoracic section of an animal which is to wear the animal refuse container. Jacket 12 has a top portion 16 and a floor portion 17. Substantially cylindrical jacket 12 has a front hemline 18. Substantially cylindrical jacket 12 terminates in a pair of rear hemlines, one of which is shown as hemline 20. A zipper 22 connects top portion 16 of the jacket 12 together. Zipper 22 terminates adjacent hemlines 18 and 20. A tail flap 24 is connected to top portion 16 of cylindrical jacket 12 adjacent hemline 20. Tail flap 24 includes a pair of snap fasteners 26 and 28. A small square pocket of the nature of a watch pocket 30 is sewn into jacket 12, adjacent zipper 22. Floor portion 17 has a pair of stitch lines, respectively numbered 34 and 36 attached thereto. Stitch lines 34 and 36 hold a receptacle loop 37 in contact with floor 17. A pair of shank flaps, respectively numbered 38 and 39 is connected to jacket 12 adjacent hemline 20. Shank flaps 38 and 39 cover a pair of hind legs of the animal. Cylindrical jacket 12 is composed of denim in this embodiment, but may be composed of other flexible materials.
Receptacle loop 37 receives a tongue portion 40 of receptacle 14. Receptacle 14 is shaped approximately pyramidally, having a back wall 44, a bottom wall 46, formed integral with back wall 44, a first pleated side wall 48 formed integral with back wall 44 and bottom wall 46 and a second pleated side wall 50 formed integral with back wall 44 and bottom wall 46. Side wall 48 has a pleat 52. Side wall 50 has a pleat 54. A reinforcing hem 56 is formed integral with walls 44, 46, 48 and 50. A loop type fastener 58 is connected to back wall 44 adjacent hem 50. A first pair of loop type fastener pads, respectively numbered 60 and 62, is connected to bottom wall 46 adjacent hem 50. A second pair of mating loop fastener pads, respectively numbered 64 and 66, is also connected adjacent hem 50 to bottom wall 46 at tongue extension 40. Receptacle 14 is composed of a clear polyethylene plastic and is easily disposable. Receptacle 14 is connected to loop 37 by passing tongue 40 between loop 37 and floor 17 so that loop 37 is positioned between fastener pads 60 and 62 and fastener pads 64 and 66, respectively. Fastener pad 64 is then pressed into contact with fastener pad 60 and fastener pad 66 is pressed into contact with fastener pad 62 to hold disposable receptacle 14 in connection with loop 37 of jacket 12.
Receptacle cover 15 is a "C" shaped receptacle cover. Receptacle cover 15 is joined to jacket 12 adjacent hem 20. Receptacle cover 15 has a pair of elastic side bands, respectively numbered 68 and 70. Bands 68 and 70 together with the rear hems of the jacket, define a pair of leg apertures numbered respectively, 72 and 74. Hems 68 and 70 terminate in a hem loop 78. Hem loop 78, together with back flap 24, defines a tail aperture 80. Receptacle cover 15 includes a fastener tab 82 positioned adjacent aperture 80. Hook type fastener tab 82 connects to fastener tab 58 of disposable receptacle 14. Receptacle cover 15 substantially covers disposable receptacle 14 with the exception of a small part of hem 56 adjacent pleats 52 and 54.
In use, the animal refuse container is unzipped along zipper 22 and snaps 26 and 28 are unsnapped, thereby allowing flap 24, which is only connected to one side of jacket 12, to be swung away from zipper 22. The animal refuse container is then lifted around the animal and zipper 22 is placed immediately adjacent a spinal column of the animal. Zipper 22 is then zipped closed and disposable receptacle 14, together with receptacle cover 15, is pulled between the animal's hind legs and snapped to flap 24 at snaps 26 and 28. The animal's tail passes through tail aperture 80 formed by receptacle cover 15 and flap 24. Receptacle 14 is thus positioned immediately below a terminus of a urinary tract and an anus of the animal. The animal is then exercised and urine or fecal matter from the animal drops into disposable receptacle 14.
After the animal's exercise, the animal refuse container is removed from the animal by unsnapping snaps 26 and 28, unzipping zipper 22 and dropping the refuse container away from the animal's body. The receptacle 14 is then removed from jacket 12 and receptacle cover 15 by releasing fasteners 60 and 64, 62 and 66 and sliding tongue 40 out from under loop 37. Fasteners 58 and 82 are then pulled apart and receptacle 14 is lifted free of receptacle cover 15. Receptacle 14 and its contents are then disposed of.
A fresh receptacle 14 is then connected to jacket 12 by sliding tongue 40 under loop 37 and closing fasteners 60 and 64 and 62 and 66. Fasteners 58 and 82 are then connected together to join wall 44 to receptacle cover 15. Receptacle cover 15 is made of an opaque cloth material for aesthetic reasons.
It may be appreciated that the instant invention has several advantages. The instant invention provides a refuse container to receive urine or fecal matter from a dog or other animal while the dog is being exercised. Thus, the animal may be exercised out doors without soiling or damaging the property of other persons. The refuse container can also be used indoors for a dog or other animal in several ways. The refuse container can be used with a female dog in oestrous. The refuse container is worn in order to prevent spotting of carpeting or furniture and any discharge from the female dog is received by receptacle 14. The discharge is not absorbed into the receptacle 14 and receptacle 14 can be quickly and easily changed. The refuse container can also be used as a housebreaking device for animals to prevent animals from having accidents within the confines of a house. It may be appreciated that the refuse container, therefore, can protect carpeting and furniture from puppy accidents before the animal is housebroken.
Although a specific embodiment of the instant invention has been described in detail above, it may be appreciated that one skilled in the art may make various modifications and changes in the disclosure without departing from the spirit and scope of the instant invention. The invention is therefore, only limited by the appended claims. | An animal refuse container is herein disclosed. The animal refuse container includes a jacket. A refuse receptacle is releasably connected to the jacket. The refuse receptacle is surrounded by a receptacle cover. The receptacle is wrapped around an abdominal portion and hindquarters portion of an animal with the refuse receptacle positioned under a pair of termini of an anal and an urinary tract of the animal. | 0 |
BACKGROUND OF THE INVENTION
[0001] This invention relates to a lap edge sealant composition for sealing the lap joints of roofing materials, and more particularly, to a lap edge sealant having a high solids content and a low volatile organic compound (VOC) content.
[0002] In the field of single-ply commercial rubber roofing, sheets of roofing material are typically laid on a roof in an overlapping fashion and spliced together to form a continuous sheet which covers the roof Lap joints are typically used to splice adjacent sheets of roofing material together. The exposed seams of the lap joints are then sealed with an adhesive, typically, a caulking compound, to act as an additional seal to prevent penetration of moisture along the external seam. Currently, solvent-based adhesive sealants are used for sealing the lap joints of i adjacent sheets of membrane roofing materials. Such sealants typically utilize aromatic solvents such as benzene, toluene, xylene, etc. However, such solvent-based sealants are environmentally undesirable as they typically contain over 350 grams per liter (3 pounds per gallon) of volatile organic compounds. Because of environmental concerns, many states are beginning to mandate products having no more than 250 grams per liter (2 pounds per gallon) of volatile organic compound (VOC) content.
[0003] Another disadvantage of solvent-based sealants currently in use is their low solids content, i.e., about 20 to 30%. As such sealants typically cure by solvent evaporation, high shrinkage (typically about 40-60%) can occur when using these sealants. As a consequence, the cured films may exhibit fissure-type cracking and degradation after long term outdoor exposure.
[0004] A number of adhesives have been developed which exhibit lower VOC levels. For example, Congelio et al., U.S. Pat. No. 5,817,708, teach a low VOC content (less than 250 g/l) solvent-based adhesive for use in joining thermoplastic materials. Patel et al., U.S. Pat. No. 5,495,040, also teaches a low VOC (less than 250 g/l) solvent-based adhesive for joining ABS molded articles. However, such adhesives are not specifically formulated for use as lap edge roofing sealants, nor do they have a high solids content.
[0005] Backenstow et al., U.S. Pat. No. 4,849,268 teach a 100% solids sealant for providing an internal seal to spliced roofing membranes which is formed from EPDM, butyl or silicone based caulking compositions. The sealant is applied in combination with a splicing cement to the internal portion of the splice. However, Backenstow et al. require that the sealant, splicing cement, and roofing membrane be compatible in order to avoid separation of the sealant from the cement. In addition, Backenstow et al. do not seal the exterior seam on the lap joint.
[0006] Accordingly, there is still a need in the art for a lap edge sealant which effectively seals the external lap joints of adjacent sheets of membrane roofing material, which has a high solids content, a low VOC content, and which exhibits low shrinkage upon curing.
SUMMARY OF THE INVENTION
[0007] The present invention meets those needs by providing a lap edge sealant composition having a high solids content, a low VOC content of less than 250 g/l, and which exhibits no more than about 35% shrinkage upon curing. By shrinkage, it is meant the decrease in volume of the sealant after curing. The sealant composition provides excellent adhesion to a variety of roofing materials such as EPDM.
[0008] In accordance with one aspect of the present invention, a lap edge sealant composition for sealing the lap joints of roofing materials is provided comprising a rubbery polymer, a thermoplastic rubber, a tackifier, and a solvent, where the composition has a solids content of from about 65 to 90% and a VOC content of less than about 250 g/l.
[0009] Preferably, the rubbery polymer comprises EPDM. The thermoplastic rubber preferably comprises a styrene-ethylene/propylene copolymer.
[0010] The tackifier is preferably selected from the group consisting of aliphatic hydrocarbon resins, polybutene, and combinations thereof.
[0011] The solvent is preferably selected from the group consisting of aliphatic hydrocarbons, para-chlorobenzotrifluoride, and blends thereof. The aliphatic hydrocarbons are preferably selected from the group consisting of n-pentane, n-hexane, n-heptane, n-octane, and naphtha. The naphtha may comprise high flash naphtha solvent or VM&P (Varnish Makers and Painters) naphtha. In one preferred embodiment of the invention, the solvent comprises from about 26% by weight para-chlorobenzotrifluoride and from about 74% by weight VM&P naphtha. In another preferred embodiment, the solvent comprises from about 33% high flash naphtha and 67% VM&P naphtha.
[0012] The sealant composition also preferably includes an accelerator/cure package, which preferably comprises a mixture of a sulfur-containing composition and zinc oxide.
[0013] In a preferred form, the sealant composition comprises: a) from about 3 to 6% by weight of a rubbery polymer; b) from about 1 to 5% by weight of a thermoplastic rubber; c) from about 1 to 10% by weight of a tackifier; d) from about 30 to 50% by weight of a filler; and e) and from about 5 to 35% by weight of a solvent.
[0014] The sealant composition of the present invention may be applied at a job site under a variety of weather conditions to the lap joints of overlapping sheets roofing materials such as EPDM. The sealant composition exhibits low shrinkage upon curing, i.e., less than about 35%.
[0015] Accordingly, it is a feature of the present invention to provide a lap edge sealant having a high solids content, a low VOC content, and which exhibits low shrinkage upon curing. Other features and advantages of the invention will be apparent from the following detailed description, the accompanying drawing, and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] [0016]FIG. 1 is a perspective view of the sealant composition of the present invention being applied to seal a lap joint of roofing membranes.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] The lap edge sealant of the present invention provides an improvement over currently available lap edge adhesives or sealants in that the VOC content of the composition is less than 250 grams per liter (about 1.7 pounds per gallon) with no more than about 35% shrinkage upon curing, and preferably, less than about 20% shrinkage. The finished cured films are typically 30% thicker than prior art cured films and do not exhibit fissure-type cracking or degradation after long term outdoor field exposure. For example, the typical film thickness in its center portion after application is about 0.20 inches. With typical lap edge sealants, the film thickness will be reduced to as thin as 0.08 inches or less after curing. With the high solids lap edge sealant of the present invention, the film thickness is reduced to only about 0.14 to about 0.16 inches thick.
[0018] The lap edge sealant composition of the present invention preferably comprises, as the rubbery polymer component, an ethylene-propylene-diene terpolymer (EPDM). A preferred EPDM rubber for use in the present invention is a low Mooney viscosity EPDM terpolymer commercially available from Uniroyal Chemical under the designation Trilene 77. Mooney viscosity is a measure of the viscosity of a rubber as determined by a Mooney shearing disk viscometer. The viscosity is indicated by the torque required to rotate a disk embedded in a rubber specimen and enclosed in a die cavity under specified conditions. For the EPDM rubbers disclosed herein, a large rotor is used, and the test temperature is 125° C. with a running time of 4 minutes. For typical commercially available EPDM rubbers, the Mooney viscosity is from about 1 to 80. The EPDM rubbers used in the present invention have a low Mooney viscosity of from about 1 to 40, which ensures that the final compounded sealant will have a high solids content with low shrinkage and a low press-flow viscosity for ease of gunnability from a tube, pail or drum.
[0019] Other suitable low Mooney viscosity EPDM terpolymers include Trilene 56, 65, 66, and 67 and Royalene LV-1125, LV-1142 and LV-1145, available from Uniroyal Chemical, and Keltan 2506 and 7040, available from DSM Copolymer. Other low Mooney viscosity EPDM terpolymers are Nordel 1320, commercially available from Dupont Dow Elastomer, and TXA-6070, commercially available from DSM Copolymer.
[0020] A thermoplastic rubber is also included in the composition to gel the sealant (provide sag resistance) and add cohesive strength. Preferably, the thermoplastic rubber comprises a copolymer of styrene-ethylene/propylene, which is commercially available from a variety of sources. A preferred copolymer for use in the present invention is available from Shell Chemical Company under the designation Kraton G-1701 (which contains 37% styrene). Other suitable thermoplastic rubbers include Kraton G-1702 (28% styrene) and Kraton G-1726 (30% styrene).
[0021] The tackifier in the sealant composition preferably comprises an aliphatic hydrocarbon resin, polybutene, or combinations thereof. The tackifier is preferably included to provide the adhesive composition with high initial adhesivity and softness. Preferred aliphatic hydrocarbon resin tackifiers for use in the present invention include Escorez 5300 and 5340, a fully hydrogenated polycyclic hydrocarbon resin available from ExxonMobil Chemical. A preferred polybutene tackifier is Indopol H-300, commercially available from Amoco Chemical. Other suitable polybutene tackifiers include Indopol H-100, H-1500 and H-1900 (available from Amoco Chemical) and Parapol 450, 700, 950, 1300, 2400 and 2500 available from ExxonMobil Chemical.
[0022] Suitable fully hydrogenated polycyclic hydrocarbon resins include Escorez 5380 and 5320, available from ExxonMobil Chemical and Regalrez 1018, 1085, 1094, 1126, 1128, 1139, 3102, 5095 and 6108, available from Hercules. Additional aliphatic hydrocarbon resins include Escorez 1102, 1304 and 1315 available from ExxonMobil Chemical; Eastotac H-100, H-115, H-130 and H-142, available from Eastman Chemical; Wingtack 10 and 95 available from Goodyear Chemical; Adtac LV, Piccopale 100, Piccotac B, 95 and 115, Piccovar AB-180, Regalrez 1018, available from Hercules; and Nevtac 10, 80, 100 and 115, available fromNeville Chemical.
[0023] The adhesive composition also preferably contains a compatible plasticizer for the rubbery polymer component which imparts softness to the composition. Suitable plasticizing agents include liquid polyisobutylene, for example, Vistanex CP-24, or LM-MH, both of which are commercially available from Exxon Chemical. Other suitable liquid polyisobutylenes include Vistanex LM-S, LM-MS and LM-H, available from ExxonMobil Chemical and Oppanol B-10, B12 and B-15, available from BASF Corporation.
[0024] The composition may also include a an oil such as mineral oil which functions as a low viscosity plasticizer to provide flexibility to the composition at low temperatures. A preferred mineral oil is available from Pennzoil Company under the designation Drakeol 10B.
[0025] Preferred solvents for use in the present invention include para-chlorobenzotriflouride or aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane and naphtha. High flash naphtha solvent or VM&P (Varnish Makers and Painters) naphtha are the preferred aliphatic hydrocarbons for use in the invention. The aliphatic hydrocarbon solvents are commercially available from a variety of suppliers including Ashland Chemical, ExxonMobil Chemical, Eastman Chemical and Shell Chemical. Para-benzotrifluoride is commercially available from Occidental Chemical Company, Dallas Tex. under the designation Oxsol 100. The solvent preferably comprises either a blend of high flash naphtha solvent (90 solvent) and VM&P naphtha or a blend of para-chlorobenzotrilfuoride and VM&P naphtha.
[0026] The sealant composition may optionally include a deodorant mask such as Cherry mask #5236, commercially available from Andrea Aromatics, Princeton, N.J., which masks the odor of the solvent. Other suitable masking agents are Cherry Almond 183-301 and Citrus 173-218, available from Alpine Aromatics International, Inc. (Piscataway, N.J.), #18293 and #18294 available from Atlanta Fragrance (Kennesaw, Ga.), Masking Fragrance AP-970, available from Kraus & Company, Inc. (Oak Park, Mich.) and Fruity 91754, Fruity Vanilla 83576 and Non-Descript 95624 available from Stanley S. Schoenmann, Inc. (Clark, N.J.).
[0027] The lap edge sealant composition also includes an accelerator/cure package or system for the rubber polymer component. The present composition may be cured using several well-known curing systems including sulfur and sulfur-containing systems as well as zinc oxide. -Typically, about 0.2 to about 2.0% by weight of the accelerator/cure package in the composition is sufficient. Preferably, the accelerator/cure package comprises a mixture of sulfur, tetramethylthiuram disulfide (TMTD), 2-mercaptobenzothiazyl disulfide (MBTS), butyl zimate, stearic acid, and zinc oxide.
[0028] Suitable accelerators for use in the present invention include, but are not limited to, thioureas such as ethylene thiourea, N,N-dibutylthiourea, N,N-diethylthiourea and the like; thiuram monosulfides and disulfides such as tetramethylthiuram monosulfide (TMTMS), tetramethylthiuram disulfide (TMTD), tetraethylthiuram monosulfide (TETMS), dipentamethylenethiruam hexasulfide (DPTH) and the like; benzothiazole sulfenamides such as N-oxydiethylene-2-benzothiazole sulfenamide, N-cyclohexyl-2-benzothiazole sulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzothiazole sulfenamide (TBBS) and the like; 2-mercaptoimidazoline, N-N-diphenylguanidine, N-N-di(2-methyl-phenyl)-guanidine, 2-mercaptobenzothiazole (MBT), 2-mercaptobenzothiazyl disulfide (MBTS), 2-(morpholinodithio)benzothiazole disulfide, zinc 2-mercaptobenzothiazole and the like; dithiocarbamates such as tellirium diethyldithiocarbamate, copper dimethyldiothiocarbarnate, bismuth dimethyldithiocarbamate, cadmium diethyldithiocarbamate, lead dimethyldithiocarbamate, zinc dibutyldithiocarbamate (butyl zimate), zinc diethyldithiocarbamate and zinc dimethyldithiocarbamate. Typically, the composition includes from about 0.5 to about 2.0% by weight of accelerator.
[0029] The cure package may also include a small amount of stearic acid (about 1 to 2 phr) to initiate the vulcanization process. The cure package may further include a surface treated activator (BIK-OT), available from Uniroyal Chemical and a substituted diphenylamine antioxidant (Naugard 445) available from Uniroyal Chemical.
[0030] The composition may further include conventional fillers such as carbon black, ground coal, and aluminum silicate. Other suitable fillers include treated fillers such as calcium stearate-treated calcium carbonate, which is available from George Marble Company of Tate, Ga. under the designation CS-11. Oleic acid may also be included as a wetting agent for the fillers. Desiccants such as calcium oxide (lime) may also be included in the composition.
[0031] The composition may also include a rheology modifier such as an organoclay and a wax such as a polyethylene wax.
[0032] The lap edge sealant composition also preferably includes an antioxidant to stabilize the thermoplastic rubber and the copolymer. While there are many suitable antioxidants, it is preferable to use a phenolic material which is commercially available from The Goodyear Tire & Rubber company under the product name Wingstay L.
[0033] The composition is preferably made by mixing all of the components in a medium to high powered mixer, such as a sigma blade or Banbury type mixer. The composition should be vigorously mixed to ensure good dispersion of all the components.
[0034] Referring now to FIG. 1, the lap edge sealant composition may be used to seal the lap joints of adjacent sheets of synthetic rubber roofing materials by applying the composition to at least one overlapping edge of the sheets. To achieve a uniform application, the lap edge sealant is preferably applied with a caulking gun nozzle as described in commonly assigned U.S. Pat. No. 5,000,361, the disclosure of which is incorporated herein by reference. As shown in FIG. 1, the sealant 10 is squeezed from the caulking gun 12 and applied to the overlap seam 20 of roofing material 18 .
[0035] The sealant composition may be applied in a variety of weather conditions and becomes fully cured at room temperature (i.e., about 24° C.) after about 21 days. The sealant preferably exhibits a sag of less than about 1½ inches when measured according to ASTM D2202.
[0036] In order that the invention may be more readily understood, reference is made to the following example which is intended to illustrate the invention, but not limit the scope thereof.
EXAMPLE 1
[0037] Three sets of lap edge sealants were prepared in accordance with the present invention. The proportions of each component in the sealants designated as 1 A, 1 B, 1 C, 2 A, 2 B, 2 C, and 3 A, 3 B. and 3 C are listed in Tables 1-3 below as parts by weight.
TABLE 1 Compound 1A 1B 1C EPDM 1 60 60 60 styrene-ethylene/propylene 48 48 48 copolymer 2 EPDM 3 20 20 20 polyisobutylene 4 80 80 80 polyethylene wax 30 30 30 carbon black 20 20 20 antioxidant 2.4 2.4 2.4 organoclay 40 40 40 treated calcium carbonate 660 660 660 metallic oxide silica 20 20 20 lime 20 20 20 tackifier(s) 88 88 88 mineral oil 30 30 30 para-chlorobenzotrifluoride 5 112 112 112 naphtha 315 310 315 n-butyl acetate — 6 — Cherry mask #5236 — — 0.6
[0038] [0038] TABLE 2 Compound 2A 2B 2C EPDM 1 70 70 70 styrene-ethylene/propylene 50 50 50 copolymer 2 polyisobutylene 3 80 80 80 polyethylene wax 30 30 30 antioxidant 2 2 2 carbon black 20 20 20 treated calcium carbonate 750 500 500 metallic oxide silica 20 20 20 aluminum silicate — 250 — tackifier(s) 95 95 95 lime 20 20 20 oleic acid 2 2 2 ground coal — — 250 organoclay 40 40 40 mineral oil 40 40 40 naphtha 100 100 100 VM&P naphtha 200 200 200
[0039] [0039] TABLE 3 Compound 3A 3B 3C EPDM 1 70 70 70 styrene-ethylene/propylene 50 50 50 copolymer 2 polyisobutylene 3 80 80 80 polyethylene wax 30 30 30 antioxidant 2 2 2 carbon black 20 20 20 calcium carbonate 750 750 750 filler 20 20 20 tackifier(s) 85 85 85 lime 20 20 20 oleic acid 2 2 2 organoclay 30 30 30 mineral oil 30 30 30 Accelerator/cure package 14 12.7 6.6 naphtha 71 71 71 VM&P naphtha 141 141 141
[0040] All of the above sealants were tested to determine VOC content, solids content, press-flow viscosity, weight per gallon, specific gravity, sag at 25° C. and 70° C., flexibility at −30° C., adhesion to EPDM, and shrinkage. The results are shown below in Table 4. VOC content was determined by ASTM Standard test method D 3960. Solids content was determined by ASTM standard test method C 681. Press-flow viscosity was determined by ASTM standard test method D 2452 (time to extrude 20 grams at 40 psi at 25° C.). The weight per gallon and specific gravity were determined by ASTM standard test method D 1475. Sag at 25° C. and 70° C. were determined by ASTM standard test method D 2202. Flexibility at −30° C. was determined by ASTM standard test method C 711. Adhesion to EPDM was determined by ASTM standard test method C 794. Shrinkage was determined by ASTM standard test method C 733 for volume shrinkage of sealants.
TABLE 4 VOC Solids Press-flow Weight Sag @ Sag @ Content Content viscosity per gallon specific 25° C. 70° C. Flexibility Adhesion Product (g/l) (%) (seconds) (lbs) gravity (inches) (inches) @ −30° C. to EPDM Shrinkage 1A 244 69.1 18 9.83 1.18 2.14 1.73 Good Good 31.4% 1B 249 68.2 16 9.75 1.17 3.48 3.11 Good Good 32.3% 1C 247 71.3 39 9.91 1.19 0.60 2.06 Good Good 29.2% 2A 194 86.4 61 11.93 1.43 0.44 0.55 Good Excellent 14.2% 2B 211 84.8 36 11.57 1.39 2.56 2.00 Good Excellent 15.8% 2C 219 83.2 36 10.9 1.31 0.08 0.10 Good Excellent 17.3% 3A 213 83.6 34 11.84 1.42 1.02 1.03 Good Good 17.1% 3B 215 84.1 35 11.94 1.43 1.16 0.87 Good Good 16.6% 3C 213 83.6 25 11.84 1.42 1.28 1.46 Good Good 17.1%
[0041] The sealants were also tested for center and edge cracking using ASTM standard test method C 1257. None of the sealants exhibited center or edge cracking.
[0042] While certain representative embodiments and details have been shown for purposes of illustrating the invention, it will be apparent to those skilled in the art that various changes in the methods and apparatus disclosed herein may be made without departing from the scope of the invention, which is defined in the appended claims. | A lap edge sealant composition is provided for adhering together overlapping sheets of roofing material which includes a rubbery polymer such as EPDM, a thermoplastic rubber, a tackifier, and a solvent, where the solvent is selected from aliphatic hydrocarbons, para-chlorobenzotrifluoride, or blends thereof. The lap edge sealant has a high solids content of about 65 to 90%, a volatile organic compound (VOC) content of less than about 250 g/l, and exhibits no more than about 35% shrinkage upon curing. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to the esterification of carboxyaromatics, particularly through the reaction of an anhydride of a carboxyaromatic with a fluorinated alcohol followed by reaction of the resulting ester/acid with an epoxide. Such an esterification process is generally known, especially in the preparation of compounds capable of imparting oil and/or water repellency to textiles such as polyester and nylon fibers.
In particular, U.S. Pat. No. 4,209,610 and G.B. Pat. No. 1,543,081 disclose compounds useful for imparting oil and water repellency which are prepared by contacting in solution an anhydride of a carboxybenzene and various fluorinated alcohols to form the corresponding fluorinated ester/acid, and then contacting said ester/acid in solution with an epoxide. More particularly, in Example VIII of U.S. Pat. No. 4,209,610, pyromellitic dianhydride (PMDA) is esterified in DMF with a mixture of perfluoroalkyl-ethanols to form the corresponding diester/diacid, which is then further reacted (in DMF) with excess epichlorohydrin, using a little triethylamine as catalyst, to esterify the remaining carboxyl groups to form the tetraester, which is precipitated out with ice water.
Similarly, in European Patent application No. 19,732, published Dec. 10, 1980, esterification of carboxybenzenes in N-methylpyrrolidone (NMP) solvent is disclosed and shown to be superior in comparative testing to a like product made in DMF.
In U.S. Pat. No. 4,252,982, such esterifications of carboxybenzenes are shown in aliphatic ester solvents such as butyl acetate. The use of the aliphatic ester solvents is said to overcome the waste water problem which results when DMF or NMP is employed as the solvent for such esterifications. When DMF or NMP is employed, the final product must be precipitated out with water, which takes up the solvent and thus requires waste water treatment. The advantage in using the aliphatic ester solvent is that it can be distilled from the desired product. However, the use of the aliphatic ester solvent results in a slower reaction rate, presents a flammability hazard, and produces a slightly inferior product in comparison with the NMP process.
SUMMARY OF THE INVENTION
Applicants have discovered an improved process for the esterification of carboxyaromatics by fluorinated alcohols and epoxides which results in substantially faster reaction times and substantially reduced waste water treatment requirements when compared with presently known processes. Applicants' improved process also results in a product which is comparable in quality to one produced in NMP, which is known to be superior to the like product produced in DMF or aliphatic ester solvent.
Applicants have discovered that the process for the esterification of a carboxyaromatic by reacting an anhydride of said carboxyaromatic with a fluorinated alcohol and then an epoxide can be improved by utilizing the epoxide as the solvent or reaction medium for the esterification when said epoxide is a liquid under the reaction conditions employed.
DETAILED DESCRIPTION OF THE INVENTION
The essence of applicants' invention is the discovery that the double esterification of carboxyaromatics by fluorinated alcohols and epoxides, which has heretofore been carried out in two steps in various solvents, may be advantageously conducted in one step without added solvent when the epoxide selected for the esterification is a liquid under the reaction conditions employed. The liquid epoxide, which is normally used in excess to drive the reaction to completion, serves to keep the reaction mixture fluid and homogeneous. Thus, the applicants' process comprises intimately mixing an anhydride of a carboxyaromatic, a fluorinated alcohol, and a liquid epoxide, and heating said mixture to esterify said carboxyaromatic.
The carboxyaromatic anhydrides which can be employed in the process of this invention may be derived from any polycarboxyaromatic wherein one or more adjacent pairs of carboxyl groups have been converted to the anhydride. The carboxyaromatics of general interest are the one and two ring aromatics such as benzene, naphthalene, pyridine, pyrazine, quinoline, indole, thiophene, furan, etc. substituted by two or more carboxyl groups, and optionally any other substituents which do not interfere with conventional esterifications. Two or more carboxyaromatics may be linked together through a chemical bond or a bridging group.
The carboxyaromatic anhydrides of choice are the anhydrides of the benzene and naphthalene carboxylic acids. Illustrative of these are the anhydrides of benzene tricarboxylic acid and tetracarboxylic acid, naphthalene tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, 2,2-bis (dicarboxyphenyl) propane dianhydride, 1,1-bis (dicarboxyphenyl) ethane dianhydride, bis (dicarboxyphenyl) methane dianhydride, bis (dicarboxyphenyl) sulfone dianhydride, bis (dicarboxyphenyl) ether dianhydride, and benzophenone tetracarboxylic dianhydride. Of course, anhydrides of the heterocyclic aromatics, such as pyrazine tetracarboxylic dianhydride and thiophene tetracarboxylic dianhydride, may also be employed. The preferred carboxyaromatic anhydrides are pyromellitic dianhydride (PMDA) and 3, 4, 3', 4'-benzophenone tetracarboxylic dianhydride (BTDA).
Numerous fluorinated alcohols are disclosed in the prior art, for example in G. B. Pat. No. 1,543,081, U.S. Pat. No. 4,209,610, U.S. Pat. No. 3,646,153, U.S. Pat. No. 3,547,861, U.S. Pat. No. 3,514,487, and U.S. Pat. No. 3,171,861, all of which alcohols are believed to be operative in the present process. These include fluorinated alcohols having straight chain, branched chain and cyclic fluorinated moiety attached to a hydroxy substituted hydrocarbon moiety, each moiety having between 2 and 20 carbon atoms, especially such alcohols in which the fluorinated moiety has between 3 and 12 carbon atoms and the hydrocarbon moiety has between 2 and 12 carbon atoms. The fluorinated moiety can be perfluorinated and can alternatively be partially fluorinated, for example having a terminal hydrogen atom. Also, either or both the fluorinated moiety and the hydroxyl substituted moiety can contain substituents such as chloro, bromo or iodo.
Specific suitable fluorinated alcohols for esterification of carboxyaromatics by the present process include the (perfluoroalkyl) ethanols and the (perfluoroalkyl) propanols having three to twelve carbon atoms in the perfluoroalkyl groups; and the (omega-perfluoroiso-propoxyperfluoroalkyl) ethanols, and the propanol homologues thereof, having two to ten carbon atoms in the perfluoroalkyl groups. Preferred alcohols of the above group, in view of their availability and effectiveness in producing esters with the desired properties, are mixtures consisting essentially of 2-(n-perfluoroalkyl)ethanols having six to twelve carbon atoms in the perfluoroalkyl groups.
Epoxides useful in the present process are those which are liquid under the reaction conditions employed for the esterification. The preferred epoxides will provide radicals designated as "B" in U.S. Pat. No. 4,209,610. Typical of these are epoxides of the formula: ##STR1## wherein n is 1 or 2 and X is hydrogen, hydroxy, halogen, or nitrile. Epichlorohydrin and glycidol are the preferred epoxides.
The process of the present invention is carried out by intimately mixing the carboxyaromatic anhydride, fluorinated alcohol and epoxide, and allowing the esterification to proceed to completion, generally at elevated temperatures. The alcohol first reacts with the anhydride to form the corresponding carboxylic acid/half ester having one fluorinated ester radical per anyhydride moiety orginally present. The free carboxyl groups formed upon opening of the anhydride (i.e. those remaining), as well as any free carboxyl groups originally present, react with the epoxide to form the corresponding ester or esters.
Generally, the fluorinated alcohol is employed in stoichiometric quantities in the present process. By stoichiometric quantities is meant that amount of alcohol which will react completely with the carboxyaromatic anhydride to give the half ester. In other words, the stoichiometric quantity of alcohol is the number of moles of carboxyaromatic anhydride multiplied by the number of anhydride groups on the carboxyaromatic anhydride. Thus, for example, one mole of alcohol reacts with one mole of a monoanhydride; two moles of alcohol react with one mole of a dianhydride, etc.
An alternative approach to defining the quantity of fluorinated alcohol employed is to say that about one equivalent of alcohol is used per equivalent of carboxyaromatic anhydride. One equivalent of alcohol is one mole. One equivalent of carboxyaromatic anhydride is one mole divided by the number of anhydride groups per molecule. Thus, one equivalent (one mole) of alcohol reacts with one equivalent (one-half mole) of dianhydride.
The epoxide is generally employed in excess quantities in order to drive the reaction to completion in a reasonable time. From a practical standpoint, it has been found desirable to use an amount which will provide a 100 to 300%, preferably a 150 to 250%, molar excess of epoxide over the stoichiometrically required amount (i.e., that amount which will react with the free carboxyl groups on the carboxyaromatic, including those formed upon esterification by the fluorinated alcohol). Thus, for example, a dianhydride such as pyromellitic dianhydride, will require about five to seven moles of epoxide to drive the reaction to completion in a reasonable time--two moles of epoxide to react with the free carboxyls formed upon esterification by the fluorinated alcohol, and three to five moles to provide the 150 to 250% molar excess needed.
The temperature and pressure employed in the present process are not critical. Their selection is based primarily on obtaining a satisfactory reaction rate while avoiding decomposition of the products. Generally, temperatures between about 40° and 60° C., give satisfactory results.
A catalyst is not necessary in the reaction of the fluorinated alcohol with the anhydride, but conventional esterification catalysts for this reaction, such as bases or Lewis acids, can be used if desired. A catalyst is helpful in the esterification by the epoxide, the organic bases being typical. Triethylamine is preferred, although pyridine and other trialkylamines may be employed.
The invention may be described in greater detail by the following examples in which the parts and percentages are by weight.
EXAMPLE 1
A dry 500 ml three-neck flask, fitted with overhead stirrer, thermometer and drying tube, was charged with 115 g of a mixture of 2-(n-perfluoroalkyl) ethanols having six to twelve carbon atoms in the perfluoroalkyl groups, 25.8 g pyromellitic dianhydride (PMDA), 1 ml triethylamine and 55.7 ml epichlorohydrin. All reactants were mixed together in the flask and the slurry heated slowly to 55° C. After 7.5 hours carboxyl titration indicated the reaction to be essentially complete and the reaction mixture was drowned into water to precipitate the product (the tetraester), which was washed to remove excess epichlorohydrin and dried under vacuum. The epichlorohydrin in the wash water was converted to glycerol by addition of sodium hydroxide.
EXAMPLE 2
Example 1 was repeated using 27.5 g PMDA and 115 g perfluoroakyl ethanol. The reaction was conducted at 45° C. and took 12.5 hours to complete.
The above products were tested for oil repellency and wash fastness in the following manner. The product was dissolved in acetone and applied onto polyester or nylon fabric through a padder. The concentration of product was adjusted so that pick up was 0.25% product compared to the weight of the fabric. After drying at room temperature, the fabric was cured (annealed) at 140° C. (nylon) or 160° C. (polyester) for 30 minutes. The fabric was then subjected to AATCC Test 61-1968 (II-A) using a launderometer from Atlas Electric Co. to simulate five home launderings at medium temperature settings. The washed fabric was evaluated for oil repellency according to AATCC Test 118-1975, the rating scale running from 0 to 8, with increasing numbers indicating greater repellency. The tested products gave oil repellency values of 5-6.
COMPARISON
The following table compares the present solvent-free process with the known esterification processes using DMF, NMP and alkyl acetate solvents according to U.S. Pat. No. 4,209,610, E.P. No. 19,732, and U.S. Pat. No. 4,252,982 respectively. As can be seen from this table, the process of the present invention produces a product (in this case, the tetraester of pyromellitic dianhydride) which is either superior or comparable to the like product produced according to the prior art processes; the present process has a substantially faster reaction time than the prior art processes; and the present process has lower waste water treatment requirements (i.e. lower BOD) than all but the alkyl acetate process which requires a difficult and hazardous distillation.
TABLE______________________________________COMPARISON OF ESTERIFICATION PROCEDURES Sol- NMP Alkyl vent- DMF Sol- Acetate Free Solvent vent Solvent______________________________________Reaction Time 7.5 17 17 >20(at 55° C. - excluding hours hours hours hourswork up)Waste Water BOD 0.25 1.2 1.2 <0.1(biological oxygen (estimate) (estimate)*demand - lbs. O.sub.2 /lb. product)Oil Repellency 5-6 4-5 5-6 4-5(0.25% application -5 wash cycles)______________________________________ *Solvent must be distilled. | An improved process for exterifying carboxyaromatics is disclosed wherein an anhydride of a carboxyaromatic, such as pyromellitic dianhydride, is reacted with a fluorinated alcohol and an epoxide to give a mixed ester capable of imparting oil and/or water repellency to textiles. The improvement comprises utilizing the epoxide as the reaction medium to reduce reaction times and waste water treatment requirements. | 2 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This is a divisional of U.S. patent application Ser. No. 14/453,843, filed on Aug. 7, 2014, which is a continuation of U.S. patent application Ser. No. 13/917,960, filed on Jun. 14, 2013 (now U.S. Pat. No. 8,827,989), which is a divisional of U.S. patent application Ser. No. 12/554,685, filed on Sep. 4, 2009 (now U.S. Pat. No. 8,486,053), which is a divisional of U.S. patent application Ser. No. 11/226,080, filed on Sep. 13, 2005 (now U.S. Pat. No. 7,713,263), which is a continuation of U.S. patent application Ser. No. 10/864,273, filed on Jun. 8, 2004 (now U.S. Pat. No. 6,974,449), which is a divisional of U.S. patent application Ser. No. 10/402,678 filed on Mar. 27, 2003 (now U.S. Pat. No. 6,899,705), which is a divisional of U.S. patent application Ser. No. 09/287,513 filed Apr. 7, 1999 (now U.S. Pat. No. 6,565,554), the full disclosures of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention is generally related to improved robotic devices and methods, particularly for telesurgery.
[0003] Minimally invasive medical techniques are aimed at reducing the amount of extraneous tissue which is damaged during diagnostic or surgical procedures, thereby reducing patient recovery time, discomfort, and deleterious side effects. Many surgeries are performed each year in the United States. A significant amount of these surgeries can potentially be performed in a minimally invasive manner. However, only a relatively small percentage of surgeries currently use these techniques due to limitations in minimally invasive surgical instruments and techniques and the additional surgical training required to master them.
[0004] Advances in minimally invasive surgical technology could dramatically increase the number of surgeries performed in a minimally invasive manner. The average length of a hospital stay for a standard surgery is significantly longer than the average length for the equivalent surgery performed in a minimally invasive surgical manner. Thus, the complete adoption of minimally invasive techniques could save millions of hospital days, and consequently millions of dollars annually in hospital residency costs alone. Patient recovery times, patient discomfort, surgical side effects, and time away from work are also reduced with minimally invasive surgery.
[0005] The most common form of minimally invasive surgery is endoscopy. Probably the most common form of endoscopy is laparoscopy which is minimally invasive inspection and surgery inside the abdominal cavity. In standard laparoscopic surgery, a patient's abdomen is insufflated with gas, and cannula sleeves are passed through small (approximately ½ inch) incisions to provide entry ports for laparoscopic surgical instruments.
[0006] The laparoscopic surgical instruments generally include a laparoscope for viewing the surgical field, and working tools defining end effectors. Typical surgical end effectors include clamps, graspers, scissors, staplers, and needle holders, for example. The working tools are similar to those used in conventional (open) surgery, except that the working end or end effector of each tool is separated from its handle by, e.g., an approximately 12-inch long, extension tube.
[0007] To perform surgical procedures, the surgeon passes these working tools or instruments through the cannula sleeves to a required internal surgical site and manipulates them from outside the abdomen by sliding them in and out through the cannula sleeves, rotating them in the cannula sleeves, levering (i.e., pivoting) the instruments against the abdominal wall and actuating end effectors on the distal ends of the instruments from outside the abdomen. The instruments pivot around centers defined by the incisions which extend through muscles of the abdominal wall. The surgeon monitors the procedure by means of a television monitor which displays an image of the surgical site via a laparoscopic camera. The laparoscopic camera is also introduced through the abdominal wall and into the surgical site. Similar endoscopic techniques are employed in, e.g., arthroscopy, retroperitoneoscopy, pelviscopy, nephroscopy, cystoscopy, cisternoscopy, sinoscopy, hysteroscopy, urethroscopy, and the like.
[0008] There are many disadvantages relating to current minimally invasive surgical (MIS) technology. For example, existing MIS instruments deny the surgeon the flexibility of tool placement found in open surgery. Most current laparoscopic tools have rigid shafts and difficulty is experienced in approaching the worksite through the small incision. Additionally, the length and construction of many endoscopic instruments reduces the surgeon's ability to feel forces exerted by tissues and organs on the end effector of the associated tool. The lack of dexterity and sensitivity of endoscopic tools is a major impediment to the expansion of minimally invasive surgery.
[0009] Minimally invasive telesurgical systems for use in surgery are being developed to increase a surgeon's dexterity as well as to allow a surgeon to operate on a patient from a remote location. Telesurgery is a general term for surgical systems where the surgeon uses some form of remote control, e.g., a servomechanism or the like, to manipulate surgical instrument movements rather than directly holding and moving the tools by hand. In such a telesurgery system, the surgeon is typically provided with an image of the surgical site at the remote location. While viewing typically a three-dimensional image of the surgical site on a suitable viewer or display, the surgeon performs the surgical procedures on the patient by manipulating master control devices at the remote location, which control the motion of servomechanically operated instruments.
[0010] The servomechanism used for telesurgery will often accept input from two master controllers (one for each of the surgeon's hands), and may include two robotic arms. Operative communication between master control and an associated arm and instrument is achieved through a control system. The control system typically includes at least one processor which relays input commands from a master controller to an associated arm and instrument and from the arm and instrument assembly to the associated master controller in the case of, e.g., force feedback.
[0011] One objective of the present invention is to provide improved surgical techniques. Another objective is to provide improved robotic devices, systems, and methods. More specifically, it is an object of this invention to provide a method of compensating for friction in a minimally invasive surgical apparatus. It is a further object of the invention to provide a control system incorporating such a method of compensating for friction.
BRIEF SUMMARY OF THE INVENTION
[0012] The present invention provides improved devices, systems, and methods for compensating for friction within powered automatic systems, particularly for telesurgery and other telepresence applications. The invention allows uninhibited manipulation of complex linkages, enhancing the precision and dexterity with which jointed structures can be moved. This enhanced precision is particularly advantageous when applied to the robotic surgical systems now being developed. The friction compensation systems of the present invention address static friction (typically by applying a continuous load in the direction of movement of a joint) and the often more problematic static friction (generally by applying alternating loads in positive and negative joint actuation directions). The invention can accommodate imprecise velocity measurements by applying an oscillating load whenever the joint velocity reading falls within a low velocity range. Preferably, the oscillating load is insufficient to move the joint without additional input, and significantly reduces the break away input required to initiate movement. In the exemplary embodiment, a duty cycle of the oscillating load varies, favoring the apparent direction of movement of a velocity reading. The amplitude of the duty cycle may also vary, typically increasing as the velocity reading approaches zero.
[0013] In a first aspect, the invention provides a method of compensating for friction in an apparatus. The apparatus has at least one component that is selectively moveable in a positive component direction, and in a negative component direction. An actuator is operatively connected to the component. The method includes obtaining a component velocity reading, and defining a velocity reading region extending between a selected negative velocity reading and a selected positive velocity reading. A duty cycle is generated so that the duty cycle has a distribution between a positive duty cycle magnitude (corresponding to a friction compensation force in the positive component direction) and a negative duty cycle magnitude (corresponding to a friction compensation force in the negative component direction). The distribution is determined by the component velocity reading when it is within the velocity reading region. The actuator is loaded with a load defined by the duty cycle signal.
[0014] Preferably, the duty cycle signal will have a continuous positive duty cycle magnitude (which corresponds to the friction compensation force in the positive direction) when the component velocity reading is greater than the selected positive velocity reading. Similarly, the duty cycle signal will have a continuous negative duty cycle magnitude (corresponding to the friction compensation force in the negative component direction) when the component velocity reading is less than the selected negative velocity reading.
[0015] In the exemplary embodiment, the distribution of the duty cycle between the positive and negative magnitudes is proportional to the component velocity reading positioned within the velocity reading region. The positive and negative duty cycle magnitudes may take a gravity compensation model into account. Such a gravity compensation model may determine a variable gravity compensation force to applied to the component, for example, to artificially balance an unbalanced linkage system. Such a gravity compensated system may further benefit from a determination of a frictional compensation force corresponding to the gravity compensation force in both the positive and negative directions. In other words, in addition to compensating for friction, the method of the present invention may accommodate compensation factors for both friction and gravity, thereby simulating or approximating a friction-free balanced system, significantly enhancing the dexterity of movement which can be accommodated.
[0016] The selection of an appropriate oscillating frequency can significantly enhance friction compensation provided by these methods and systems. Hence, the frequency will preferably be selected so as to be sufficiently slow to enable the actuator (often including an electrical motor and a transmission system such as gears, cables, or the like) to respond to the directing duty cycle signal by applying the desired load, and sufficiently rapid so that the load cannot actually be felt, for example, by physically moving the joint and varying a position of an input master control device held by a surgeon. In other words, the frequency is preferably greater than the mechanical time constraints of the system, yet less than the electrical time constants of an electrical motor used as an actuator. Preferred duty cycle frequency ranges of the exemplary telesurgical system described herein are in a range from about 40 Hz to about 70 Hz, preferably being in a range from about 50 Hz to about 60 Hz. Application of these oscillating loads can facilitate movement of a joint in either a positive or negative direction, particularly when the velocity reading is so low that the system cannot accurately determine whether the system is at rest, moving slowing in a positive direction, or moving slowly in a negative direction. Once velocity measurement readings are high enough (a given measurement reading accuracies) in a positive or negative direction, a continuous (though not necessarily constant) force in the desired direction can overcome the dynamic friction of the joint.
[0017] In yet another aspect, the invention provides a method comprising manipulating an input device of a robotic system with a hand of an operator. An end effector is moved in sympathy with the manipulating step using a servomechanism of the robotic system. A velocity reading is obtained from a joint of the robotic system. An oscillating friction compensation load is applied on the joint when the velocity reading is within a first reading range.
[0018] Preferably, a continuous friction compensation load is applied when the reading is within a second reading range, typically above (either in the positive or negative direction) a minimum value. The continuous load can compensate for friction of the joint, and may vary so as to compensate for gravity when an orientation of the joint changes. The oscillating load similarly compensates for static friction of the joint in the positive and negative directions, at varying points along the load oscillation duty cycle. This method is particularly advantageous for compensating for friction and/or gravity in a joint of the input device for the robotic system, particularly where the oscillating load is less than a static friction of the joint so that the end effector can remain stationary in the hand of the operator.
[0019] In another aspect, the invention provides a telesurgery method comprising directing a surgical procedure by moving an input device of a telesurgery system with a hand of an operator. Tissue is manipulated by moving a surgical end effector in sympathy with the input device using a servomechanism of the telesurgery system. Static friction is compensated for in at least one joint of the robotic system by applying an oscillating load to the at least one joint when an absolute value of a velocity reading from the at least one joint is less than a velocity reading error range.
[0020] While the friction compensated joint may support the surgical end effector, it will preferably support the input device. The oscillating load is generally effected by applying a duty cycle to an actuator, and preferably by altering the duty cycle in response to the velocity reading so as to facilitate movement of the joint towards the positive orientation when the velocity reading is positive, and toward the negative orientation when the velocity reading is negative.
[0021] In yet another aspect, the invention provides a telepresence system comprising a master including an input device supported by a driven joint. A slave includes an end effector supported by a driven joint. A controller couples the master to the slave. The controller directs the end effector to move in sympathy with the input device. A sensor operatively associated with at least one of the driven joints generates a velocity reading. An actuator drivingly engages the at least one driven joint. The actuator applies an oscillating load on the joint to compensate for static friction of the joint when the velocity reading is within a low velocity range.
[0022] Preferably, the oscillating load is insufficient to move the at least one driven joint when the master remains stationary. In the exemplary embodiment, the end effector comprises a surgical end effector, and the slave is adapted to manipulate the surgical end effector within an internal surgical site through a minimally invasive surgical access.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The invention will now be described, by way of example, and with reference to the accompanying diagrammatic drawings, in which:
[0024] FIG. 1A shows a three-dimensional view of a control station of a telesurgical system in accordance with the invention;
[0025] FIG. 1B shows a three-dimensional view of a cart or trolley of the telesurgical system, the cart carrying three robotically controlled arms, the movement of the arms being remotely controllable from the control station shown in FIG. 1A ;
[0026] FIG. 2A shows a side view of a robotic arm and surgical instrument assembly; FIG. 2B shows a three-dimensional view corresponding to FIG. 2A ;
[0027] FIG. 3 shows a three-dimensional view of a surgical instrument;
[0028] FIG. 4 shows a schematic kinematic diagram corresponding to the side view of the robotic arm shown in FIG. 2A , and indicates the arm having been displaced from one position into another position;
[0029] FIG. 5 shows, at an enlarged scale, a wrist member and end effector of the surgical instrument shown in FIG. 3 , the wrist member and end effector being movably mounted on a working end of a shaft of the surgical instrument;
[0030] FIG. 6A shows a three-dimensional view of a hand-held part or wrist gimbal of a master control device of the telesurgical system;
[0031] FIG. 6B shows a three-dimensional view of an articulated arm portion of the master control device on which the hand-held part of FIG. 6A is mounted in use;
[0032] FIG. 6C shows a three-dimensional view of the master control device, the wrist gimbal of FIG. 6A shown in a mounted condition on the articulated arm portion of FIG. 6B ;
[0033] FIG. 7 shows a schematic three-dimensional drawing indicating the positions of the end effectors relative to a viewing end of an endoscope and the corresponding positions of master control input devices relative to the eyes of an operator, typically a surgeon;
[0034] FIG. 8 shows a schematic graphical relationship between measured velocity (v) and a required force (f) to compensate for friction;
[0035] FIG. 9 shows the graphical relationship shown in FIG. 8 and one method of compensating for friction represented in dashed lines superimposed thereon;
[0036] FIG. 10 shows the graphical relationship shown in FIG. 8 and another method of compensating for friction represented in dashed lines superimposed thereon;
[0037] FIG. 11 shows the graphical relationship shown in FIG. 8 and further indicates detail used to exemplify a method of compensating for friction in accordance with the invention superimposed thereon;
[0038] FIGS. 12 to 16 show different duty cycle distributions determined by values derived from velocity measurements indicated in FIG. 11 ;
[0039] FIG. 17 shows an algorithm representing an overview of the method of compensating for friction in accordance with the invention;
[0040] FIG. 18 shows further detail of the algorithm shown in FIG. 17 relating to gravity compensation;
[0041] FIG. 19 shows as an alternative to FIG. 18 , further detail of the algorithm shown in FIG. 17 relating to Coulomb friction compensation; and
[0042] FIG. 20 shows a schematic diagram exemplifying a required gravity compensating force on a master control and how the gravity compensating force and consequently also frictional force, varies depending on master control position.
DETAILED DESCRIPTION OF THE INVENTION
[0043] This application is related to the following patents and patent applications, the full disclosures of which are incorporated herein by reference: PCT International Application No. PCT/US98/19508, entitled “Robotic Apparatus”, filed on Sep. 18, 1998; U.S. Application Ser. No. 60/111,713, entitled “Surgical Robotic Tools, Data Architecture, and Use”, filed on Dec. 8, 1998; U.S. Application Ser. No. 60/111,711, entitled “Image Shifting for a Telerobotic System”, filed on Dec. 8, 1998; U.S. Application Ser. No. 60/111,714, entitled “Stereo Viewer System for Use in Telerobotic System”, filed on Dec. 8, 1998; U.S. Application Ser. No. 60/111,710, entitled “Master Having Redundant Degrees of Freedom”, filed Dec. 8, 1998; and U.S. Pat. No. 5,808,665, entitled “Endoscopic Surgical Instrument and Method for Use”, issued on Sep. 15, 1998; the full disclosures of which are incorporated herein by reference.
[0044] It is to be appreciated that although the method and control system of the invention is described with reference to a minimally invasive surgical apparatus in this specification, the application of the invention is not to be limited to this apparatus only, but can be used in any type of apparatus requiring friction compensation. Thus, the invention may find application in the fields of satellite dish tracking, handling hazardous substances, to name but two of many possible qualifying fields in which precisional movement is required. In some cases, it may be required to compensate for friction on a single part of a system such as on a master controller only.
[0045] Referring to FIG. 1A of the drawings, a control station of a minimally invasive telesurgical system is generally indicated by reference numeral 200 . The control station 200 includes a viewer 202 where an image of a surgical site is displayed in use. A support 204 is provided on which an operator, typically a surgeon, can rest his forearms while gripping two master controls (not shown in FIG. 1A ), one in each hand. The master controls are positioned in a space 206 inwardly beyond the support 204 . When using the control station 200 , the surgeon typically sits in a chair in front of the control station 200 , positions his eyes in front of the viewer 202 and grips the master controls one in each hand while resting his forearms on the support 204 .
[0046] In FIG. 1B of the drawings, a cart or trolley of the telesurgical system is generally indicated by reference numeral 300 . In use, the cart 300 is positioned close to a patient requiring surgery and is then normally caused to remain stationary until a surgical procedure to be performed has been completed. The cart 300 typically has wheels or castors to render it mobile. The control station 200 is typically positioned remote from the cart 300 and can be separated from the cart 300 by a great distance, even miles away.
[0047] Cart 300 typically carries three robotic arm assemblies. One of the robotic arm assemblies, indicated by reference numeral 302 , is arranged to hold an image capturing device 304 , e.g., an endoscope, or the like. Each of the two other arm assemblies 10 , 10 respectively, includes a surgical instrument 14 . The endoscope 304 has a viewing end 306 at a remote end of an elongate shaft thereof. It will be appreciated that the endoscope 304 has an elongate shaft to permit it to be inserted into an internal surgical site of a patient's body. The endoscope 304 is operatively connected to the viewer 202 to display an image captured at its viewing end 306 on the viewer 202 . Each robotic arm assembly 10 , 10 is operatively connected to one of the master controls. Thus, movement of the robotic arm assemblies 10 , 10 is controlled by manipulation of the master controls. The instruments 14 of the robotic arm assemblies 10 , 10 have end effectors which are mounted on working ends of elongate shafts of the instruments 14 . It will be appreciated that the instruments 14 have elongate shafts to permit the end effectors to be inserted into an internal surgical site of a patient's body. The end effectors are orientationally moveable relative to the ends of the shafts of the instruments 14 . The orientational movement of the end effectors are also controlled by the master controls.
[0048] In FIGS. 2A and 2B of the drawings, one of the robotic arm assemblies 10 is shown in greater detail.
[0049] The assembly 10 includes an articulated robotic arm 12 , and the surgical instrument, schematically and generally indicated by reference numeral 14 , mounted thereon. FIG. 3 indicates the general appearance of the surgical instrument 14 in greater detail.
[0050] In FIG. 3 the elongate shaft of the instrument 14 is indicated by reference numeral 14 . 1 . A wrist-like mechanism, generally indicated by reference numeral 50 , is located at the working end of the shaft 14 . 1 . A housing 53 , arranged releasably to couple the instrument 14 to the robotic arm 12 , is located at an opposed end of the shaft 14 . 1 . In FIG. 2A , and when the instrument 14 is coupled or mounted on the robotic arm 12 , the shaft 14 . 1 extends along an axis indicated at 14 . 2 . The instrument 14 is typically releasably mounted on a carriage 11 , which is selectively driven to translate along a linear guide formation 24 of the arm 12 in the direction of arrows P.
[0051] The robotic arm 12 is typically mounted on a base by means of a bracket or mounting plate 16 . The base is defined on the mobile cart or trolley 300 , which is normally retained in a stationary position during a surgical procedure.
[0052] The robotic arm 12 includes a cradle, generally indicated at 18 , an upper arm portion 20 , a forearm portion 22 and the guide formation 24 . The cradle 18 is pivotally mounted on the plate 16 gimbaled fashion to permit rocking movement of the cradle in the direction of arrows 26 as shown in FIG. 2B , about a pivot axis 28 . The upper arm portion 20 includes link members 30 , 32 and the forearm portion 22 includes link members 34 , 36 . The link members 30 , 32 are pivotally mounted on the cradle 18 and are pivotally connected to the link members 34 , 36 . The link members 34 , 36 are pivotally connected to the guide formation 24 . The pivotal connections between the link members 30 , 32 , 34 , 36 , the cradle 18 , and the guide formation 24 are arranged to constrain the robotic arm 12 to move in a specific manner. The movement of the robotic arm 12 is illustrated schematically in FIG. 4 .
[0053] With reference to FIG. 4 , the solid lines schematically indicate one position of the robotic arm 12 and the dashed lines indicate another possible position into which the arm 12 can be displaced from the position indicated in solid lines.
[0054] It will be understood that the axis 14 . 2 along which the shaft 14 . 1 of the instrument 14 extends when mounted on the robotic arm 12 pivots about a pivot center or fulcrum 49 . Thus, irrespective of the movement of the robotic arm 12 , the pivot center 49 normally remains in the same position relative to the stationary cart 300 on which the arm 12 is mounted during a surgical procedure. In use, the pivot center 49 is positioned at a port of entry into a patient's body when an internal surgical procedure is to be performed. It will be appreciated that the shaft 14 . 1 extends through such a port of entry, the wrist-like mechanism 50 then being positioned inside the patient's body. Thus, the general position of the mechanism 50 relative to the surgical site in a patient's body can be changed by movement of the arm 12 . Since the pivot center 49 is coincident with the port of entry, such movement of the arm does not excessively effect the surrounding tissue at the port of entry.
[0055] As can best be seen with reference to FIG. 4 , the robotic arm 12 provides three degrees of freedom of movement to the surgical instrument 14 when mounted thereon. These degrees of freedom of movement are firstly the gimbaled motion indicated by arrows 26 , pivoting movement as indicated by arrows 27 and the linear displacement in the direction of arrows P. Movement of the arm as indicated by arrows 26 , 27 and P is controlled by appropriately positioned actuators, e.g., electrical motors, which respond to inputs from an associated master control selectively to drive the arm 12 to positions as dictated by movement of the master control. Appropriately positioned sensors, e.g., encoders, potentiometers, or the like, are provided on the arm to enable a control system of the minimally invasive telesurgical system to determine joint positions.
[0056] Thus, by controlling movement of the robotic arm 12 , the position of the working end of the shaft 14 . 1 of the instrument 14 can be varied at the surgical site by the surgeon manipulating the associated master control while viewing the responsive positional movement of the working end of the shaft 14 . 1 in the viewer 202 .
[0057] Referring now to FIG. 5 of the drawings, the wrist-like mechanism 50 will now be described in greater detail. In FIG. 5 , the working end of the shaft 14 . 1 is indicated at 14 . 3 . The wrist-like mechanism 50 includes a wrist member 52 . One end portion of the wrist member 52 is pivotally mounted in a clevis, generally indicated at 17 , on the end 14 . 3 of the shaft 14 . 1 by means of a pivotal connection 54 . The wrist member 52 can pivot in the direction of arrows 56 about the pivotal connection 54 . An end effector, generally indicated by reference numeral 58 , is pivotally mounted on an opposed end of the wrist member 52 . The end effector 58 is in the form of, e.g., a clip applier for anchoring clips during a surgical procedure. Accordingly, the end effector 58 has two parts 58 . 1 , 58 . 2 together defining a jaw-like arrangement. It will be appreciated that the end effector can be in the form of any required surgical tool having two members or fingers which pivot relative to each other, such as scissors, pliers for use as needle drivers, or the like. Instead, it can include a single working member, e.g., a scalpel, cautery electrode, or the like. When a tool other than a clip applier is required during the surgical procedure, the tool 14 is simply removed from its associated arm and replaced with an instrument bearing the required end effector, e.g., a scissors, or pliers, or the like.
[0058] The end effector 58 is pivotally mounted in a clevis, generally indicated by reference numeral 19 , on an opposed end of the wrist member 52 , by means of a pivotal connection 60 . It will be appreciated that free ends 11 , 13 of the parts 58 . 1 , 58 . 2 are angularly displaceable about the pivotal connection 60 toward and away from each other as indicated by arrows 62 , 63 . It will further be appreciated that the members 58 . 1 , 58 . 2 can be displaced angularly about the pivotal connection 60 to change the orientation of the end effector 58 as a whole, relative to the wrist member 52 . Thus, each part 58 . 1 , 58 . 2 is angularly displaceable about the pivotal connection 60 independently of the other, so that the end effector 58 , as a whole, is angularly displaceable about the pivotal connection 60 as indicated in dashed lines in FIG. 5 . Furthermore, the shaft 14 . 1 is rotatably mounted on the housing 53 for rotation as indicated by the arrows 59 . Thus, the end effector 58 has three orientational degrees of freedom of movement relative to the working end 14 . 3 , namely, rotation about the axis 14 . 2 as indicated by arrows 59 , angular displacement as a whole about the pivot 60 and angular displacement about the pivot 54 as indicated by arrows 56 . It will be appreciated that orientational movement of the end effector 58 is controlled by appropriately positioned electrical motors which respond to inputs from the associated master control to drive the end effector 58 to a desired orientation as dictated by movement of the master control. Furthermore, appropriately positioned sensors, e.g., encoders, or potentiometers, or the like, are provided to permit the control system of the minimally invasive telesurgical system to determine joint positions.
[0059] In use, and as schematically indicated in FIG. 7 of the drawings, the surgeon views the surgical site through the viewer 202 . The end effector 58 carried on each arm 12 is caused to perform movements and actions in response to movement and action inputs of its associated master control. It will be appreciated that during a surgical procedure responsive movement of the robotic arm 12 on which the surgical instrument 14 is mounted causes the end effector to vary its position at the surgical site whilst responsive movement of the end effector relative to the end 14 . 3 of the shaft 14 . 1 causes its orientation to vary relative to the end 14 . 3 of the shaft 14 . 1 . Naturally, during the course of the surgical procedure the orientation and position of the end effector is constantly changing in response to master control inputs. The images of the end effectors 58 are captured by the endoscope together with the surgical site and are displayed on the viewer 202 so that the surgeon sees the positional and orientational movements and actions of the end effectors 58 as he or she controls such movements and actions by means of the master control devices.
[0060] An example of one of the master control devices is shown in FIG. 6C and is generally indicated by reference numeral 700 . The master control 700 includes a hand-held part or wrist gimbal 699 and an articulated arm portion 712 . The hand-held part 699 will now be described in greater detail with reference to FIG. 6A .
[0061] The part 699 has an articulated arm portion including a plurality of members or links 702 connected together by joints 704 . The surgeon grips the part 699 by positioning his or her thumb and index finger over a pincher formation 706 of the part 699 . The surgeon's thumb and index finger are typically held on the pincher formation 706 by straps (not shown) threaded through slots 710 . The joints of the part 699 are operatively connected to electric motors to provide for, e.g., force feedback, gravity compensation, and/or the like. Furthermore, appropriately positioned sensors, e.g., encoders, or potentiometers, or the like, are positioned on each joint of the part 699 , so as to enable joint positions of the part 699 to be determined by the control system.
[0062] The part 699 is mounted on the articulated arm portion 712 indicated in FIG. 6B . Reference numeral 4 in FIGS. 6A and 6B indicates the positions at which the part 699 and the articulated arm 712 are connected together. When connected together, the part 699 can displace angularly about an axis at 4 .
[0063] Referring now to FIG. 6B , the articulated arm 712 includes a plurality of links 714 connected together at joints 716 . Articulated arm 712 may have appropriately positioned electric motors to provide for, e.g., force feedback, gravity compensation, and/or the like. Furthermore, appropriately positioned sensors, e.g., encoders, or potentiometers, or the like, are positioned on the joints 716 so as to enable joint positions of the master control to be determined by the control system.
[0064] When the pincher formation 706 is squeezed between the thumb and index finger, the fingers of the end effector 58 close. When the thumb and index finger are moved apart the fingers 58 . 1 , 58 . 2 of the end effector 58 move apart in sympathy with the moving apart of the pincher formation 706 . To cause the orientation of the end effector 58 to change, the surgeon simply causes the pincher formation 706 to change its orientation relative to the end of the articulated arm portion 712 . To cause the position of the end effector 58 to change, the surgeon simply moves the pincher formation 706 to cause the position of the articulated arm portion 712 to change.
[0065] The electric motors and sensors associated with each robotic arm 12 and the surgical instrument 14 mounted thereon, and the electric motors and the sensors associated with each master control device 700 , namely the part 699 and the articulated arm portion 712 , are operatively linked in the control system (not shown). The control system typically includes at least one processor for effecting control between master control device input and responsive robotic arm and surgical instrument output and for effecting control between robotic arm and surgical instrument input and responsive master control output in the case of, e.g., force feedback.
[0066] As can best be seen in FIG. 6C , each master control device 700 is typically mounted on the control station 200 by means of a pivotal connection, as indicated at 717 . As mentioned hereinbefore, to manipulate each master control device 700 , the surgeon positions his thumb and index finger over the pincher formation 706 . The pincher formation 706 is positioned at a free end of the articulated arm portion of the part 699 , which in turn is positioned on a free end of the articulated arm 712 . It will be appreciated that the master control device 700 has a center of gravity normally removed from the vertical relative to its pivotal connection 717 on the control station 200 . Thus, should the surgeon let go of the pincher formation 706 , the master control device 700 would drop due to gravity. It has been found that providing the master controls 700 , 700 with gravity compensation so that whenever the surgeon lets go of the pincher formations 706 , 706 , the master controls 700 , 700 remain at their positions and orientations is beneficial. Furthermore, since performing surgical procedures involves precision movements, it is beneficial that the surgeon does not need to cope with a weighted feeling when gripping the pincher formations 706 , 706 of the master controls 700 , 700 . Thus, the control system of the telesurgical minimally invasive system is arranged to provide gravity compensation to the master control devices 700 , 700 . This gravity compensation can be achieved passively by use of counterbalancers, and/or springs, and/or the like, and/or actively by appropriate application of forces or torques on the motors operatively associated with each master control 700 . In the present case, the gravity compensation is achieved actively by means of appropriate compensating torques on motors associated with each master control 700 .
[0067] It will be appreciated that operative connection between the electrical motors and the master controls 700 , 700 , is typically achieved by means of transmissional components. These transmissional components typically include gear trains. Naturally, other transmissional components such as pulley and cable arrangements, and/or the like, can be used instead, or in addition. Regardless of the specific transmission used, these components will generally induce both static and dynamic friction in the telesurgical system.
[0068] It has been found that in providing gravity compensation, the gear trains between the motors and the master controls are typically under load. This increases the frictional forces between meshing gears and leads to increased friction when the master control is moved or urged to move by the surgeon. It has been found that the increase in frictional forces, due to gravity compensation in particular, renders master control movement uncomfortable and unpleasant (and may lead to imprecise movements) due to hysteresis.
[0069] Referring to FIG. 8 of the drawings, a typical graphical relationship between velocity and a desired force for compensation of friction is indicated by reference numeral 510 . Velocity is indicated on the horizontally extending axis and the required compensating frictional force is indicated on the vertically extending axis. To the left of the vertical axis a force in an arbitrary negative direction is indicated, and to the right of the vertical axis a force in an arbitrary positive direction is indicated. When movement is to be induced from a rest position, the force required to induce movement from rest is normally higher than that required to maintain movement after movement is initiated. This characteristic of friction is indicated by the opposed “spikes” at 512 in FIG. 8 , and is referred to as “stiction.” The spikes have been indicated in extended fashion along the velocity axis for the sake of clarity. However, it is to be appreciated that the spikes normally occur on the force axis and need not extend along the velocity axis as indicated. Note that the dynamic friction forces may not be perfectly constant, but may vary with velocity. When movement is initiated friction can readily be compensated for by applying a corresponding compensating force. However, to achieve adequate friction compensation when initiating movement from rest, or when changing direction, is more problematic.
[0070] A first friction compensation technique can best be described with reference to the following simple electromechanical system, by way of example. The example of the electromechanical system includes a motor and an articulated arm. The motor is arranged to drive the articulated arm through a transmission arrangement, e.g., a gear train, or the like. For the sake of this example, the graphical relationship between velocity and frictional force shown in FIG. 8 represents the mechanical friction in the electromechanical system as a function of velocity. It is generally desirable to compensate for this friction within the electromechanical system, as the friction can be distracting to the operator, limiting the operator's dexterity and effectiveness.
[0071] One method of compensating for friction, in particular for compensating for stiction, when the arm of the example is at rest, is to inhibit the electromechanical system from ever fully being at rest. This method includes cyclically supplying a current to the motor to prevent the electromechanical system from fully coming to rest. Thus, the motor is caused cyclically to move angularly in opposed directions. Thus a cyclical torque is supplied to the motor causing the slave to oscillate. This method is referred to as “dithering.”
[0072] Although this method inhibits the system from coming to rest and thus obviates stiction when movement is to be induced from a rest position, it has been found that dithering causes vibration in the system which is uncomfortable in some applications, particularly in minimally invasive surgical procedures. Furthermore, dithering can lead to excessive wear and ultimately damage to the apparatus.
[0073] Another method of compensating for friction is represented in FIG. 9 . This method involves supplying a force of a magnitude approximating the frictional force in the system whenever it is in motion. This type of compensation is referred to as “Coulomb” friction compensation. Such a force is induced in the electromechanical system by means of motor torque of a magnitude corresponding to the frictional force required to maintain movement in a specific direction after movement is achieved in that direction. The compensating force is indicated in dashed lines by reference numeral 520 with the sign of the compensating force being determined by the sign of the measured velocity.
[0074] This method also does not make allowance for the spikes at 512 . Thus, a degree of “sticking,” or stiction, is still felt when movement is initiated. Since it is difficult to measure velocity accurately when a system is at rest due to measurement inaccuracies, noise, and the like, it is problematic in applying the compensating force in the correct direction. Accordingly, when movement is to be initiated in one direction from rest, the system could be measuring a velocity in the opposed direction, in which case the compensating force is applied in the same direction as the frictional force thus aggravating stiction. Should the velocity reading fluctuate at zero, a compensating force which fluctuates in opposed directions is generated which introduces unpredictable energy into the system tending to destabilize it and giving it an active “feel.”
[0075] Another method of compensating for friction is indicated in FIG. 10 in dashed lines generally indicated by reference numeral 530 . This method is similar to the “Coulomb” type of compensation. However, inaccuracy in measurement around a zero velocity reading is compensated for by slanting the compensation across zero velocity. Although this method compensates for system uncertainty at zero velocity, it does not always accurately compensate for friction forces at low velocity, nor compensate for stiction when movement is to be initiated from rest. Thus, stiction is normally still present.
[0076] The preferred method of compensating for friction in accordance with the invention will now be described with particular reference to compensating for friction in a gear train of one of the master controls 700 , 700 due to gravity compensation. It will be appreciated that the description which follows is by way of example only and that the method of compensating for friction is not limited to this application only, but can be readily adapted to compensate for other sources of friction such as, e.g., at pivotal joints, between components which translate relative to each other, and/or the like. Furthermore, the method can enjoy universal application to compensate for friction in any system whether to compensate for friction due to gravity compensation or merely to compensate for friction in general irrespective of the source. For example, gear train loads imposed for purposes other than gravity compensation, for example, by a controller other than gravity controller, may induce friction that can be compensated for.
[0077] The method of compensating for friction in accordance with the invention can be understood with reference to a single joint of the master control 700 , for example the joint 704 B in FIG. 6B of the drawings, and an electrical motor associated with that joint through a gear train. It will be appreciated that friction compensation can be provided for each joint of the master control 700 .
[0078] Referring to FIG. 11 of the drawings, a graphical relationship between angular velocity (v) of the joint 704 B (as measured by the control system) and the force (f) which will compensate for force in the gear train associated with the joint 704 B is generally indicated by reference numeral 110 . Velocity (v) extends along the horizontal axis and the required force (f) to compensate for friction in the gear train extends along the vertical axis.
[0079] It has been found that when the arm members or links 702 A connected together by means of the joint 704 B are in a stationary position relative to one another, and the surgeon wishes to move the master control 700 in a manner initiating movement of the arm members 702 A about the joint 704 B, friction is particularly evident. The reason for this is that the force required to overcome friction from a stationary position is higher than the force required to maintain movement after movement is achieved. As soon as movement is achieved, the frictional force decreases and then stays approximately constant as velocity increases. This phenomenon is schematically indicated by the opposed spikes at 112 around the zero velocity region and is termed stiction. Once movement is achieved, the frictional force requiring compensation is generally constant as indicated by the straight line portions 114 .
[0080] It will be appreciated that movement of the pincher formation 706 is achieved through a plurality of joints, namely joints 704 , 716 and 717 . Thus, during any given pincher formation movement any one or more of the joints 704 , 716 , 717 may be at rest so that initiating movement about an arbitrary stationary joint or joints may be required while the pincher formation is actually moving. Thus, since there are a plurality of joints, stiction has a cumulative effect which renders precise movement of the master 700 difficult to maintain even while the pincher formation 706 is actually moving. When the pincher formation 706 is to be moved very slowly, stiction of any one or more of the joints 704 , 716 and 717 is particularly problematic and renders precise movement of the pincher formation 706 (and also responsive movement by the end effector 58 ) difficult to maintain. In fact, smooth motion of pincher formation 706 will involve directional changes of some of the joints. This can lead to significant changes in the cumulative friction force, again rendering precise movements difficult to maintain. To overcome or compensate for stiction and the differences between static and dynamic frictional forces is particularly advantageous, since slow precise movements are often employed during a surgical procedure. Compensating for stiction and the static/dynamic differential is also particularly problematic. One reason for this is that available sensors used to measure angular velocity are not entirely accurate so that precisely measuring zero velocity of the joint when at rest is difficult. Another reason is that noise may be superimposed on the sensor signal which further aggravates the problem of measuring zero velocity when the joint is at rest. Thus, when the joint is at rest, the sensors can be registering movement and, consequently, apparent velocity.
[0081] The joint can move in an arbitrary positive and an arbitrary negative direction. The velocity reading may have a negative value, a positive value, or may be fluctuating about the zero velocity reading when the joint is at rest due to the noise and measurement inaccuracies. If the velocity reading is used to determine a frictional compensation force, it is difficult to determine when and in what direction to apply the frictional force since the velocity reading does not correspond with the actual velocity of the joint particularly when the joint is at rest. Even with an accurate velocity measurement, using a sensor which accurately measures zero velocity when the joint is actually at rest, it would still be problematic to apply a frictional compensation force to compensate for stiction since it is not easy to anticipate in which of the arbitrary positive and negative directions the joint will be moved.
[0082] To overcome these problems, and to compensate for stiction in particular whilst accommodating measurement inaccuracies, a velocity region indicated between the arrows X-X is chosen, such that if the velocity reading is within this region, a cyclical torque, varying in a positive and a negative direction is supplied to the motor so that irrespective of the direction in which movement is to be initiated from rest, a friction compensation torque is provided at least part of the time. This will be described in greater detail below.
[0083] The indicated velocity region X-X can be chosen based on measurement accuracy such that outside the region the joint is actually moving whilst inside the region the joint could either be moving very slowly in either direction or may be stationary. Outside the region X-X, it is assumed that the velocity reading does indicate joint movement in a correct direction and that movement has been initiated. A uniform compensating torque is then applied corresponding with the constant friction experienced when movement is achieved, as will be described in greater detail herein below.
[0084] Still referring to FIG. 11 of the drawings, the control system of the invention is arranged to generate compensating values determined by the velocity reading within the region X-X. This can best be explained by means of the slanted dashed line in FIG. 11 . The slanted dashed line DL extends between opposed intersections of the chosen velocity reading region X-X, and the required force for compensating for friction. Naturally, the slanted line need not be linear but could be rounded at its corners, and/or the like. Furthermore, the width of the region between X-X can be tailored to suit the system friction characteristics.
[0085] The friction compensating force values along dashed line DL can be represented as percentages for generating a duty cycle appropriate to a measured velocity. Should the velocity reading be at +v 1 a force value of 100% is generated. Similarly, if the velocity reading is at −v 1 , a value of 0% is generated. In similar fashion a specific value ranging between 0% and 100% is generated depending upon the measured velocity reading position between +v 1 and −v 1 .
[0086] The value thus generated can be used to determine a duty cycle signal distribution between the arbitrary positive and the arbitrary negative direction of movement about the joint 704 B. Thus, where a value of 0% is generated, the reading then being negative, in other words, in an arbitrary negative direction, a duty cycle as indicated in FIG. 12 is generated. The distribution of the duty cycle in FIG. 12 is correspondingly fully negative, or 100% negative. The region X-X can be chosen such that at this point, taking noise and measurement inaccuracies into account, the master may be either about to actually move in the negative direction or may already be moving in the negative direction.
[0087] Similarly, should a value of 20% be generated, for example, a duty cycle as indicated in FIG. 13 is generated. The distribution of the duty cycle in FIG. 13 is correspondingly 20% positive and 80% negative.
[0088] Should a value of 50% be generated, a duty cycle as indicated in FIG. 14 is generated. The distribution of the duty cycle in FIG. 14 is correspondingly 50% positive and 50% negative.
[0089] Similarly, should a value of 80% be generated, a duty cycle as indicated in FIG. 15 is generated. The distribution of the duty cycle in FIG. 15 is correspondingly 80% positive and 20% negative.
[0090] In the case where a value of 100% is generated, a duty cycle as indicated in FIG. 16 is generated. The distribution of the duty cycle in FIG. 16 is correspondingly fully positive, or 100% positive. At this point, taking noise and measurement inaccuracies into account, the master can be either about to actually move in the positive direction or may already be moving in the positive direction.
[0091] It will be appreciated that the duty cycles shown need not necessarily have generally rectangular waveforms.
[0092] It will further be appreciated that when the joint is at rest, the velocity reading is typically fluctuating within the X-X region so that the duty cycle distribution is continually varying.
[0093] The method of compensating for friction will now be described in further detail with reference to FIG. 17 .
[0094] In FIG. 17 , a block diagram indicating steps corresponding to the method of compensating for friction in accordance with the invention is generally indicated by reference numeral 410 .
[0095] The velocity readings as described above are indicated at 412 . The compensating values determined from the velocity readings is indicated at 414 . The compensating values are input to a duty cycle generator such as a PWM generator at 416 . The resultant duty cycle signal distribution is output from the PWM generator.
[0096] It will be appreciated that the steps from 412 to 416 are used to determine only the percentage distribution of the duty cycle signal between the arbitrary negative and positive joint movement directions. This determination is directly related to the velocity measurements between arrows XX. The determination of the amplitude or magnitude of the duty cycle signal will now be described.
[0097] As mentioned earlier, the control system compensates for gravity. The master control 700 is moveable about a pivot at 717 and the pincher formation 706 is connected to the pivot 717 through the joints 704 , 716 and the intervening arm members. The master control 700 as a whole is thus displaceable about the pivot 717 . A horizontal component of the center of gravity varies as the pincher formation 706 is displaced. Accordingly, the torque supplied to an electrical motor operatively associated with the master control 700 and which balances and compensates for gravity also varies. Thus, the gravity compensating torque on the electrical motor is determined in part by the position of the center of gravity. This is indicated schematically in FIG. 20 of the drawings by way of example. In FIG. 20 , it can be seen that the torque required on a motor M 1 to hold an arm A 10 in a position as indicated in solid lines to compensate for gravity is greater than that required to hold the arm in the position indicated in dashed lines. A similar principal applies for each joint of the master control 700 . Naturally, the higher the gravity compensating torque supplied to the motor, the higher the transmission loading on the associated gear train and therefor the higher the frictional force and vice versa.
[0098] Each joint 704 , 716 , 717 may have an actuator, e.g., electric motor, operatively associated therewith to provide for, e.g., force feedback. Furthermore, for each joint employing gravity compensation, a corresponding gravity compensating torque is supplied to the motor operatively associated therewith. The gravity compensation torque magnitude varies depending on master control position. The motor operatively associated with each joint employing gravity compensation can be provided with a friction compensation torque in accordance with the method of the invention. The friction compensation torque magnitude applied to a particular joint varies in accordance with the gravity compensation torque. It will be appreciated that the effects of friction can be negligible on some of the joints. Hence, friction compensation may not be provided for all joints of the master and/or slave.
[0099] The friction compensation loads induced by the gravity compensation system need not, and generally will not, be applied separately. The exemplary friction compensation system described herein incorporates the gravity model, so that the gravity compensation torques become part of the load applied by the friction compensation system. Alternatively, separate gravity compensation and friction compensation loads might be maintained.
[0100] Referring once again to FIG. 17 of the drawings, a gravity compensating model is indicated at 418 whereby gravity compensation forces for the joints requiring gravity compensation are determined. For each of the joints 704 , 716 , 717 employing gravity compensation, the gravity compensation model determines the torque which can hold the part of the master control 700 extending from that joint in the direction of the pincher formation 706 in a stationary position. Naturally, this torque varies for each joint in sympathy with positional variation of that joint as the master control 700 is moved from one position to a next position.
[0101] Referring now to FIG. 18 of the drawings, the gravity and friction (efficiency) model 418 will now be described in greater detail. From the gravity model, indicated at 419 , the magnitude of a desired gravity compensating force for the joint, e.g., joint 704 B, is determined. The gravity compensating force is then forwarded to a friction compensation determining block 451 for determining friction compensation in the arbitrary positive joint movement direction as indicated by line 452 . The gravity compensation force is also forwarded to a friction compensation determining block 453 for determining friction compensation in the arbitrary negative joint movement direction as indicated by line 454 .
[0102] In the block 451 , the magnitude of the gravity compensating force is represented along a horizontally extending axis and the corresponding required frictional compensating force for the positive joint movement direction is represented along a vertically extending axis. The corresponding frictional compensating force is determined taking the gear train efficiency into account as indicated by the lines 1/eff and eff, respectively (eff being efficiency, typically less than 1).
[0103] In similar fashion, in the block 453 , the magnitude of the gravity compensating force is represented along a horizontally extending axis and the corresponding required frictional compensating force for the negative joint movement direction is represented along a vertically extending axis. The corresponding frictional compensating force is determined taking the gear train efficiency into account as indicated by the lines 1/eff and eff, respectively.
[0104] The magnitudes of the frictional compensating forces in respectively the positive and the negative joint movement directions determined in the blocks 451 , 453 represent the magnitudes of the frictional forces in respectively the positive and negative joint movement directions after movement of the joint has been initiated. Thus, they correspond with the lines 114 in FIG. 11 of the drawings.
[0105] The magnitude of these forces are used to determine the amplitude of the duty cycle signal at 416 . Thus, from 414 the percentage distribution between the arbitrary positive and negative directions were determined, and from the gravity model at 418 , the magnitude or amplitude of the duty cycle signal is determined for each arbitrary positive and negative joint movement direction. It will be appreciated that these magnitudes correspond to dynamic friction compensating forces. Depending on actual joint position, these compensating forces can be dissimilar.
[0106] As mentioned earlier, overcoming friction when at rest involves a higher force than is applied to maintain movement. This characteristic of friction is compensated for at 420 when the velocity reading lies in the region Y-Y as indicated (also designated as the region between −V 2 and V 2 ). The force which can cause an object, in this case the meshing gears of the gear train, to break away from a rest position is typically some factor higher than 1, often being about 1.6 times the force to maintain movement after movement is achieved. This factor can vary depending on the application. In this case, the factor or ratio corresponds to the relationship between the force which will overcome friction in the gear train when at rest and to maintain movement in the gear train once movement has been initiated. More specifically, the ratio corresponds to the change in efficiency of the gear train when at rest versus when in motion. It will be appreciated that at 420 , the ratio and effective range Y-Y can be tailored to suit a specific application. The range Y-Y could correspond with the range X-X, for example.
[0107] Referring now to 420 in greater detail, and assuming the region Y-Y corresponds with the region X-X, at 0% and 100% values, a factor of 1 is generated. At a 50% value a maximum factor is generated. Between 50% and 100% and between 50% and 0% a linear relationship between the maximum factor value, in one example 1.6, and the minimum factor value, namely 1, is established. Thus, at a value of 75% or 25% a factor of 1.3 would be generated. It will be appreciated that the relationship need not necessarily be linear.
[0108] The factor ranging between 1 and the maximum factor determined at 420 from the velocity reading is then output or forwarded to factoring or adjusting blocks at 422 and 421 , respectively.
[0109] The friction compensation force for movement in the positive joint direction is input to the block 422 as indicated by line 424 . In the block 422 , this friction compensation value is indicated along the horizontal axis. The actual friction compensation force magnitude to compensate for stictions is indicated along the vertical axis. The value of the factor is indicated by the letters “fac.” This value determines the relationship between the actual required friction compensation forces and the friction force requiring compensation when movement in the positive joint direction is achieved. Thus, the value fac determines the gradient of the lines indicated by fac and 1/fac, respectively. Naturally, when fac=1, the lines fac and 1/fac extend at 45° resulting in the actual required friction being equal to the friction requiring compensation. This corresponds with a condition in which the velocity reading is outside or equal to the outer limits of the Y-Y region. It will be appreciated that at 421 , a similar adjustment takes place for friction compensation force in the negative direction.
[0110] It will be appreciated that a larger force to compensate for friction in one direction may be required than in the opposed direction, in particular because our compensation torque here indicates both friction compensation torque and gravity compensation torque. This depends on the actual position of the joint. Normally, to cause the arm member extending from the joint toward the pincher formation 706 to move in an operatively downward direction requires less friction compensation torque than moving it in an operatively upward direction. Thus, should the arbitrary positive joint movement direction correspond with an upward movement, a greater frictional compensating force is required than that in the arbitrary negative direction, and vice versa. Thus, the amplitude of the duty cycle can be higher or lower on the positive side than the negative side depending on the position of the joint, and whether the arbitrary positive joint movement direction corresponds with an upward or downward movement of the arm member extending from the joint. Indeed, the “positive” compensation load need not be in the positive direction and the “negative” load need not be in the negative direction, although the positive load will be greater than or equal to the negative load.
[0111] After the friction compensation force magnitudes have been determined in this manner, they are forwarded to the PWM signal generator at 416 as indicated by lines 462 and 464 , respectively. At the PWM signal generator, the force magnitudes are combined with the duty cycle distribution signal determined at 414 to determine a resultant duty cycle signal as indicated at 466 . The resultant duty cycle signal 466 is then passed from the PWM signal generator along line 468 .
[0112] The duty cycle signal thus determined by the PWM signal generator 416 by combining outputs from 414 , 421 and 422 is then passed to an amplifier so that the required electrical current can be passed to the electrical motor operatively associated with the joint 704 B so as to generate corresponding cyclical torques on that motor.
[0113] The frequency of the duty cycle output from 416 is predetermined so as to be low enough to enable the electrical motor to respond and high enough so as not to be felt mechanically. Thus, the frequency is greater than the mechanical time constants of the system yet less than the electrical time constants of the electric motor. A suitable frequency in the exemplary telesurgical system falls in the range between 40 Hz to 70 Hz, preferably about 55 Hz.
[0114] It will be appreciated that where it is possible accurately to read zero velocity when the master control 700 is at rest, the above method of compensating for friction can also be used. For example, when the master control 700 is stationary and a zero velocity reading is measured, a duty cycle is forwarded to the motors, the duty cycle having a magnitude corresponding to the required frictional compensating force and having a 50% distribution. Thus, when an external force is applied to the hand control by the surgeon in a specific direction, a friction compensating force is delivered 50% of the time to assist in initiating movement of the master control 700 , thus to compensate for stiction. As movement is then induced and the velocity reading increases in a specific direction, the distribution of the cycle changes in a direction corresponding to the direction of movement of the master control. Eventually, when the master control is being moved at a velocity corresponding to a velocity reading outside the range XX, the compensating force, or torque to the motors, is distributed 100% in a direction corresponding to the direction of movement of the master control. The duty cycle has a predetermined frequency so that, irrespective of the direction of required movement induced on the master control 700 when the master control 700 is moved, e.g., by the surgeon's hand, a corresponding friction compensating force is supplied at a percentage of the time determined by the velocity reading. The effect of this is that during movement initiation, the sticking sensation is compensated for. This enables smooth precision movements to be induced on the master control without sticking, particularly at small velocities.
[0115] As mentioned, the method of compensating for friction is not limited to friction resulting from gravity compensation. In other words, gravity model might be replaced by some other controller determining torques to be applied to the motors for another purpose. The method can be used to compensate for friction per se.
[0116] Referring now to FIG. 19 , a method of compensating for friction as applied to friction per se will now be described. The method is similar to the method described above with reference to gravity compensation. However, in this case, the gravity model is replaced by a Coulomb friction model which provides a fixed compensating friction value in the arbitrary positive and negative joint movement directions. The fixed compensating friction can be set to correspond with an actual constant friction value for friction compensation as defined by actual system parameters. The adjustment factor simply may multiply these fixed values in 421 and 422 . This method can be used to overcome actual friction in the joint itself, for example, should the friction in the joint require compensation. In other respects, the method of compensating for friction, and stiction, as discussed above applies. Hence, this method can be combined with the system described above or with another gravity and/or friction model using appropriate adjustments 421 and 422 .
[0117] While the exemplary embodiment has been described in some detail, by way of example and for clarity of understanding, a variety of changes and modifications will be obvious to those of skill in the art. Hence, the scope of the present invention is limited solely by the appended claims. | Devices, systems, and methods for compensate for friction within powered automatic systems, particularly for telesurgery and other telepresence applications. Dynamic friction compensation may comprise applying a continuous load in the direction of movement of a joint, and static friction compensation may comprise applying alternating loads in positive and negative joint actuation directions whenever the joint velocity reading falls within a low velocity range. | 0 |
The present disclosure relates to a tracheal catheter or tube used for mechanical ventilation of a hospital patient, by insertion of the tube into the trachea of the patient. In particular, the present disclosure relates to a tracheal tube having means for irrigating and/or evacuating contaminated secretions accumulating above the tracheal tube cuff and thereby reducing the risk of such contaminated secretions entering the lungs of the patient.
There are two principle types of tracheal catheters or tubes; the endotracheal tube (ET tube) and the tracheostomy tube (trach tube). The ET tube is inserted through the mouth of a patient and guided past the vocal cords and glottis into the trachea. The trach tube is inserted directly into the trachea through a stoma created in the throat and the tracheal wall by surgical means and enters the trachea below is the glottis. Both types of tube have a relatively large main ventilating lumen that delivers the air from a mechanical ventilating device to the lungs. Both types of tubes typically terminate at a position above the carina, anterior to a position between the second and fourth thoracic vertebrate. Gases may then be introduced through the tracheal tube and into the lungs of the patient.
The primary purposes of tracheal intubation, are to mechanically ventilate the patient's lungs, when a disease prevents the patient from normal, breathing induced ventilation, or to apply anesthetic gases during surgical intervention. In order to create enough air pressure to accomplish such mechanical ventilation and to prevent escape of gases past the tube, it is necessary to seal the passageway around the tracheal tube. A seal may be produced by the use of an inflatable cuff or balloon formed integrally with and surrounding the tracheal tube. When the tracheal tube has been introduced into the patient's trachea, the inflatable cuff will normally be located about 3 to 5 centimeters above the carina and within the tube-like trachea.
The inflatable cuff is then inflated so as to engage the wall of the trachea and thereby seal the trachea and prevent gases being introduced through the tracheal tube from simply turning back up around the tube and passing out of the patients mouth and nose. While treatment of this sort has proved successful for patients having chronic or acute respiratory diseases, there is a constant risk of several complications.
In particular, many patients receiving tracheal intubation develop pneumonia, resulting from an infection of the lungs, possibly induced by contaminated, pooled secretions entering the trachea and the lungs after bypassing the inflatable cuff during intubation. This problem, ventilator acquired pneumonia or VAP, occurs with ET and trach tubes. It is more frequent in the case of ET tubes since when an ET tube is in place the epiglottis, which normally operates as a valve that selectively closes the entry into the trachea and lungs to prevent the introduction of secretions and particulate matter, is held in an open position and secretions which would normally be directed away from the trachea and into the digestive system, instead follow the path of the ET tube and pool above the inflatable cuff of the tracheal tube.
There is a risk of the infectious secretions reaching the lungs during the intubation, by aspiration of the secretions that are able to get past the tracheal tube cuff. However, the greatest risk of such infectious secretions reaching the lungs is upon the cessation of mechanical ventilation. In particular, when the need for tracheal intubation ends, the inflatable cuff of the tracheal tube is deflated so that the tracheal tube may be withdrawn from the patient. The infectious secretions which have pooled above the inflatable cuff are then released and are free to flow into the lungs, where bronchitis or pneumonia may rapidly develop.
To overcome these risks, it is known in the prior art to combine a single suction tube or lumen with a tracheal tube. The suction lumen is joined to the tracheal tube in a suitable manner, the end of the suction lumen terminating at a port in a position above the inflatable cuff. The suction lumen provides means for suction or evacuation of any pooled secretions which accumulate in the trachea above the inflatable cuff. Such prior art devices have the disadvantage that the suction lumen must terminate some distance above the upper or proximal shoulder of the cuff in order to allow for the attachment of the cuff to the tracheal tube body. This distance allows some volume of secretions to be, in effect, unreachable by the suction lumen. In addition, since the suction lumen port is spaced a distance from the cuff, such prior art tubes can allow the suction lumen port to adhere to the tracheal wall during suctioning, causing trauma to the tracheal wall and occluding the suction lumen port.
U.S. Pat. No. 4,840,173 to Porter III, describes an ET tube having a single suction tube merged thereto. In particular, this patent describes a device wherein the suction tube is laminated to the outside of the ventilation tube, so that the suction tube terminates at a position just above the inflatable cuff. The suction tube includes multiple openings which may be used to evacuate secretions which pool above the inflatable cuff. In addition, the inflatable cuff includes a section immediately adjacent to the end of the suction tube that is less flexible than the rest of the inflatable cuff, to ensure that the flexible material of the inflatable cuff is not sucked up against the suction tube openings. The tracheal tube described in the Porter III patent has the disadvantages noted above, that the single lumen suction tube terminates a distance above the upper surface of the cuff, allowing a certain volume of secretions to is remain above the cuff, even after suctioning.
US patent publication 2008/0053454 to Pasillas et al. describes an ET tube wherein the cuff is attached to the tube so that the proximal collar of the cuff is partially inverted, producing a double thickness collar. The publication teaches that this double thickness collar may help reduce or eliminate possible occlusion of the port and may help prevent the port from coming in contact with the tracheal wall.
What is needed is a tracheal catheter capable of suctioning secretions that have pooled above the inflatable cuff, more thoroughly than has been the case so far, with less chance that it will cause trauma to the tracheal wall.
SUMMARY
The present disclosure improves upon a tracheal catheter by attaching the cuff to the tube in a manner that overlays or covers part of the suction port. Part of the collar of the cuff may actually be located partially inside the suction lumen port, without obstructing the part of the suction lumen proximal to the suction lumen port. The proximal collar of the cuff may also block the part of the suction lumen that is distal to the port, instead of merely laying in or on the port.
In one embodiment, the tracheal tube is formed from a flexible cannula having a length, a distal end, and a proximal end. The cannula consists of a plurality of walls extending substantially along the length of the cannula, dividing the cannula into a plurality of separate lumens including a respiratory lumen, a suction lumen, a rinse lumen, and an inflation lumen. An inflatable cuff surrounds the cannula proximal to the distal end. The inflatable cuff is adapted to seal the trachea of a patient. The inflation lumen is in fluid communication with the inflatable cuff. The cuff is attached so that an upper part (collar) of the cuff partially overlays the suction lumen port. This allows the port to be located closer to the cuff and so provides better liquid removal and reduces the possibility that the tube may suck itself onto the tracheal wall.
Other objects, advantages and applications of the present disclosure will be made clear by the following detailed description of a preferred embodiment of the disclosure and the accompanying drawings wherein reference numerals refer to like is or equivalent structures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view of an ET tube of the prior art.
FIG. 2 is a cross-sectional view of the area of attachment of the cuff to the tube of FIG. 1 .
FIG. 3 is a cross-sectional view of the area of attachment of the cuff to the tube of according to this disclosure.
FIG. 4 is a close-up side view of the suction port of FIG. 3 .
FIG. 5 is a frontal close-up view of the suction port according to this disclosure.
DETAILED DESCRIPTION
Reference will now be made to the drawings in which the various elements of the present disclosure will be given numeral designations and in which the disclosure will be discussed so as to enable one skilled in the art to make and use the disclosure. It is to be understood that the following description is only exemplary of the principles of the present disclosure, and should not be viewed as narrowing the pending claims. In particular, though most references herein are to an ET tube since the problem of aspirated secretions is greater when using ET tubes, these teachings apply equally to trach tubes. Those skilled in the art will appreciate that aspects of the various embodiments discussed may be interchanged and modified without departing from the scope and spirit of the disclosure.
In manufacturing a tracheal tube, the main cannula is generally extruded by conventional means. As it is extruded in a never ending tube, the cannula is given three lumens; the main respiratory lumen, a cuff inflation lumen, and a suction lumen, separated by internal walls. There may be more lumens extruded into the cannula for additional functions, but the three recited are the lumens of concern for this disclosure. These lumens extruded into the cannula extend the entire length of the cannula. Once the cannula is cut to the proper length, the cuff inflation port and the suction port are located and “skived” or cut out, a technique that is well known to those skilled in the art. This allows liquid communication of each lumen (suction and inflation) through the wall of the cannula to its respective port, opening into the space outside the cannula. The remaining distal portion of the cuff inflation and suction lumens are then blocked below the skived port, generally with a sealing plug. The respiratory lumen extends the entire length of the cannula and is not skived out.
Turning to the drawings, FIG. 1 illustrates a prior art ET tube 10 including an inflatable cuff 12 . Tube 10 includes a cannula 16 having an open proximal end 18 and an open distal end 20 . The cannula 16 defines a gas-conveying lumen 22 for mechanical ventilation of a patient. The proximal end 18 usually includes a connector 24 configured for attachment to a mechanical ventilator (not shown). An inflatable cuff 12 is mounted on the cannula 16 adjacent the distal end 20 of the cannula 16 , covering the skived out inflation lumen port(s) 31 . The cuff 12 is mounted on the cannula 16 by one or more collars. In FIG. 1 , cuff 12 may be mounted on cannula 16 by a first or proximal collar 26 and a second or distal collar 28 . During the insertion of the tube 10 , the cuff 12 is at least partially collapsed. Once properly in place, the cuff 12 may be inflated via an inflation lumen 30 and cuff inflation port(s) 31 formed in or otherwise associated with the cannula 16 . The inflation lumen 30 may be coupled to an inflation line 32 terminating at its proximal end in a fitting 34 that allows inflation of the cuff 12 via the inflation lumen 30 and cuff inflation port(s) 31 . The cannula also includes a suction lumen 36 formed in or otherwise associated with the cannula 16 . The suction lumen 36 is in liquid communication with a suction lumen port 38 extending through the wall of the cannula 16 through which secretions or other matter accumulated on or proximate the cuff 12 may be removed. The suction lumen 36 extends to the distal end 20 of tubular body 16 and usually includes a sealing plug 39 . The suction lumen 36 may be blocked by the sealing plug 39 before the distal end 20 of tubular body 16 or just beyond opening 38 . An exterior suction tube 40 is connected to the suction lumen 36 for removing secretions or other matter through the port 38 . The suction tube 40 may include an end fixture 42 for attachment to a source of suction (not shown) including a cap 44 .
Referring to FIG. 2 , a cross-sectional view of the cuff 12 and the area of is attachment of the collars 26 , 28 to the cannula 16 of FIG. 1 is shown. Both collars 26 , 28 are attached around the cannula 16 and sealed and the suction port 38 is spaced some distance from the proximal collar 26 . There may be a sealing plug 39 in the suction lumen 36 , located distally of the port 38 .
FIG. 3 is a cross-sectional view of the cuff and area of attachment of an embodiment of the disclosed device. In some respects it is similar to the device of FIG. 2 , however, the placement of the port 38 and the attachment of the proximal collar 26 are quite different. In this embodiment, a portion of the proximal cuff collar 26 partially covers or overlays the suction lumen port 38 . Part of the collar 26 may actually be located partially inside the port 38 , without obstructing the liquid communication between the port 38 and the suction lumen 36 proximal to the port 38 . This allows the port 38 to be located very close to the cuff 12 which should provide for more thorough suctioning of secretions from the subglottic space above the cuff.
The proximal collar 26 may also block the part of the suction lumen 36 that is distal to the port 38 , instead of merely laying in or on the port 38 . Purposely occluding the suction lumen 36 in this manner makes the sealing plug 39 unnecessary, though it may still be used to ensure that the suction lumen 36 distal to the suction port 38 is completely sealed.
FIG. 4 is a close-up side view of the suction port at the circle 4 of FIG. 3 . In this view, the proximal part of the suction lumen 36 is open just above the cuff 12 and communicates with the suction lumen port 38 . The proximal collar 26 is attached to the cannula 16 in a manner that allows it to enter the port 38 . It may block the distal part of the suction lumen 36 . Since the collar 26 enters into the distal or lower portion of the open port 38 , it affects only the part of the suction lumen 36 distal to the port 38 while still allowing liquid communication between the proximal portion of the suction lumen 36 with the port 38 .
FIG. 5 shows a frontal close-up view of the suction lumen port 38 , partially is covered by the collar 26 . The proximal part of the suction lumen 36 is in liquid communication with the suction lumen port 38 . Note, in FIGS. 2-5 the distal direction is to the left of the drawings. It should also be noted that although the port 38 shown in FIG. 5 is oval shaped, the depicted shape is not meant as a limitation. The port may be round, square or any other shape that is functional.
The tracheal tube of the embodiments shown in FIGS. 3-5 and described above allows for the suction lumen port to be placed in close proximity to the inflatable cuff. This allows for better, more thorough suctioning of secretions from the subglottic space. This also reduces the likelihood that the suction port will attach to the tracheal wall during the application of suction, and so reduces the chance of tracheal trauma.
The collar 26 is usually attached to the cannula 16 with an adhesive. A suitable adhesive is available from Dymax Corporation of Torrington, Conn. as item number 1163-M#F0024-FH076 though other suitable adhesives are available. This Dymax adhesive is an ultra-violet curable adhesive. Other methods of attaching the collars to the cannula may also be used. These include thermal bonding, solvent bonding, radio frequency and ultrasonic bonding and other means known to those skilled in the art.
In order to minimize leakage past the cuff and into the lungs, the disclosed tracheal tube desirably uses an improved cuff design. A tracheal tube using the cuffs taught in U.S. Pat. No. 6,526,977 or 6,802,317 results in much less leakage past the cuff into the lungs than conventional thick cuffs allow. The '977 and '317 cuffs are desirably made from a soft, pliable polymer such as polyurethane, polyethylene teraphihalate (PETP), low-density polyethylene (LDPE), polyvinyl chloride (PVC), polyurethane (PU) or polyolefin. The cuff should be very thin; with a thickness on the order of 25 microns or less, e.g. 20 microns, 15 microns, 10 microns or even as low as 5 microns in thickness, though at least 1 micron. The cuff should also desirably be a low pressure cuff operating at an inflation pressure of about 30 mmH 2 O or less, such as 25 mmH 2 O, 20 mmH 2 O, 15 mmH 2 O or less.
U.S. Pat. No. 6,802,317 describes a tracheal tube for obturating a patient's trachea as hermetically as possible, comprising: a cuffed balloon which blocks the trachea below a patient's glottis, an air tube, the cuffed balloon being attached to the air tube and being sized to be larger than a tracheal diameter when in a fully inflated state and being made of a soft, flexible foil material that forms at least one draped fold in the cuffed balloon when inflated in the patient's trachea, wherein the foil has a wall thickness below or equal to 0.01 mm and the at least one draped fold has a loop found at a dead end of the at least one draped fold, that loop having a small diameter which inhibits a free flow of secretions through the loop of the at least one draped fold.
U.S. Pat. No. 6,526,977 teaches a cuff for obturating a patient's trachea as hermetically as possible, comprising a cuffed balloon which blocks the trachea below a patient's glottis, an air tube, the cuffed balloon being attached to the air tube and being sized to be larger than a tracheal diameter when in a fully inflated state and being made of a sufficiently soft, flexible foil material that forms at least one draped fold in the cuffed balloon when fully inflated in the patient's trachea, wherein the at least one draped fold formed has a capillary size which arrests free flow of secretions across the balloon by virtue of capillary forces formed within the fold to prevent aspiration of the secretions and subsequent infections related to secretion aspiration.
Since the '977 and 317 cuffs inhibit or arrest the free flow of secretion past the cuff, the secretions build up above the cuff and discontinuous or intermittent suctioning may be used. Intermittent suctioning is safer for the tracheal wall since it reduces the chance that the suction lumen inlet will adhere to the wall and subject it to the force of suction.
At the discretion of the caregiver and particularly immediately prior to removal of the tracheal tube, the subglottic space within the patient's trachea may be suctioned through the suction lumen 36 via the port 38 through the wall 25 of the cannula 16 . During this process, ventilation of the patient through the respiratory gas-conveying lumen 22 may of course continue unaffected.
Other arrangements are included in the spirit and scope of the disclosure. For example, the layout of the lumens within the cannula 16 may be altered, moreover, the suction lumen 36 may be formed in another wall or it may be a self contained lumen not embedded within any one of the walls of the cannula 16 . In addition, as alluded to above, other lumens may be present in the cannula 16 , such as rinse lumens to deliver fluid to loosen or dilute thick secretions prior to suctioning or lumens to deliver anesthesia or other medicaments. These additional lumens are not depicted though are understood by those skilled in the art.
As used herein and in the claims, the term “comprising” is inclusive or open-ended and does not exclude additional unrecited elements, compositional components, or method steps.
While various patents have been incorporated herein by reference, to the extent there is any inconsistency between incorporated material and that of the written specification, the written specification shall control. In addition, while the disclosure has been described in detail with respect to specific embodiments thereof, it will be apparent to those skilled in the art that various alterations, modifications and other changes may be made to the disclosure without departing from the spirit and scope of the present disclosure. It is therefore intended that the claims cover all such modifications, alterations and other changes encompassed by the appended claims. | Endotracheal and tracheostomy tubes have an inflatable cuff for sealing the trachea so that a patient may be ventilated through a respiratory lumen of the tube. As a result of sealing the trachea outside of the tube, liquids accumulate above the cuff. If these liquids are allowed to move into the lungs, they may cause ventilator acquired pneumonia (VAP). The liquids may be removed by suction applied to a suction lumen terminating in a port above the cuff, but suctioning can cause damage to the trachea if the tube is sucked up against the tracheal wall. A tracheal catheter having a unique method of attaching the balloon cuff is provided. The cuff is to attached so that an upper part (collar) of the cuff is used to cover the distal end of a suction lumen port. This allows the port to be located closer to the cuff and so provides more thorough liquid removal and reduces the possibility that the tube may suck itself onto the tracheal wall. | 0 |
FIELD OF THE INVENTION
[0001] This invention relates to a flame resistant bag, and particularly relates to a heat-resistant and refractory bag.
BACKGROUND OF THE INVENTION
[0002] In an accident of fire, our precious treasure such as jewelry and important personal property such as ID card and data disk is in the risk of damage. If not kept in safe, it is almost impossible not to be destroyed. Moreover, in an extremely dangerous situation of fire accident, people are usually too panic to immediately find a flame resistant device to protect the personal property from fire. Therefore, the present invention provides a flame resistant bag not only for keep the personal property but also for protecting human life from heat and fire.
SUMMARY OF THE INVENTION
[0003] The object of the present invention is to provide a storage bag that is flame resistant, lifesaving, and easy carry. In a regular day, it is an easy carry storage bag. In an accident of fire having a big fire and high temperature, the flame resistant bag of the present invention provides users another chance to save our property and our lives in such a delicate situation.
[0004] In order to achieve the above object, the present invention provides A flame resistant bag comprising a bag body and a flame resistant block within the bag body, wherein from inner to outer, the bag body comprises: a first flame resistant layer, a thermal insulating layer, and a second flame resistant layer, wherein the inner surface of the second flame resistant layer is coated with a coating layer, and the flame resistant block is for enhancing effect of preventing heat and fire from incursion to the bag body, and the flame resistant block is either a flame resistant zipper or a flame resistant easy tape, and the bag body is a single bag or is separated to multiple bags, and joint in the bag body is sewed with a flame resistant thread.
[0005] In another viewpoint of the present invention, the present invention provides a flame resistant bag, wherein when the flame resistant block is located in position closed to an opening of the bag body, straps are installed on the back of the bag body, when the flame resistant block is located in position far from the opening of the bag body, a flame resistant rope is installed around the opening of the bag body, in one end of the flame resistant rope, a fixer is located to fix the flame resistant rope after the flame resistant rope is pulled to close the opening of the bag body, an aluminum layer is arranged between the first flame resistant layer and the thermal insulating layer, and a bag cover is installed on the opening edge of the bag body so as to substantially cover the opening after the bag cover is fixed on the opening.
[0006] In another viewpoint of the present invention, the present invention provides a flame resistant bag, wherein there provides an emergency bag on the back of the bag body to keep an emergency blanket inside. A flame resistant soft fabric cloth extends from the opening edge of the bag body to cover the flame resistant rope therein. A plurality of holes in the opening edge are installed to have the flame resistant rope passing through therein. The bag cover is fixed by means of a flame resistant strap and a metal ring, or by means of flame resistant easy tapes when the flame resistant rope is installed, straps is set up on back of the bag body, and a handle is set up on the opening edge of the bag body.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1( a ), FIG. 1( b ), FIG. 1( c ), FIG. 1( d ) are embodiments of flame resistant bag of the present invention.
[0008] FIG. 2 shows a structure from inner to outer surface of the bag body 2 of the present invention.
[0009] FIG. 3 and FIG. 4 show a flame resistant rope of the present invention.
[0010] FIG. 5 and FIG. 6 show a bag cover of the present invention.
[0011] FIG. 7 shows an emergency bag 71 on the back of the bag body 2 of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0012] In FIG. 1( a ), FIG. 1( b ), FIG. 1( c ), FIG. 1( d ), a flame resistant bag 1 of the present invention comprises a bag body 2 , and a flame resistant block 3 within the bag body 2 . In FIG. 1( a ) and FIG. 1( c ), the flame resistant block 3 is a flame resistant easy tape 3 a. In FIG. 1( b ) and FIG. 1( d ), the flame resistant block 3 is a flame resistant zipper 3 b. The flame resistant block is for enhancing the effect to prevent from the incursion of fire.
[0013] The bag body is made of heat-resistant and refractory material, such as Dupont's Nomax, Kevlar, but not limited to these, which can withstand high temperature of even more than 1000° C. The structure from inner to outer surface of the bag body 2 as shown in FIG. 2 is composed of: (1) a first layer 201 which is a first flame resistant layer made of glass fibers, oxidized fibers, silica fabric, TEFLON, ceramic fiber, NOMAX, KEVLAR or the combination thereof by means of blending and weaving these fibers according to a range between 250° C. and 2000° C.; (2) a second layer 202 , which is a layer of aluminum material optionally coated on the first layer 201 to enhance the refractory effect; (3) a third layer 203 which is thermal insulating material used as a block layer for air permeability, flame retarding and fire refractory with refractory temperature within 1000° C.; and (4) a fourth layer 204 which is a second flame resistant layer taken as a lining layer made of flame resistant material same as the first layer 201 or non-flame-protecting material for protecting the inside product. The inner surface, i.e., the surface toward the third layer 203 , of the fourth layer 204 is optically coated with a coating layer taken as a waterproof layer made of aluminum, PVC, Teflon, silicone, PU material (not shown in FIG. 2 ) so as to enhance the refractory effect and prevent from incursion of water. In the above structure, the bag body 2 will not be easily destroyed by high temperature or flame in a short time. Any joint 6 of the bag body 2 is sewed with flame resistant thread. Thus the first layer 201 and the fourth layer 204 which are both flame-protecting layers withstand high temperature. The third layer 203 which is thermal insulating material dissipates the heat.
[0014] When the flame resistant block 3 is located in position A closed to an opening of the bag body as shown in FIG. 1( a ) and FIG. 1( b ), straps 5 a , 5 b are installed on the back of the bag body. When the flame resistant block 3 is located in position B far from the opening of the bag body as shown in FIG. 1( c ) and FIG. 1( d ), a flame resistant rope 5 c , 5 d is installed around the opening of the bag body.
[0015] The flame resistant rope 5 c, 5 d is either installed as single-side flame resistant rope, as shown in FIG. 1( c ) and FIG. 1( d ) or installed on opposite sides of the opening such as on the left side and right side (not shown).
[0016] The bag body 2 inside the flame resistant block 3 can be a single bag or be separated as multiple bags 21 , 22 by means of flame resistant thread as shown by dot lines in the figure, wherein the joint C is sewed by the flame resistant thread.
[0017] FIG. 3 and FIG. 4 shows two embodiments of the flame resistant rope 32 . In FIG. 3 , it shows a soft fabric cloth 31 extending from the opening. The flame resistant rope 32 is covered within and by the soft fabric cloth 31 . There is a flame resistant fixer 33 such as a buckle to fix the flame resistant rope 32 after being tight. In FIG. 4 , it shows a plurality of holes 41 in the opening to have the flame resistant rope 42 passing therethrough. In one end of the flame resistant rope, a fixer 43 such as a buckle is located to fix the flame resistant rope 42 after the flame resistant rope 42 is pulled to close the opening of the bag body. An aluminum layer 202 is optically arranged between the first flame resistant layer 201 and the thermal insulating layer 203 to further enhance the refractory effect.
[0018] FIG. 5 and FIG. 6 show a bag cover 51 of the present invention. After the flame resistant rope 52 is tight to close the opening (element 34 in FIG. 3 and element 44 in FIG. 4 ), the bag cover 51 is used to cover the opening. In FIG. 5 , a flame resistant strap 53 and a buckle 54 are used to fix the bag cover 51 with a flame resistant easy tape 55 . In FIG. 6 , a plurality of flame resistant easy tapes 61 are provided to fix the bag cover. The bag cover is made of flame resistant material.
[0019] In FIG. 7 , there provides an emergency bag 71 on the back of the bag body 2 . In FIG. 7 , the opening of the emergency bag 71 is installed with a flame resistant zipper, but not limit to this. The emergency bag 71 is provided to keep a folded flame resistant detachable carpet inside (not shown). The folded flame resistant detachable carpet consititued of a flame-protecting fabric layer only is kept in the emergency bag 71 so that when it is in a fire a user can immediately use that flame resistant detachable carpet in the emergency bag 71 to cover human body to preventing from fire and high temperature heat. A flame resistant handle 72 is provided for handling the flame resistant bag.
[0020] It should be understood by those skilled in the art that various modifications, combinations, sub-combinations and alternations may occur depending on design requirements and other factors insofar as they are within the scope of the appended claims or the equivalents thereof. | The object of the present invention is to provide a flame resistant storage bag that is flame resistant, lifesaving, and easy carry. The present invention provides a flame resistant bag comprising a bag body and a flame resistant block within the bag body, wherein the bag body comprises: a first flame resistant layer, a thermal insulating layer, and a second flame resistant layer, wherein the inner surface of the second flame resistant layer is coated with a coating layer. | 0 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application is a Continuation in Part of co-pending U.S. patent application Ser. No. 15/247,049 filed on Aug. 25, 2016, entitled “PROCESS FOR MAKING HIGH MOLECULAR WEIGHT TETRAPOLYMER AND ARTICLES PRODUCED THEREFROM”, which is a Continuation in Part of co-pending U.S. patent application Ser. No. 15/235,971 filed on Aug. 12, 2016, entitled “PROCESS FOR MAKING DAMPING HIGH STRENGTH ETHYLENE PROPYLENE DIENE POLYMER”. These references are hereby incorporated in their entirety.
FIELD
The present embodiments generally relate to a process for continuously forming a tetrapolymer for use in anti-vibration applications using two reactors in series and one or two metallocene catalyst systems.
BACKGROUND
A need exists for a continuous, limited fouling process to create a tetrapolymer with high strength polymer, high density impact absorbance, and high heat resistance using two reactors in series.
A need exists for a process to create a low damping high strength polymer with a significant degree of long chain branching, a high degree of diene content, a branched molecular structure, and favorable elasticity characteristics.
The present embodiments meet these needs.
BRIEF DESCRIPTION OF THE DRAWINGS
The detailed description will be better understood in conjunction with the accompanying drawing as follows:
FIG. 1 depicts examples of tetrapolymers that can be prepared by the processes according to one or more embodiments.
The present embodiments are detailed below with reference to the listed FIGURE.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Before explaining the present process in detail, it is to be understood that the process is not limited to the particular embodiments and that it can be practiced or carried out in various ways.
The embodiments generally relates to a continuous process for making an ethylene propylene diene polymer utilizing ethylene, propylene, and diene monomers in two reactors connected in series with the first reactor containing a metallocene catalyst and the second reactor containing the same or different metallocene catalyst.
The process enables a person ordinarily skilled in the art to create an ethylene propylene diene polymer containing high diene content without reactor fouling due to gelling (or uncontrolled branching reactions).
The process further allows generating an ethylene propylene diene polymer with high degrees of long chain branching, a high molecular weight, a broad molecular weight distribution (MWD), a low tangent delta, and a high diene content while making use of known catalyst and two reactors in series.
Use of two reactors in series eliminates the need for a blending process, to combine two ethylene propylene diene polymers with different compositions and molecular weight distributions into a single polymer product enabling faster processing than other known processes.
No post reactor blending is needed with this new process.
The final high molecular weight tetrapolymer product contains ethylene propylene diene monomer (EPDM) polymer with high molecular weight having a very high state of cure with a lower diene content than previously developed EPDM polymers.
Stronger polymers provide improved mechanical properties, particularly for anti-vibration purposes.
The term “diene” as used herein can refer to an organic compound containing two double bonds. Usable dienes can be those that are capable of being polymerized by metallocene catalysts. In embodiments, the metallocene is a zirconocene or hafnocene.
The term “high molecular weight” as used herein can refer to an EPDM polymer with molecular weights as described below:
Mn>350,000 Dalton
Mw>500,000 Dalton
wherein Mn is defined as number average molecular weight, Mw is defined as weight average molecular weight.
The term “molecular weight distribution” or (MWD) as used herein can refer to the weight average molecular weight of a polymer (Mw) divided by the number average molecular weight of a polymer (Mn). Mw and Mn are determined as follows:
M
n
=
∑
i
N
i
M
i
∑
i
N
i
and
M
w
=
∑
i
N
i
M
i
2
∑
i
N
i
M
i
The term “tangent delta” as used herein can refer to a measure of the relationship between viscosity and elasticity that is known to those ordinarily skilled in the art.
The descriptions below make use of norbornene derivatives as the diene for exemplary reasons. In particular, vinyl norbornene is usable herein. However, other dienes with similar chemical and reactive characteristics can be substituted by persons ordinarily skilled in the art.
In this process, a 5-Ethylidene-2-norbornene (ENB) can be used. In embodiments, it can comprise the structure:
Molecular Structure:
Formula: C 9 H 12
Molecular Weight: 120.19
Synonyms for this molecule can include: ENB; Ethylidene Norbornene; 5-Ethylene-2-Norborene; Ethylidene-2-Norbornene; 5-Ethylidene Norbornene; 5-Ethylidene-2-Norbornen; 5-Ethylidenenorborn-2-ene; 5-ethylidene-5-norbornene; Ethylidene Norbornene (ENB)
Boiling Point: 146 degrees Celsius at 760 mmHg
Flash Point: 38.3 degrees Celsius
In this process, a 5-vinyl-2-norbornene (VNB) can be used which is known by the structure:
Molecular Structure:
Formula: C 9 H 12
Molecular Weight: 120.21
Synonyms for this molecule can include: 2-Norbornene,5-vinyl-(6CI,7CI,8CI); 2-Vinyl-5-norbornene; 2-Vinylbicyclo[2.2.1]hept-5-ene; 2-Vinylnorbornene; 5-Ethenylbicyclo[2.2.1]hept-2-ene; 5-Vinyl-2-norbornene; 5-Vinylbicyclo[2.2.1]hept-2-ene; 5-Vinylnorbornene; NSC 61529; V 0062; VBH; Vinylnorbornene
Boiling Point: 141 degrees Celsius at 760 mmHg
Flash Point: 28 degrees Celsius
VNB is a non-conjugated diene with which it is known to be difficult to create copolymers due to its propensity to branch uncontrollably, create gels during polymerization, and foul a reactor.
The embodiments are a process for continuously making a high molecular weight tetrapolymer using two reactors connected in series for continuous polymerization.
In embodiments, a first reactor continuously can receive a saturated hydrocarbon stream.
The first reactor continuously receives a propylene monomer into the saturated hydrocarbon stream at a rate sufficient to achieve a propylene content of 20 percent to 35 percent based on total weight in a high molecular weight tetrapolymer product.
If needed, hydrogen gas can be introduced to the saturated hydrocarbon stream at a rate sufficient to control the molecular weight of the high molecular weight tetrapolymer product.
Next, a first non-conjugated diene can be introduced to the saturated hydrocarbon stream at a rate sufficient to achieve a desired first non-conjugated diene content in the high molecular weight tetrapolymer product.
In the first reactor, a second non-conjugated diene can be introduced to the saturated hydrocarbon stream at a rate sufficient to achieve a desired second non-conjugated diene content in the high molecular weight tetrapolymer product.
An ethylene monomer can be introduced to the saturated hydrocarbon stream at a rate sufficient to initiate a polymerization reaction and achieve a desired ethylene content of 50 percent to 80 percent based on total weight in the high molecular weight tetrapolymer product.
The combined saturated hydrocarbon stream, the propylene monomer, the optional hydrogen gas, the first non-conjugated diene, the second non-conjugated diene, and the ethylene monomer can be cooled to below 35 degrees Celsius to create a cooled mixture.
Concurrently a metallocene catalyst and a metallocene co-catalyst can be added to the cooled mixture in the first reactor.
The metallocene catalyst can be diphenylmethylene(cyclopentadienyl, 9-fluorenyl) zirconium dichloride, diphenylmethylene(cyclopentadienyl, 9-fluorenyl) hafnium dichloride, diphenylsilyl(cyclopentadienyl, 9-fluorenyl) zirconium dichloride, and dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamido titanium dichloride.
The metallocene catalyst can be introduced at a feed rate sufficient to sustain a continuous reaction.
The metallocene co-catalyst can be at least one of: N,N-dimethylanilinium tetrakis (pentaflourophenyl) borate, a methyl aluminoxane (MAO) or combination of the two, a trialkyl aluminum such as triisobutylaluminum, lithium tetrakis(pentafluorophenyl) borate, trityl tetrakis(pentafluorophenyl) borate, trispentafluorophenyl boron, and modified methylaluminoxane (MMAO).
In this process, the cooled mixture can be reacted with the metallocene catalyst and the metallocene co-catalyst for 15 minutes to 60 minutes at a temperature from 35 degrees Celsius to 65 degrees Celsius and at a pressure from 190 psig to 230 psig forming a high molecular weight tetrapolymer product.
The high molecular weight tetrapolymer product of the first reactor can have the following characteristics: polymer chain branching as characterized by a tangent delta ranging from 0.15 to 1.1 measured at 150 degrees Celsius, 0.84 rad/sec, and 13.95 percent strain amplitude on a rubber process analyzer RPA 2000™ made by Alpha Technologies.
Additionally, the characteristics can be a non-linear relationship between viscosity and shear as characterized by the tangent delta from 0.15 to 1.1 measured at 150 degrees Celsius, 0.84 rad/sec, and 13.95 percent strain amplitude on a rubber process analyzer RPA 2000™ made by Alpha Technologies.
In embodiments, the characteristics of the tetrapolymer formed in the first reactor can include a weight average molecular weight from 500,000 Daltons to 1,000,000 Daltons measured using a high temperature GPC (HTGPC) system equipped with triple detector array (TDA) manufactured by Malvern Instruments, Inc. at 125 degrees Celsius.
The characteristics of the tetrapolymer formed in the first reactor can have a dynamic complex viscosity from 250,000 Pa·sec to 1,200,000 Pa·sec measured at 150 degrees Celsius, 0.1 rad/sec and 13.95 percent strain amplitude on a rubber process analyzer RPA 2000™ made by Alpha Technologies.
In embodiments, the characteristics of the tetrapolymer formed in the first reactor can have an ethylene to propylene ratio ranging from 50:50 to 90:10 by weight forming an ethylene rich high molecular weight tetrapolymer product.
The characteristics of the tetrapolymer formed in the first reactor can have a molecular weight distribution ranging from 1.0 to 2.2 needed for producing a higher mechanical strength in the final high molecular weight tetrapolymer product.
In embodiments, the characteristics of the tetrapolymer formed in the first reactor can include a first non-conjugated diene content of 0.2 percent to 2 percent by weight content based upon the total weight.
The characteristics of the tetrapolymer formed in the first reactor can have a second non-conjugated diene content of 0.2 percent to 15 percent by weight content based upon the total weight, wherein the first non-conjugated diene is different from the second non-conjugated diene.
The second reactor can continuously receive the high molecular weight tetrapolymer product from the first reactor.
A saturated hydrocarbon stream can be continuously introduced in the second reactor at a rate to maintain a desired total residence time.
A propylene monomer can be introduced into the saturated hydrocarbon stream to the second reactor at a rate sufficient to achieve total propylene content of from 29 percent to 45 percent of total weight in the final high molecular weight tetrapolymer product produced by the second reactor.
A first non-conjugated diene can be introduced to the saturated hydrocarbon stream in the second reactor at a rate sufficient to achieve the desired 0.2 percent to 2 percent by weight of the final high molecular weight tetrapolymer product.
A second non-conjugated diene can be introduced to the saturated hydrocarbon stream at a rate sufficient to achieve the desired 0.2 percent to 15 percent by weight of the final tetrapolymer produced in the second reactor.
An ethylene monomer can be introduced to saturated hydrocarbon stream of the second reactor at a rate sufficient to initiate a polymerization reaction and achieve a desired ethylene content of 60 percent to 80 percent of total weight in the final tetrapolymer produced in the second reactor.
In embodiments, the combined saturated hydrocarbon stream, propylene monomer, first non-conjugated diene, second non-conjugated diene, and ethylene monomer in the second reactor can be cooled to a temperature below 35 degrees Celsius to create a cooled mixture.
A metallocene catalyst and co-catalyst can be concurrently and continuously introduced into the second reactor receiving the cooled mixture.
The metallocene catalyst can include a group IVB transition metal such as zirconium or hafnium. The metallocene catalyst can be introduced at a feed rate sufficient to sustain a continuous reaction.
The metallocene co-catalyst or co-catalysts can be the same as those introduced into the first reactor.
In embodiments, the combined ingredients of the cooled mixture, metallocene catalyst, and co-catalyst are reacted together in solution phase for 15 minutes to 60 minutes at a temperature from 35 degrees Celsius to 65 degrees Celsius at a pressure from 190 psig to 230 psig which is lower than the pressure used in the first reactor, forming a final high molecular weight tetrapolymer product.
The final high molecular weight tetrapolymer product can have the following characteristics: polymer chain branching as characterized by a tangent delta ranging from 0.15 to 1.1, a non-linear relationship between viscosity and shear as characterized by the tangent delta from 0.15 to 1.1, a weight average molecular weight of 500,000 to 1,500,000 Daltons, a dynamic complex viscosity of 600,000 Pa·sec to 1,400,000 Pa·sec, an ethylene to propylene ratio ranging from 50:50 to 90:10 by weight forming an ethylene rich high molecular weight tetrapolymer product with a molecular weight distribution ranging from 2.3 to 10.0 a first non-conjugated diene content of 0.2 percent to 2 percent by weight content based upon the total weight final tetrapolymer, and a second non-conjugated diene content of 0.2 percent to 15 percent by weight content based upon the total weight of the final high molecular weight tetrapolymer product.
In embodiments, the process contemplates adding 0.1 weight percent to 0.5 weight percent of an antioxidant to the final high molecular weight tetrapolymer product produced in the second reactor.
In embodiments, the saturated hydrocarbon stream can be a hexane or an isoparaffinic fluid.
In embodiments, the first non-conjugated diene and the second non-conjugated diene can have ethylidene norbornene, vinylnorbornene, dicyclopentadiene, and/or octadiene or combinations thereof.
In embodiments, the first non-conjugated diene can be a vinyl norbornene or 1,7-octadiene or dicylopentadiene.
Example 1
The methodology described above was used to produce the following high molecular weight tetrapolymer.
Reactor #1
A saturated hydrocarbon stream can be introduced to a first reactor at 6,000 grams per hour.
A first propylene monomer can be introduced to the first saturated hydrocarbon stream at a rate of 420 grams per hour to achieve the first propylene content of 27 to 30 percent of total weight in a high molecular weight tetrapolymer product formed in the first reactor.
A hydrogen gas can be introduced to the first saturated hydrocarbon stream at 1.5 standard liters per hour to control the molecular weight of the high molecular weight tetrapolymer product formed in the first reactor.
A first non-conjugated diene of vinyl norbornene can be introduced to the first saturated hydrocarbon stream at a rate of 30 milligrams per hour to achieve a desired first non-conjugated diene content of 0.2 percent to 2 percent by weight in the high molecular weight tetrapolymer product formed in the first reactor.
A second non-conjugated diene of ethylidene norbornene can be introduced to the first saturated hydrocarbon stream at a rate of 10 grams per hour to achieve a desired second non-conjugated diene content of 0.2 percent to 15 percent by weight in the high molecular weight tetrapolymer product from the first reactor.
A first monomer of ethylene can be introduced to the first saturated hydrocarbon stream at a rate of 210 grams per hour to initiate the polymerization reaction and achieve desired ethylene content of 68 to 70 percent of total weight of the high molecular weight tetrapolymer formed in the first reactor.
The first saturated hydrocarbon stream, the first propylene monomer, the hydrogen gas, the first non-conjugated diene, the second non-conjugated diene, and the ethylene can be cooled to below 35 degrees Celsius as the components enter the reactor to create a cooled mixture.
In embodiments, a metallocene catalyst and co-catalysts can be simultaneously flowed into the first reactor.
The metallocene catalyst diphenylsilyl(cyclopentadienyl, 9-fluorenyl) zirconium dichloride was introduced at a feed rate sufficient to sustain a continuous reaction. In this example catalyst was introduced at a rate of 4.0 milligrams per hour neat.
The co-catalysts: methylaluminoxane (406 milligrams per hour), N,N-dimethylanilinium tetrakis(pentaflourophenyl) borate (56 milligrams per hour), and triisobutylaluminum (692 milligrams per hour) were all introduced at the specified rates to sustain the polymerization reaction.
The cooled mixture, the metallocene catalyst and co-catalysts, reacted for 25 minutes and at a temperature of 40 degrees Celsius and a pressure of 230 psig yields a high molecular weight tetrapolymer in the first reactor.
The high molecular weight tetrapolymer product has the following characteristics: polymer chain branching as characterized by a tangent delta of 0.698, a weight average molecular weight of 650,274 Daltons, a dynamic complex viscosity of 700,000 Pa·sec, an ethylene to propylene ratio 70:30 by weight, a molecular weight distribution of 2.2, a combined weight content of ethylene and propylene of 95.2 percent based upon the total weight of the resultant high molecular weight tetrapolymer, a first non-conjugated diene content of 0.227 percent by weight content based upon the total weight of the resultant high molecular weight tetrapolymer, and a second non-conjugated diene content of 4.73 percent by weight content based upon the total weight of the resultant high molecular weight tetrapolymer.
Reactor #2
In embodiments, a second reactor can continuously receive the high molecular weight tetrapolymer product from the first reactor. A second saturated hydrocarbon stream can be introduced into the second reactor at a rate to maintain the desired residence time; in this example the flow is 3,600 grams per hour.
A second propylene monomer can be introduced to the second saturated hydrocarbon stream at a rate of 180 grams per hour, which is sufficient to achieve total propylene content of 29 percent of total weight in the final high molecular weight tetrapolymer product.
A first non-conjugated diene (vinyl norbornene) can be introduced to the second saturated hydrocarbon stream to the second reactor at a rate of 2.0 grams per hour which is sufficient to achieve the desired 0.2 percent to 2 percent by weight first non-conjugated diene content in the final high molecular weight tetrapolymer product.
A second non-conjugated diene of ethylidene norbornene can be introduced to the second saturated hydrocarbon stream in the second reactor at a rate of 25 grams per hour, which is sufficient to achieve the desired second non-conjugated diene content of 0.2 percent to 15 percent by weight in the final high molecular weight tetrapolymer product.
A second ethylene monomer can be introduced to the second saturated hydrocarbon stream at a rate of 330 grams per hour that is sufficient to initiate the polymerization reaction and achieve desired ethylene content in the final high molecular weight tetrapolymer product.
The second saturated hydrocarbon stream, the propylene monomer, the first non-conjugated diene, the second non-conjugated diene, and the ethylene monomer can be cooled to below 35 degrees Celsius to create a second cooled mixture.
In embodiments, and all at once, additional metallocene catalyst diphenylsilyl(cyclopentadienyl, 9-fluorenyl) zirconium chloride, can be added at 3.5 milligams per hour neat, co-catalysts methylaluminoxane at 365 milligrams per hour neat, dimethylanilinium tetrakis(pentaflourophenyl) borate at 50.4 milligrams per hour neat and triisobutylaluminum at 623 milligrams per hour neat, all sufficient to sustain a continuous reaction.
The cooled mixture can react with additional metallocene catalyst, and the additional co-catalysts in solution phase for 20 minutes at a temperature of 36 degrees Celsius and a pressure of 190 psig, which is lower than the first reactor.
The final high molecular weight tetrapolymer product can have a polymer chain branching as characterized by a tangent delta of 0.70, a non-linear relationship between viscosity and shear as characterized by the tangent delta of 0.70, a weight average molecular weight of 773,387 Daltons, a dynamic complex viscosity of 760,000 Pa·sec, an ethylene to propylene ratio of 70.5:29.5 by weight, a molecular weight distribution of 2.4, a first non-conjugated diene, vinyl norbornene, content of 0.214 percent by weight content based upon the total weight of the final high molecular weight tetrapolymer product, and a second non-conjugated diene, ethylidene norbornene, content of 4.6 percent by weight content based upon the total weight of the final high molecular weight tetrapolymer product.
Example 2
The methodology described above was used to produce the following high molecular weight tetrapolymer.
Reactor #1
A saturated hydrocarbon of hexane can be introduced to a first reactor at 6,000 grams per hour.
A first propylene monomer can be introduced to the first saturated hydrocarbon stream at a rate of 420 grams per hour to achieve the first propylene content of 27 percent to 30 percent of total weight in a high molecular weight tetrapolymer product formed in the first reactor.
A hydrogen gas can be introduced to the first saturated hydrocarbon stream at 1.0 standard liters per hour to control the molecular weight of the high molecular weight tetrapolymer product formed in the first reactor.
A first non-conjugated diene of vinyl norbornene can be introduced to the first saturated hydrocarbon stream at a rate of 30 milligrams per hour to achieve a desired first non-conjugated diene content of 0.2 percent to 2 percent by weight in the high molecular weight tetrapolymer product formed in the first reactor.
A second non-conjugated diene of ethylidene norbornene can be introduced to the first saturated hydrocarbon stream at a rate of 10 grams per hour to achieve a desired second non-conjugated diene content of 0.2 percent to 15 percent by weight in the high molecular weight tetrapolymer product from the first reactor.
A first monomer of ethylene can be introduced to the first saturated hydrocarbon stream at a rate of 210 grams per hour to initiate the polymerization reaction and achieve desired ethylene content of 68 weight percent to 70 weight percent of total weight of the high molecular weight tetrapolymer formed in the first reactor.
The first saturated hydrocarbon stream, the first propylene monomer, the hydrogen gas, the first non-conjugated diene, the second non-conjugated diene, and the ethylene can be cooled to below 35 degrees Celsius as the components enter the reactor to create a cooled mixture.
In embodiments, a metallocene catalyst and co-catalysts can be simultaneously flowed into the first reactor.
The metallocene catalyst, a diphenylsilyl(cyclopentadienyl, 9-fluorenyl) zirconium dichloride can be introduced at a feed rate sufficient to sustain a continuous reaction. In this example the metallocene catalyst can be introduced at a rate of 4.0 milligrams per hour neat.
The co-catalysts: methylaluminoxane (406 milligrams per hour), N,N-dimethylanilinium tetrakis(pentaflourophenyl) borate (56 milligrams per hour), and triisobutylaluminum (692 milligrams per hour) can be introduced at the specified rates for each to sustain the polymerization reaction.
The cooled mixture at a temperature below 35 degrees Celsius, the metallocene catalyst and co-catalysts, are reacted for 25 minutes enabling a reaction temperature in the reactor of 40 degrees Celsius and a pressure of 230 psig yields a high molecular weight tetrapolymer in the first reactor.
The high molecular weight tetrapolymer product has the following characteristics: polymer chain branching as characterized by a tangent delta of 0.65, a weight average molecular weight of 715,300 Daltons, a dynamic complex viscosity of 850,000 Pa·sec, an ethylene to propylene ratio 70:30 by weight, a molecular weight distribution of 2.0, a combined weight content of ethylene and propylene of 95.2 percent based upon the total weight of the resultant high molecular weight tetrapolymer, a first non-conjugated diene content of 0.227 percent by weight content based upon the total weight of the resultant high molecular weight tetrapolymer, and a second non-conjugated diene content of 4.5 percent by weight content based upon the total weight of the resultant high molecular weight tetrapolymer.
Reactor #2
In embodiments, a second reactor can continuously receive the high molecular weight tetrapolymer product from the first reactor. A second saturated hydrocarbon stream can be introduced into the second reactor at a rate to maintain the desired residence time. In this example, the flow is 3,600 grams per hour.
A second propylene monomer can be introduced to the second saturated hydrocarbon stream at a rate of 180 grams per hour, which is sufficient to achieve total propylene content of 28 percent to 32 percent of total weight in the final high molecular weight tetrapolymer product.
A first non-conjugated diene (vinyl norbornene) can be introduced to the second saturated hydrocarbon stream to the second reactor at a rate of 2.0 grams per hour, which is sufficient to achieve the desired 0.2 percent to 2 percent first non-conjugated diene content in the final high molecular weight tetrapolymer product.
A second non-conjugated diene of ethylidene norbornene can be introduced to the second saturated hydrocarbon stream in the second reactor at a rate of 25 grams per hour, which is sufficient to achieve the desired second non-conjugated diene content of 0.2 percent to 15 percent in the final high molecular weight tetrapolymer product.
A second ethylene monomer can be introduced to the second saturated hydrocarbon stream at a rate of 360 grams per hour that is sufficient to initiate the polymerization reaction and achieve desired ethylene content in the final high molecular weight tetrapolymer product.
The second saturated hydrocarbon stream, the propylene monomer, the first non-conjugated diene, the second non-conjugated diene, and the ethylene monomer can be cooled to below 35 degrees Celsius to create a second cooled mixture.
Additional metallocene catalyst diphenylsilyl(cyclopentadienyl, 9-fluorenyl) zirconium chloride, can be added at 3.5 milligams per hour neat and co-catalysts dimethylanilinium tetrakis(pentaflourophenyl) borate at 50.4 milligrams per hour neat, and triisobutylaluminum at 623 milligrams per hour neat, all sufficient to sustain a continuous reaction.
The cooled mixture at a temperature below 35 degrees Celsius, the metallocene catalyst and co-catalysts, are reacted for 20 minutes enabling a reaction temperature in the reactor of 40 degrees Celsius and a pressure of 190 psig yields a high molecular weight tetrapolymer in the second reactor.
The final high molecular weight tetrapolymer product can have a polymer chain branching as characterized by a tangent delta of 0.645, a non-linear relationship between viscosity and shear as characterized by the tangent delta of 0.645, a weight average molecular weight of 805,900 Daltons, a dynamic complex viscosity of 950,000 Pa·sec, an ethylene to propylene ratio of 71:29 by weight, a molecular weight distribution of 2.4, a first non-conjugated diene, vinyl norbornene content of 0.21 percent by weight content based upon the total weight of the final high molecular weight tetrapolymer product, and a second non-conjugated diene, ethylidene norbornene content of 4.6 percent by weight content based upon the total weight of the final high molecular weight tetrapolymer product.
Example 3
Reactor #1
A saturated hydrocarbon stream can be introduced to a first reactor at 6,000 grams per hour.
A first propylene monomer can be introduced to the first saturated hydrocarbon stream at a rate of 420 grams per hour to achieve the first propylene content of 27 to 30 percent of total weight in a high molecular weight tetrapolymer product formed in the first reactor.
A hydrogen gas can be introduced to the first saturated hydrocarbon stream at 1.5 standard liters per hour to control the molecular weight of the high molecular weight tetrapolymer product formed in the first reactor.
A first non-conjugated diene of vinyl norbornene can be introduced to the first saturated hydrocarbon stream at a rate of 30 milligrams per hour to achieve a desired first non-conjugated diene content of 0.2 percent to 2 percent by weight in the high molecular weight tetrapolymer product formed in the first reactor.
A second non-conjugated diene of ethylidene norbornene can be introduced to the first saturated hydrocarbon stream at a rate of 10 grams per hour to achieve a desired second non-conjugated diene content of 0.2 percent to 15 percent by weight in the high molecular weight tetrapolymer product from the first reactor.
A first monomer of ethylene can be introduced to the first saturated hydrocarbon stream at a rate of 210 grams per hour to initiate the polymerization reaction and achieve desired ethylene content of 68 to 70 percent of total weight of the high molecular weight tetrapolymer formed in the first reactor.
The first saturated hydrocarbon stream, the first propylene monomer, the hydrogen gas, the first non-conjugated diene, the second non-conjugated diene, and the ethylene can be cooled to below 35 degrees Celsius as the components enter the reactor to create a cooled mixture.
In embodiments, a metallocene catalyst and co-catalysts can be simultaneously flowed into the first reactor.
The metallocene catalyst diphenylsilyl(cyclopentadienyl, 9-fluorenyl) zirconium dichloride can be introduced at a feed rate sufficient to sustain a continuous reaction. In this example, the catalyst can be introduced at a rate of 4.0 milligrams per hour neat.
The co-catalysts: methylaluminoxane (406 milligrams per hour), N,N-dimethylanilinium tetrakis(pentaflourophenyl) borate (56 milligrams per hour), and triisobutylaluminum (692 milligrams per hour) can be introduced at the specified rates to sustain the polymerization reaction.
The cooled mixture, the metallocene catalyst and co-catalysts, reacted for 25 minutes at a temperature of 40 degrees Celsius and a pressure of 230 psig yields a high molecular weight tetrapolymer in the first reactor.
The high molecular weight tetrapolymer product can have the following characteristics: polymer chain branching as characterized by a tangent delta of 1.098, a weight average molecular weight of 831,555 Daltons, a dynamic complex viscosity of 550,000 Pa·sec, an ethylene to propylene ratio 71:29 by weight, a molecular weight distribution of 1.9, a combined weight content of ethylene and propylene of 97.6 percent based upon the total weight of the resultant high molecular weight tetrapolymer, a first non-conjugated diene content of 0.2 percent by weight content based upon the total weight of the resultant high molecular weight tetrapolymer, and a second non-conjugated diene content of 2.2 percent by weight content based upon the total weight of the resultant high molecular weight tetrapolymer.
Reactor #2
In embodiments, a second reactor can continuously receive the high molecular weight tetrapolymer product from the first reactor. A second saturated hydrocarbon stream can be introduced into the second reactor at a rate to maintain the desired residence time; in this example the flow is 3,600 grams per hour.
A second propylene monomer can be introduced to the second saturated hydrocarbon stream at a rate of 200 grams per hour, which is sufficient to achieve total propylene content of 29 percent of total weight in the final high molecular weight tetrapolymer product.
A first non-conjugated diene (vinyl norbornene) can be introduced to the second saturated hydrocarbon stream to the second reactor at a rate of 2.0 grams per hour, which is sufficient to achieve the desired 0.2 percent to 2 percent by weight first non-conjugated diene content in the final high molecular weight tetrapolymer product.
A second non-conjugated diene of ethylidene norbornene can be introduced to the second saturated hydrocarbon stream in the second reactor at a rate of 25 grams per hour, which is sufficient to achieve the desired second non-conjugated diene content of 0.2 percent to 15 percent by weight in the final high molecular weight tetrapolymer product.
A second ethylene monomer can be introduced to the second saturated hydrocarbon stream at a rate of 330 grams per hour that is sufficient to initiate the polymerization reaction and achieve desired ethylene content in the final high molecular weight tetrapolymer product.
The second saturated hydrocarbon stream, the propylene monomer, the first non-conjugated diene, the second non-conjugated diene, and the ethylene monomer can be cooled to below 35 degrees Celsius to create a second cooled mixture.
In embodiments, and all at once, additional metallocene catalyst diphenylmethylene(cyclopentadienyl, 9-fluorenyl) zirconium chloride, can be added at 3.3 milligams per hour neat, co-catalysts, dimethylanilinium tetrakis(pentaflourophenyl) borate at 7.1 milligrams per hour neat and triisobutylaluminum at 650 milligrams per hour neat, all sufficient to sustain a continuous reaction.
The cooled mixture can react with additional metallocene catalyst, and the additional co-catalysts in solution phase for 20 minutes at a temperature of 36 degrees Celsius and a pressure of 190 psig, which is lower than the first reactor.
The final high molecular weight tetrapolymer product can have a polymer chain branching as characterized by a tangent delta of 0.7095, a non-linear relationship between viscosity and shear as characterized by the tangent delta of 0.7095, a weight average molecular weight of 752,403 Daltons, a dynamic complex viscosity of 760,000 Pa·sec, an ethylene to propylene ratio of 70.7:29.3 by weight, a molecular weight distribution of 2.93, a first non-conjugated diene of vinyl norbornene content of 0.214 percent by weight content based upon the total weight of the final high molecular weight tetrapolymer product, and a second non-conjugated diene, ethylidene norbornene content of 4.8 percent by weight content based upon the total weight of the final high molecular weight tetrapolymer product.
FIG. 1 shows examples of tetrapolymers that can be prepared by the processes described above. Examples 4 and 5 can be prepared according to the methodologies described in Example 1. Examples 6 through 10 can be prepared according to methodologies described in Example 3.
While the embodiments have been described with emphasis on the embodiments, it should be understood that within the scope of the appended claims, the embodiments might be practiced other than as specifically described herein. | A process and articles for continuously making a tetrapolymer using two reactors connected in series with two saturated hydrocarbon streams, two injections of ethylene monomer, two injections of propylene monomer, and two injections of two different non-conjugated diene monomers simultaneously with two metallocene catalysts and two metallocene co-catalysts. This process allows for the creation of products with high molecular weights while utilizing continuous flow reactors in series, preventing an additional blending step. The process allows for manufacture of anti-vibration articles made by the tetrapolymers. | 2 |
This is continuation application Ser. No. 08/664,250, filed Jun. 7, 1996, now U.S. Pat. No. 6,159,175 which is a division of application Ser. No. 08/458,409 filed Jun. 2, 1995, now abandoned other divisions of application Ser. No. 08/458,409 are:
Ser. No. 08/660,287 filed Jun. 7, 1996 now U.S. Pat. No. 5,725,495 granted Mar. 10, 1998
Ser. No. 08/664,239 filed Jun. 7, 1996 now U.S. Pat. No. 5,741,226 granted Apr. 21, 1998 and
Ser. No. 08/660,284 filed Jun. 7, 1996 now U.S. Pat. No. 5,743,871 granted Apr. 28, 1998.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus for surgically removing a cataractous lens from a human eye. More specifically, the present invention relates to an improved flexible phacoemulsification sleeve with a built in reinforcing member, a phacoemulsification sleeve with a barrier connected to the tip to direct infusion from a single or multiple infusion hole while permitting minimal or no occlusion, a tip for a phacoemulsification handpiece with different configuration of barriers and baffles to increase cutting and a side opening to amplify fluid flow to the tip, a phacoemulsification handpiece with a valve to regulate the rate of evacuation, a phacoemulsification handpiece with a variable aperture aspiration line, a sleeve that includes a built-in reservoir, a stepped inside ultrasonic needle to direct ultrasonic waves to enhance emulsification and aspiration, and a sleeve that is compressible and rotatably connected to the handpiece in a fluid tight manner.
2. Discussion of the Related Art
The human eye contains a lens which focuses on the retina, the sensory membrane that lines the eye and receives the image formed by the lens. Through trauma, age, disease, mutation, or naturally occurring processes, the natural crystalline lens may become opaque or cloudy and thus cease to clearly transmit and focus light. This clouding of the lens is known as a cataract.
In the last few decades, techniques have been developed to surgically remove the cataract lens and replace it with an artificial or intraocular lens. This cataract lens extraction process may be performed by a number of medically recognized techniques. One of the more well known and widely used techniques is phacoemulsification.
The phacoemulsification procedure involves placing two concentric tubes through a corneal incision of approximately three millimeters. This incision is made in the region of the limbus where a colored portion of the eye meets a white portion of the eye. The incision can also be made in the cornea. The inner tube, known as a needle, is ultrasonically vibrated such that its vibrating tip member operates to emulsify the hard nuclear material of the cataract lens.
In this type of surgery, the vibrating inner tube also functions as an aspirator so that the emulsified cataract lens material may be aspirated out of the eye. The outer tube, known as a sleeve, functions as an irrigator allowing for inflow of saline fluid into the eye. The saline fluid serves several purposes. First, the presence of the saline fluid prevents the cornea from collapsing as the lens material is emulsified and aspirated. Second, the saline aids in the aspiration of the cataract lens material out of the eye. The concentric tubes of a handpiece of the system are attached to an external power source, fluid source, and vacuum source, which provide for controlled ultrasonic vibration, inigation, and suction.
The importance of infusing a fluid into the eye during cataract surgery cannot be understated. The fluid infusion serves to maintain the eye in an inflated, pressurized condition during cataract removal. However, there are several factors that increase the difficulty with which the eye structure can be maintained and supported in an inflated, pressurized condition during cataract surgery.
One of the prevalent causes of diminished inflation of the eye during cataract surgery is leakage of fluid from the eye. This leakage normally occurs between the edges of the incision and the exterior surface of the infusion sleeve. This leakage can have significant deleterious consequences to the success of the surgery being performed.
One of the adverse consequences of fluid leakage is that there is a tendency for the eye to deflate during the operation. This deflation causes certain tissues within the eye to collapse on each other or on the surgical instrument that extends into the eye. The tissues most likely to be damaged from the consequences of such fluid loss are the cornea, the iris, and the lens capsule, which surround the cataract. One method of counteracting this fluid leakage is to increase the amount of fluid flow in order to maintain proper inflation of the eye. However, this approach is not a satisfactory solution to the problem of fluid leakage from the eye because the greater the infusion of fluid into the eye, the more the flow becomes rapid and even turbulent. This can cause damage to the cornea, especially to the fragile cells that line the inside of the cornea.
The fragile cells that line the inside of the cornea are known as corneal endothelitim and cannot be regenerated by the eye. Once these cells are damaged or destroyed, they cannot be repaired or replaced by human regeneration. Also, damage to the corneal endothelium can cause permanent damage to the cornea, resulting in corneal clouding and decreased vision, all of which may require a corneal transplant. It should be noted that the most common cause of corneal clouding and corneal transplantation in the United States today are complications from eye surgery for cataract removal and intraocular lens insertion.
As a result, the phacoemulsification procedure would be significantly improved if corneal damage as a result of fluid flow leakage during intraocular surgery could be reduced or eliminated.
Most infusion sleeves used for phacoemulsification or intraocular surgery are made of silicone or silicone-type material. However, the use of silicone sleeves presents significant problems with respect to fluid leakage between the incision edge in the eye and the exterior surface of the silicone infusion sleeve. This is due to the fact that the incision in the eye must be larger than the silicone infusion sleeve, since the silicone infusion sleeve is made from a soft, compressible material and cannot be used safely when inserted through an incision in the eye where there is a minimal amount of clearance between the incision and the exterior of the silicone infusion sleeve.
When there is a minimal amount of clearance between the exterior of the silicone infusion sleeve and the incision in the eye, the incision tends to compress the non-rigid silicone sleeve against the vibrating tip, resulting in a relative rubbing movement between the silicone sleeve and the vibrating tip. This rubbing movement generates undesirable heat as the needle in the tip is vibrated at relatively high frequencies. The heat thus generated is extremely undesirable and can result in thermal burns and shrinkage of ocular tissue surrounding the silicone infusion sleeve.
The burning and shrinkage of ocular tissue is a serious problem that has sight threatening implications. The rubbing of the infusion sleeve against the vibrating needle also constricts the path for fluid flow into the eye, thus impeding efforts to keep the eye pressurized and inflated.
In an attempt to reduce the infusion fluid leakage and the deleterious effects that can be caused by the undesirable friction, some infusion sleeves have been constructed from rigid non-compressible materials. Generally, these materials have consisted of teflon or metallic-based compositions. These rigid non-compressible infusion sleeves have been somewhat successful in solving the constriction problems in the fluid flow path between the distal end of the infusion sleeve and the vibrating tip. In addition, these sleeves have also reduced the heat generation and thermal burns associated with silicone-type sleeves.
While rigid, non-compressible sleeves are capable of being inserted through smaller incisions that reduce leakage through the clearance between the rigid, non-compressible sleeve and the incision, there is still a significant amount of leakage. The primary cause of this remaining leakage is that the cross section of the rigid, non-compressible sleeve does not match the shape or contour of the eye incision. As a result, there are fairly substantial gaps between the rigid, non-compressible sleeve exterior surface and the eye incision. This is due to the fact that the collagen fiber structure of the cornea resists deformation and does not readily assume the shape of the infusion sleeve.
Other attempts to reduce the infusion fluid leakage and associated side effects, such as the one disclosed in U.S. Pat. No. 5,084,009 to Mackool, include using a double sleeve system with the inner sleeve being made from a rigid material such as teflon and the outer sleeve being made from a flexible material such as silicone. However, there are still many problems with this type of approach. For example, a double sleeve system requires a stepped titanium needle. The needle 106 is not illustrated as being stepped in the '009 patent, however, only the most distal end of the needle is illustrated. In practice, this double sleeve arrangement requires a stepped titanium needle. Additionally, this arrangement requires more parts (i.e., teflon sleeve inside and a silicone outside sleeve). The teflon sleeve must be cut along its entire axial length to be placed around the posterior part of the needle, because the needle contains a threaded posterior part and a stepped anterior part. Since both the thread and step are larger than the diameter of the sleeve, the only way to get the teflon sleeve on the needle is to cut the sleeve along its entire length.
Additionally, with respect to the phacoemulsification sleeve, prior art devices use two infusion ports in order to improve fluid flow. However, the use of two ports or holes tends to cause turbulence in the eye. Thus, there is a need for improved flow sleeves that reduce or completely eliminate turbulence in the eye and direct infusion away from the aspiration hole.
As to the handpiece used in phacoemulsification procedures, it should be recalled that the inner tube is used for aspiration, while the outer tube is used for irrigation. During surgery, it is often desirous to change the rate of aspiration. However, if the rate of evacuation or aspiration is too high, undesirable intra-ocular surges may occur. Thus, there exists a need for a phacoemulsification handpiece, where the aspiration can be reliably and accurately controlled.
Regarding the tip or needle that performs the actual cutting away of the nuclear material as it is ultrasonically vibrated, different designs have been proposed in order to increase cutting. However, these designs suffer from emitting ultrasonic energy in the eye and not emulsifying efficiently.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a phacoemulsification sleeve that significantly reduces infusion fluid leakage by providing a silicone sleeve with a built-in reinforcing member. It is also an object of the present invention to provide a phacoemulsification sleeve with barriers or vanes or steps that direct infusion fluid flow away from the aspiration hole and minimize turbulence in the eye.
It is yet a further object of the present invention to provide a, phacoemulsification handpiece having a valve which will close when the rate of evacuation is too high, in order to prevent intraocular surges. A still further object of the present invention is to provide a phacoemulsification handpiece with a variable capacity reservoir in the infusion line to vary the amount of infusion flow to account for surges in the aspiration line tubing. The surges in the aspiration line would decrease the intraocular pressure.
It is a further object of the present invention to provide a phacoemulsification needle with a single aspiration hole on one side to amplify the flow coming to the tip. It is a further object to provide a needle with different configuration of barriers, baffles, steps in order to increase cutting and suction effect within the needle.
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious to those skilled in the art from the description itself, and further will be appreciated by those practicing the invention and using the resulting phacoemulsification device.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and still further objects, features and advantages of the present invention will become apparent upon consideration of the following detailed description of a specific embodiment thereof, especially when taken in conjunction with the accompanying drawings wherein like reference numerals in the various figures are utilized to designate like components, and wherein:
FIGS. 1A and 1B are cross-sectional and front views, respectively, of the of the silicone phacoemulsification sleeve with a built-in reinforcing member;
FIGS. 2A and 2B are cross-sectional and front views respectively of the silicone sleeve inserted through an incision in the cornea;
FIGS. 3A-G are a top and side views of a phacoemulsification sleeve with a single infusion hole with internal or external steps to direct infusion;
FIG. 4 is a side view of a phacoemulsification handpiece or an irrigation aspiration handpiece having a valve to constrict the aspiration line;
FIG. 5 is a schematical side view of a phacoemulsification handpiece with a variable aperture aspiration line;
FIGS. 6A-F are side and front views showing various shaped needles;
FIGS. 7A-B are side views of a phacoemulsification needle with a hole on one side and a single infusion hole in the sleeve;
FIGS. 8A-D, 9 A-D, 10 A-D, 11 A-D, 12 A-D show different shapes of the emulsification end of the needle;
FIGS. 13A-B, 14 A-B, 15 A-B, 16 A-B, 17 A-B show different sizes and shapes of aspiration holes;
FIGS. 18A-B, 19 A-B, 20 A-B show concave, convex and angled surfaces which are designed to direct ultrasonic waves;
FIGS. 21A-B, 22 A-B, 23 A-B, 24 A-B, 25 A-B, 26 A-B and 27 A-B show multiple aspiration holes;
FIG. 28 is a side view of handpiece assembly including a silicone membrane which acts as a reservoir chamber for infusion fluid;
FIG. 29 is a side view of the handpiece assembly of FIG. 28 with the silicone membrane being shown collapsed during an aspiration surge;
FIG. 30 is a side view of a phacoemulsification needle showing one of the different configurations of barriers and baffles;
FIG. 31 is a front view of a phacoemulsification needle employing one of the different configurations of barriers and baffles;
FIG. 32 is a front view of a phacoemulsification needle employing one of the different configurations of barriers and baffles;
FIGS. 33A-B, 34 A-B, 35 A-B, 36 A-B, 37 A-B and 38 - 42 show various shape barriers which can be placed on the inside or outside of the needle
FIGS. 43 and 44 show a top and side view of a needle having a single aspiration hole and specially designed internal and external surfaces to enhance the emulsification and the aspiration effect;
FIG. 45 shows a barrier similar to the embodiment illustrated in FIGS. 33A-B but with the barriers set further back within the needle;
FIGS. 46 and 47 illustrate various barrier shapes and steps disposed within the needle to enhance the emulsification and aspiration;
FIG. 48 illustrates a stepped needle which enhances emulsification and the aspiration effect;
FIGS. 49 and 50 are sectional views of additional embodiments of needle tip;
FIG. 51 is a side view of a compressible sleeve according to the present invention; and
FIG. 52 is a anterior view of the compressible sleeve inserted into an incision in the cornea.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The phacoemulsification sleeve 10 of the present invention is a silicone sleeve with a built-in reinforcing member. The sleeve can be used in an ultrasonic handpiece similar to the one disclosed in Applicant's commonly owned U.S. Pat. No. 5,242,385 to Strukel, the disclosure of which is hereby incorporated by reference. The sleeve is essentially a silicone sleeve of approximately 0.005 inches thickness with an overall dimension of approximately 1.0 inch, as shown in FIG. 1 . In a preferred embodiment of the present invention, interwoven in the silicone walls of the sleeve are strands of teflon or metallic-based material 12 to provide a rigid frame for the silicone walls. In an alternative embodiment, the teflon or metallic material is in the form of a spiral or single strand that are embedded in the silicone walls of the sleeve. Alternatively, the sleeve could be impregnated with strands of fiber glass or kevlar which will also act as a reinforcing member. Of course, the sleeve could be reinforced with any number of different devices so long as the reinforcing member has a higher durometer (i.e., is harder) than the silicone.
The resulting sleeve has the advantages of both a rigid sleeve and a compressible sleeve, without suffering from the deleterious effects that plague each individual approach. By having a relatively compressible outer layer, the sleeve of the present invention is able to be deformed slightly in order to match the shape or contour of the eye incision 14 , in the cornea 16 , as illustrated in FIGS. 2A-2B. However, because the present sleeve has a built-in rigid frame, it is not deformable to the extent that a completely compressible silicone sleeve would be deformed. This reduction in deformation avoids the prior art disadvantages such as rubbing between the silicone sleeve and the vibrating tip that results in heat generation and thermal bums, as well as constriction of the fluid flow path into the eye.
During phacoemulsification the ultrasonic needle radiates ultrasonic energy from its tip into the eye and pushes fluid and lens material away from the tip. The flow through the aspiration port brings the material to the tip. The ideal effect is to efficiently bring the cataract to the tip, completely emulsify the cataract and aspirate the emulsified cataract through the ultrasonic needle. To enhance the emulsification, surfaces can be added to the inside or outside of the ultrasonic needle which will direct ultrasonic waves in the desired direction.
Ultrasonic needles are currently manufactured of titanium and have a generally circular cross-section as illustrated in FIGS. 6A and 6B. The needles 16 are used for phacoemulsification and for cutting and removing tissue during surgery. Other cross sectional shapes such as a triangle, as illustrated in FIGS. 6C and 6D, or polygonal shapes, such as a hexagon, as illustrated in FIGS. 6E and 6F can be used to improve the cutting and emulsification properties of the needle. In addition, the use of non-circular cross-sectional needle shapes will provide a flat surface which may be a more practical surface to work with to weld or machine other surfaces to the needle. These additional surfaces would then vibrate with the needle. The surfaces, which will generate ultrasonic energy, can be arranged so that the ultrasonic energy is directed in the preferred areas.
Conventionally, ultrasonic needles have been manufactured having circular openings at the distal end. This opening is known as the aspiration hole 18 . The aspiration opening within the needle is simply made by drilling a throughbore in the titanium shaft. An alternative method of forming the needle 16 would be to not drill the hole completely through the needle but to leave the distal end of the needle closed. In other words, a blind bore would be drilled into the needle. An aspiration hole 18 would then be provided on the side of the needle 16 . An advantage of providing the aspiration hole 18 in the side of the needle is that the distal axial end of the needle can then be made, by machining, to any desired shape, such as a flat surface or a slanted wedge shape, as illustrated in FIGS. 7A and 7B. Numerous other end configurations are illustrated in FIGS. 8A-27B. A further advantage of placing the aspiration hole 18 in the side of the needle 16 is that the hole 18 can be placed anywhere along the needle surface and can be sized and/or shaped depending on the needs of the user. A further advantage is that with the closed tip, additional ultrasonic energy will be emitted from the closed tip surface which will aid in emulsifying tissue. The specific shape of the tip, including the angle, concavity, convexity, etc. can be designed to selectively focus ultrasonic energy. Additionally, surface area can be designed to emit either a large or small amount of ultrasonic energy. Generally, the larger the surface area, the larger the amount of ultrasonic energy which will be generated. In certain portions of the tip it is important to emit less ultrasonic energy to reduce the likelihood of breakage to the posterior capsule.
The ultrasonic waves radiate from the metallic surfaces. Accordingly, the surface of the tip could be modified so that it will intensely focus the ultrasonic energy to emulsify tissue. However, if the surface is designed to focus low ultrasonic energy, that surface can be used to selectively clean tissue without the emulsification of tissue taking place. Additionally, if the ultrasonic energy is finely focused, that energy can be used to cut the tissue. Accordingly, the surfaces of the tip can be designed to be tissue specific in its ability to focus ultrasonic energy. Various embodiments of ultrasonic needles 16 are illustrated in FIGS. 7A-27B. Each of these needle embodiments have holes of various sizes and shapes and various needle surfaces to vary the amount of focusing of the ultrasonic energy and the amount of aspiration through the aspiration hole 18 .
As discussed above, conventional ultrasonic needles have only one aspiration port 18 which is disposed at the axial distal end of the needle. Applicants have discovered that the addition of a second aspiration port, disposed near the main aspiration port or even as part of the main aspiration port can provide numerous advantages in the use of the needle 16 . FIGS. 24A and B illustrate an embodiment where the second aspiration port 18 ′ can be disposed as being a part of the main aspiration port 18 . For example, during certain uses of the needle you will want to build a vacuum in order to hold tissue at the tip. This is especially true during certain types of cataract surgery, where it is desirous to occlude the tip during either the “divide and conquer” or the “phaco chop” techniques of cataract surgery. During these techniques, it is often desirable to hold the nucleus on the phaconeedle tip. Obviously, it will be necessary to cover both aspiration holes to build a vacuum. However, during the emulsifying of tissue in the primary port, it is often advantageous to have a secondary aspiration port available to assist in the further aspiration of the emulsified tissue.
Referring to FIGS. 3A-3F, a sleeve 10 having an infusion port 17 is illustrated. Sleeve 10 is illustrated as having baffles 19 disposed on either the interior or exterior surface adjacent to the infusion port 17 to assist in directing the flow of infusion fluid. As illustrated in FIG. 3A, the baffle 19 can be disposed on the outer portion of the sleeve 10 in an area disposed between infusion port 17 and the distal end of the sleeve 10 . In FIG. 3A the baffle directs an infusion fluid away from the aspiration port. However, if desirable, the baffle 19 can be placed on the opposite side of the infusion port 17 , as illustrated in FIG. 3B to direct the infusion fluid in the forward direction towards the distal end of the sleeve 10 .
As illustrated in FIG. 3E, the baffle 19 can be disposed within the interior of the sleeve 10 between the infusion port 17 and the distal end of the sleeve. Alternatively, as illustrated in FIG. 3F, the baffle 19 can be disposed on the proximal side of the infusion port 17 . Additionally, as illustrated in FIG. 3G, a baffle 19 can be disposed on both the exterior and interior surface of sleeve 10 . As illustrated in FIG. 3G, the baffles are located on the distal side of infusion port 17 . However, just as has been illustrated in FIGS. 3B, 3 D and 3 F, baffles 19 could be disposed on the proximal side of the infusion port 17 .
Referring now to FIGS. 4 and 5, a phacoemulsification handpiece 11 according to the present invention is shown. The handpiece 11 has a valve 20 in the aspiration line. The function of the valve is to constrict the flexible tubing of the aspiration line to create resistance in the aspiration line. Also, the valve may be used to change the flow characteristics at the needle tip. The valve may be controlled either at the phacoemulsification machine control panel or directly at the handpiece. It should be pointed out that the valve control can be simply an on/off valve or a valve that allows for analog-type control whereby the valve can be adjusted to any precise level between completely on and completely off. In the preferred embodiment of the present invention, the valve is located at the anterior portion of the handpiece.
The handpiece of FIG. 4 has a valve 20 which is preferably controlled so that it can be adjusted to any precise level between completely on and completely off. The valve can be positioned at position C in FIG. 4 which is within the handpiece, or at position B immediately behind the handpiece or at position A, which is adjacent to the housing for the aspiration pump. The valve is controlled by a control console which receives signals from a pressure transducer (not shown) which detects the fluid pressure within the aspiration conduit. Upon the detection of the varying pressure within the aspiration line, the control console automatically actuates the valve to variably increase or decrease the cross-sectional area of the aspiration conduit to ensure substantially constant pressure within the conduit.
In the embodiment illustrated in FIG. 5, a valve 21 is disposed within the handpiece 11 . This valve 21 is preferably of the type that is an on/off valve, as discussed above. Upon the detection of a pressure surge, the control console immediately sends a signal to close valve 21 . Simultaneously, valve 23 is opened to release relatively high pressure fluid from a sterile fluid container into the aspiration conduit. Thereafter, the bottom valve 21 is opened, the full effect of the surge is erased and then valve 23 is closed once again. The system is then ready to detect and control the next surge within the aspiration line.
The advantages of an on/off valve, such as valve 21 , include that when a piece of cataract occludes the phaco tip, vacuum will build up in the aspiration line. When that occluded piece is emulsified, there still will be a vacuum in the aspiration line and a surge will be created thus reducing the intraocular pressure. When a pressure transducer in the aspiration line detects a rapid change in vacuum the valve in the handpiece, can be instantaneously closed and a release of sterile fluid in the aspiration line can occur to remove the vacuum and the handpiece valve can then reopen. This valve, by closing instantaneously and opening immediately after fluid is released into the aspiration line will prevent surges of intraocular pressure.
Referring now to FIGS. 28 and 29, a handpiece assembly 11 that includes a collapsible silicone membrane 22 is illustrated. The silicone membrane 22 is disposed radially outside of the needle 16 and defines an annular reservoir chamber 24 disposed between the silicone membrane 22 and needle 16 . The reservoir is in fluid communication with the infusion fluid as it passes through the handpiece assembly and out through the infusion sleeve port near the needle tip. The silicone membrane is made from a soft elastic material so that the membrane 22 can collapse during an aspiration surge during use of the ultrasonic handpiece. Typically, when an aspiration surge occurs the relatively large amount of fluid within reservoir 24 is of a sufficient volume so that this fluid can be immediately withdrawn from the reservoir and introduced into the intraocular area, which results in an immediate compensation for the fluid lost from the surge. As is well known, a drop in intraocular pressure can cause considerable problems such as collapse of the intraocular tissue onto the vibrating phaco needle. Accordingly, the reservoir 24 is designed to provide additional infusion fluid in the intraocular area as soon as an aspiration surge occurs. The reservoirs is located immediately adjacent to the needle tip to minimize the time it takes to replace the intraocular fluid. The surge will cause a decrease of intraocular pressure and will therefore provide a suction effect to withdraw the fluid contained within reservoir 24 . This suction effect causes the membrane 22 to collapse, as illustrated in FIG. 29 . An air vent 26 is provided radially outside of the silicone membrane 22 to permit membrane 22 to collapse freely.
Referring now to FIGS. 30-42, a series of barriers are illustrated, which are attached to the walls of the ultrasonic needle 16 . The barriers permit limited or no occlusion at the tip of the needle to enhance emulsification of tissue. As discussed above, occlusion of the tip can create a surge of fluid flow upon break up of the tissue causing the occlusion. This surge in fluid flow can cause a collapse of the intraocular pressure within the eye which is a condition that should be avoided. In addition, the barriers also provide an additional ultrasonic cutting surface to enhance the cutting and emulsification ability of the tip. The barriers are structural members, such as bars, baffles, wedges, etc. which are attached to the walls of the needle 16 . A barrier 28 is illustrated in FIG. 30 . Other embodiments of barriers including a single bar 30 disposed in the center of the needle or double bars 32 , 34 disposed about the center of the needle are illustrated in FIGS. 31 and 32, respectively. The bars 30 , 32 , 34 prevent nuclear tissue from penetrating into the tip beyond a predetermined amount. Other embodiments of barriers are illustrated in FIGS. 33A-42. For example, in FIGS. 33A and B, an annular ramp shaped barrier 36 is disposed within the tip 16 . A wedge shaped plate barrier 38 which does not extend fully across the inside of the tip is illustrated in FIGS. 34A and B. A pair of spaced apart bars 40 , 42 are illustrated in FIGS. 36A and B. A barrier 44 , 46 , illustrated in FIGS. 35A and B, is disposed on the outer surface of sleeve 16 . These barriers 44 , 46 do not assist in preventing an occlusion, but they do provide an additional surface from which ultrasonic energy can be generated. Other barrier embodiments are illustrated in cross-section in FIGS. 38 and 42. Clearly, almost any type of geometric shape can be used to assist in permitting a limited occlusion of the tip and to aid in emulsifying tissue.
Referring now to FIGS. 37A and B, barrier 42 is illustrated for use in a modified tip 16 ′. Tip 16 ′ has a wedge shaped distal end surface 48 which provides a large metallic surface area for ultrasonically cutting tissue. The ultrasonic energy from surface 48 is directed in an opposite direction with respect to the aspiration port 18 . A tip similar to the one illustrated in FIGS. 37A and B is illustrated in FIGS. 43 and 44. The angled surface 50 disposed inside of the needle 16 ′ can be used to focus energy towards the aspiration port 18 , but within the needle 16 ′, to aid in the emulsification of tissue. Other surfaces within that needle including surface 52 and a stepped shoulder surface 54 assist in the suction of the nuclear tissue after it has been emulsified. Surface 52 also is disposed within the line of ultrasonic energy that has been generated from surface 50 to effectively prevent this energy from causing damage to the surrounding tissue. Surface 52 is preferably a spherical surface, and can simply be formed by drilling a blind bore into the shaft 16 ′. Surface 52 would be the distal portion of the blind bore. Exterior surface 53 is a blunt surface which emits ultrasonic energy at a sufficient energy level to be able to split the cataract. However, the energy generated by surface 53 dissipates quickly so as to minimize the risk of damaging to the posterior capsule.
FIG. 45 illustrates a needle that includes a ramp shaped annular barrier 56 whose ramp shaped surface 58 is directed towards the needle tip to focus ultrasonic energy across the aspiration port 18 . The stepped rear shoulder surface 60 of the ramp 56 is used to assist in the suction of the nuclear tissue after it has been emulsified. In most uses it is desirous to contain the ultrasonic energy within the needle to minimize the ultrasonic radiation which can cause damage to the intraocular tissue. In the embodiment illustrated in FIG. 45, ultrasonic energy generated by ramp surface 58 is prevented from exiting the needle by the needle's interior surface.
The present inventors have found the use of steps, angles, and barriers within the ultrasonic needle useful to focus ultrasonic energy across the aspiration port to aid in emulsifying nuclear tissue and to aid in pushing emulsified material in the direction of the aspiration flow.
FIGS. 46-50 illustrate various embodiments of needle tips which achieve these results. FIG. 46 illustrates a tapered needle 16 that has an internal annular shaped ramp 62 similar to ramp 56 illustrated in FIG. 45 . In addition, the front tapered end surface 64 of the needle 16 also radiates ultrasonic energy within the internal area of the tip to assist in the emulsification of nuclear tissue.
FIG. 47 illustrates an annular shaped ramp surface 66 that has a forwardly directed ramp surface 68 , a reduced diameter passageway 70 , and a stepped shoulder surface 72 . Ramp surface 68 emits ultrasonic energy to aid in the emulsification of tissue, whereas shoulder surface 72 emits ultrasonic energy to assist in the suction of the emulsified tissue.
FIG. 48 illustrates a needle tip 16 that has the tip end 71 off-center (i.e., not concentric) with respect to the main portion of the tip 16 . An internal ramp surface 74 emits ultrasonic energy adjacent to the aspiration port 18 to assist in the emulsification of nuclear tissue. A stepped shoulder surface 76 assists in the suction of that emulsified tissue by generating ultrasonic waves in the direction of flow. Additionally, an external ramped surface 73 emits ultrasonic energy to aid in the cutting and emulsifying of nuclear tissue.
FIG. 49 illustrates a needle tip 16 that has a wedged shape front tip surface 78 . Surface 78 emits ultrasonic energy outside and forward of the tip end to assist in the cutting of nuclear tissue. In addition, a shoulder surface 80 disposed adjacent to the aspiration port 18 assists in pushing the material into the interior of the needle tip 16 . Internal surfaces 82 , 83 also emit ultrasonic radiation energy to assist in the emulsification of nuclear tissue.
FIG. 50 illustrates an embodiment similar to that illustrated in FIG. 49 in that a front wedged shape surface 84 and ramp surfaces 86 , 87 are utilized in a similar manner to surfaces 78 , 82 and 83 in the embodiment illustrated in FIG. 49 .
Referring now to FIGS. 51 and 52. A compressible sleeve 88 is illustrated. Sleeve 88 includes an accordion section 90 to permit the sleeve 88 , once it is connected to the handpiece 11 (not shown in FIGS. 51 and 53) at area A, to move axially with respect to the handpiece. Sleeve 88 is connected to the handpiece by a fluid tight connection, which permits the handpiece 11 to rotate freely with respect to the sleeve 88 . When the tip end of the needle 16 is inserted into the incision 14 of the cornea 16 , the forward end 92 of the sleeve 88 extends through the corneal surface 16 , such that forward end 92 substantially matches to the incision 14 in the cornea. Due to the accordion design and to the rotational coupling, the handpiece and needle can be manipulated to a limited extent in the axial direction and rotated freely about the longitudinal axis while the sleeve 88 will remain stationary with respect to the cornea 16 . Thus, this forward portion 92 of the sleeve acts similar to a plug to completely seal the incision in the cornea. In addition, the infusion port at the distal end of the sleeve 92 is located near the cornea and away from the aspiration hole 18 of the needle. Thus, there is considerably less turbulence within the eye which provides for better aspiration of emulsified tissue. In other words, if the infusion port is located too close to the aspiration port, the fluid will naturally follow a path of least resistance and short circuit directly from the infusion port to the aspiration port, which clearly reduces the amount of tissue that can be removed from the eye or at the very least reduces the amount of time it takes to remove the desired amount of tissue from the eye.
Having described the presently preferred exemplary embodiment of a new and improved phacoemulsification handpiece, sleeve, and tip, in accordance with the present invention, it is believed that other modifications, variations and changes will be suggested to those skilled in the art in view of the teachings set forth herein. It is, therefore, to be understood that all such variations, modifications, and changes are believed to fall within the scope of the present invention as defined by the appended claims. | A phacoemulsification instrument that significantly reduces infusion fluid leakage by providing a silicone sleeve with a built in reinforcing member. Also, the sleeve has only a single infusion hole in order to provide better infusion fluid flow without causing turbulence in the eye. In addition, the present invention provides either a valve or a variable aperture aspiration tube in order to regulate the aspiration rate. Also, the present invention includes a single aspiration hole at the tip in order to amplify flow coming to the tip. To assist in cataract removal, the tip may be provided with a variety of different barrier and baffle configuration. A handpiece includes a variable capacity reservoir in the infusion line to account for surges in the aspiration line. The needle includes steps, angles and barriers to focus ultrasonic energy to aid in emulsifying nuclear tissue and to aid in pushing emulsified material in the direction of aspiration flow. A compressible sleeve is rotatably coupled to the handpiece to permit the handpiece and needle to be manipulated to a limited extent in the axial direction and rotated freely about the longitudinal axis while the sleeve remains stationary with respect to the cornea. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of Invention
[0002] The present invention relates generally to toy building sets for children, and more particularly, to toy sets made up of stackable structural members and construction fastening devices from which composite building structures of sufficient complexity may be erected to challenge a range of child ages and interests.
[0003] 2. Description of the Prior Art
[0004] Toys are an important ingredient in childhood development. Toys not only offer amusement, but they can effect the physical, cognitive, emotional and social growth of children. For example, age-appropriate hands-on toys help develop fine-tuning motor skills and hand-to-eye coordination in children. Structural building blocks are especially suitable for facilitating those attributes in children, and have been known in the art for many years going back at least to 1922 when U.S. Pat. No. 1,402,438 to Nichols was issued for Lincoln Logs© type building blocks. Many toy building block sets, as described below, are limited to simple structural members that can be interfitted or stacked to erect small, modular, building structures like houses.
[0005] U.S. Pat. No. 2,110,990 to Forbes, for example, discloses a toy building set having various linear wooden structural members with multiple notches that allow the members to be stacked in the shape of a cabin having vertical walls and a pitched roof. The stated advantage of the toy set is the ability to form gable-ended roof structures to demonstrate the superior rigidity of the structure compared to previous toy sets.
[0006] U.S. Pat. No. 4,270,304 to Sofer improves on the basic structural member building block toy set by providing structural members having multiple numbers of rectangular notches along the length of the members. Those multi-notched members facilitate erection of not only plane and horizontal surfaces, but also stepped (i.e., slopped) surfaces.
[0007] U.S. Pat. No. 4,372,076 to Beck discloses a toy set having modular interlocking structural construction pieces made of wood that may be assembled in the shape of a cabin or house. The toy set preferably includes up to twenty different shaped members having rectangular notches at the ends on one or more sides that allow the pieces to stack together thereby, forming crossed, half-lap joints. It is stated that the toy set enhances rational thinking and reasoning in children and adults as a result of the assembly process and also teaches the relationship between orderliness and efficiency.
[0008] Simple building block toy sets like the aforementioned toy sets rely entirely on notches that form loose joints and friction for holding the assembled modular structure together. Interfitting or stackable wood pieces with fastening devices add a degree of complexity to the toy set and enhance their educational value. U.S. Pat. No. 4,389,808 to Podell et al., for example, discloses a toy set having multiple wood pieces with pre-drilled aperatures for receiving oversized wooden bolts and nuts. U.S. Pat. No. 5,881,515 to George discloses a toy set having several different shaped modular structural members and fasteners for erecting toy structures. George discloses structural members with evenly spaced, pre-drilled apertures along the length of the members for receiving fasteners. In George, the different types of fasteners include dowels, pegs, bolts, screws, pins and flexible barbs made of various materials.
[0009] Toy sets that involve using a hammer or other striking tool to strike pegs or objects can further enhance development of motor skills and hand-to-eye coordination in children. U.S. Pat. No. 3,138,894 to Reaux, for example, discloses a peg board toy that allows a child to strike wooden pegs in pre-drilled holes using a hammer. The object of the toy is to provide amusement and assist developing physical coordination. Similarly, U.S. Pat. No. 1,555,993 to Larson discloses a toy block set having a nail connected to a spring that can be repeatedly driven into the block by striking it with a hammer.
[0010] Combining building block toy sets with toys having hammerable fasteners would offer increased complexity and, therefore, enhance the physical, cognitive, and emotional growth of children while providing a source of amusement.
SUMMARY AND OBJECTS OF THE INVENTION
[0011] In view of the foregoing, it should be apparent that there exists a need in the art for a building block toy set that includes interfitting and/or stackable structural members and hammerable construction fasteners that challenge the development of a range of children of different ages and interests.
[0012] Accordingly, it is a principal object of the present invention to provide a structural member that is stackable on other structural members and has one or more apertures extending through the structural member for receiving a fastener, and to provide a fastener that is insertable in the aperture of the structural members for connecting two or more of the structural members together.
[0013] It is another object of the present invention to provide a fastener in the shape of a nail that can be struck with a hammer.
[0014] It is still another object of the present invention to provide structural members and fasteners of various sizes for erecting a modular structure that is sufficiently complex to challenge a wide range of children, both physically, cognitively, emotionally, and socially and that is entertaining and interesting.
[0015] Briefly described, these and other objects and features of the present invention are accomplished, as embodied and fully described herein, by a series of linear structural members made of virgin or recycled wood, plastic, metal or other lightweight yet rigid material or a combination of those materials having a generally rectangular profile that can be stacked together to form horizontal and vertical planar surfaces defining the walls, ceiling, floor and roof of a building structure, such as a cabin or a house. Windows, doors, dormers, chimneys and other conventional items may be integrated into the composite building structure. There are two types of linear structural members: base pieces and stacking pieces. The base and stacking pieces have approximately the same width, but the height of the base pieces is generally half the height of the stacking pieces. The lengths of each piece varies.
[0016] To provide dimensional stability in the modular structure, each structural member may include one or more apertures that is pre-drilled in the member and extends through the member for receiving a fastener. Each aperture is counterbored to provide a countersink recess for the head of a nail-like fastener. The nail-like fastener is made of virgin or recycled plastic, wood, metal or other material or a combination of those materials and has a generally flat head, round shank and flat or tapered tip. The diameter of the shank is equal to or slightly larger than the diameter of the aperture so that when the fastener is inserted in the aperture it is held in place by friction contact with the surface of the walls of the aperture. The fastener is designed not to fail under moderate compressive forces from a hammer striking the head of the fastener and also from moderate bending or torsional forces applied to the head and shank.
[0017] The objects and features of the invention are also accomplished by a method of using the linear structural members and fasteners. With a supplied hammer, a child may outline the shape of a building structure using base pieces and then begin adding stacking pieces on top of the base pieces to form walls. One or more fasteners are inserted into one or more apertures on the pieces and driven into the apertures with the hammer to hold them together.
[0018] With these and other objects, advantages and features of the invention that may become hereinafter apparent, the nature of the invention may be more clearly understood by reference to the following detailed description of the invention, the appended claims and to the several drawings attached herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] [0019]FIG. 1 is a drawing of a perspective view of the set of linear structural members of the present invention showing both base and stacking pieces;
[0020] [0020]FIG. 2 is a partial, cross-sectional, perspective view of one of the base pieces shown in FIG. 1;
[0021] [0021]FIG. 3 is a partial, cross-sectional, perspective view of one of the stacking pieces shown in FIG. 1;
[0022] [0022]FIG. 4 a is a side view of one embodiment of a fastener of the present invention;
[0023] [0023]FIG. 4 b is a side view of another embodiment of a fastener of the present invention;
[0024] [0024]FIG. 4 c is a side view of another embodiment of a fastener of the present invention;
[0025] [0025]FIG. 5 is a perspective view of some of the base and stacking pieces of FIG. 1, and the fastener of FIG. 4 b being inserted into an aperture on the pieces;
[0026] [0026]FIG. 6 is a perspective view of a toy claw and anvil hammer with an oversized grip;
[0027] [0027]FIG. 7 is a perspective view of a finished composite building made from the base and stacking pieces shown in FIG. 1 and the fasteners shown in FIGS. 4 a , 4 b and 4 c ; and
[0028] [0028]FIG. 8 is a drawing of a child using the fasteners shown in FIGS. 4 a , 4 b and 4 c , the base and stacking pieces shown in FIG. 1, and the hammer shown in FIG. 6.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0029] Several preferred embodiments of the invention are described for illustrative purposes, it being understood that the invention may be embodied in other forms not specifically shown in the drawings.
[0030] Referring now in detail to the drawings, wherein like parts are designated by like reference numerals throughout, FIG. 1 is a perspective drawing of a set of linear structural members of the present invention each made from virgin or recycled wood, plastic, metal or other lightweight yet rigid material or a combination of those materials. As shown in FIG. 1, there are two kinds of structural members: base pieces 102 , 104 and 106 , and stacking pieces 108 , 110 , 112 , 114 , 116 , 118 and 120 . The base pieces 102 - 106 are approximately rectangular and have a width W b , height h b , and length l b such that l b >W b and l b >h b (see FIG. 2). The width and height dimensions can be linearly related according to W b ≈p×h b , where p=2, 3, . . . n; however, it is preferred that W b ≈2×h b . That is, the width dimension is approximately twice the height dimension. It is contemplated that the width dimension may be slightly greater than or less than twice the height dimension.
[0031] The stacking pieces 108 - 120 are approximately rectangular and have a width w s , height h s , and length l s such that l s >w s and l s >h s (see FIG. 3) The width and height dimensions can be linearly related according to w s ≈p×h s , where p=1, 2, 3, . . . n; however, it is preferred that w s ≈h s . That is, the width dimension is approximately equal to the height dimension. Again, it is contemplated that the width dimension can be slightly greater than or less than the height dimension. It is also preferred that W b ≈w s . That is, the width dimension of the base pieces should be approximately equal to the width dimension of the stacking pieces. The cross-sectional dimensions W b and h b , in the case of the base pieces 102 - 106 , and w s and h s , in the case of the stacking pieces 108 - 120 , are nearly constant along the length of the individual pieces.
[0032] As shown in FIG. 1, the base pieces 102 - 106 and the stacking pieces 108 - 120 have apertures A drilled through the pieces so that the longitudinal axes of the apertures are approximately perpendicular to the longitudinal axis of the pieces. The apertures A are separated by a distance d apart. Preferably, the apertures A are evenly spaced along the length l b and l s of the pieces. The number of apertures A on each piece depends on the lengths l b and l s and the separation distance d. For example, as shown in FIG. 1, when d is approximately 0.75-inches, there would be 20 holes on a base or stacking piece that is 15-inches long (see base piece 106 and stacking piece 120 , for example), 18 holes on a piece that is 13.5-inches long (not shown), 10 holes on a piece that is 7.5-inches long (base piece 104 and stacking piece 118 ), 6 holes on a piece that is 4.5-inches long ( 102 , 116 ), 5 holes on a 3.75-inch piece ( 114 ), 4 holes on a 3-inch piece ( 112 ), 3 holes on a 2.25-inch piece ( 110 ), and 2 holes on a 1.5-inch piece ( 108 ). If the distance d is greater than or less than 0.75-inches, then a fewer or greater number of apertures A may be included on each piece.
[0033] Some of the pieces may include apertures A that are not equally separated by the same distance d. For example, on one piece the apertures A may be spaced 0.75 inches apart and on another piece the apertures A may be spaced 1.5-inches apart. Further, the apertures A may be grouped at a particular end of the pieces or grouped on both ends with the center portions having no apertures A at all. As shown in FIG. 1, it is preferred that the apertures A be round; however, they may also be square, rectangular, triangular, oval or other non-round shape. Further, each piece 102 - 120 may have a combination of different shaped apertures A.
[0034] [0034]FIG. 2 is a partial, cross-sectional, perspective view of one of the base pieces shown in FIG. 1. Each aperture A has an outside diameter D 1 that is pre-drilled in the piece. The apertures A are preferably pre-drilled completely through the piece forming a hole 204 . In some instances, however, the apertures A may be pre-drilled to a depth that is less than the height of the piece. Each aperture may be counterbored to provide a countersink recess 202 to accept the shape of a fastener (see FIGS. 4 a , 4 b and 4 c ) so that the fastener is flush with the top surface of the base or stacking piece. The countersink is made to a depth s on one end of the aperture and has a diameter D 2 such that D 2 >D 1 .
[0035] Similarly, FIG. 3 is a partial, cross-sectional, perspective view of one of the stacking pieces shown in FIG. 1. As shown in FIG. 3, each aperture A has a countersink 302 and a pre-drilled hole 304 and is separated by a distance d. The dimensions of each aperture A in FIG. 3 are the same as the dimensions of the apertures A on the base piece shown in FIG. 2.
[0036] The apertures A on the linear structural members are designed to accept a fastener like that shown in FIG. 4 a . FIG. 4 a is a side view of one embodiment of a fastener 400 according to the present invention. The fastener 400 is made of virgin or recycled plastic, wood, metal or other material or a combination of those materials and generally resembles a flat-head nail having a head, shank and tip. Although a nail-like fastener is preferred, other types of fasteners may also be used without departing from the nature and scope of the invention, such as screws, pins, rivets, bolts and the like.
[0037] The shank 406 of the fastener 400 should have a diameter D 3 that is equal to or (preferably) slightly larger than the diameter D 1 of the aperture A so that the fastener 400 is held in the aperture A by friction contact with the surface of the walls of the aperture hole 204 (FIG. 2). It will be appreciated by one of ordinary skill in the art that the size of D 3 will vary depending on the tightness of the friction fit desired. When the fastener 400 is inserted in the aperture A, the radial force exerted by the shank 406 of the fastener 400 against the surface of the aperture hole 204 should be sufficient to hold the fastener 400 in place but not too great that a child will not be able to readily separate the linear structural members with reasonable force. Further, it is contemplated that the friction force will be small enough so that a child of reasonable strength can manually insert the fastener 400 by using, for example, a thumb or finger pressed against the top of the head 402 and applying a force in the direction of the longitudinal axis of the fastener 400 . Separation of the linear structural members connected by a fastener 400 , or removal of the fastener 400 from an aperture A, is facilitated by the opening 408 in the shank 406 that flexes inward when the fastener 400 is inserted in the aperture A. The slit-type opening 408 reduces some of the friction force exerted by the shank 406 of the fastener 400 against the surface of the hole 204 .
[0038] As also shown in FIG. 4 a , the head 402 has a height s equal to the depth s of the countersink of the apertures A. This allows the fastener 400 to fit approximately flush in the aperture A. The head 402 has a diameter D 2 approximately equal to the diameter D 2 of the countersink of the apertures A.
[0039] The shank 406 of the fastener 400 is long enough to hold two linear structural members together. Clearly, when a stacking piece is on top of a base piece, the shank 406 should be equal to or less than the combined height of those two pieces, or h b +h s . However, when a stacking piece is stacked on top of another stacking piece, the shank 406 should be equal to or less than the combined height of those two pieces, or h s +h s . Thus, it is contemplated that different lengths of fasteners 400 will be required.
[0040] [0040]FIG. 4 b is a side view of another embodiment of a fastener 420 according to the present invention. The fastener 420 has all of the same features and attributes of the fastener 400 , except for the opening 428 and lower shank 430 shown in FIG. 4 b . The fastener 420 includes a top 422 , head 424 , upper shank 426 , opening 428 , lower shank 430 and tip 432 . The opening 428 is larger than the opening 408 on the fastener 400 and extends along a larger length of the upper shank 426 of the fastener 420 compared to opening on the shank 406 of the fastener 400 . The lower shank 430 has a slightly smaller diameter of length h t , such that h t <h b and h t <h s . The lower shank 430 and the tip 432 have a diameter D 4 that is equal to or (preferably) slightly smaller than the diameter D 1 of the aperture A. The smaller diameter of the lower shank 430 and the tip 432 act as a guide when inserting the fastener 420 in the aperture A and allow that portion of the fastener 420 to be loosely held in the aperture A by friction contact with the walls of the aperture hole 304 (FIG. 3). Most of the friction force will be exerted by the upper shank 426 .
[0041] [0041]FIG. 4 c is a side view of another embodiment of a fastener 440 of the present invention. The fastener 440 includes a top 442 , head 444 , shank 446 and tip 450 . The end of the shank 446 and the tip 450 have a diameter D 3 that is equal to or (preferably) slightly larger than the diameter D 1 of the aperture A so that the fastener 440 is held in the aperture A by friction contact with the surface of the walls of the aperture hole 204 (FIG. 2) or the hole 304 (FIG. 3). The shank 446 shown in FIG. 4 c is hour-glass shaped (exaggerated for clarity) to reduce the friction force exerted by the fastener 440 .
[0042] [0042]FIG. 5 is a perspective view of a composite structure 500 made from the base pieces 102 and 104 and the stacking pieces 108 and 116 being connected together using the fasteners 420 inserted into the apertures A on the pieces.
[0043] [0043]FIG. 6 is a perspective view of a toy claw and anvil hammer 600 with an oversized grip. Any type of striking device suitable for use by children in connection with the present invention may be used.
[0044] [0044]FIG. 7 is a perspective view of a finished composite building 700 made from the base pieces 102 - 106 and the stacking pieces 108 - 120 shown in FIG. 1, and the fasteners 400 , 420 and 440 shown in FIGS. 4 a , 4 b and 4 c , respectively. Composite building 700 may include a separately assembled roof 702 with one or more optional dormers 704 , upper windows 706 , lower windows 708 , front entrance 710 , garage door 712 and chimney 714 (not shown). Some of those building items may be attached to the outside of the building structure 700 , like the dormers 704 , the upper windows 706 , and the front entrance 710 . Other building items may be integrated into the building structure 700 , like the garage door 712 . However, each of the aforementioned building items may be either integrated into the building structure 700 or attached to the outside, depending on the desires of the user. It will be appreciated by one of ordinary skill in the art that other sizes and configurations of building structures may be assembled from the pieces 102 - 120 shown in FIG. 1.
[0045] [0045]FIG. 8 is a drawing of a child using the fasteners 400 , 420 and 440 shown in FIGS. 4 a , 4 b and 4 c , the base pieces 102 - 106 and the stacking pieces 108 - 120 shown in FIG. 1, and the hammer 600 shown in FIG. 6. To assemble a building structure 800 , a user outlines the foundation 802 of the structure 800 using base pieces 102 - 106 and then begins building walls 804 by stacking one or more stacking pieces 108 - 120 as shown in FIG. 8. After each layer is added, a fasteners 806 may be inserted into one of the apertures A. Using the hammer 600 , the fastener 806 is inserted into the aperture A by striking the top of the fastener 806 with the hammer 600 .
[0046] Although only preferred embodiments are specifically illustrated and described herein, it will be appreciated that many modifications and variations of the present invention are possible in light of the above teachings and within the purview of the appended claims without departing from the spirit and intended scope of the invention. | A toy log assembly set is disclosed having various length stackable log-like structural members, nail-like fasteners and a hammer for building composite structures like a house or cabin and stimulating child development. Structural members may include base pieces and/or stacking pieces that are used to form the foundation and walls of the composite building structure. Each of the pieces has an aperture for receiving the fasteners to secure the pieces together and some or all of the apertures are countersunk to receive the head of the fasteners. A hammer may be used to insert the fasteners completely in the apertures. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to salt, pepper and granular, powdery, or other particle condiment dispensers. More particularly, the present invention relates to sprayers utilizing air pressure within a container to eject particles stored within the container to form a spray of air and suspended particles.
2. Description of the Prior Art
The common and readily available salt and pepper shaker, as well as similar structures for other condiments, are well known. The salt and pepper, hereinafter referred to generally as particulate material, are stored within a container and poured from the container onto food through a pattern of holes in a top of the container. The principal drawback to the common device is the inability to measure even reasonably precisely the amount of particulate material to be deposited onto the food. In addition, material is easily spilled if the common devices are turned over or upset for any reason. Though salt and pepper are dispensed in a single grinder, none of the common devices are capable of dispensing both without a grinder. Finally, virtually all spice dispensers use screw on and off caps or lids, which are inconvenient.
U.S. Pat. No. 2,609,971 to M. Vivolo shows a salt dispenser in which salt flows by gravity into an air passage in a small but uncontrolled accumulation. Squeezing a bulb generates a pulse of compressed air, which flows through the passage and carries the salt out of the dispenser. Vivolo incorporates a storage area with a convex bottom having a hole at the lowermost position for the feeding of the particulate material through the hole and into the passage. The passage communicates with the bulb to receive compressed air to force the particulate material through a projecting nipple for dispensing onto the food.
The difficulty with Vivolo, as well as all of the prior art using air pressure to force particulate material along a passage, is that the air which flows along the passage must force the material directly from the dispenser. This process has three drawbacks. Firstly, the passage is more likely to be clogged by the particulate material as some material is pushed by air pressure, while other material is moved by collisions with the material directly influenced by air pressure. Secondly, the particulate material is not necessarily dispersed evenly into the spray of air by the pulse of air generated. Thirdly, it is not likely that any preselected amount of particulate material will be dispensed, since the volume of the passage available for a pulse of air is not controlled nor controllable.
Italian Pat. No. 449,894 is also a sprayer utilizing a piston and bellows to eject particulate material from the device. As in Vivolo the material is deposited into a passage and then air pressure is used to eject the material. A linkage meters the particulate material into the passage tube.
U.S. Pat. No. 3,785,568 to E. Pfingsten passes a gaseous fluid at pressure through a tube which intersects and communicates with a second depending tube. The depending tube extends into a reservoir of material. The passage of the gaseous fluid develops a low pressure area in the depending tube which causes the material to be elevated into the gaseous fluid stream and carried away. Pfingsten does not use direct air pressure to move particulate material and therefore defines a more evenly dispersed spray. However, Pfingsten still moves material with direct air pressure down a common feed tube, which is more likely to be clogged.
U.S. Pat. No. 2,126,924 to W. Rose is a dust sprayer utilizing a manually operated plunger to force air through openings over one end of a tube. The other end of the tube communicates with a dust filled zone above powder stored in a container. The air flow generated by the plunger over the openings generates a low pressure zone, which draws dust up the tube. The same plunger action forces air down another tube and through a powder body to enhance the efficiency of the sprayer by creating a dust cloud into which the first tube depends. Rose is similar to Pfingsten in using high velocity air, created by a plunger, to draw powder into a tube by creating a low pressure zone.
U.S. Pat. No. 4,120,427 to J. McRoskey, et al. shows a powder container including an annular air channel through which air is forced by the action of a diaphragm. This action reduces the volume of the container. Venturi openings connect the interior of the container with a channel which allows powder to be drawn into the channel and exhausted through a discharge nozzle.
U.S. Pat. No. 1,554,991 to J. Crowley forces air through a nozzle to draw powder from a reservoir. Crowley uses gravity in combination with air pressure to move the powder.
U.S. Pat. No. 2,202,079 to W. Ayres shows a dispenser for powder which employs air flow through tubes to generate suction at venturi locations, drawing powder into the air flow for transport out of the dispenser. Again, positive air pressure, rather than negative or low pressure, is used to move the material.
U.S. Pat. No. 2,358,329 to E. Houghton compresses air in a chamber by depression of a member, forcing air through a tube, past a slot and to a tube exit. The slot communicates with powder in a container. The passage of the high pressure air over the slot draws powder into the air stream under the influence of the low pressure thereby created.
U.S. Pat. No. 3,904,087 to J. McRoskey, et al. uses a longitudinally extending tube with spaced venturi openings to pull powder into an air stream passing vertically upward through the tube. Squeezing and releasing an outer container forces the material from an inner container into the tube, through a nozzle, ejecting the material from the device.
OBJECTS AND SUMMARY OF THE INVENTION
It is the principal object of the present invention to provide a dispenser for particulate material using air pressure to create a low pressure area to draw particulate material from the bottom of a container and eject the particulate material in an evenly dispersed spray.
In accordance with the objects of the invention, a particulate material sprayer includes a container divided into an upper air compartment and a lower storage compartment. The air compartment is separated from the storage compartment by a mid portion bulkhead. A piston or air moving means is slideably mounted in the air compartment and is biased away from the bulkhead by a spring. Manual downward displacement of the piston forces air from the air compartment through an air passageway.
A vertical tube extends downwardly into the storage compartment, which storage compartment holds salt, pepper or other condiments, hereinafter referred to as particulate material. The vertical tube is in air flow communication with the air passageway, a venturi opening is located in the air passageway at the intersection of the vertical tube and the air passageway. High pressure or compressed air in the air passageway results from downward movement of the piston in the air compartment. The air flows past the venturi opening at an increased velocity and creates a low pressure area or zone at the top of the vertical tube. The low pressure zone draws particulate material from the storage compartment via the vertical tube. The material is dispersed into the air ejecting from the sprayer through an outlet, creating a spray of air dispersed with suspended material.
The creation of a low pressure area by a venturi opening outside the flow path of the particulate material minimizes the chances of clogging the air passageway or the vertical tube. Each actuation of the piston disperses a spray having an amount of material which is directly proportional to the extent that the piston is depressed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a partical sprayer of the present invention.
FIG. 2 is a full sectional view taken along line 2--2 of FIG. 1.
FIG. 3 is a sectional view similar to FIG. 2, a piston being shown in a depressed position.
FIG. 4 is a perspective view of an alternative embodiment of the particle sprayer shown in FIG. 1.
FIG. 5 is a sectional view taken along line 5--5 of FIG. 4.
FIG. 6 is a sectional view taken along line 6--6 of FIG. 4.
FIG. 7 is a sectional view taken along line 7--7 of FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring first to FIG. 1, a particle sprayer 10 is used to dispense a spray 11 (FIG. 3) of air and salt, pepper or other condiment, hereinafter referred to as particulate material 12. (FIG. 2). The sprayer 10 is particularly useful to dispense, in the spray 11 of air and suspended particulate material 12, a predetermined amount of the material 12. The spray 11 dispenses the material 12 at the predetermined amount by manually pressing a button 14 to the limit of its downward motion. Lesser amounts can be measured by depressing the button 14 over lesser downward motions.
As seen in FIG. 2, the button 14 is integrally connected to a circular piston 16, comprising air moving means, which slides along an inner surface of a main body 18 of the sprayer 10. The movement of the piston 16 creates air pressure along an air passageway 20 of essentially constant cross sectional area and past an outlet orifice 22 of a vertical discharge tube 24. The tube 24 extends into the air passageway 20 to provide air flow communication between the tube 24 and the air passageway 20. The tube 24 partially closes the air passageway 20, forming a restriction in the cross sectional area of the air passageway 20, hereinafter referred to as a venturi opening 64.
The other end of the tube 24 is inserted into the particulate material 12. Low pressure developed at the outlet orifice 22, located immediately adjacent the venturi opening 64, draws the particulate material 12 up the discharge tube 24, where the material 12 is mixed with the air in the passageway 20. An outlet 26 formed in the main body 18 is immediately downstream of the outlet orifice 22 and registers with the air passageway 20. The material 12 is dispersed into the air and ejected from the sprayer 10 through the outlet 26. The result is an even dispersion of the particulate material 12 with the air. The chance of blocking either the air passageway 20 or the discharge tube 24 is significantly reduced.
The main body 18 is of generally cylindrical shape and of a suitable size to be grasped easily by the human hand. The body 18 includes a top end 28 and a bottom end 30. The top end 28 includes a raised portion 32 integrally connected to a land portion 34 through an arcuate surface 36. The button 14 projects through a slot 38 formed in the land portion 34 and the arcuate surface 36.
The bottom end 30 of the main body 18 includes a circular opening 40 through which opening 40 the particulate material 12 is deposited into a storage compartment 42 formed interiorly of the main body 18. An end cap 44 threadably connects to the bottom end 30 to close the circular opening 40 and maintain the material 12 in the sprayer 10. (FIG. 2). Alternative end cap 45 is seen in FIG. 3.
The button 14 and the piston 16 are integrally formed as by plastic injection molding or similar conventional manufacturing process. The button 14 is biased by spring 46 to a position wherein a finger pad 48 of the button is essentially flush with and coplanar with the raised portion 32 of the main body 18. The integral piston 16 is of disc shape and extends radially from a longitudinal axis of the main body 18 to sealingly contact an inner surface 50 of the main body. An air compartment 52 defined by the inner surface 50 of the main body 18 extends downwardly from the top end 28 a predetermined distance equal to the stroke of the piston 16 as established by manually depressing the button 14.
A bulkhead or middle portion 54 separates the air compartment 52 from the storage compartment 42. The bulkhead 54 is separately formed, as by injection molding. During assembly of the sprayer 10, the bulkhead 54 is inserted through the circular opening 40 into the main body 18 and connected to the inner surface 50 at a preselected location in any conventional manner.
The piston 16 includes an integral central post 56 lying along the longitudinal axis of the sprayer 10 and projecting downwardly from the piston 16 directly under the finger pad 48 of the button 14. The spring 46 is coaxial with the central post 56, which post 56 is inserted into the spring 46. The bulkhead 54 includes an upward sleeve or guide 58 which is circumscribed by the spring 46.
Manually actuating the button 14 causes the piston 16 to descend into the air compartment 52 and compresses the spring 46 about the central post 56 and the sleeve or guide 58. (FIG. 3). As the piston 16 descends in the air compartment 52, the air is forced into the air passageway 20. The air passageway 20 includes an inlet 60 formed by drilling, molding or similar process in a top planar surface 62 of the bulkhead 54. From the inlet 60, the air passageway 20 turns through an elbow to extend radially away from the longitudinal axis of the sprayer 10 toward the vertical discharge tube 24 and the outlet 26. The vertical discharge tube 24 frictionally fits into a bore 61 formed in the bulkhead 54. The outlet orifice 22 of the discharge tube 24 extends into the air passageway 20 and restricts the cross-sectional area of the air passageway 20 through which air flows, defining the venturi opening 64.
A low pressure area 66 is defined adjacent to the outlet orifice 22 of the discharge tube 24. The low pressure area 66 acts with the discharge tube 24 to pull the particulate material 12 from the storage compartment 42 and out the outlet 26.
The end cap 44 includes a raised central portion 68 which directs the material 12 downwardly to a peripheral feed trough 70 adjacent to an input orifice 72 of the discharge tube 24. A sloping surface 69 is used by the alternative cap 45 to achieve the same result.
In operation, the button 14 and integral piston 16 are depressed into the air compartment 52. Air under pressure is forced into the inlet 60 and directed along the air passageway 20. The venturi opening 64 increases the velocity of the air flowing in the air passageway 20, creating the low pressure area 66. The particulate material 12, which is directed into the feed trough 70, and/or is located in the discharge tube 24, is drawn up the discharge tube 24 and dispersed into air exiting through the outlet 26 as the spray 11. The particulate material 12 is deposited in an amount depending on the extent to which the piston 16 is depressed.
Release of the piston 16 creates some back pressure along the air passageway 20. Any of the particulate material 12 deposited in the air passageway 20 downstream of the venturi opening 64, and not discharged, might be drawn back into the air passageway 20, or even the air compartment 52. This is undesirable and might ultimately cause corrosion, blockage or deterioration of the seal between the piston 16 and the interior surface 50. This is substantially prevented by the fact that the outlet orifice 22 of the discharge tube 24 extends partially across the air passageway 20 to create the venturi opening 64. Any back pressure along the air passageway 20 will draw the granular material 12 toward the outlet orifice 22 where the granular material 12 will be physically blocked from further travel up the air passageway 20 by the outlet orifice 22. The orifice 22 includes a chamfer surface 65, which angles downwardly from the venturi opening 64 to a position flush with the air passageway 20. The orifice 22 is of substantially the same diameter as the air passageway 20, so that any material 12 suspended in a back flow will strike the discharge tube 24, and because of the chamfer surface 65, drop down the tube 24 and remain in the tube 24 until discharged, or will drop into the storage compartment 42.
In an alternative embodiment, a sprayer 80 is seen in FIGS. 4-7. The alternative embodiment includes two buttons 82a for salt and 82b for pepper. The buttons 82a and 82b are nested within an outer wall 84 integrally formed with a main body 86. Mechanically, the sprayer 80 operates in the identical manner to the sprayer 10. Physically, the main body 86 is divided into two portions, a salt portion 88 and a pepper portion 90. Thus there are two pistons 92a and 92b, two air compartments 94a and 94b and two storage compartments 96a for salt and 96b for pepper. The air compartments 94a and 94b and storage compartments 96a and 96b are separated by an integral separation wall 99. A pair of bulkheads 98a and 98b include a pair of outlets 100a and 100b associated with a pair of horizontal air passageways 102a and 102b. Discharge tubes 104a and 104b project upwardly from the storage compartments 96a and 96b to connect through the bulkheads 98a and 98b, defining venturi openings 105a and 105b. Between the bulkheads 98a and 98b and the buttons 82a and 82b a pair of leaf springs 106a and 106b, associated with the pistons 92a and 92b, are received.
Operation of the alternative embodiment of the sprayer 80 is identical to that of the sprayer 10 with the exception that a choice of dispensing salt or pepper can be made. The alternative embodiment of the sprayer 80 is advantageous in that a single sprayer is used which is both aesthetically pleasing to look at, efficient and attractive to the consumer.
Although the present invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made by way of example, and changes in detail or structure may be made without departing from the spirit of the invention, as defined in the appended claims. | A particle sprayer includes a hollow body divided into an air compartment and a storage compartment for particulate material. The air compartment receives a piston which is manually slideable along the length of the air compartment to create air pressure within the air compartment. An air passageway provides air flow communication between the air compartment and the exterior of the sprayer. A discharge tube extends into the material in the storage compartment at one end and at the other end intersects the air passageway near a restriction in the air passageway defining a venturi opening. Depression of the piston creates increased air flow velocity past the venturi opening and the resultant low pressure area draws material up the discharge tube from the storage compartment to be dispersed in a uniform amount into the air in the air passageway and ejected from the sprayer as a spray. | 1 |
[0001] This is a Continuation-in-Part Application of International Application No. PCT/JP01/09257 filed Oct. 22, 2001 which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to compositions for lowering the total amount of cholesterol in the blood, said compositions comprising pravastatin and one or more vitamins selected from the group consisting of riboflavins, d-α-tocopherols, ascorbic acids and inositol hexanicotinate.
[0003] Pravastatin exhibits activity in lowering the total amount of cholesterol in the blood due to HMG-CoA reductase inhibition in vivo. In addition, it is known that each of riboflavins, d-α-tocopherols, ascorbic acids and inositol hexanicotinate themselves have activity in lowering the total amount of cholesterol in the blood. Furthermore, it is also known that the total amount of cholesterol in the blood can be kept at a low level and the amount of d-α-tocopherols and ascorbic acid in the body is decreased by HMG-CoA reductase inhibitors and this can be supplemented by the combination of an HMG-COA reductase inhibitor and a d-α-tocopherol or an ascorbic acid (Japanese Patent Application Publication (Kohyo) No. Hei 8-505853).
[0004] However it has not previously been disclosed that the total amount of cholesterol in the blood is synergistically lowered by a combination of pravastatin and a riboflavin, d-α-tocopherol, ascorbic acid or inositol hexanicotinate. Pravastatin is a safe pharmaceutical agent, but it is administered for a long period. Therefore it has been required that lowering the total amount of cholesterol in the blood could be accomplished with a lower administered amount of pravastatin.
BRIEF DESCRIPTIONS OF THE INVENTION
[0005] The inventors of this invention have made a great effort to study compositions for lowering the total amount of cholesterol in the blood and found that lowering the total amount of cholesterol in the blood can be accomplished by a combination of pravastatin and a certain vitamin(s), even though a lower amount of pravastatin than that usually used before is administered.
[0006] The present invention is a composition for lowering the total amount of cholesterol in the blood, said composition comprising pravastatin and one or more vitamins selected from the group consisting of riboflavins, d-α-tocopherols, ascorbic acids and inositol hexanicotinate. Preferably, said composition comprises a combination of pravastatin and one or more vitamins selected from the group consisting of riboflavin tetrabutyrate, d-α-tocopherol butyrate, ascorbic acid and inositol hexanicotinate.
DETAILED DESCRIPTION OF THE INVENTION
[0007] Pravastatin (compound name: (+)-(3R,5R)-3,5-dihydroxy-7-[(1S,2S,6S, 8S,8aR)-6-hydroxy-2-methyl-8-[(S)-2-methylbutyryloxy]-1,2,6,7,8,8a-hexahydro-1-naphthyl]heptane) includes the compound of the following formula and a salt (particularly sodium salt) thereof; and is prepared according to the description of the specification of Japanese Patent Application Publication No. Sho 57-2240 and is commercially available.
[0008] Riboflavins refer to riboflavin itself and esters of riboflavin such as riboflavin tetrabutyrate.
[0009] Tocopherols refer to tocopherol itself (racemic form and optically active form) and esters of tocopherol such as tocopherol butyrate (racemic form and optically active form).
[0010] Ascorbic acids refer to ascorbic acid itself, salts of ascorbic acid such as the sodium salt of ascorbic acid and esters of ascorbic acid such as the stearate of ascorbic acid.
[0011] Inositol hexanicotinate refers to the ester of inositol wherein six hydroxyl groups are esterifed with nicotinic acid.
[0012] The total amount of cholesterol in the blood refers to the total amount of cholesterol and esters of cholesterol existing in the blood.
[0013] “Lowering” of the total amount of cholesterol in the blood means lowering to a
[0014] clinically significant degree.
[0015] The solid dosage form of the composition for improving lipid content in the blood of this invention usually contains 0.01 to 5 wt % (preferably 0.05 to 3 wt %) of pravastatin; 0.002 to 40 wt % (preferably 0.01 to 20 wt %) of riboflavins; 0.05 tc 50 wt % (preferably 0.5 to 25 wt %) of ascorbic acids; 0.002 to 40 wt % (preferably 0.02 to 20 wt %) of tocopherols and 0.05 to 50 wt % (preferably 0.5 to 25 wt %) of inositol hexanicotinate.
[0016] The liquid dosage form of the composition for lowering the total amount of cholesterol in the blood of this invention usually contains 0.01 to 10 mg/ml (preferably 0.05 to 5 mg/ml) of pravastatin; 0.05 to 5 mg/ml (preferably 0.1 to 3 mg/ml) of riboflavins; 1 to 10 mg/ml (preferably 3 to 7 mg/ml) of ascorbic acids; 0.5 to 5 mg/ml (preferably 1.5 to 3 mg/ml) of tocopherols; and 1 to 40 mg/ml (preferably 2 to 20 mg/ml) of inositol hexanicotinate.
[0017] An exemplary dosage form of the composition of this invention for lowering the total amount of cholesterol in the blood includes, for example, a tablet, a fine granule (including a powder), a capsule or a liquid dosage form. Each dosage form can be prepared by using an appropriate additive(s) and an active ingredient(s) according to a conventional procedure described in literature such as the Pharmacopeia of Japan.
[0018] In the dosage forms described above, various additives usually used can be employed depending on each dosage form.
[0019] For example, in the case of tablets, lactose, crystalline cellulose or the like can be used as an excipient; magnesium aluminometasilicate or the like can be used as a stabilizing agent; hydroxypropylcellulose or the like can be used as a binding agent; and magnesium stearate or the like can be used as a lubricating agent.
[0020] In the case of fine granules or capsules, lactose, purified sucrose or the like can be used as an excipient; magnesium aluminometasilicate or the like can be used as a stabilizing agent; corn starch or the like can be used an absorbing agent; and hydroxypropylcellulose, polysorbate or the like can be used as a binding agent.
[0021] In the case of liquid dosage forms, D-sorbitol solution, honey or the like can be used as a sweetening agent; dl-malic acid or the like can be used as a corrigent; disodium edatate or the like can be used a stabilizing agent; ethanol or the like can be used as a solubility-adjuvant agent; and polyoxyethylene stearate and hydrogenated castor oil 60 can be used as a solubilizing agent.
[0022] In each dosage form described hereinbefore, if necessary, a disintegrating agent such as crospovidone or the like; an absorbing agent such as calcium silicate or the like; a coloring agent such as iron sesquioxide, caramel or the like; a pH-adjusting agent such as sodium benzoate or the like and a flavoring agent can be added.
EXAMPLES
[0023] Throughout the Tables the following abbreviations are used with the following meanings.
[0024] ribo.: riboflavin, asco.: ascorbic acid, toco.: tocopherol
[0025] inos.: inositol hexanicotinate,
[0026] asco.+toco.: ascorbic acid and tocopherol
[0027] a.a.: appropriate amount, t.a.: trace amount
Example 1
Tablet
[0028] (1) Ingredients
TABLE 1 asco. in ribo. four tablets toco. (680 mg) (1440 mg) (840 mg) pravastatin sodium 20 mg 20 mg 20 mg riboflavin tetrabutyrate 12 mg — — ascorbic acid — 500 mg — tocopherol succinate — — 200 mg crystalline cellulose 120 mg 12 mg 12 mg magnesium aluminometasilicate 144 mg — — fatty acid ester of sucrose — 140 mg 108 mg Hydroxypropylcellulose 96 mg 48 mg 48 mg magnesium stearate 24 mg 24 mg 24 mg crospovidone 100 mg 48 mg 48 mg Lactose a.a a.a a.a
[0029] [0029] TABLE 2 inos. asco. + toco. in four tablets (1400 mg) (1400 mg) pravastatin sodium 20 mg 20 mg inositol hexanicotinate 500 mg — Ascorbic acid — 500 mg tocopherol succinate — 200 mg crystalline cellulose 12 mg 12 mg fatty acid ester of sucrose 140 mg 140 mg hydroxypropylcellulose 96 mg 48 mg magnesium stearate 24 mg 24 mg crospovidone 100 mg 48 mg Lactose a.a a.a
[0030] (2) Method for Preparation
[0031] Tablets are prepared in a similar procedure to that described in the general rules for preparation in the “tablet” section of the Pharmacopeia of Japan using the ingredients shown in Tables 1 and 2.
Example 2
Fine Granules
[0032] (1) Ingredients
TABLE 3 ribo. asco. toco. in four unit dosages (4 g) (5.2 g) (4.8 g) pravastatin sodium 20 mg 20 mg 20 mg riboflavin tetrabutyrate 12 mg — — ascorbic acid — 1.0 g — tocopherol succinate — — 200 mg purified sucrose 1.4 g 1.6 g 1.4 g extract from stevia — 16 mg — corn starch 1.2 g 1.2 g 1.2 g polysorbate-80 80 mg 48 mg 48 mg magnesium aluminometasilicate 144 mg — 128 mg magnesium stearate 24 mg 24 mg 24 mg Lactose a.a a.a a.a
[0033] [0033] TABLE 4 inos. asco. + toco. in four unit dosages (5 g) (5 g) pravastatin sodium 20 mg 20 mg inositol hexanicotinate 1000 mg — ascorbic acid — 1000 mg tocopherol succinate — 200 mg purified sucrose 1400 mg 1600 mg extract from stevia 16 mg 16 mg corn starch 1200 mg 1200 mg polysorbate-80 80 mg 48 mg magnesium aluminometasilicate 144 mg 144 mg magnesium stearate 24 mg 24 mg lactose a.a a.a
[0034] (2) Method for Preparation
[0035] Fine granules are prepared in a similar procedure to that described in the general rules for preparation of the “granule” section of the Pharmacopeia of Japan using the ingredients shown in Tables 3 and 4.
Example 3
Capsules
[0036] (1) Ingredients
TABLE 5 ribo. asco. toco. in 4 in 8 in 4 capsules capsules capsules pravastatin sodium 20 mg 20 mg 20 mg riboflavin tetrabutyrate 12 mg — — Ascorbic acid — 500 mg — tocopherol succinate — — 200 mg corn starch 960 mg 960 mg 840 mg polysorbate-80 80 mg 48 mg 48 mg magnesium aluminometasilicate 144 mg — 128 mg magnesium stearate 24 mg 24 mg 24 mg Lactose a.a a.a a.a Subtotal 1520 mg 1940 mg 1580 mg Capsule 320 mg 640 mg 320 mg Total 1840 mg 2580 mg 1900 mg
[0037] [0037] TABLE 6 inos. asco. + toco. in 8 capsules pravastatin sodium 20 mg 20 mg inositol hexanicotinate 500 mg — Ascorbic acid — 500 mg tocopherol succinate — 200 mg corn starch 960 mg 960 mg polysorbate-80 80 mg 48 mg magnesium aluminometasilicate 144 mg 144 mg magnesium stearate 24 mg 24 mg Lactose a.a a.a Subtotal 2000 mg 2000 mg Capsule 640 mg 640 mg Total 2640 mg 2640 mg
[0038] (2) Method for Preparation
[0039] Capsules are prepared in a similar procedure to that described in the general rules for preparation in the “granule” section of the Pharmacopeia of Japan using the ingredients shown in Tables 5 and 6, followed by filling the resulting fine granules into each capsule.
Example 4
Liquid Dosage Forms
[0040] (1) Ingredients
TABLE 7 ribo. asco. toco. in 100 ml pravastatin sodium 20 mg 20 mg 20 mg riboflavin sodium phosphate 20 mg — — ascorbic acid — 500 mg — d-α-tocopherol acetate — — 50 mg D-sorbitol solution (70%) 4 g 6 g 4 g Honey 7 g 8 g 7 g dl-malic acid 200 mg — 200 mg sodium edatate 20 mg 20 mg 20 mg Ethanol 2 ml 2 ml 2 ml polyoxyethylene stearate 100 mg 100 mg 100 mg hydrogenated castor oil 60 sodium benzoate 60 mg 60 mg 60 mg flavoring agent t.a. t.a. t.a. purified water a.a. a.a. a.a
[0041] [0041] TABLE 8 inos. asco. + toco. in 100 ml pravastatin sodium 20 mg 20 mg inositol hexanicotinate 500 mg — ascorbic acid — 500 mg d-α-tocopherol acetate — 50 mg D-sorbitol solution (70%) 4 g 6 g honey 7 g 8 g dl-malic acid 200 mg 200 mg sodium edetate 20 mg 20 mg ethanol 2 ml 2 ml polyoxyethylene stearate 100 mg 100 mg hydrogenated castor oil 60 sodium benzoate 60 mg 60 mg flavoring agent t.a. t.a. purified water a.a. a.a.
[0042] (2) Method for Preparation
[0043] Liquid dosage forms are prepared in a similar procedure to that described in the general rules for preparation in the “liquid dosage form” section of the Pharmacopeia of Japan using the ingredients shown in Tables 5 and 6.
Example 5
Evaluation of Serum Lipid Level
[0044] Test Method
[0045] (1) Test Substance
[0046] Pravastatin with a purity of 99.4%, manufactured at Sankyo Co. Ltd., was employed in the study. Riboflavin acetate, d-α-tocopherol acetate, ascorbic acid, and inositol hexanicotinate were purchased from Mitsubishi Tokyo Pharmaceutical Co., Eisai, Nippon Roche K. K., and Shiratori Pharmaceutical Co. Ltd., respectively.
[0047] (2) Test Animal
[0048] Male beagle dogs were purchased at 5 months old from Covance Research Products Inc., as the test animals, and were used after quarantine and acclimatization periods of approximately 1 month.
[0049] (3) Dosage Form, Preparation and Storage of the Dosage Form
[0050] The required amounts of pravastatin or each combination drug as calculated based on the body weight of each animal were placed in a gelatin capsule (½-ounce volume) purchased from TORPAC Co. Capsules filled with pravastatin were stored in a cold room and with combination drugs at room temperature until use.
[0051] Combination drugs were put in identical geltin capsules.
[0052] (4) Route of Administration and Administration Period
[0053] Capsules filled with pravastatin or combination drugs were orally administered once daily between 9:00 and 12:30 to the test animals. All test animals were fasted 2-3 hr prior to administration. The administration period was 11 successive days.
[0054] (5) Preparation of Test Samples and Assay Methods
[0055] Approximately 10 ml of blood were collected from the cephalic vein on 14 and 7 days before administration (2 and one week before the drug administration) and 4, 8, and 12 days after administration of the capsules. The animals were fasted for approximate 18 hr prior to blood collection. Collected blood was placed into test tubes and left for 0.5-1 hr at room temperature. The test tubes were then centrifuged at 3,000 rpm for 10 min to isolate serum. Levels of total cholesterol and ALP in the serum were determined by the CEH-COD-POD and Bessey-Lowry methods, respectively.
[0056] For quantitative analyses, an automatic analyzer, Monarch (Instrumentation Laboratory), was used.
[0057] Results
[0058] Levels of serum lipids following single or combined administration of pravastatin, riboflavin acetate, d-α-tocopherol acetate, ascorbic acid, and inositol hexanicotinate relative to their average serum levels 2 and one week before administration (100) were calculated. Each value represents the mean value calculated from 5 animals.
[0059] (Effects of Co-Administered Pravastatin and Riboflavin Acetate)
TABLE 9 Total Cholesterol Level in Serum After Administration Test substance (mg/kg) 4 days 8 days 12 days Pravastatin alone (2) 93.6 90.0 93.0 Riboflavin acetate alone (6) 103.9 101.6 100.5 Pravastatin (2) + 91.4 82.6 85.8 Riboflavin acetate (6)
[0060] [0060] TABLE 10 ALP level (after administration) Test substance (mg/kg) 4 days 8 days 12 days Pravastatin alone (2) 97.4 96.7 92.2 Riboflavin acetate alone (6) 98.1 98.8 93.9 Pravastatin (2) + 90.8 89.1 89.5 Riboflavin acetate (6)
[0061] (Effects of Co-Administered Pravastatin and d-α-tocopherol Acetate)
TABLE 11 Total Cholesterol Level in Serum Test substance After Administration (mg/kg) 4 days 8 days 12 days Pravastatin alone (2) 93.6 90.0 93.0 d-α-tocopherol acetate alone (10) 96.3 92.8 95.9 Pravastatin (2) + 92.8 82.7 79.3 d-α-tocopherol acetate (10)
[0062] (Effects of Co-Administered Pravastatin and Ascorbic Acid)
TABLE 12 Total Cholesterol Level in Serum Test substance After Administration (mg/kg) 4 days 8 days 12 days Pravastatin alone (2) 93.6 90.0 93.0 Ascorbic acid alone (50) 98.7 98.2 103.4 Pravastatin (2) + 89.4 84.1 80.9 Ascorbic acid (50)
[0063] (Effects of Co-Administered Pravastatin and Inositol Hexanicotinate)
TABLE 13 Total Cholesterol Level in Serum Test substance After Administration (mg/kg) 4 days 8 days 12 days Pravastatin alone (2) 93.6 90.0 93.0 Inositol hexanicotinate (400) 99.2 99.8 100.0 Pravastatin (2) + 86.5 83.3 81.6 Inositol hexanicotinate (400)
[0064] (Effects of Co-Administered Pravastatin, d-α-tocopherol Acetate, and Ascorbic Acid)
TABLE 14 Total Cholesterol Level in Serum Test substance After Administration (mg/kg) 4 days 8 days 12 days Pravastatin alone (2) 93.6 90.0 93.0 d-α-tocopherol acetate alone (10) 97.8 96.4 96.1 Pravastatin (2) + 89.3 87.8 82.4 d-α-tocopherol acetate (10) + ascorbic acid (50)
[0065] The composition of the present invention comprising a combination of pravastatin and ascorbic acid and/or the like exhibits excellent activity for lowering the total amount of cholesterol in the blood and is useful as an agent for lowering the total amount of cholesterol in the blood.
[0066] Although the dose of compounds used according to the invention may widely vary depending on the extent of diseases and age of patients, (e.g. a human patient), the dose of one administration of pravastatin is normally within the range of from 0.01 mg/kg to 10 mg/kg, preferably from 0.1 mg/kg, administered once or several times a day depending on the extent of diseases.
[0067] The dose of one administration of riboflavins is normally within the range of from 0.004 mg/kg to 24 mg/kg, preferably from 0.04 mg/kg to 2.4 mg/kg, administered once or several times a day depending on the extent of diseases.
[0068] The dose of one administration of tocopherols is normally within the range of from 0.02 mg/kg to 60 mg/kg, preferably from 0.2 mg/kg to 6 mg/kg, administered once or several times a day depending on the extent of diseases.
[0069] The dose of one administration of ascorbic acids is normally within the range of from 0.1 mg/kg to 400 mg/kg, preferably from 1 mg/kg to 40 mg/kg, administered once or several times a day depending on the extent of diseases.
[0070] The dose of one administration of inositol hexanicotinate is normally within the range of from 0.16 mg/kg to 36 mg/kg, preferably from 1.6 mg/kg to 3.6 mg/kg, administered once or several times a day depending on the extent of diseases. | The present invention relates to compositions for lowering the total amount of cholesterol in the blood and methods of using the compositions. The compositions are a mixture of pravastatin and one or more vitamins selected from riboflavins, d-α-tocopherols, ascorbic acids and inositol hexanicotinate. | 0 |
FIELD OF THE INVENTION
This invention relates to a novel method of conducting electrolysis. The method is of interest in destroying cyanide in cyanide-containing waste liquor and has particular application to the destruction of cyanide in electroplating solutions, particularly in the rinse water produced in a barrel electroplating system.
DESCRIPTION OF THE PRIOR ART
The acute toxicity of the cyanide ion is well known. It is clearly necessary that the cyanide ion be removed from industrial effluents before those effluents can be passed to water courses and sewage systems. There are, of course, laws governing the amount of cyanide ion and other toxic ions that may be contained in effluents. In 1962 the United States Public Health Service set 0.2 mg/liter of cyanide as a maximum allowable limit in potable water. The Ohio River Valley Sanitation Commission considers that a free cyanide content in excess of 0.025 mg/liter is unsafe for fish. Bacteria appear to have a higher tolerance to cyanide and sewage plants will generally take a higher concentration of cyanide than can be tolerated in water supporting fish life. Figures have indicated that an upper limit of 2 mg per liter of cyanide is acceptable for anaerobic sludge digestion without upsetting the bacteria in the sludge treatment tank.
Generally speaking cyanide concentration in effluents may be controlled by:
1. Dilution
2. Chemical Treatment
3. Electrolytic Treatment and
4. Concentration for reuse.
Dilution is of decreasing importance. Pollution control authorities generally prefer the destruction of cyanide rather than its dilution to acceptable levels as outlined above.
The chemical treatment generally comprises the use of chlorine to oxidize the cyanide to cyanate. if required further oxidation and hydrolysis of the cyanate to carbon dioxide, nitrogen and ammonia may be carried out.
Electrolytic treatment is of increasing interest but is expensive in that it requires the operation of quite complicated separate systems. Furthermore, in the prior art the procedure has not been useful for dilute solutions, such as rinse waters without first concentrating them because of low conductivity, which results in poor current efficiency. The prior art has been to add sodium chloride to the cyanide containing waste to improve the conductivity. Clearly this involves an additional expense but, also, it may be that the addition of fairly large quantities of sodium chloride, as required by the prior art, will be frowned upon by pollution control authorities although, at the moment, there is no objection to the feeding of sodium chloride to water courses.
Concentration for reuse is of relatively minor importance. Vacuum evaporation and ion exchange have been used.
SUMMARY OF THE INVENTION
The destruction of the cyanide ion by reaction with the hypochlorite ion is well known. In one valuable aspect of the invention a method of producing hypochlorite ion is provided. The particular advantage in cyanide destruction of hypochlorite addition is that very dilute waste can be treated economically by the hypochlorite.
In its preferred aspects the present invention seeks to provide a method of destroying cyanide in cyanide containing waste liquors, particularly waste liquors produced in electroplating, or to provide a method of producing hypochlorite solution useful in cyanide destruction. The invention permits the electroplater to use the majority of his available capital equipment during its normal "down" time. Most electroplaters do not operate their production lines for 24 hours a day and therefore have substantial equipment-including their D.C. power supplies, plating barrels, pumps, storage and rinse tanks--available for waste treatment. Use of on site production equipment for waste treatment or production of solutions useful in waste treatment eliminates a considerable amount of capital expenditure involved in the electrochemical oxidation of cyanide wastes.
Accordingly, in one aspect, the present invention is a method of conducting an electrolysis comprising tumbling an anode comprising a plurality of electrically conducting particles in an electrolyte while feeding a positive direct current to the particles via an anode feeder connected to a positive direct current supply; maintaining a cathode in electrical contact with the electrolyte, said cathode being spaced from the anode, and applying a negative direct current to the cathode.
In one aspect, the present invention is a method of destroying cyanide in cyanide containing waste liquor comprising tumbling an anode comprising a plurality of electrical conducting particles in the liquor while feeding a positive direct current to the particles via an anode feeder connected to a positive direct current source, maintaining a cathode in electrical contact with the liquor, said cathode being spaced from the anode, and applying a negative direct current to the cathode, whereby the cyanide present is anodically oxidized.
In a preferred embodiment the anode particles are particles of graphite and they are contained in a porous barrel, preferably of a plastic material. The barrel may be formed in two sections, bolted together at a central plane. A hinged or sliding door may be provided to permit the addition and removal of the particles. A plastic barrel, for example, of polymethylmethacrylate, has proved useful.
The cathode may be a metal or graphite sheet inserted into a plastic tank. Alternatively the electrolysis may be carried out in a metal tank which can be used as the cathode. Which ever cathode form is used waste metal can usually be recovered from the cathode by simple scraping at the conclusion of the electrolytic destruction of the cyanide.
Desirably, the anode feeder is a non-rotating graphite cylinder or rod positioned in the liquid and upon which the barrel is rotated. The barrel may be rotated by a belt drive from an electric motor. Typically, the barrel may be rotated at about 81/2 revolutions per minute.
It is desirable that the waste liquor be recycled through the tank in which electrolysis is carried out during electrolysis.
It is particularly preferred that the barrel used be a barrel that is normally used for plating. Normally the barrel will be used as a cathode during electroplating but, in the process of the present invention, it will be used as an anode.
In a particularly preferred aspect, the invention provides a method of destroying cyanide in an electroplating solution that comprises collecting counterflow rinse water from a barrel plating counterflow rinse line, at the conclusion of the electroplating immersing a barrel containing a particulate, electrically conducting solid into the rinse water in a tank, circulating the rinse solution through the tank and rotating the barrel to tumble the particulate anode while maintaining electrical contact between the particles and a positive source of direct current, maintaining a cathode spaced from the rotating barrel and applying a negative direct current to that cathode and maintaining the electrolysis until the residual cyanide level is at an acceptable level.
It can be desirable to incorporate sodium chloride into the process in order to develop hypochlorite during the electrolysis and increase the conductivity of the cyanide waste. Similarly at the conclusion of the electrolysis it may be necessary to destroy small or residual amounts of cyanide by adding a hypochlorite solution.
In a desirable aspect the invention is a method of producing a solution of a hypochlorite in which the electrolyte is an alkaline solution of a chloride.
The solution produced may be stored or used immediately for cyanide destruction.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is illustrated, merely by way of example, in the accompanying drawings in which:
FIG. 1 illustrates a typical three stage counterflow rinse solution in a barrel plating system;
FIG. 2 illustrates an electrolytic oxidation system according to the present invention;
FIGS. 3 and 4 illustrate the apparatus in which the method of the present invention may be carried out in more detail; and
FIG. 5 shows results achieved with the apparatus of FIGS. 3 and 4.
DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 illustrates a counterflow rinse system for a barrel plating apparatus. The barrel electroplating is carried out in a first tank 2 and the rinse is carried out by the use of tanks 4, 6 and 8 using a main supply of water at a rate of 60 gallons per hour into the third rinse tank 8. Typical concentrations of the various consituents (in this case the cyanide ion and the copper ion) are shown in the boxes representing the various rinse tanks. As is conventional the electroplating is carried out at alkaline pH, typically sodium hydroxide is used to maintain the alkalinity.
Rinse water is stored in rinse water holding tank 10 throughout all the time that the electroplating is carried out, for example during the day shift in an electroplating plant. It should be noted that there is a flow of approximately 4 gallons per hour between the tanks 2, 4, 6 and 8 and there are evaporations from each of the rinse tanks of about two gallons per hour. The rinse water flow from the first rinse tank 4 to the rinse water holding tank 10 is, as indicated, about 58 gallons per hour.
At the end of the last electroplating shift the rinse water is used in an electrolytic process according to the present invention. That process is illustrated diagrammatically in FIG. 2. In FIG. 2 the same rinse tanks 4, 6 and 8 are shown along with the same rinse water holding tank 10. However, the rinse water tanks 4, 6 and 8 now each contain a barrel, 12, 14 and 16 respectively. These barrels may be the barrels used in the conventional electroplating system or they may be separate barrels specially used for the cyanide electro-oxidation. Each barrel has a positive connnection to a direct current source. Each tank 4, 6 and 8 is shown attached to a negative direct current source. This may be either by a direct link to a metal tank or by the use of a separate cathode, for example a lead cathode, where a plastic tank is used.
As illustrated each of the tanks 12, 14 and 16 contains graphite pellets 18. There are also conduits, generally indicated at 20 in order to pump the rinse water throughout the system. The direction of flow illustrated is from the rinse waste holding tank 10 to the rinse tank 8 through the rinse tank 6 to the rinse tank 4 and back to the rinse water holding tank 10. In addition other cyanide wastes may be fed through the rinse water holding tank 10 through an inlet 22. The effluent from the rinse water holding tank 10 may be discharged to a sewer through an outlet 24. A hypochlorite or sodium chloride solution may be introduced through an inlet 26 in order to assist in the in situ destruction of the cyanide ion. This is shown in a broken lines in FIG. 2 as it is purely optional.
The system of FIG. 2 operates as follows. The plating barrels (or separate barrels) 12, 14 and 16 are partially filled with graphite pellets 18 at the end of the electroplating shift. The barrels are then hoisted into the counterflow rinse tanks 4, 6 and 8. Cyanide rinse water accumulated in rinse water holding tank 10 is recycled through the system using the conduits 20 illustrated. The barrels 12, 14 and 16 are tumbled and operated as anodes for cyanide electro-oxidation. In that electro-oxidation the tank walls are, as indicated, used as the cathode although a separate cathode or cathodes may be provided.
The rinse water is treated overnight or at any other convenient time, preferably during the down time of the electroplating plant. During the cyanide electro-oxidation metal values 28 are plated on the walls of the tanks 4, 6, and 8 as a loosely adherent metal sponge.
When the residual cyanide level is, for example, about 100 parts per million it is destroyed with a small amount of hypochlorite and flushed to the sewer through the outlet 24. At this time the graphite pellets 18 are removed from the plating barrel and stored for subsequent treatment. However, if separate barrels are used just for the cyanide electro-oxidation process then, of course, the pellets may remain in those barrels. Metal sponge 28 adhering to the tanks 4, 6, and 8 is scraped off and recovered.
The rinse tanks 4, 6 and 8 and the barrels 12, 14 and 16 are flushed with water to remove any abraded graphite or metal sponge particles and the barrels 12, 14 and 16 are returned to electroplating tank or to storage. When returned to the electroplating tank the barrels are used as cathodes in the normal barrel electroplating method.
In the illustrated embodiment, particularly in FIG. 1, copper is shown as the ion being plated but the system has given excellent results with alkaline copper, zinc and cadmium cyanide electroplating wastes. In this matter it should be emphasized that spent plating baths other than the electrolytes from barrel electroplating systems can also be used.
FIGS. 3 and 4 illustrate an experimental apparatus equivalent to a rinse tank 4, 6 or 8 containing a barrel 12, 14 or 16 respectively as illustrated in FIG. 2. The system illustrated in FIG. 3 comprises a tank 30 in which the electrolysis is carried out. The tank has an inlet 32 and an outlet 34. There is a barrel 36 positioned within the tank and driven on a centre, fixed anode feeder 38 (see FIG. 4). A positive direct current is fed to the anode feeder 38 via lead 40 which connects with a copper lug 42 attached to a graphite bus bar 44. It will be appreciated that the materials used are unimportant. It is merely necessary that they be electrically conducting and as corrosion-resistant as possible. The feed from the bus bar 44 to the anode feeder 38 is through a bar not shown but contained within the insulating coating 46. The coating 46 may, for example, be of a silicone rubber.
The barrel is rotated upon the anode feeder 38 by a belt 48 engaging on a pulley 50 attached to the barrel. At its other end the drive is through a pulley system generally indicated at 52 via a belt 54 from an electric motor 56. The drive system is mounted on a bench 58.
There is a cathode 60 positioned within the tank 30, there is a bus bar and contact system generally indicated at 62 to provide a negative supply of direct current to the cathode 60. As illustrated in the drawing-particularly FIG. 4-the barrel 36 is formed in two parts held together at flanges 64 by bolts 66. Although not shown in the drawings the barrel 36 is porous so that the rinse water electrolyte can pass through it.
Using the apparatus illustrated in FIGS. 3 and 4 experimental results were achieved indicating the value of the present invention. The barrel illustrated in FIGS. 4 was supplied with 3,100 graphite pellets 4.9 millimeters in diameter and 4.9 millimeters long. A lead plate 14 × 23 centimeters was used as a cathode 60. The tank 30 was of polymethylmethacrylate. A stationary graphite centre shaft 38 was connected to the graphite bus bars 44 via the conducting rods protected by the insulator 46. The barrel was tumbled at 8.5 revolutions per minute through the drive from the electric motor 56. Six liters of simulated cyanide plating rinse water were pumped through the barrel 36 in a recycle system through the inlet 32 and from the outlet 34 to storage, back through the inlet 32 through the tank 30 and out through outlet 34. Direct current was applied to the system as illustrated in FIG. 3. 50 milliliter aliquots of electrolyte were removed periodically from the cyanide waste holding tank for chemical anaylsis. No attempt was made to maintain constant temperature in the test system and losses due to evaporation were not compensated. Cyanide was analyzed as the total cyanide using the well known distillation-silver nitrate titration method. Metal analysis was carried out using atomic absorption. Calibration standards were prepared from the starting effluent solutions.
After electrolysis of the rinse water to the desired cyanide level the lead cathode 60 was removed from the tank 30 and scraped with a spatula to simulate industrial recycling. The recovered metal was then dissolved in nitric acid to determine its lead content.
A series of results were obtained with simulated zinc cyanide plating wastes, simulated copper cyanide plating wastes and simulated cadmium cyanide plating waste. The results and conditions of the experiments were as follows. The results are plotted, in part, on FIG. 5. Applied voltages were in the range 12 to 18 volts. cl ZINC CYANIDE TREATMENT
Table 1 sets out electrolysis conditions and treatment efficiency for electrolysis of a simulated zinc cyanide plating waste. Interpolation of this data shows that zinc cyanide wastes of 4000 to 1000 ppm cyanide concentration are treatable to 50 ppm residual cyanide- see FIG. 5. Zinc recovery is greater than 99% to > 25 ppm zinc at 50 ppm cyanide residual.
COPPER CYANIDE TREATMENT
Table 2 sets out electrolysis conditions and treatment efficiency for electrolysis of a simulated copper cyanide plating waste. Interpolation of this data indicates that copper cyanide wastes of 4000 to 1000 ppm cyanide concentration are treatable to 50 ppm cyanide residual - see FIG. 5. Copper recovery is greater than 91% to ≦ 300 ppm at 50 ppm cyanide residual.
CADMIUM CYANIDE TREATMENT
Table 3 sets out electrolysis conditions and treatment efficiency for electrolysis of a simulated cadmium plating waste. Interpolation of this data indicates that cadmium cyanide wastes of 4000 to 1000 ppm cyanide concentration are treatable to 50 ppm cyanide residual. Cadmium recovery is greater than 96% to - 50 ppm at 50 ppm cyanide residual.
TABLE 1______________________________________ELECTROLYSIS OF ZINC CYANIDE WASTE______________________________________Cell Descriptionanode current feeder - graphite rodanodes 3100 4.9 mm × 4.9 mm graphite pelletscathode - lead sheet 14 cm × 23 cmOperating Moderecycle flow rate - 780 ml/minbarrel rpm - 8.5anode current density (C.D.) - 10 mamp/cm.sup.2cathode C.D. - 99 mamp/cmTest Solution6 liters deionized water containing 48 g NaOH57 g tech. grade NaCN, 18.7 g Zn0RESULTSTime (min) 0 30 60 120 185 240Current (amp) 32 32 32 32 32 32Average retentiontime (min) 3.85Temp. ° C. 64 74 74 75 75 75Electrolytevolume (1) 5.9 5.6 5.3 4.7 3.5 3.0pH 12.7 12.7ppm Cyanide 4576 3640 2808 1014 182 13ppm Zinc 2500 2080 1280 350 54 12______________________________________
TABLE 2______________________________________ELECTROLYSIS OF COPPER CYANIDE WASTE______________________________________Cell Descriptionanode current feeder - graphite rodanodes - 3100 4.9 mm × 4.9 mm graphite pelletscathode - lead sheet 14 cm × 23 cmOperating Moderecycle flow rate 780 ml/minbarrel rpm - 8.5anode C.D. - 10 mamp/cm.sup.2cathode C.D. - 99 mamp/cm.sup.2Test Solution6 liters deionized water containing 21.6 g copper powder, 72.6 g KCN, 12.7 g KOHRESULTSTime (min) 0 60 120 190Current (amps) 32 32 32 32Average retention time(min) 3.85Temp. ° C. 74 89 89 91Electrolyte Volume(1) 5.95 5.0 3.9 2.9pH 12.6 12.6 10.1 9.7ppm Cyanide 4576 1959 29 3.6ppm Copper 3600 1550 216 4______________________________________
TABLE 3______________________________________ELECTROLYSIS OF CADMIUM CYANIDE WASTE______________________________________Cell Descriptionanode current feeder - graphite rodanodes - 3100 4.9 mm × 4.9 mm graphite pelletscathode - lead sheet 14 cm × 23 cmOperating Moderecycle flow rate - 780 ml/minbarrel rpm - 8.5anode C.D. - 9.4 mamp/cm.sup.2cathode C.D. - 99 mamp/cm.sup.2Test Solution6 liters deionized water containing 10.2 g CdO, 34.2 g. tech. grade NaCN, 6.4 g NaOH.RESULTSTime (min) 0 60 105 165Current (amp) 26 30 30 30Average retention time(min) 3.85Temp. ° C. 67 95 95 98Electrolyte volume (1) 5.9 4.8 3.8 2.5pH 12.5 11.9 9.9 9.7ppm Cyanide 2800 218 12.9 1.3ppm Cadmium 1490 300 5.0 3.9______________________________________
SODIUM CYANIDE TREATMENT
Tables 4 and 5 set out electrolysis conditions and treatment efficiency for a sodium cyanide waste at 10 mamp/cm 2 , 15 mamp/cm 2 anode current densities respectively. This data was produced to establish a baseline for comparison of plating waste treatment data.
TABLE 4______________________________________ELECTROLYSIS OF SODIUM CYANIDE WASTE______________________________________Cell Descriptionanode current feeder - graphite rodanodes - 3100 4.9 mm × 4.9 mm graphite pelletscathode - lead sheet 14 cm × 23 cmOperating Moderecycle flow rate - 780 ml/minbarrel rpm - 8.5anode C.D. - 10 mamp/cm.sup.2cathode C.D. - 99 mamp/cm.sup.2Test Solution6 liters deionized water containing 48 g NaOH, 62 g tech. grade NaCNRESULTSTime (min) 0 30 60 90 120 150 205Current (amp) 32 32 32 32 32 32 32Average retentiontime (min) 3.85Temp. ° C. 50° C. 72 73 73 73 73 73pH 13.0 13.0ppm Cyanide 5400 3900 2700 1650 790 270 15______________________________________
TABLE 5______________________________________ELECTROLYSIS OF SODIUM CYANIDE WASTE______________________________________Cell Descriptionanode current feeder - - graphite rodanodes - 3100 4.9 mm × 4.9 mm graphite pelletscathode - lead sheet 14 cm × 23 cmOperating Moderecycle flow rate - 780 ml/minbarrel rpm - 8.5anode C.D. - 15 mamp/cm.sup.2cathode C.D. - 149 mamp/cm.sup.2Test Solution6 liters deionized water containing 48 g NaOH, 61 g NaCN tech. gradeRESULTSTime (min) 0 30 60 90 120Current (amp) 45 48 48 48 48Average retention time(min) 3.85Temp. ° C. 49 85 91 91 91pH 12.8 12.8ppm Cyanide 4800 3150 1500 470 47Electrolyte volume (1) 5.95 5.9 4.9 3.9 3.0______________________________________
METAL RECOVERY DURING PLATING WASTE TREATMENT
Cadmium and zinc were easily scraped from the lead cathode as a wet powder. Some non-powdery cadmium and zinc remained attached to the lead cathode and could not be removed by scraping. Copper was more difficult to scrape.
All scraped metals were of high purity as follows:
Copper = 97%
Zinc = 96%
Cadmium = 97%
The metals all contained a small amount of nitric acid insoluble material (probably graphite).
The present invention thus offers a complete program for treatment of virtually any cyanide waste, each method of treatment has its own advantages, for example the production of an initial hypochlorite solution has the advantage that very dilute cyanide containing waste may be treated. | A method of conducting an electrolysis is described. The method comprises tumbling an anode made up of a plurality of electrically conducting particles in an electrolyte while feeding a positive D.C. current to the particles. The current is fed via an anode feeder that is connected to a positive D.C. supply. A cathode is maintained in electrical contact with the electrolyte and is spaced from the anode. A negative direct current is applied to the cathode. | 2 |
This application is a continuation-in-part of U.S. patent application Ser. No. 172,268, filed Mar. 23, 1988, now U.S. Pat. No. 4,932,951 entitled "Method and Apparatus for Controlling Tissue Growth with An Applied Fluctuating Magnetic Field", which is expressly incorporated herein by reference. Also, United States Patent application entitled "Improved Method and Apparatus for Regulating Transmembrane Ion Movement", filed by the inventors of this application Ser. No. 278,688 filed Dec. 1, 1988 is expressly incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates generally to devices for generating magnetic fields for therapeutic purposes. More specifically, the present invention relates to an apparatus which includes two coils which can be conformed to the anatomical contour of a living subject such as a human. The apparatus includes means for regulating a magnetic field in a predetermined space, the predetermined space being occupied by a target tissue to be treated by the therapeutic magnetic field, which gives precise and automatic control of the magnetic field regulation.
BACKGROUND OF THE INVENTION
The inventors of the present invention devised a method and apparatus for regulating the transport of a preselected ion across a cell membrane utilizing an applied, oscillating magnetic field. This remarkable achievement is disclosed in U.S. patent application Ser. No. 923,760, now U.S. Pat. No. 4,818,697 entitled, "Techniques for Enhancing the Permeability of Ions", which was filed on Oct. 27, 1986, and the disclosure of which is incorporated herein by reference. Therein, a method and apparatus are disclosed by which transmembrane movement of a preselected ion is magnetically regulated using a time-varying magnetic field tuned to the cyclotron resonance energy absorption frequency of the preselected ion. This important discovery brought to light the interplay of local magnetic fields and the frequency dependence of ion transport mechanisms.
Having established a method by which selective ion transport can be regulated, the present inventors discovered that certain characteristics of living tissue could be controlled by application of an oscillating magnetic field having a non-zero average value. Significantly, it was determined that selected ratios of the frequency of the applied field to the flux density of the total magnetic field passing through the tissue along a predetermined axis were capable of stimulating the growth and development of the target tissue. This was demonstrated to be effective in promoting the growth of bone tissue. As a result, U.S. patent application Ser. No. 172,268, entitled "Method and Apparatus for Controlling Tissue Growth with an Applied Fluctuating Magnetic Field" was filed on Mar. 23, 1988, the disclosure of which is incorporated herein by reference.
Therein, there is provided an apparatus for controlling the growth of living tissue. The apparatus includes magnetic field generating means such as a field coil for generating a controlled, fluctuating magnetic field which penetrates a tissue, and an associated magnetic field sensing device for measuring the intensity of the magnetic field present in the tissue. In one embodiment, the magnetic field generating means and magnetic field sensor are enclosed within a housing along with a power source.
The work with tissue growth control was extended and it was discovered that tissue development can be regulated to control the growth characteristics of non-osseous, non-cartilaginous connective tissue proper and cartilaginous tissue. These inventions are disclosed, respectively, in U.S. patent application Ser. No. 254,438, entitled "Method and Apparatus for Controlling the Growth of Non-Osseous, Non-Cartilaginous Solid Connective Tissue", which was filed Oct. 6, 1988, the disclosure of which is incorporated by reference, and in U.S. patent application Ser. No. 265,265, entitled "Method and Apparatus for Controlling the Growth of Cartilage", which was filed Oct. 31, 1988, the disclosure of which is incorporated by reference.
This work further resulted in an apparatus which utilizes a feedback system to provide automatic control of the magnetic field in any application of cyclotron resonance transmembrane ion regulation. This invention is disclosed in U.S. patent application Ser. No. 278,688, filed Dec. 1, 1988, entitled "Improved Method and Apparatus for Regulating Transmembrane Ion Movement" by the inventors of this application, now U.S. Pat. No. 5,059,298. This disclosure has been incorporated by reference.
In U.S. Pat. No. 4,616,629, to Moore, a single-coil configuration adapted for embedment in an orthopedic cast for use in applying electromagnetic signals for osteogenic therapy is provided. Therein, an otherwise flat circular multiple turn coil is permanently deformed and is preferably embedded within a cast. The disclosure does not include the use of a Helmholtz configuration of a coil pair to create a uniform magnetic field within a predetermined space. The Moore disclosure does not recognize any need to determine the local magnetic field component nor is any means for measuring and automatically compensating for fluctuations in the local field provided.
It will be recognized by those skilled in the art that an idealized magnetic field occupying the space between two coils in Helmholtz configuration can be easily predicted where the coils are flat and circular. However, as the coils deviate from this geometry calculation of an applied field becomes more difficult.
It will also be appreciated that the application of a therapeutic magnetic field to a region of body tissue of either man or animal generally requires that the patient remain ambulatory to the extent possible. Thus, it is highly desirable to have an apparatus such as that disclosed by the present inventors in prior applications which can be attached to a patient and which does not substantially restrict patient movement. It would also be desirable to provide such an apparatus in which the coils that make up the Helmholtz coil pair could be adapted to conform to differences in the shape of the site of application i.e. leg, arm, or the like, and which could be reused on a number of patients having different morphological characteristics. The present invention meets these goals.
In accordance with the present invention, there is provided a deformable tissue growth stimulator which includes a pair of field coils which can be deformed to fit a range of sizes and shapes of patients and body regions. In one aspect, each coil is encased or embedded in a plastically deformable medium to form twin deformable coil pads. The pads are interconnected by a flexible belt which is provided with means for attaching the belt around a region of living tissue to be treated such as a patient's leg. In use, the treatment pads are simply bent with one's hand or the like to match the contour of the patient's body, such as a patient's arm or leg. The nature of the material in which the coils are embedded allows this plastic deformation without any resilient recoil. Once the treatment pads have been deformed in this manner, the belt is secured in position on the subject limb and treatment is administered. As will be explained more fully, the precise ratio of frequency to average magnitude of a composite magnetic field which permeates the target tissue is maintained in a manner which automatically corrects for deviations in the local magnetic field to which the tissue is subjected.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides an apparatus for controlling the growth of living tissue which can be adapted to fit a variety of anatomical sites of differing geometries. The novel apparatus includes a deformable magnetic field generating means such as a pair of field coils each embedded in a plastically deformable pad for generating a controlled, fluctuating magnetic field which penetrates living tissue in man and animals and an associated magnetic field sensing device for measuring the intensity of the magnetic field present in the tissue. In a preferred embodiment, the deformable field coils are encased or embedded in a plastically deformable pad formed of non-magnetic material. A magnetic field sensor is also embedded in one of the plastically deformable pads along with a power source such as a battery or the like. In operation, the deformable coils of the magnetic field generating means are manually deformed or shaped to approximate the contour of the body region to which they will be applied. The deformable coils are then placed in position in opposed relation on the target body region such as a human limb having a fractured femur. A fluctuating, directional magnetic field is then generated by the magnetic field generating means. The applied magnetic flux density is directed along a predetermined axis which passes through the tissue to be affected. In one embodiment, the applied magnetic flux density along the axis is superimposed on that component of the local or ambient magnetic field which is parallel to the predetermined axis to create a fluctuating composite field. The resultant combined magnetic flux density which is parallel to the predetermined axis and which passes through the tissue to be affected is measured by the magnetic field sensor. The magnetic field sensor determines the net average value of the magnetic flux density which passes through the targeted tissue along the predetermined axis. In one embodiment, the frequency of the fluctuating magnetic field is set at a predetermined value and the net average value of the magnetic flux density is then regulated by adjusting the magnitude of the applied magnetic field to produce a combined magnetic field having a preselected ratio of frequency-to-field magnitude which affects the growth characteristics of the target tissue. In a preferred embodiment, changes in the magnitude of the local magnetic field along the predetermined axis which would otherwise alter the magnetic flux density of the combined magnetic field parallel to the predetermined axis and which would thus produce a deviation from the desired ratio are counterbalanced by adjustment of the magnitude of the applied, fluctuating magnetic field. This adjustment is preferably made by microprocessing means in association with both the magnetic field generating means and the magnetic field sensor. Preferred ratios of frequency-to-field magnitude are determined with reference to the equation:
f.sub.c /B=q/(2πm)
where f c is the frequency of the combined magnetic field in Hertz, B is the non-zero average value of the magnetic flux density of the combined magnetic field parallel to the axis in Tesla, q/m is in Coulombs per kilogram and has a value of from about 5×10 5 to about 100×10 6 . B preferably has a value not in excess of about 5×10 -4 Tesla. In one embodiment, the values of q and m are selected with reference to the charge and mass of a preselected ion.
In another embodiment, changes in the ambient magnetic field which would otherwise alter the ratio of frequency-to-magnetic field are counterbalanced by adjusting the frequency of the applied magnetic field to maintain the preferred ratio. The present invention also contemplates the adjustment of both frequency and field magnitude to maintain the predetermined preferred ratio. Preferably, the peak-to-peak amplitude of the AC component is in the range of about 2.0×10 -7 to about 2.0×10 -4 Tesla. The waveform is preferably substantially sinusoidal, but other waveforms are suitable.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevational view of the present invention as applied to the treatment of a fractured femur.
FIG. 2 is a front elevational view of the present invention with two deformable treatment pads having deformable field coils and magnetic field sensing means shown in phantom.
FIG. 3 is a front elevational view of one deformable treatment pad of the present invention with the pad broken away to illustrate the magnetic field sensing means.
FIG. 4 is a block diagram of an embodiment of the present invention in which the circuit of the inventive apparatus is arbitrarily divided into convenient functional sections.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1 of the drawings, deformable tissue growth regulator 120 is shown in position on leg 122 of a human subject. It is to be understood that both the apparatus and the method of the present invention are suitable for use in controlling tissue growth in an animal subject or a human subject. Thus, the target tissue which is to be controlled is a region of living tissue in a subject, in other words, an "in vivo" target tissue. As used herein, the term "living tissue" shall be defined, without limiting its customary meaning, as living tissue which is capable of conducting metabolic functions such as cellular respiration and which possesses viable growth characteristics. "Growth characteristics" shall be defined, without limiting its customary meaning, as those attributes of living tissue which serve to mediate replication, growth, maintenance and repair. Although the stimulation of tissue growth will be emphasized in this description of preferred embodiments of the present invention, it is to be understood that the present invention can also be used to retard or impede the development of living tissue and may be suitable for other applications, including the prevention of abnormal tissue development.
Fractured femur 124 is shown having ends 126 and 128 which are to be stimulated by the present invention to enhance the rate at which union of the ends occurs. As will be appreciated by those skilled in the art, the natural developmental processes by which ends 126 and 128 reunite may be interrupted by a factor of known or unknown etiology resulting in delayed healing. In this embodiment, deformable tissue growth regulator 120 includes two deformable treatment pads 130 and 132 which are positioned on leg 122 in the region of ends 126 and 128 in the opposed fashion illustrated in FIG. 1. As will be explained more fully, it is important that deformable treatment pads 130 and 132 be placed adjacent the target connective tissue proper such that the tissue is within the range of the magnetic flux generated by the treatment pads. Also, although it is preferred that two treatment pads be employed in an opposed fashion as illustrated in FIG. 1, a plurality of deformable treatment pads greater than two may be suitable in some applications.
Referring now to FIG. 2 of the drawings, retaining straps 134 and 136 are seen by which deformable tissue growth regulator 120 is preferably secured into position on leg 122. Other securing means may be suitable or desirable in a particular application. Straps or belts 134 and 136 are attached to deformable treatment pads 130, 132 by any convenient means in a manner which allows the distance between deformable treatment pads 130, 132 to be adjusted to attain the substantially opposed orientation shown in FIG. 1. Hence, straps 130, 132 also facilitate adjustment so that deformable tissue growth regulator 120 can be used on limbs of various sizes. Treatment pads 130 and 132 should be snugly but comfortably in position to prevent substantial movement relative to the target tissue, illustrated here as fractured femur ends 126 and 128.
Referring now to FIGS. 2 and 3, each deformable treatment pad 130, 132 preferably includes a support matrix or structure 138, 140 of a non-magnetic material which can be plastically deformed by manual manipulation such as by one's hands or the like. Each field coil 142, 144 is embedded in the deformable support structure 138, 140. Although in FIG. 3 support structure 140 appears hollow for purposes of illustration, each support structure is preferably solid. Field coils 142 and 144 can be partially encased or fully encased in the support matrix as shown in FIGS. 2 and 3. A number of materials are suitable for use in forming each support structure 138, 140 such as latex or another pliable material. As will be appreciated by those skilled in the art, the field coils are typically formed of a predetermined number of turns of copper wire which is quite ductile. Hence, the material used to form support structures 138 and 140 can comprise a material which yields easily as the field coil metal is deformed to a desired shape, but which is not overly resilient; that is, it does not rebound to change the configuration of the deformed field coils. A shape-retaining material can also be used which has a clay-like consistency. In other words, a material can be used which is moldable in a given shape at room temperature and which can be remolded numerous times. Although not necessarily preferred, clay could be used to form the support structures 138 and 140.
At least one deformable treatment pads includes a magnetic field sensing device 146, such as a Hall-effect device, shown in support structure 140 of deformable treatment head 130. Sensing device 146 can be completely embedded in support matrix 140. Power source 148 is provided, preferably enclosed within one of the deformable treatment pads. Power source 148 may comprise a dry cell battery or the like. It is preferred that two or more separate power sources be provided to minimize the number of circuit elements required. While it is a significant feature and advantage of the present invention to provide a deformable tissue growth regulator which includes a self-contained power source, and thus which is both lightweight and mobile, other power sources such as an ac line source may be used in connection with an ac/dc converter where mobility is not required.
As stated, field coils 144 and 142 are the preferred means by which an applied magnetic field is generated in the present invention. The radius of each field coil 144 and 142, as well as the turns of winding, may vary in accordance with the principles of the present invention. Those skilled in the art will appreciate that plastically deformable electromagnets or possibly permanent magnets may be adapted for use in the present invention and any such use is intended to come within the scope of the present invention. Field coils 144 and 142 are most preferred since they may be formed of ductile metals and they provide a simple means for concentrating magnetic lines of force. Also, the present invention includes several components within a single pad, and therefore shielding may be employed to prevent undesired interactions between components.
In the most preferred arrangement, the geometry and relative position of field coils 144, 142 during treatment are such that they approximate the magnetic field generated by a pair of Helmholtz coils. In most instances, true Helmholtz coils are considered to be flat, a geometry which does not lend itself well to the morphology of the human anatomy. Those skilled in the art will thus appreciate that in the most preferred arrangement, field coils 144, 142 are substantially identical, field-aiding, parallel coaxial coils separated by a distance equal to the radius of each coil, but curved somewhat to more closely conform to the region of the body to which they are applied. By constructing the coils in accordance with the present invention, this arrangement is made possible. In this most preferred embodiment, the configuration of the field coils produces an applied magnetic field in a predetermined space between the coils. Since the field so generated is not a idealized field of true Helmholtz coils, that is, the field may not be truly uniform in the predetermined space, it is important to monitor the resultant field which permeates the tissue being treated. This is accomplished in the present invention by magnetic field sensor 146.
It will be appreciated that the target tissue will be subject to local magnetic influences. As used herein, "local magnetic field" shall be defined as the magnetic influences, including the earth's magnetic field or geomagnetic field, which create a local magnetic flux that flows through the target tissue. "Magnetic flux density" shall be defined in the customary manner as the number of magnetic field lines per unit area of a section perpendicular to the direction of flux. Factors contributing to the local magnetic field in addition to the geomagnetic field may include localized regions of ferromagnetic materials or the like. In one embodiment of the present invention, field coils 142 and 144 are used to create an applied, fluctuating magnetic field which when combined with the local magnetic field parallel to a predetermined axis extending through the target tissue produces a resultant or combined magnetic field having a precisely controlled, predetermined ratio of magnetic flux density to frequency.
Referring now to FIG. 3 of the drawings, magnetic field sensing device or magnetometer 146 is shown in pad 140 with the appropriate leads 154, 156, 158 and 160, by which the field-sensing device is electrically connected to power source 148 and in one embodiment to microprocessing means 162. The direction of the applied magnetic flux defines the direction of predetermined axis A shown in FIG. 1. That is, the flux of the applied magnetic field is always in the same direction as predetermined axis A. In the preferred embodiment of the invention, this applied magnetic flux is superimposed on the local magnetic flux in predetermined space 168.
Magnetometer 146 is positioned in deformable tissue growth regulator 120 to measure the total or composite magnetic flux which passes through predetermined space 168 parallel to predetermined axis A. It will be understood, then, that magnetometer 146 is provided to measure the composite magnetic field along axis A. The local field component either augments or decreases the applied magnetic flux unless the local field component is zero. This is an important feature of the present invention. The relatively low applied flux densities and precise predetermined relationships of combined flux density and frequency provided by the present invention must be maintained during treatment, notwithstanding the influence of the local magnetic field. This is achieved in essentially two preferred manners which will be explained more fully herein. Thus, magnetometer 146 is provided to determine the magnitude of the magnetic flux density of the local magnetic field and measures the magnitude of the applied field which may vary somewhat depending on the degree that the field coils are deformed to match the contour of the body region to which they are fitted. Hence, in one embodiment of the invention, predetermined space 168 is occupied by a region of living tissue of a human or animal subject. Predetermined axis A which projects through predetermined space 168 and thus through the target tissue is defined by the relative position of deformable tissue growth regulator 120 with respect to the target tissue. Predetermined axis A is in the same direction as the applied magnetic flux generated by field coils 142, 144 through predetermined space 168. During this procedure, magnetometer 146 measures the total magnetic flux density parallel to predetermined axis A which passes through the target tissue. This total or composite magnetic flux density is the sum of the applied component and the local component. The local component may at times be in the same direction as the applied flux and at other times be in directions other than the applied flux. At times the local component may also be zero. These changes in the local component along the axis are produced by changes in the direction of predetermined axis A as deformable tissue growth regulator 120 is repositioned such as when an ambulatory patient receiving treatment moves leg 122. The net average value of magnetic flux density is accordingly regulated to adjust to the change in composite flux. Therefore, deformable tissue growth regulator 120 is preferably a mobile unit which is a significant advantage.
In the present invention, a fluctuating combined or composite magnetic field is created having a magnetic flux density parallel to predetermined axis A, where the combined magnetic flux density along axis A is maintained at a predetermined relationship to the frequency of the fluctuations. In this embodiment, the combined magnetic flux density parallel to predetermined axis A has a non-zero net average value. The therapeutic magnetic field of the present invention can be thought of as a static field having reference level on which a fluctuating magnetic field is superimposed. It comprises an ac component which varies in amplitude but not direction and a dc reference around which the ac component varies. Therefore, the reference level is the non-zero average value of the flux density (B). Therefore, it will be understood that the non-zero average or net average value of the composite magnetic flux density along predetermined axis A is utilized since the magnitude B of the composite flux density changes at a predetermined rate due to oscillation or fluctuation of the applied magnetic flux. Thus, an average value is utilized which is a non-zero average value. This reflects that although the composite magnetic flux density along the axis is oscillating at a controlled rate, the composite field is regulated by the intensity of the applied field to ensure that the composite field is always unipolar; that is, the composite field is always in the same direction along predetermined axis A.
As stated, it has been found that rather precise relationships of the flux density of the combined magnetic field to the frequency of the fluctuations are used in the present invention to provide therapeutic results. These ratios of frequency to composite flux density are found in accordance with the following equation:
f.sub.c /B=q/(2πm)
where f c is the frequency of the combined magnetic field in Hertz, B is the net average value of the magnetic flux density of the combined magnetic field parallel to predetermined axis 50 in Tesla, q/m has a value of from about 5×10 5 to about 100×10 6 Coulombs per kilogram. B preferably has a value not in excess of about 5×10 -4 Tesla.
In another embodiment of the present invention, values for q and m are determined with reference to a preselected ionic species. It will be known by those skilled in the art that the biochemical milieu of a particular tissue comprises a mixture of various ions in the intercellular and interstitial fluid. These ions include potassium ions, magnesium ions, sodiums ions, chloride ions, phosphate ions, sulfate ions, carbonate ions, bicarbonate ions and the like and various ions formed by the dissociation of amino acids, proteins, sugars, nucleotides and enzymes. Applicants have found that by utilizing the values of charge and mass for a preselected ion in the equation set forth above, which will be recognized by those skilled in the art as the cyclotron resonance relationship solved for f c /B, ratios of frequency to magnetic flux density can be determined which serve to regulate growth characteristics of living tissue in accordance with the present invention. By using the charge-to-mass ratio of a preselected ion, a specific cyclotron resonance frequency for the ion can be determined. By then tuning deformable tissue growth regulator 120 to maintain a combined magnetic flux density having the proper cyclotron resonance frequency, living tissue containing the preselected ion can be treated to being about changes in growth characteristics. Again, evidence indicates that the beneficial results of the present invention in this embodiment are achieved when the preselected ion absorbs energy from the magnetic field of the present invention having the desired parameters.
It will be appreciated by the prior explanation of preferred embodiment of the present invention and from the equation for establishing a cyclotron resonance relationship, that either the frequency of the fluctuating magnetic field or the magnitude or intensity of the magnetic flux density along the predetermined axis, or both the frequency and the intensity of the flux density, can be adjusted to provide a magnetic field within volume 168 which has the desired characteristics. However, as stated, it is preferred to maintain a constant frequency which thus requires that the intensity of the applied magnetic flux density be adjusted to compensate for changes in the local magnetic field in order to maintain a constant ratio of frequency to magnetic flux density. This is most preferably performed by the microcontroller in connection with both the field generating means and the field-sensing device. Alternatively, as stated, if changes in the combined magnetic flux density along the axis will occur due to changes in the orientation of deformable tissue growth regulator 120 with respect to the local magnetic field, the frequency of the oscillations can then be changed so that the preferred therapeutic ratio is maintained. Once again, it is important to realize that the value of B is the average composite magnetic flux density parallel to the predetermined axis since the magnitude of the flux density changes as the field is oscillated. It will be understood that detection of changes in the magnetic field due to changes in the ambient component should be at intervals frequent enough to provide a frequency-to-magnetic field ratio which is substantially constant, notwithstanding the changes in the local field component.
Referring now to FIG. 2 of the drawings, each field coil 142, 144 preferably has up to about 3000 turns or loops of conducting wire the diameter of each loop being preferably up to about 300 centimeters. The number of turns of wire n, the diameter of the coils, the separation of the coils, and the wire gauge are critical only insofar as conventional practice requires constraints on these and other design parameters to allow optimal performance characteristics in achieving predetermined flux densities as required in the preferred practice of the present invention. As stated, other magnetic field generating means may be suitable for use in the present invention and are contemplated as falling within the scope of this invention. In another embodiment, field coils 142 and 146 are simply coated with latex or the like by dipping the coils in a latex bath which produces a latex coating that allows the coils to be easily deformed to a desired shape.
It may also be appropriate in some instances to reduce components of the local magnetic field which are not parallel to predetermined axis A to zero through the use of additional coils positioned at right angles to deformable treatment pads 130, 132 to create an opposite but equal field, but this is not deemed necessary.
Referring now to FIG. 4 of the drawings, a block diagram is shown which depicts one preferred arrangement of the circuits of deformable treatment pads 120 in functional segments. Numerous other circuit arrangements may be possible if the principles of the present invention are faithfully observed. Microcontroller or microprocessor 200 is seen by which the composite magnetic field is maintained at a constant predetermined level despite changes in the ambient component as previously described. In this respect, input 202 is provided by which a set point value of the predetermined composite magnetic flux density along a predetermined axis through the target tissue is input into microprocessor 200. As will be shown, the composite field strength is compared to this set point value to generate an error equal to the difference in the set point value and the measured value of the composite magnetic flux density along the axis.
Magnetic field sensor 204 is provided by which the magnitude of the composite field which passes through the target tissue along the axis is measured. It is preferred that magnetic field sensor 204 comprise a Hall-effect device which, as will be known by those skilled in the art, produces an analog signal. The magnetic field sensor 204 constantly monitors the composite magnetic field, sending a signal to microprocessor 200. It will be understood that the output of a Hall-effect magnetic sensor is relatively small; thus, magnetic field sensor amplifier 206 is provided by which the signal from magnetic field sensor 204 is amplified, for example, up to three thousand times its original value. Since a Hall-effect device produces an analog signal, analog-to-digital converter 207 is provided by which the amplified signal from magnetic field sensor 204 is converted to a digital signal which can be used by microprocessor 200. It is preferred that the analog-to-digital converter be provided on-board the microprocessor chip.
As will be appreciated, the amplification of the magnetic field sensor signal may produce an unwanted noise level. Also, sudden changes in the magnetic field intensity may occur which make it difficult to determine the true average value of the composite magnetic flux density. Hence, the signal from analog-to-digital convertor 206 which is input into microprocessor 200 is filtered by software filter 208 to remove shot noise and sudden fluctuations in the composite field detected by magnetic field sensor 204. Although it is preferred that filter 208 comprise software in microprocessor 200, a discrete filter could be used. In this embodiment, software filter 208 is a digital filter, preferably an integrator with a time constant of approximately 0.5 seconds. In other words, the changes in the magnitude of the composite magnetic field which are compensated for by increasing or decreasing the applied field are long-term changes of 0.5 seconds or more which result primarily from changes in the orientation of regulator 120 with respect to the ambient field component. Hence, the time constant of filter 208 should be such that momentary fluctuations are filtered out.
Microprocessor 200 includes logic which calculates the non-zero net average value of the composite magnetic flux density. This non-zero average value is then compared at comparator 210 in microprocessor 200 to the predetermined dc reference or offset value which is input into microprocessor 200 via input 202. It should be noted that this reference value is preferably established by dedicated circuitry in microprocessor 200, although variable input means could be included by which the set point value could be changed. An error statement is then generated defining the difference in the measured value of the composite magnetic flux density and the set point or reference value. Microprocessor 200 then determines the magnitude of the output necessary to drive magnetic field generating coils 212 to bring the composite magnetic flux density back to the set point.
Software field modulator or oscillator 214 is provided by which an ac or fluctuating component is superimposed on the digital output signal which is input into digital-to-analog converter 216. From the previous discussion of the present invention, it will be understood that software field modulator 214 of microprocessor 200 in the preferred embodiment of the present invention is preset to a fixed, predetermined frequency to produce the desired predetermined, growth-regulating ratio of frequency-to-magnetic flux density value. In another embodiment, the feedback system of the present invention is such that changes in the composite magnetic flux density are measured, whereupon microprocessor 200 determines the necessary change in frequency to maintain the predetermined relationship. In that embodiment, software field modulator 214 produces the requisite ac frequency. It is again preferred that digital-to-analog converter 216 be provided on-board the microprocessor chip. Hence, software field modulator 214 provides the ac component at node 218.
The signal from digital-to-analog converter 216 is fed to voltage-to-current amplifier 220, the output of which drives magnetic field generating coils 212 in the desired manner. Hence, the composite field is held substantially constant despite changes in the ambient component.
While several arrangements of power sources are suitable, it is preferred that power supply 222 be provided to power magnetic field sensor amplifier 206, microprocessor 200 and magnetic field sensor 204, the latter via bias circuitry 224. A separate power source 226 is preferred for voltage to current amplifier 220.
The present invention further includes a method of controlling the growth of living tissue which encompasses the use and operation of the apparatus of the present invention as described more fully in the aforementioned U.S. patent application Ser. No. 172,268.
While a particular embodiment of this invention is shown and described herein, it will be understood, of course, that the invention is not to be limited thereto since many modifications may be made, particularly by those skilled in this art, in light of this disclosure. It is contemplated therefore by the appended claims to cover any such modifications that fall within the true spirit and scope of this invention. | An apparatus and method for regulating the growth of living tissue are provided. The apparatus includes a deformable magnetic field generator and a magnetic field detector for producing a controlled, fluctuating, directionally oriented magnetic field parallel to a predetermined axis projecting through the target tissue. The deformable magnetic field generator includes a pair of field coils embedded in a flexible material which allows the field coils to be plastically deformed to fit the contour of a body region such as a patient's limb. The field detector samples the magnetic flux density along the predetermined access and provides a signal to a microprocessor which determines the average value of the flux density. The applied magnetic field is oscillated at predetermined frequencies to maintain a preselected ratio of frequency to average flux density. This ratio is maintained by adjusting the frequency of the fluctuating magnetic field and/or by adjusting the intensity of the applied magnetic field as the composite magnetic flux density changes in response to changes in the local magnetic field to which the target tissue is subjected. By maintaining these precise determined ratios of frequency to average magnetic flux density, growth characteristics of the target tissue are controlled. | 0 |
BACKGROUND OF THE INVENTION
The present invention relates to systems which automatically regulate the transport of longitudinally transported strip material, especially large-width photographic roll paper transported through a copying machine, in such a manner that sensors at the lateral edges of the transported strip detect transverse shifting of the strip and initiate corrective recentering action performed by position-correcting means.
In a great variety of practical applications, it is necessary to assure that the longitudinal transport of strip material is performed with great exactness. This is an important concern, for example, in photographic copying or printing machines, which must be capable of handling paper strips of various different breadths up to a breadth of about 30 cm or more. If the transported strip is quite narrow, then rigid, stationary transverse or lateral guide structures may often be adequate, depending upon the type of strip stock employed. However, generally, if the breadth of the strip stock exceeds about 10 cm, stationary lateral guide structures are no longer adequate; instead of providing lateral guidance and positioning force, applied to the strip transverse to its transport direction, the lateral guide structure merely deform the edge portions of the strip, due to the strip's tendency to curl up and/or due to its relatively low stiffness.
It is known, for example from U.S. Pat. No. 3,001,680, to provide sensing rollers at the lateral edges of the transported strip. The sensing rollers sense transverse shifting of the transported strip and, through the intermediary of a lever coupling, activate the drive motor for a transverse-shifting structure serving to shift the transported strip transversely back to centered position. Such known systems, however, are quite expensive and complicated in their operation. A particular disadvantage of them, is that the transverse-shifting structure used to return the strip to centered position presses on the edges of the strip; if the strip has a marked tendency to roll or curl up, or is otherwise very flexible, little or no corrective transverse shifting may actually result. In particular, photographic roll paper of the type nowadays typically empolyed cannot be adequately centered using such systems; the inherent stiffness of the paper is so low that its edges cannot in general follow along the recentering structure, and instead may often merely become deformed. Furthermore, such deformation, i.e., the pressure applied to the strip in the course of such deformation, can result in improper exposure of the strip at its edges.
SUMMARY OF THE INVENTION
Accordingly, it is the general object of the invention to provide an automatic strip centering system of the type in question, but capable of sensitively correcting even small transverse shifts even in the case where the transported strip is of a material having very low stiffness.
This is accomplished using a transport roller pair, one roller of which can be swung about an axis which is perpendicular to the rotation axis of the other transport roller, or the equivalent. If a transport roller pair is employed, then the swinging of the swingable transport roller is performed in automatic response to transverse-shift detection performed by strip-edge sensors.
With the inventive system, even if the transverse shift detected by the edge sensors is quite small, the system reacts quickly and decisively to recenter the transported strip. Preferably, the edge sensors are displaceable structures which are displaced by the strip edges when the strip goes uncentered, and the force thusly exerted upon the edge sensor is multiplied by a transmission and used as the corrective force serving to swing the swingable roller of the transport roller pair, or the like. Even if the force thusly exerted upon the edge sensor is quite small, the corrective force transmitted to the swingable transport roller, or the equivalent, is strong and decisive enough to result in exact recentering. In this way, automatic centering can be accurately performed, even if the transported strip material is of relatively great breadth and softness, i.e., of relatively low stiffness.
In one embodiment of the invention, the swingable transport roller can be a so-called self-aligning roller, i.e., a roller carried on a self-aligning ball roller bearing, the roller bearing being pressed by biasing springs against the non-swingable other one of the two transport rollers. The self-aligning roller is controlled by wheels bearing upon it at its sides, these wheels being coupled via a lever-type transmission to the edge sensors for the strip. In this embodiment, the adjusting of the arrangement is performed particularly simply. Furthermore, the provision of a lever-type transmission between the edge sensors and the wheels bearing on the self-aligning roller produces decisive corrective force even if the amount of the transverse shift of the transported strip is very small.
The novel features which are considered as characteristic for the invention are set forth in particular in the appended claims. The invention itself, however, both as to its construciton and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic top view looking down upon a first embodiment of the invention;
FIG. 2 is a schematic top view looking down upon a second embodiment of the invention; and
FIG. 3 is a side view showing the shapes of preferred transport rollers.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, numeral 1 denotes the framework of a photographic copying or printing machine, through which is being transported a photographic emulsion strip 2, i.e., photographic roll paper. The strip 2 travels between two lateral guidance elements 3, which simultaneously serve as transverse-shift sensors. Sensors 3 are mounted on a common bar 5 which extends perpendicular to the transport direction 4 of the strip 2. The sensors 3 are adjustably mounted on the transverse bar 5, so as to be able to accommodate strips 2 of differing breadths, as indicated by the broken-line depictions at 3'. The transverse bar 5 is mounted by (non-illustrated) means for sliding motion in the direction of its elongation, or preferably is spring-supported in a manner described below in connection with another embodiment.
Articulately coupled to the transverse bar 5 is one end of a long transmission lever 6, the other end 7 of which is swing mounted on the copying-machine framework 1, i.e., mounted for swinging motion about a swing axis which is normal to the illustration-plane in FIG. 1. At a point on lever 6 which is closer to end 7 than to transverse bar 5, there is articulately coupled to lever 6 one end of a lever 8, whose other end is articulately coupled to one end of a crank 9. The other end of crank 9 is mounted in a portion 1a of framework 1 and, at this other end of crank 9, crank 9 is swingable about a swing axis 13 extending normal to the illustration-plane in FIG. 1. Rigidly connected to crank 9, and therefore sharing its swinging capability, is a mounting bracket 10, for example a generally U-shaped bracket whose side legs extend vertically downwards, i.e., normal to and into the illustration-plane in FIG. 1. Mounting bracket 10, for example at the lower ends of its two depending legs, supports the axial bearing 11 of a small transport roller 12.
Small roller 12 cooperates with a larger, non-swingable roller 15, forming a transport roller pair. Larger roller 15 may be a driven roller exerting transport force, or may be a roller passively driven by the transported strip 2. The cooperating transport rollers 12, 15 press the transported strip 2 between them.
When swingable roller 12 is in its normal position, its rotation axis 11' is parallel to the rotation axis 14 of cooperating larger roller 15. However, the rotation axis 11' of swingable roller 12 can be swung about swing axis 13, so that rotation axis 11' turns in a horizontal plane (i.e., in the illustration-plane of FIG. 1), as indicated by the double-headed curved arrow.
The system depicted in FIG. 1 operates as follows:
When the strip 2 is being properly transported, it travels exactly in the direction of arrow 4, and does not shift transversely and become decentered. If, for any reason, a transverse shift of the transported strip 2 develops, for example in the direction of solid-line arrow P, one of the sensors 3 and accordingly the transverse bar 5 shift in this direction. Accordingly, the long lever 6 turns clockwise (as viewed in FIG. 1) about its swing axis at 7, thereby drawing lever 8 in the same direction as the transverse strip shift, here rightwards. This turns crank 9 counterclockwise (as viewed in FIG. 1) about vertical swing axis 13, the mounting bracket 10 and smaller roller 12 sharing this swinging movement about vertical swing axis 13. As a result, the rotation axis 11' of smaller roller 12 is no longer parallel to the rotation axis 14 of larger roller 15, the roller 12 now having swung in the direction indicated by the curved broken-line arrow P. As a result of the now angular relationship between the rotation axes 11', 14 of the two rollers 12, 15, the strip 2 transported between these rollers is subjected to a force Q, whose transverse vectorial component is directed opposite to the direction of the transverse strip shift P. This sidewards corrective force Q returns the strip 2 to its centered position, and in the course of this return the sensors, lever arms and roller 12 return to their initial positions, the strip 2 now again being transported exactly in the direction of arrow 4.
If the sense of the transverse strip shift were in the other direction, i.e., leftwards as viewed in FIG. 1, the components referred to would perform equivalently, but moving in the directions opposite to those just mentioned.
As shown in FIG. 1, the swingable roller 12 is kept quite narrow (of short axial length) relative to the breadth of strip 2, to minimize the mass of the swinging structure. Also, it will be noted that the force needed to swing roller 12 and thereby effect the shift correction is actually derived from the sensors 3 themselves. Because the lever 8 is coupled to long lever 6 near the swing axis of the latter, the force exerted upon the affected one of sensors 3 by the edge of the transversely shifted strip 2 is considerably multiplied, during its transmission to swinging roller 12.
FIG. 2 is a top view looking down upon a second embodiment of the invention. For the sake of clarity the non-swingable one of the two rollers, which is located above the transported strip 2, is omitted from the drawing. In this embodiment, the swingable roller is located beneath the transported strip 2, and the sensors are located upstream of the corrective elements, as considered in the direction of strip transport.
In this embodiment, the lateral guide elements 3, also constituting the strip edge sensors, are again mounted on a transverse bar 5. Here, the mounting of transverse bar 5 is a spring-hung one, the bar 5 being hung from framework 1b by means of two tension springs 20. As before, the transverse bar 5 shifts in the direction of its elongation, in response to transverse shifting or decentering of the transported strip 2. Midway between its ends, the transverse bar 5 is provided with a pin 21 which extends into a slot 61 formed at one end of a lever 60. The other end of lever 60 is mounted at 62 for swinging movement about a stationary vertical pivot axis at 62, i.e., a pivot axis extending normal to the illustration-plane in FIG. 2. At this end of lever 60 there is secured to lever 60, to share its swinging movement, a shaft 22 which extends generally parallel to the axes of the rollers of the transport roller pair. Rotatably mounted on the ends of shaft 22 are wheels 23 which bear upon the cylindrical peripheral surface of the swingable roller 24. The mounting shaft 25 of swingable roller 24 is borne by the side walls 1b of the machine's framework 1. Midway between its ends, mounting shaft 25 comprises a spherical bearing portion 26. The inner surface of hollow swingable roller 24 is provided with a radially inwardly extending bearing 27, the radially innermost surface 27a of which is spherical in correspondence to the spherical bearing portion 26. Bearing 27 is rigid with the casing 28 of the swingable roller 24.
This self-aligning-type roller 24, with its self-aligning bearing 26, 27, 27a, is open at its axial ends, to maximize the angle through which roller 24 can swing relative to its mounting shaft 25. In cooperation with the (non-illustrated) transport roller above strip 2 and with the wheels 23, the self-aligning roller 24 can be swung, its swinging axis being more or less limited to an axis 29 extending vertically, i.e., normal to the illustration-plane in FIG. 2, the axis 29 passing through the geometrical center of the spherical bearing portion 26 of mounting shaft 25.
The system depicted in FIG. 2 operates as follows:
If the transported strip 2 transversely shifts in the direction of solid-line arrow P', the transverse bar 5 and accordingly the slot 61 in lever 60 likewise shift in this direction. As a result, the shaft 22 swings clockwise (as viewed in FIG. 1) about its swing axis at 62, and the self-aligning roller 24 similarly swings clockwise about its swing axis 29; i.e., the roller 24 swings in the direction of curved broken-line arrow P'. Because the strip 2 is now being pressed and transported between two cooperating rollers whose rotation axes are not parallel to each other, the strip 2 is subjected to a generally transverse force component Q', the exactly transverse component of which is directed opposite to the direction of the transverse shift. As a result, the strip 2 is returned to its centered position.
FIG. 3 depicts a particular design for the upper counterpressure roller 30 not shown in FIG. 2. Midway between its axial ends, roller 30 has a radially inward recess 31 of axial length a; the radial depth of the recess is for the most part uncritical. The purpose of this recess 31 is as follows:
If both rollers of the transport roller pair have simple cylindrical surfaces, then when one roller is swung to an angle relative to the other, the contact between the surfaces of the rollers is essentially a point-contact. This point or small spot of contact may vary in position, as the surfaces of the rollers wear with use. Providing the recess 31, in contrast, establishes two well defined contact points X when the rotation axes of the two rollers are not parallel. Selection of the axial length a of the recess 31 can be performed in dependence upon the physical properties of the particular strip material to be transported, and can also be performed to preselect the sensitivity of the system.
To facilitate automatic thread-in of the leading end of a strip to be transported, it is advantageous that the transport roller pair having the self-aligning roller be located downstream of the edge sensors. In this connection, the spring-hung mounting of transverse bar 5 also serves to assure that the edge sensors are always properly centered.
It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of constructions differing rom the types described above.
While the invention has been illustrated and described as embodied in the guidance and automatic centering of longitudinally transported photographic roll paper in a photographic copying or printing machine, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constiture essential characteristics of the generic or specific aspects of this invention. | The longitudinally transported strip passes and is pressed between two cooperating transport rollers. The rotation axes of the two rollers are normally parallel to each other. One roller is swingably mounted about a swing axis which intersects and is perpendicular to the rotation axis of the other, non-swingable roller. Edge sensors are displaced by the lateral edges of the transported strip, when the strip improperly shifts transversely. The force thusly exerted upon an edge sensor is transmitted, via a force-multiplying lever system, to the swingable transport roller, swinging the latter to a position such that the swung transport roller exerts upon a major surface of the transported strip a force whose transverse component is directed opposite to the direction of the improper transverse shift, resulting in automatic recentering. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is being filed under 35 USC 111 and is a continuation of, and claims the benefit of the filing date of U.S. patent application Ser. No. 12/876,765, which application is a continuation of Ser. No. 12/702,723 and U.S. patent application Ser. No. 12/702,647, both of which were filed on Feb. 9, 2010 and both of which claim priority to U.S. patent application Ser. No. 10/931,271 that was filed on Sep. 1, 2004 and bears the title of METHOD AND SYSTEM FOR INVASIVE SKIN TREATMENT and which has now been abandoned.
FIELD OF THE INVENTION
[0002] The invention relates to methods and systems for skin treatment.
BACKGROUND OF THE INVENTION
[0003] Directed damage of the skin is used to stimulate regrowth of collagen and to improve skin appearance. A well known method of directed damage is ablating the epidermis using laser radiation having wavelengths strongly absorbed by water so as to heat the water to above boiling temperature. Typical lasers used for epidermis ablation are CO.sub.2 and Er:YAG lasers. Ablating the epidermis using RF (radiofrequency) current is described in U.S. Pat. No. 6,309,387. This treatment significantly reduces wrinkles and improves the skin appearance. The main disadvantages of skin resurfacing are the long healing period that can be over a month long and the high risk of dischromia. These disadvantages have reduced the popularity of ablative skin resurfacing in recent years.
[0004] Non-ablative skin resurfacing is based on heating of the dermis to a sub-necrotic temperature with simultaneous cooling of the skin surface. U.S. Pat. No. 5,810,801 describes penetrating the dermis with infrared laser radiation with dynamic cooling of the skin surface using a cryogen spray.
[0005] Wrinkles are created in skin due to the breakage of collagen fibers and to the penetration of fat into the dermal structure. Thus, destroying adipose cells and structure, can improve the surface structure. However, most wrinkle treatment methods target the collagen and do not have a significant effect on deep wrinkles Radio frequency (RF) energy has been used for the treatment of the epidermal and dermal layers of the skin. For example, U.S. Pat. No. 6,749,626 describes use of RF for collagen formation in dermis. This patent describes a method for collagen scar formation. U.S. Pat. Nos. 6,470,216, 6,438,424, 6,430,446, and 6,461,378 disclose methods and apparatuses for affecting the collagen matrix using RF with special electrode structures together with cooling and smoothing of the skin surface. U.S. Pat. Nos. 6,453,202, 6,405,090, 6,381,497, 6,311,090, 5,871,524, and 6,452,912 describe methods and apparatuses for delivering RF energy to the skin using a membrane structure. U.S. Pat. Nos. 6,453,202 and 6,425,912 describe methods and apparatuses for delivering RF energy and creating a reverse temperature gradient on the skin surface. Although a non-ablative treatment is much safer and does not scar the skin tissue, the results of non-ablative treatments are less satisfactory.
[0006] A method described in U.S. patent application No. 20030216719 attempts to maintain the efficiency of ablative treatment with a shorter healing time and a lower risk of adverse effects. The device described in that patent coagulates discrete regions of the skin where the regions have a diameter of tens of micrometers and the distance between the regions is larger than the regions themselves. This treatment provides skin healing within a few days but the results are very superficial and less spectacular than with CO.sub.2 laser treatment, even after multiple treatments.
[0007] U.S. Pat. No. 6,277,116 describes a method of applying electromagnetic energy to the skin through an array of electrodes and delivery electrolyte using a microporous pad.
[0008] A device for ablation of the skin stratum corneum using RF electrodes is described in U.S. Pat. Nos. 6,711,435, 6,708,060, 6,611,706, and 6,597,946. However, the parameters of this device are optimized for the ablation of the stratum corneum so as to enhance drug penetration into the skin, and not for thermal collagen remodeling.
SUMMARY OF THE INVENTION
[0009] The present invention provides a system and method for simultaneously heating skin at a plurality of discrete regions of the skin. The invention may be used for collagen remodeling. In accordance with the invention RF energy is applied to the skin at a plurality of discrete locations on the skin. The RF energy is applied using an electrode having a plurality of spaced apart protruding conducting pins. When the electrode is applied to the skin surface, each protruding conducting pin contacts the skin surface at a different location, so that the plurality of pins contacts the skin at a plurality of discrete locations. An RF voltage is then applied to the electrode so as to generate an electric current in the skin that heats the skin to a coagulation temperature simultaneously at a plurality of discrete regions of the skin. Coagulation temperatures are typically in the range of about 60.degree. C. to about 70.degree. C.
[0010] The protruding pins may have blunt tips which do not penetrate into the skin when the electrode is applied to the skin. In this case, the discrete regions of treated skin are located at the skin surface in the epidermis. Alternatively, the pins may have sharp tips that allow the protruding pin to penetrate the skin into the dermis. In this way, the discrete regions of treated skin are located in the dermis.
[0011] In another embodiment, the protruding elements are provided with sharp tips that allow the elements to penetrate into the skin. After application of the RF current in the skin, the protruding elements are pressed into the skin and an electrical current is then generated that coagulates tissue in the vicinity of the tip of each protruding element. The mechanical properties of the skin are changed after coagulation and the protruding elements may penetrate inside the skin without excessive pressure. A pre-pulse of RF energy can be applied to the skin in order to soften the skin tissue so as to facilitate penetration of the protruding elements into the skin.
[0012] The surface of the skin may be pre-cooled and/or cooled during the treatment to avoid damage to the skin in the area between protruding elements Skin cooling may be provided by contact cooling or by applying a pre-cooled liquid or cryogen spray.
[0013] The invention may be used in wrinkle treatment, collagen remodeling, skin tightening, loose skin treatment, sub-cutaneous fat treatment or skin resurfacing.
[0014] Thus in its first aspect, the invention provides a system for simultaneously heating a plurality of discrete skin volumes to a coagulation temperature, comprising:
(a) an applicator comprising an electrode having a plurality of spaced apart protruding conducting elements configured to contact the skin surface at a plurality of discrete locations; and (b) a controller configured to apply a voltage to the electrode so as to simultaneously heat a plurality of skin volumes to a coagulation temperature when the applicator is applied to the skin surface.
[0017] In its second aspect, the invention provides a method for simultaneously heating a plurality of discrete skin volumes to a coagulation temperature, comprising:
(a) applying an applicator to the skin surface, the applicator comprising an electrode having a plurality of spaced apart protruding conducting elements configured to contact the skin surface at a plurality of discrete locations; and (b) applying a voltage to the electrode so as to simultaneously heat a plurality of skin volumes to a coagulation temperature.
[0020] In the case when protruding part of the electrode penetrates within the skin the size of protruding elements should be small enough to avoid significant damage of the skin surface. Preferable size of protruding elements is from 10 to 200 microns and coagulation depth can be varied from 100 microns up to 2 mm for invasive electrodes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] In order to understand the invention and to see how it may be carried out in practice, preferred embodiments will now be described, by way of non-limiting examples only, with reference to the accompanying drawings, in which:
[0022] FIG. 1 shows a system for treating skin simultaneously at a plurality of discrete regions of skin, in accordance with the invention;
[0023] FIG. 2 shows an applicator for use in the system of FIG. 1 ;
[0024] FIG. 3 shows a second applicator for use in the system of FIG. 1 ; and
[0025] FIG. 4 shows a third applicator for use in the system of FIG. 1 .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0026] FIG. 1 shows a system for applying RF energy to a plurality of discrete regions of skin in accordance with the invention. The system includes an applicator 13 , to be described in detail below, configured to apply RF energy simultaneously to a plurality of discrete regions of skin of an individual 22 . The applicator 13 is connected to a control unit 11 via a cable 12 . The control unit 11 includes a power source 18 . The power source 18 is connected to an RF generator 15 that is connected to electrodes in the applicator 13 via wires in the cable 12 . The control unit 11 has an input device such as a keypad 10 that allows an operator to input selected values of parameters of the treatment, such as the frequency, pulse duration and intensity of the RF energy. The control unit 11 optionally contains a processor 9 for monitoring and controlling various functions of the device.
[0027] FIG. 2 shows an applicator 13 a that may be used for the applicator 13 in accordance with one embodiment of the invention. The applicator 13 a comprises an electrode 1 from which a plurality of protruding conducting elements 5 extend. Each protruding element 5 (referred to herein as a “pin”) terminates in a tip 7 having a high curvature. The electrical current from the tips is much higher than from flat parts 6 of the electrode Skin volumes 4 around the tips 7 are therefore heated to a much higher temperature than the surrounding dermis 3 and epidermis 2 , so that the skin volumes 4 may be heated to a coagulation temperature, while the skin temperature in the outside the volumes 4 are not heated to a coagulation temperature. The electrical energy is adjusted to selectively damage skin adjacent to tips so that the treatment of the skin occurs simultaneously at a plurality of discrete volumes 4 . The pulse duration is preferably short enough to prevent significant heat diffusion far from the tips. In order to limit significant heat transfer from the tips, the pulse duration should preferably not exceed 200 ms. The selectivity of the treatment can be improved by electrode cooling of the skin surface. Cooling also causes a more uniform heat distribution at the tips. This can be achieved by circulating a cooling fluid through tubes 8 in the flat regions 6 between the pins 5 . The electrode 1 is contained in a housing 10 connected to the cable 12 . The cable 12 electrically connects the electrode 1 with a terminal of the power source 18 . A second terminal of the power supply 18 may be connected to a ground electrode 20 via a cable 23 (See FIG. 1 ).
[0028] FIG. 3 shows an applicator 13 b that may be used for the applicator 13 in accordance with another embodiment of the invention. The applicator 13 b comprises an electrode 100 consisting of a plurality of conducting pins 101 extending from a conducting plate 102 . The pins 101 are separated by electrical insulating material 105 . The applicator 13 b is used similarly as the applicator 13 a to deliver electrical current to discrete volumes of skin 4 .
[0029] The pins 5 in the applicator 13 a and the pins 101 in the applicator 13 b are provided with blunt tips 7 and 107 , respectively. This prevents the pins 5 and 101 from penetrating into the skin when the electrode 13 a or 13 b is applied t the skin surface. Thus, the applicators 13 a and 13 b provide simultaneous non-invasive coagulation of skin regions 4 .
[0030] FIG. 4 shows an applicator 13 c that may be used for the applicator 13 in accordance with another embodiment of the invention. The applicator 13 c is configured to be used for invasive collagen remodeling. The applicator 13 c includes an electrode 201 having a plurality of protruding conducting pins 205 . The pins 205 have sharp tips 206 that are configured to penetrate through the epidermis 202 into the dermis 203 when pressed on the skin as shown in FIG. 4 . The applicator 13 c is used similarly to the applicators 13 a and 13 b so that the treatment of the skin occurs simultaneously in a plurality of discrete skin volumes 204 . However, unlike the discrete volumes 4 , which are located in the epidermis (see FIGS. 2 and 3 ), the volumes 204 are located below the surface in the dermis 203 ( FIG. 4 ). This reduces skin redness that sometimes occurs when the treated regions are in the epidermis. A maximal current density is created at the tips of the pins 205 . The sides of the protruding elements may be coated with insulating material to avoid skin heating around the pins 205 (not shown).
[0031] The present invention can be combined with other methods of skin treatment including laser treatment. For example non-ablative collagen remodeling by laser radiation may be combined with the invasive RF heating of the skin dermis in accordance with the invention.
[0032] The preferable parameters for non-invasive skin coagulation in accordance with the invention are as follows: [0032] Electrode size above 0.3 cm; [0033] Protruding element at contact with the skin up to 0.5 mm [0034] Protruding element height about 1 mm. [0035] Distance between protruding elements at least twice the element diameter; [0036] Current density: over 1 A/cm.sup.2; [0037] RF current pulse duration: not longer than 0.5 sec; [0038] The optimal parameters for invasive skin coagulation:
[0033] Electrode size above 0.3 cm; [0040] Pin diameter at contact with the skin not larger than 0.3 mm [0041] Pin protruding height above 1 mm. [0042] Distance between pins at least 1 mm; [0043] Current density above 0.1 A/cm.sup.2; [0044] RF current pulse duration not longer than 0.5 sec. | A system and method for simultaneously heating a plurality of discrete skin volumes to a coagulation temperature. The system comprises an applicator containing an electrode having a plurality of spaced apart protruding conducting elements configured to contact the skin surface at a plurality of discrete locations. A controller applies a voltage to the electrode so as to simultaneously heat a plurality of skin volumes to a coagulation temperature when the applicator is applied to the skin surface. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 941,540, filed Sept. 15, 1978, being abandoned Sept. 15, 1979, which in turn is a continuation-in-part of application Ser. No. 767,388, filed Feb. 10, 1977 and abandoned Sept. 15, 1978, which in turn is a continuation-in-part of application Ser. No. 581,094, filed May 27, 1975 and abandoned Feb. 11, 1977, which in turn is a continuation-in-part of application Ser. No. 413,372, filed Nov. 6, 1973 and abandoned Tuesday, May 27, 1975.
BACKGROUND OF THE INVENTION
This invention relates to coating compositions based on a water-borne reaction product of a carboxyl-functional polymer, an epoxide, and a tertiary amine, having general utility in coating metallic and paper substrates. It is more particularly directed to coating compositions useful as automotive and can coatings.
Coatings of the prior art are often dissolved or dispersed in organic solvents. Among commonly utilized thermosetting compositions are those based on epoxy resins crosslinked with nitrogen resins, usually in an acid catalyzed process.
Increased awareness of the environmental hazards of allowing organic solvent vapors to enter the atmosphere, the desirability of a single system that can be applied not only by the more conventional techniques of spray, roller or flow coating but also by electrodeposition, and the economy resulting from the substitution of water for some or all of the solvents in a coating composition, are all factors mitigating in favor of water-borne coating compositions.
Aqueous epoxy-acrylic-amine coating compositions of other investigators, including U.S. Pat. Nos. 3,969,300--Nagata (1976) and 4,021,396--Wu (1977) are less stable than desired or lack advantages of the present invention.
The composition of this invention is an aqueous solution or dispersion of the reaction product of a carboxyl-functional polymer, a terminally functional epoxy resin, and a tertiary amine. Such a water-borne system can optionally contain a crosslinking agent, is stable, and can be applied to metallic substrates by spray, roller, dip or flow coating or by electrodeposition at the anode and to paper.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a water-borne coating composition based on polymeric quaternary salts of polymeric acids which are the reaction product of:
(A) not less than 50%, based on the weight of (A) plus (B), preferably not less than 65%, most preferably about 78%, of an epoxy resin containing, on the average, two terminal 1,2-epoxy groups per molecule and having an epoxy equivalent weight of 750-5000, preferably about 1500-4000, most preferably about 3000;
(B) a carboxyl-functional polymer in an amount sufficient to provide at least 1.25, preferably at least about 1.75, most preferably about 4.6, equivalents of carboxyl groups, when the source of the carboxyl group is a mono-protic acid, and at least 2.0 equivalents of carboxyl groups, when the source of such groups is a diprotic acid, per equivalent of 1,2-epoxy groups in the epoxy resin of (A), said polymer having a weight average molecular weight (determined by light scattering) of 10,000-160,000, preferably about 10,000-80,000, most preferably about 13,000-18,000, and an acid number of 100-500, preferably about 150-350, most preferably about 300; and
(C) an aqueous solution of at least 1.25, preferably at least about 1.75, most preferably about 3.0, equivalents of a tertiary amine per equivalent of 1,2-epoxy groups in the epoxy resin of (A), said tertiary amine being selected from the group consisting of R 1 R 2 R 3 N, pyridine, N-methyl pyrrole, N-methyl piperidine, N-methyl pyrrolidine, N-methyl morpholine, and mixtures therein and wherein R 1 and R 2 are substituted or unsubstituted monovalent alkyl groups containing one or two carbon atoms in the alkyl portion and R 3 is a substituted or unsubstituted monovalent alkyl group containing 1-4 carbon atoms; and
(D) optionally, 10-90% of the amount required for stoichiometric reaction with the carboxylfunctional polymer of (B) of at least one primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide, wherein Y is at least about 6+0.75(2 X ) wherein Y is the milliequivalent of carboxyl groups neutralized by primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide per 100 grams of acid polymer plus epoxy, and X is the epoxy equivalent weight divided by 1000; and wherein for increasing ratios of carboxyl groups to 1,2-epoxy groups, the amount of amine is increased to keep the carboxyl-functional polymer water dispersible. Preferably, components (A), (B) and (C) are capable of forming a hydrogel structure with components (A), (B) and (C) comprising about 0.1-50% of the coating composition and the remainder comprising water and, optionally, organic liquid(s) in a volume ratio of from 70:30 to all water, sometimes preferably 80:20. (Percentages, proportions and ratios herein are by weight except where indicated otherwise.)
The water-borne coating composition can be crosslinked without the addition of a crosslinking agent or, optionally, it can contain crosslinking agents such as a nitrogen resin or a phenolic resin, as well as additives commonly utilized in coating compositions such as pigments, fillers, UV absorbers, and the like.
DESCRIPTION OF THE INVENTION
The water-borne coating composition of the invention is a solution or dispersion of the reaction products of an epoxy resin, a tertiary amine, and a carboxyl-functional polymer. By mixing these components in a random order and utilizing aqueous solutions of highly specific tertiary amines such as dimethyl ethanol amine, a stable, water soluble or dispersible salt of a polymeric quaternary ammonium hydroxide and a carboxyl-functional polymer results which can be crosslinked without the addition of external crosslinking agents. The optional addition of an external crosslinking agent, such as a nitrogen resin, also affords a crosslinkable solution or dispersion which is stable at room temperature. Both compositions, the salt and the solution or dispersion containing an external crosslinking agent, are infinitely dilutable with water.
Whether the coating composition is a solution or a dispersion is largely dependent on the nature of the particular amine used, the stoichiometry of the system, and the epoxy equivalent weight. Even when the composition is opaque some of the resinous components may be dissolved, and when the composition appears to be a clear solution it is possible that small amounts of the components are in a dispersed state. For sake of simplicity, hereafter the term "dispersion" will be used to denote the water-borne coating composition.
The dispersion, with or without an external crosslinking agent, as prepared, usually has a pH of above 7 and a nonvolatile content of up to 50%. Upon drying, a hard, solvent-resistant film having excellent resistance to acids, bases, hot water, and detergent results.
The low molecular weight epoxy resins to be utilized in the present invention are commonly known in the art. One class of such resins has the generalized formula ##STR1## wherein R is an alkylene group of 1-4 carbon atoms and n is an integer from 1-12. The epoxy resins utilized in this invention contain an average of two terminal 1,2-epoxy groups per molecule and are in the epoxy equivalent weight range of 750-5000, preferably 1500-4000. They can also contain substituted aromatic rings.
One such preferred epoxy resin is "Epon 1004" where R is isopropylidene, the average value of n is 5, having an epoxy equivalent weight of 875-1025, with an average of about 950±50. The epoxy equivalent weight is defined as the grams of resin containing 1 gram-equivalent of epoxide as measured by ASTM-D-1652. The coating composition containing "Epon 1004" affords a glossy, flexible, chemically-resistant film. Another preferred epoxy resin is "Epon 1007" where R is isopropylidene, the average value of n is 11, having an epoxy equivalent weight of 2000-2500, with an average of about 2175±50. The coating composition containing "Epon 1007" affords glossy, tough, flexible films upon cure. Another preferred epoxy is an analog of "Epon 1009" with an average epoxy eqivalent weight of 3000 made by chain extending "Epon 829" (EW 195) with bisphenol A.
The quantity of the epoxy resin to be utilized in the coating composition of this invention is determined in relation to the amount of carboxyl-functional polymer and the relative amounts are dependent on the end use application of the coating but there must be at least 50%, preferably in the range of 65-90%, of epoxy resin present. There must be, furthermore, at least 1.25, preferably at least 1.75, and most preferably about 4.6, equivalents of carboxyl groups per equivalent of 1,2-epoxy groups in the epoxy resin. This minimum equivalent requirement is valid for those carboxyl-functional polymers which contain monoprotic acids derived from alpha,beta-ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid, monoesters of alkanols having 1-8 carbon atoms with diacids, such as maleic acid, itaconic acid, fumaric acid, mesaconic acid, citraconic acid and the like, and mixtures thereof. For those carboxyl-functional polymers which contain diprotic acids derived from diacids such as maleic acid, itaconic acid, fumaric acid, mesaconic acid, citraconic acid, and mixtures thereof, the minimum requirement is 2.0 equivalents, preferably at least 2.5 equivalents, of carboxyl group per 1,2-epoxy groups. Usually, no more than 10.0, and preferably no more than 6.0, equivalents of carboxyl groups, per equivalent of 1,2-epoxy groups, will be present.
The carboxyl-functional polymers utilized in this invention are prepared by conventional free radical polymerization techniques from at least one ethylenically unsaturated monomer and at least one ethylenically unsaturated acid monomer. The choice of the alpha,beta-unsaturated monomer(s) is dictated by the intended end use of the coating composition and is practically unlimited. A variety of acid monomers can be used; their selection is dependent on the desired final polymer properties.
This acid monomer can be an ethylenically unsaturated acid, mono-protic or diprotic, anhydride or monoester of a dibasic acid, which is copolymerizable with the other monomer(s) used to prepare the polymer.
Illustrative monobasic acids are those represented by the structure ##STR2## where R is hydrogen or an alkyl radical of 1-6 carbon atoms.
Suitable dibasic acids are those represented by the formula ##STR3## where R 1 and R 2 are hydrogen, an alkyl radical of 1-8 carbon atoms, halogen, cycloalkyl of 3-7 carbon atoms or phenyl, and R 3 is an alkylene radical of 1-6 carbon atoms. Half-esters of these acids with alkanols of 1-8 carbon atoms are also suitable.
The most preferred acid monomers are acrylic acid, methacrylic acid, and itaconic acid.
The acid number of the polymers is 100-500, which corresponds to concentrations of about 10-77% of the acid monomers by weight of the polymer. The acid number is the number of miligrams of potassium hydroxide required to neutralize one gram of the polymer. For purposes of illustration, an acid number of 100 corresponds to the presence in the polymer of either 12.8% acrylic acid, 15.3% of methacrylic acid, 11.5% of itaconic acid, or 10.3% of maleic or fumaric acid. An acid number of 500 corresponds to 64% of acrylic acid, 76.5% of methacrylic acid, 57.5% of itaconic acid, or 51.5% of maleic or fumaric acid in the polymer. Preferred acid number values are 150-350.
Vinyl aromatic monomers are commonly utilized to be copolymerized with the acid monomers. They are represented by the structure: ##STR4## where R, R 1 , R 2 , and R 3 are hydrogen or an alkyl radical of 1-5 carbon atoms. Illustrative of these monomers are styrene, α-methyl styrene, vinyl toluene, and the like. The best polymers, in terms of final film properties, are those in which this type of monomer is styrene. The vinyl aromatic monomers can be present from 0-80% of the carboxyl-functional polymer, preferably from 40-80%, most preferably from 40-70%, and specifically at concentrations of about 42, 53, and 66%. For some purposes 10-45% may be preferred and, in some applications, the polymer contains no such monomer.
Other commonly utilized monomers are the α,β-unsaturated nitriles represented by the structure: ##STR5## where R and R 1 are hydrogen, an alkyl radical of 1-18 carbon atoms, tolyl, benzyl or phenyl, and R 2 is hydrogen or methyl. Most commonly utilized are acrylonitrile and methacrylonitrile. The nitrile monomer can be present from 0-40% based on the carboxyl-functional polymer. The polymers preferably contain 10-30% and more preferably 18-22% of the polymer, of the nitrile monomer. For certain purposes it may be desirable to use 5-10% of the nitrile monomer and in some cases no such monomer is included in the polymers.
Other suitable monomers are esters of acrylic acid, methacrylic acid or mixtures thereof with C 1 -C 16 alkanols. Preferred esters are the methyl, ethyl, propyl, n-butyl isobutyl, and 2-ethylhexyl esters of acrylic acid or methacrylic acid or mixtures of such esters. These esters can be present in concentrations of 0-97%, preferably 50-90% for automotive finishes and coil coatings and, for can coatings and appliance finishes, preferably 0-50%.
One can also utilize hydroxyalkyl (meth)acrylate monomers such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate or mixtures thereof. Up to 20% of such ester(s) can be incorporated.
It may be desirable, for certain uses, to include in the polymer acrylamide, methacrylamide or an N-alkoxymethyl (meth)acrylamide such as N-isobutoxymethyl (meth)acrylamide. Alternatively, a polymer containing copolymerized acrylamide or methacrylamide can be post-reacted with formaldehyde and an alkanol to produce an N-alkoxymethylated polymer.
Choice of the particular monomers to be utilized is made with respect to the end use of the coating composition. Preferred polymer compositions include: styrene/acrylonitrile/α,β-ethylenically unsaturated acid//45-84/10-30/15-54, for can coating; styrene/acrylonitrile/alkyl (meth) acrylate/α,β-ethylenically unsaturated acid//30-60/10-30/10-50/15-54, for can coatings and applicance finishes; styrene/alkyl (meth)acrylate/α,β-ethylenically unsaturated acid//20-70/10-60/15-54 or, even more preferably, 35-60/30-50/15-54, for automotive topcoats and primers; methyl methacrylate/alkyl (meth)acrylate/α,β-ethylenically unsaturated acid//20-40/30-74/15-54, for automotive and coil coating applications. Any of the above can also include hydroxylalkyl (meth)acrylate and/or (meth)acrylamide. The alkyl group of the alkyl (meth)acrylate monomer is preferably ethyl, n-butyl, iso-butyl or 2-ethyl-hexyl.
The carboxyl-functional polymers can be prepared by polymerizing suitable monomers, in proper amounts, in an organic liquid medium. In general, this liquid is an organic liquid capable of medium hydrogen bonding, or a combination of this liquid with less than about 50% of an organic liquid capable of strong hydrogen bonding.
Preferably, the liquid medium for the polymerization is an alcohol mixture, generally 62% butanol and 38% of butyl cellosolve. Other media which could be used include either water-soluble or insoluble ketone. Optionally, the ketone can also contain less than about 50% of an ethylene glycol- or diethylene glycol monoalkyl ether (where the alkyl group contains 1-4 carbon atoms), or diacetone alcohol, and/or an alkanol of 1-4 carbon atoms or an alkanediol of 1-7 carbon atoms. A preferred medium is methyl ethyl ketone used by itself. Another preferred medium for the polymerization is a mixture of methyl ethyl ketone and ethylene glycol monobutyl ether.
A catalyst or polymerization initiator is ordinarily used in the polymerization of the carboxylfunctional polymers, in the usual amounts. This can be any free radical initiator that decomposes with a halflife of 0.5 to 2.5 hours at the reflux temperature of the organic liquid medium being used. Tertiary butyl perbenzoate, tertiary butyl peroxypivalate, and tertiary butyl peroxyisobutyrate are preferred.
The polymers utilized in the water-borne coating composition of this invention have a weight average molecular weight, as determined by light scattering or, more conveniently, gel permeation chromatography, using a polystyrene standard, calibrated by light scattering methods of about 10,000-160,000. The preferred weight average molecular weight range is 10,000-80,000. For some applications a 13,000-18,000 molecular weight is preferred.
During the preparation of the coating composition of this invention, an aqueous solution of a tertiary amine, specified below, is brought in contact with a solution of an epoxy resin in organic liquid(s) or with a solutin of an epoxy resin and a carboxyl-functional polymer. A wide variety of organic liquids can be used to dissolve the epoxy resins and the carboxyl-functional polymers. Among the most commonly used solvents are alcohols such as isopropanol, the butyl alcohols, 2-hydroxy-4-methyl-pentane, 2-ethylhexyl alcohol, cyclohexanol, glycols such as ethylene glycol, diethylene glycol, 1,3-butylene glycol, ether alcohols such as ethylene glycol mono-ethyl ether, ethylene glycol mono-butyl ether, diethylene glycol mono-methyl ether, mixtures thereof, and many aliphatic and aromatic hydrocarbons if used admixed with at least one of the above.
While the exact mode of the reaction is not fully understood, it is believed that the tertiary amine first reacts with the carboxyl-functional polymer to form the corresponding salt which, in turn, can dissociate to allow the amine to react with the 1,2-epoxy groups of the epoxy resin. It is also possible, however, that the tertiary amine reacts directly with the 1,2-epoxy groups. In either case, the resulting quaternary ammonium hydroxide can react with the carboxyl-functional polymer to yield a polymeric quaternary ammonium-amine mixed salt of a polymeric acid.
The reaction of tertiary amines with materials containing epoxy groups, to yield adducts containing quaternary ammonium groups, is known. Such reaction, when carried out in presence of water, can afford a product that contains both a hydroxyl group and a quaternary ammonium hydroxide. The reaction can be represented schematically as follows: ##STR6## While most tertiary amines react with epoxy resins to form quaternary ammonium hydroxides, the preparation of the water-borne coating composition of this invention is carried out utilizing at least one tertiary amino selected from the group: R 1 R 2 R 3 N, N -methyl pyrrolidine, N-methyl morpholine, pyridine, N-methyl pyrrole, N-methyl piperidine, and mixtures thereof, wherein R 1 and R 2 are substituted or unsubstituted monovalent alkyl groups containing one or two carbon atoms in the alkyl portion and R 3 is a substituted or unsubstituted monovalent alkyl group containing 1-4 carbon atoms. Some examples of R 1 R 2 R 3 N are: trimethyl amine, dimethyl ethanol amine (also known as dimethyl amino ethanol), methyl diethanol amine, ethyl methyl ethanol amine, dimethyl ethyl amine, dimethyl propyl amine, dimethyl 3-hydroxy-1-propyl amine, dimethylbenzyl amine, dimethyl 2-hydroxy-1-propyl amine, diethyl methyl amine, dimethyl 1-hydroxy-2-propyl amine, and mixtures thereof. Most preferably trimethyl amine or dimethyl ethanol amine is used.
The generation of a polymeric quaternary ammonium hydroxide which is water soluble or dispersible when in presence of a nitrogen resin crosslinking agent is described in U.S. Pat. No. 4,076,676, granted Feb. 28, 1978, and its relevant portions are hereby incorporated by reference.
The amount of tertiary amine needed in the preparation of the water-borne coating composition of this invention is determined by two factors. As a minimum, there is required at least 1.25 equivalents of tertiary amine per equivalent of 1,2-epoxy groups, preferably at least 1.75 equivalents, more preferably 3.0, for the formation of stable dispersions. As the ratio of the number of carboxyl groups in the carboxyl-functional polymer to the number of 1,2-epoxy groups in the epoxy resin increases, the amount of amine is also increased to keep the carboxyl-functional polymer water dispersible. This excess amine is believed to form a salt with some or all of the excess carboxyl groups of the polymer. It is preferred that no excess amine, over the total number of equivalents of carboxyl groups, be used in the coating composition of this invention. The amine utilized in excess of the 1.25 equivalents of the highly specific tertiary amine per equivalent of 1,2-epoxy groups need not be the same as, nor does it necessarily have to be selected from the group of, the highly specific tertiary amines. Any primary, secondary of tertiary amine or monofunctional quaternary ammonium hydroxide can be utilized in neutralizing carboxyl groups of the carboxyl-functional polymer which are not already neutralized. Among such tertiary amines are included: triethyl amine, diethyl ethanol amine, dimethyl cyclohexyl amine, triethanol amine, tributyl amine, dimethyl n-butyl amine, tripropyl amine, dimethyl lauryl amine, and γ-picoline. Primary and secondary amines preferably should not be used along with tertiary amines in the neutralization of the epoxies because unwanted covalent bonds could be formed, and this can interfere with the desired hydrogel formation.
The water-borne coating composition of this invention can be prepared without regard to the sequence of addition of the various components. It is preferred, however, to first dissolve the epoxy resin in the carboxyl-functional polymer, in presence of suitable organic liquids. Addition of a suitable tertiary amine, usually dissolved in water, completes the preparation of the polymeric quaternary ammonium salt of a polymeric acid. Additional water can then be added to achieve the final volume rate of water and organic liquid of from 70:30 preferably to 90:10. Additional amine can also be added to insure dispersibility.
A preferred ratio of tertiary amine to water is approximately 1:5 by weight.
The reaction can be carried out between room temperature and below the boiling point of the reaction medium, preferably between 50°-100° C., most preferably 90°-100° C. In this temperature range there is a rapid rate of reaction.
In another preferred method of preparation of the coating composition, an epoxy resin is dissolved in a suitable organic liquid such as the mono-butyl ether of ethylene glycol or diethylene glycol, followed by the addition of a suitable tertiary amine. After the formation of the polymeric quaternary ammonium hydroxide is substantially complete, a carboxyl-functional polymer, dissolved in a suitable organic liquid is mixed with it with agitation. This latter solution can also contain any additional primary, secondary or tertiary amine, dissolved in water, necessary for dispersability of the coating composition. Mixing of the components completes the preparation of the water-borne coating composition. This sequence of steps can also be carried out between room temperature and temperatures below the boiling point of the reaction media.
Yet another preferred method of preparation comprises the steps of dissolving the carboxyl-functional polymer in a suitable organic liquid, addition of an aqueous solution of a suitable tertiary amine, mixing in of an epoxy resin, and heating, preferably between 50°-100° C. and, more preferably, between 90°-100° C., followed by the requisite amount of water to obtain the final water-to-organic liquid volume ratio of from 70:30 to 90:10.
The polymeric quaternary ammonium-amine mixed salt of the carboxyl-functional polymer of the water-borne coating composition of this invention preferably is a complex hydrogel structure. It is the generation, during the epoxy/carboxyl/amine reaction, of such a hydrogel structure which affords the solubility or dispersibility, and stabilization, in water of the coating composition. A possible schematic formula is shown by the formula below. The exact nature of the bonding is not known. The number of carboxyl groups in the schematically shown polymer molecules and of the relative portion of free acid groups to the amine salt groups are determined by the stoichiometry employed during the preparation of the coating composition. The schematic representation is shown to further the understanding of the nature of the invention: ##STR7## where M.sup.⊕ is hydrogen or a protonated primary, secondary or tertiary amine or a monofunctional quaternary ammonium group and ##STR8## is formed from a tertiary amine selected from the group: R 1 R 2 R 3 N, N-methyl pyrrolidine, N-methyl morpholine, pyridine, N-methyl pyrrole, N-methyl piperidine, and mixtures thereof, wherein R 1 and R 2 are substituted or unsubstituted monovalent alkyl groups containing one or two carbon atoms in the alkyl portion and R 3 is a substituted or unsubstituted monovalent alkyl group containing 1-4 carbon atoms.
The water-borne coating composition of this invention is a stable solution or dispersion and can be used as prepared. It can be crosslinked without the addition of an external crosslinking agent and can also be crosslinked with external crosslinking agent such as phenol formaldehyde resins or, preferably, nitrogen resins.
The nitrogen resins are well known. They are the alkylated products of amino-resins prepared by the condensations of at least one aldehyde with at least one of urea, N,N'-ethyleneurea, dicyandiamide, and aminotriazines such as melamines and guanamines. Among the aldehydes that are suitable are formaldehyde, revertible polymers thereof such as paraformaldehyde, acetaldehyde, crotonaldehyde, and acrolein. Preferred are formaldehyde and revertible polymers thereof. The amino-resins are alkylated with at least one and up to and including six alkanol molecules containing 1-6 carbon atoms. The alkanols can be straight chain, branched or cyclic.
Among the preferred nitrogen resins are partially methylated melamines, partially butylated melamines, hexaethoxymethylmelamine, hexamethoxymethylmelamine, dimethoxytetraethoxymethylmelamine, dibutoxytetramethoxymethylmelamine, butylated benzoguanamine, partially methylated urea, fully methylated urea, fully butylated urea hexabutoxymethylmelamine, and mixtures thereof.
These nitrogen resins can be blended directly into the coating composition at the completion of the preparation or before final dilution with water, either as a solid or as a solution in some miscible organic liquid.
The nitrogen resins are ordinarily added to the compositions of the invention at concentrations ranging from 5 to 35%, preferably 8 to 20%, even more preferably 10 to 15%. The exact amount will be dictated primarily by the final properties desired of the composition and can be determined by one skilled in this art.
In the claims, the term "consisting essentially of" means not including other ingredients in amounts which change the basic and novel characteristics of the invention, including providing an aqueous acid-polymer-modified epoxy coating composition that can form a hydrogel and is useful as an interior coating for cans. Other commonly utilized additives such as coalescing aids, flow-control agents, pigments and the like can be added, in the usual amounts, if this appears necessary or desirable.
The water-borne composition can be applied by a variety of techniques and to a variety of substrates known in industry. For example, the coating composition of this invention can be utilized in the can manufacturing industry which utilizes mainly metallic cans, many of them cylindrical, made from aluminum, tin-free steel, electrolytic tin-plate, and quality-as-rolled steel, among others. Cans utilized for packaging and shipping food and beer or other beverages are mostly of the three-piece or the two-piece drawn-and-ironed (D and I) variety. Cans constructed from three pieces (body, top and bottom) can be roller coated before the metallic sheet is formed into the body of the can or can be spray coated after partial fabrication. The D and I cans, where the metal sheet is stamped to form a cylindrical body closed at one end, are generally spray coated.
The coating composition of this invention can also be applied by electrodeposition. In the electrodeposition process the water-borne composition is placed in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the anode. During the process an adherent film is deposited at the anode. The substantial lack of film formation at the cathode is thought to be due to the preferential dissociation of the amine salt of the carboxyl groups over the polymeric quaternary ammonium salt of the carboxyl groups. It is believed that both electronic and steric factors are involved in the control of the dissociation. The negatively charged carboxylate anion migrates to the anode. The nitrogen resin crosslinking agent, if present in the coating composition, also migrates, in a possible physical entanglement with the polymeric quaternary ammonium salt of the carboxyl-functional polymer, to the anode.
The conditions under which the electrocoating is carried out are similar to those used in the electrodeposition of other types of coatings. The applied voltage can be varied, can range from 1 to 1000 volts, and is typically between 25 and 500 volts. The current density is usually between about 1 milliampere and 100 milliamperes per square centimeter. The current density tends to decrease during the coating process as the coating thickness increases. The coating time can vary from 1 to 20 seconds or longer and is typically between 1 and 5 seconds for coating cans.
The concentration of the coating composition depends upon the process parameters to be used and is not generally critical. Ordinarily the film-forming components comprise 0.1-50% and preferably 5-30%, for conventional coating methods, and 1-20%, for electrodeposition, of the total composition, the remainder being water and organic liquid(s). The latter are present in a volume ratio of from 90:10 preferably to 70:30.
The freshly deposited films are capable of being immediately dried and/or crosslinked, without regard to the method of coating used to obtain them.
The coating compositions of this invention can be dried to useful films as is or can be cured thermally as is or when containing, for example, a nitrogen resin crosslinking agent. After the composition has been applied to the substrate, baking at elevated temperatures brings about the desired crosslinking. Temperatures of 150° C. to 260° C., for 0.1 to 30 minutes, are typical baking schedules utilized.
The water-borne coating composition of this invention is useful in a variety of applications. This coating composition finds particular utility in the can industry where the composition can be applied to the interior of two-piece drawn-and-iron and three-piece beer and beverage cans, to the exterior of three-piece beer and beverage cans, to the interior and/or exterior ends of two- or three-piece cans or two- or three-piece sanitary cans. When the coating composition of this invention is applied to the interior of food and beer or beverage cans by spray-coating, a thin uniform film is deposited which, after curing, corresponds to a coating weight of 0.3 to 1.3 milligrams per square centimeter (2-8 milligrams per square inch). Coatings utilized as an interior enamel have excellent taste and odor characteristics, that is to say, low extractables and sorption to prevent taste adulteration.
The water-borne composition also has utility, expecially when crosslinked with a nitrogen resin, in automotive primer, appliance finish, and coil coating applications, the final coated articles having especially desirable hardness and acid, base, solvent, and detergent resistance properties. The cured coatings are also resistant to salt spray and "processing." This latter property is tested in a steam-pressure cooker at approximately 120° C.
The invention is further illustrated by the following examples.
EXAMPLE 1
(A)
A polymer having the composition of styrene/ethyl acrylate/methacrylic acid//34.7/40/25.3 (percent by weight) is prepared similarly to the method of preparation used for the polymer of Example 3(A). The final polymer has an acid number of 164 and a solids content of 55%.
(B)
To a 457.9-gram portion of the polymer from (A) above, are added 666.6 grams of "Epon 1007" (average epoxy equivalent weight about 2,175); butyl cellosolve, 81.5 grams; and butyl carbitol, 81.5 grams. The mixture is heated to between 80°-100° C. and mixed to dissolve the epoxy resin. A solution of 65.9 grams of dimethylamino ethanol in 131.8 grams of water is then added and the reaction mixture is maintained at 75°-80° C. for 30 minutes. To this mixture is then added a fully alkoxylated methoxybutoxymethyl melamine, 181.5 grams, followed by, after mixing for 5 minutes, 2333.1 grams of water. The mix is stirred at 50°-60° C. until uniform. A stable dispersion is obtained having a solids content of 27.5% and a pH of 9.0.
The resulting product contained about 72.6% epoxy resin, 27.4% acrylic resin, by weight, and the equivalent ratios of acid polymer/amine/epoxy was about 2.4/2.4/1. X was 2.175, and Y was 47.
The product is applied to untreated aluminum with a #25 wire-wound rod and baked at 205° C. to afford a coating weight of 25.9 mg/4 square-inch surface. Comparison test data, with product from (C) below, are shown in (D) below.
(C)
Example 1(B) is repeated with the exception that no external crosslinking agent is utilized. The following quantities are added in the same manner as in (B) above:
______________________________________ Grams______________________________________Polymer [from (A) above] 548.4"Epon 1007" 798.4Butyl Cellosolve 54.6Butyl Carbitol 54.6Dimethyl Ethanol Amine 79.0Water (for the amine) 157.9Water 2307.1______________________________________
The stable dispersion so obtained has a solids content of 27.5% and a pH of 9.0. This is applied to untreated aluminum as above and baked to afford a coating weight of 25.1 mg/4 square inch. Test data are shown in (D) below.
(D)
The coated panels from (B) and (C) above are tested as follows: The hard, glossy films from both (B) and (C) pass 40 rubs with methyl ethyl ketone and show no blush and excellent adhesion after a 30-minute exposure to boiling water.
These results indicate that good film properties can be obtained with this invention in presence or absence of an external crosslinking agent.
EXAMPLE 2
(A)
To a suitable reactor is charged the following parts by weight:
______________________________________Styrene 83.318Ethyl Acrylate 78.868Methacrylic Acid 71.850Acetone 35.226Monobutyl Ether of Ethylene Glycol 81.076Normal Butanol 28.518______________________________________
The charge is heated to 85° C. and the heat is turned off. A solution of 1.403 parts of tertiary butyl peroxy isobutyrate in 2.349 parts of monobutyl ether of ethylene glycol is added and the batch exotherms to reflux temperature and is held there for ninety minutes. A second addition of 1.403 parts of tertiary butyl peroxy isobutyrate in 2.349 parts of monobutyl ether of ethylene glycol is added rapidly and reflux is maintained for an additional 60 minutes. A third addition of 1.403 parts of tertiary butyl peroxy isobutyrate in 2.349 parts of monobutyl ether of ethylene glycol is added rapidly and reflux is maintained for an additional 60 minutes. 69.890 parts of normal butyl alcohol and 43.611 parts of monobutyl ether of ethylene glycol are added. 35.226 parts of acetone is removed by distillation. 54.373 parts of diemethylethanol amine and 326.240 parts of deionized water are added. The acid number of the product is 200.
(B)
To a suitable reactor is charged the following parts by weight:
"Epon 829": 1854.6
Bisphenol A: 985.4
Monobutyl Ether of Ethylene Glycol: 424.8
The charge is heated to 130°-140° C. and allowed to exotherm to about 200° C. Temperature is maintained above 165° C. for two hours after peak exotherm temperature is reached. 778.7 Parts of normal butanol are added.
The "Epon 829" has an epoxy equivalent weight of about 195, and it is chain-extended by the bisphenol A to an epoxy equivalent weight of about 3000.
The batch is cooled to 100° C. 2358.8 Parts of the neutralized acrylic polymer prepared in A are added. The batch is maintained at 80°-85° C. for 25 minutes. 5597.7 Parts of deionized water, preheated to 80° C. are added evenly over a 1 hour period, and the batch is mixed an additional 30 minutes.
The resulting product contained about 81% epoxy resin and 19% acrylic resin, by weight, with an equivalent ratio of acid polymer/amine/epoxy of about 2.5/1.8/1. X was 3, and Y was 22.5.
EXAMPLE 3
Into a suitably equipped kettle, inerted with nitrogen, are added the following parts by weight:
Monobutyl Ether of Ethylene Glycol: 91.567
Normal Butanol: 32.503
Ethyl Acrylate: 14.453
Tertiary Butyl Perbenzoate: 0.026
In a separate vessel, the following are added and mixed:
Ethyl Acrylate: 54.764
Methacrylic Acid: 122.060
Styrene: 72.919
Normal Butanol: 2.050
Tertiary Butyl Perbenzoate: 2.351
The reactor is heated to reflux and the monomer mixture is added evenly to the refluxing reactor over a two-hour period. Then 7.932 parts of monobutyl ether of ethylene glycol are added as a rinse for monomer feed lines. Reflux is maintained for one hour, at which point 55.500 parts of normal butanol is added. Reflux temperatures are maintained for an additional hour at which point the heat is turned off and 72.623 parts of normal butanol are added, followed by 82.312 parts of dimethyl ethanol amine and 246.940 parts of deionized water. The product is a solution of a styrene/ethyl acrylate/methacrylic acid//27.6/26.2/46.2 polymer at 30.8% solids in solvent, water and amine. The acid number of the product is 300.
Into a suitably equipped kettle, inerted with nitrogen, are added the following parts by weight:
Monobutyl Ether of Ethylene Glycol: 8.400
"Epon 829": 86.978
Bisphenol A: 46.835
The kettle charge is heated to 130°-140° C., heat removed and allowed to exotherm to 175°-200° C. After the exotherm is exhausted, heat is applied and the reaction mass is maintained above 165° C. for two hours after peak exotherm. At this point, a sample can be removed for determination of completion of reaction. Theoretical epoxy equivalent weight is 3000. 6.655 Parts of monobutyl ether of ethylene glycol and 27.366 parts of normal butanol are added to dilute the reaction mass and cool it to 100° C.
121.131 Parts of the neutralized acrylic polymer prepared in (A) are added rapidly following by 23.181 parts of deionized water. The mass is heated to reflux temperature and held for twenty-five minutes. Heat is turned off and 288.155 parts of deionized water, preheated to 70°-80° C. is added evenly over a one-hour period. This dispersion may be isolated here at 28% solids. It may also be further diluted to 20% solids with 220.159 parts of deionized water and 23.288 parts of normal butanol to provide a ready-to-spray product at water/organic solvent of 80/20 by volume.
The resulting product contained about 77.8% epoxy resin and 22.2% acrylic resin, by weight, with an equivalent ratio of acid polymer/amine/epoxy of about 4.6/3.0/1.0. X was 3, and Y was 51.5.
EXAMPLE 4
Add to 100 grams of Example 3(B) 5.6 grams Cymel 373, partially alkylated melamine formaldehyde resin which is 85% solids in water plus 14.2 water and 3.1 grams normal butanol. This acts as an external crosslinker to aid in curing coated films.
COMPARATIVE TEST 1
Certain tests were performed to determine the relative merits of water-borne coating compositions of the invention with the minimum claimed level of an acid number of 100 and epoxy content of 50% versus comparable compositions outside the invention with an acid number of 65 and an epoxy content of 40%. Minor adjustments had to be made in the equivalent ratios of acid polymer/amine/epoxy in order to accommodate the difference in acid number and epoxy content.
(A)
Compositions of the invention were represented by the reaction product of 50% of an acid polymer with an acid number of 100 made of
styrene: 42.4
ethyl acrylate: 42.3
methacrylic acid: 15.3
and 50% of "Epon 1007" epoxy resin with an average epoxy equivalent weight of about 2175, analyzed at 2368. The acid polymer has been neutralized with enough dimethyl ethanol amine to give theoretical equivalent ratios of acid polymer/amine/epoxy of 3.87/3.87/1 and actual analyzed ratios of 4.21/4.21/1. X was 2.175; Y was 66.1.
(B)
Compositions outside the invention were represented by the reaction product of 60% of an acid polymer with an acid number of 65 made of
styrene: 45
ethyl acrylate: 45
methacrylic acid: 10
and 40% of "Epon 1007" epoxy resin. The reaction product was made in the same manner as in (A) above with enough dimethyl ethanol amine to give theoretical equivalent ratios of acid polymer/amine/epoxy of 3.79/3.79/1 and actual analyzed ratios of 4.13/4.13/1. X was 2.175, and Y was 51.1.
The compositions of (B) were significantly less stable than those of (A). (B) separated by settling in 2-3 weeks under ordinary laboratory conditions, while (A) remained well dispersed. Although (B) could be redispersed by stirring, this settling would be expected to be more severe under stress conditions such as freezing and thawing. Such a lack of stability undesirable and probably commercially unacceptable when a stable product is available.
COMPARATIVE TEST 2
By empirically testing a large number of different compositions, it has been determined that a relationship exists between the epoxy equivalent weight and the milliequivalents (MEQ) of amine-neutralized carboxylic acid polymer for obtaining a stable dispersion. This relationship is expressed by a curve wherein Y is 6+0.75(2 X ), wherein Y is the milliequivalent of carboxyl groups neutralized with primary, secondary or tertiary amine or monofunctional quaternary ammonium hydroxide per 100 grams of acid polymer plus epoxy, and X is the epoxy equivalent weight divided by 1000. The curve represents the approximate locus of borderline stability. Above the curve, the compositions are stable if the other conditions of the invention are met including the acid number and the epoxy equivalent weight; below the curve, they are not. Although there is some flexibility in the precise location of the curve, it lies approximately where this definition puts it.
Data points of borderline stability have been determined as follows:
______________________________________X Y______________________________________0 63/41 71/22 93 124 18______________________________________ | Water-borne reaction products of (a) carboxyl-functional polymers; (b) polyepoxides; and (c) tertiary amines are useful as film-forming components of coating compositions which can be spray-, flow-, dip-, roller-, or electro-coated. The coating compositions are useful as such or can be crosslinked with crosslinking agents such as a nitrogen resin and, when coated on metal and paper substrates, they provide coatings of improved properties, including a high degree of flexibility during machining and stamping of the coated articles, corrosion resistance, gloss, hydrolytic stability, and nonadulterating of foods and beverages in contact therewith. | 2 |
This is a continuation of application Ser. No. 162,782, filed Mar. 2, 1988, now abandoned.
FIELD OF THE INVENTION
The present invention relates to photographic compositions and elements having fluorinated sulfosuccinated compounds as coating aids.
BACKGROUND OF THE INVENTION
In the preparation of a photographic material, a support is usually coated with one or more layers comprising an aqueous solution of a hydrophilic colloid binder, such as gelatin. Such layers include, for example, silver halide emulsion layers, intermediate layers, antihalation layers, filter layers, antistatic layers, protective layers, and the like. For multilayer materials, the layers may be coated simultaneously, as described in U.S. Pat. Nos. 2,761,791 and 3,508,947.
In the preparation of hydrophilic colloid layers, the coating solutions must be coated uniformly with a minimum of repellency spots, or repellencies. A repellency is a coating unevenness, such as a round, oval, or comet-shaped indentation or crater in the layer or layers. Repellencies are often caused by the presence in the coating composition of finely-divided insoluble materials in the form of addenda, impurities, or contaminants that are surface active. Solutions coated in the preparation of photographic materials often contain dispersed insoluble photographic addenda, such as organic solvents, or addenda to alter certain physical properties, such as lubricants. Many of these addenda are capable of imparting repellencies to coated layers.
Photographic gelatin may contain insoluble residues of certain naturally-occurring animal fats and fatty acids, which can impart repellencies to the coated layer. Also, surface active contaminants may be introduced from external sources during preparation of the coating composition or during coating. For example, a layer may be contaminated during or immediately after coating by various oils used to lubricate the coating apparatus.
A wide variety of surface active agents have been suggested for use as coating aids to control the uniformity of photographic layers. For example, Japanese Kokai No. 49/046733 describes the use of certain fluoroalkyl sulfosuccinates as coating aids for photographic materials. These compounds, however, often do not prevent repellencies caused by surface active materials having low surface tension properties, such as silicone fluids used as lubricants and sealants.
It would therefore be highly desirable to provide a coating aid for photographic compositions that effectively reduce repellencies, especially those caused by materials from external sources, such as silicone fluids used as lubricants and sealants.
SUMMARY OF THE INVENTION
The present invention provides a photographic composition comprising a hydrophilic colloid binder and a fluoroalkyl surface active agent having the formula: ##STR2## where M is a cation,
x and y are each independently 0 or an integer of from 1 to 6 such that the sum of x and y is an integer of from 2 to 6,
p and q are each independently 1 or 2, with the proviso that when the sum of x and y is 6, p and q are each 1, and when the sum of x and y is 2, p and q are each 2.
The coating aids used in the present invention have the advantage that they reduce repellencies to a greater extent than prior art coating aids, especially those caused by external contaminants.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In one embodiment of the invention, the fluoroalkyl surface active agent has the formula: ##STR3## where M is a cation,
m is an integer of from 1 to 3, and
n is 1 or 2,
with the proviso that if m=1, then n=2, and if m=3, then n=1.
In a preferred embodiment of formula (II), m is 2 and n is 1.
Examples of cations useful as M in the above formula include alkali metal ions derived from sodium, lithium, or potassium, ammonium groups such as tetraalkyl ammonium, ethanolamine, or diethanolamine, or other organic salts that do not render the compound insoluble in the coating medium.
Preferably, the coating aid is used in an amount from 0.01 to 0.3, and more preferably from 0.02 to 0.15, weight percent based on the weight of the hydrophilic colloid coating composition. The optimum concentration range for the coating aid depends on the source of the repellency and on whether other surface active agents are present.
The preferred hydrophilic colloid is gelatin (e.g., alkali-treated gelatin (cattle bone or hide gelatin) or acid-treated gelatin (pigskin gelatin)), or a gelatin derivative (e.g., acetylated gelatin or phthalated gelatin). Other hydrophilic colloids useful in the invention include naturally-occurring substances, such as proteins, protein derivatives, cellulose derivatives (e.g., cellulose esters) polysaccharides (e.g., dextran, gum arabic, zein, casein, and pectin), collagen derivatives, agar-agar, arrowroot, and albumin. The examples of synthetic hydrophilic colloids useful in the invention include polyvinyl alcohol, acrylamide polymers, maleic acid copolymers, acrylic acid copoylmers, methacrylic acid copolymers, and polyalkylene oxides.
The photographic composition of the invention may be used to coat any layer of a photographic element. Such layers are well-known in the art, and include silver halide emulsion layers, intermediate layers, antihalation layers, filter layers, antistatic layers, protective layers, and others as described in Research Disclosure, Item 17643, December, 1978 [hereinafter referred to as Research Disclosure], the disclosure of which is incorporated herein by reference. In a preferred embodiment, the composition of the invention is coated as a protective overcoat of a photographic element.
The material of this invention may comprise a negative-working or positive-working silver halide emulsion layer. Suitable emulsions and their preparation are described in Research Disclosure Section I and II and the publications cited therein. Suitable vehicles for the emulsion layers and other layers of elements of this invention are described in Research Disclosure Section IX and the publications cited therein.
For color photographic materials, references giving information on couplers and on methods for their dispersion are given in Sections VII and XIV, respectively, of Research Disclosure. An account of dye-forming development is given in `Modern Photographic Processing`, Vol. 2, Grant Haist, Wiley, N.Y., 1978, Chapter 9.
The photographic materials of this invention, or individual layers thereof, can contain brighteners (see Research Disclosure Section V), antifoggants and stabilizers (see Research Disclosure Section VI), antistain agents and image dye stabilizers (see Research Disclosure Section VII, paragraphs I and J), light absorbing and scattering materials (see Research Disclosure Section VIII, hardeners (see Research Disclosure Section XI), plasticizers and lubricants (see Research Disclosure Section XII), antistatic agents (see Research Disclosure Section XIII), matting agents (see Research Disclosure Section XVI), and development modifiers (see Research Disclosure Section XXI).
The photographic materials can be coated on a variety of supports as described in Research Disclosure section VII and the references described therein.
The photographic materials can be exposed to actinic radiation, typically in the visible region of the spectrum, to form a latent image as described in Research Disclosure Section XVIII and then processed to form a visible dye image as described in Research Disclosure Section XIX. Processing to form a visible dye image includes the step of contacting the element with a color developing agent to reduce developable silver halide and oxidize the color developing agent. Oxidized color developing agent in turn reacts with the coupler to yield a dye.
Development is followed by the conventional steps of bleaching, fixing, or bleach-fixing, to remove silver and silver halide, washing and drying.
Methods of synthesizing difluoroalkyl sulfosuccinates are known. In order to prepare a coating aid for use in the present invention, an appropriate fluoroalcohol can be reacted with fumaryl chloride in the presence of a base to give the corresponding difluoroalkyl fumarate or or it can be reacted with maleic anhydride in the presence of an acid to give the difluoroalkyl maleate. Difluoroalkyl fumarates and difluoroalkyl maleates both yield sodium difluoroalkyl sulfosuccinate when treated with sodium metabisulphite. An example of the preparation of a coating aid used in the invention is given below.
Preparation of sodium diheptafluorobutyl sulfosuccinate
Fumaryl chloride (18.36 g, 0.12 mol) was added dropwise to a stirred solution of 1H,1H -heptafluorobutan-1-ol (48.00 g, 0.24 mol) and dimethylaniline (30.43 ml, 0.24 mol) in tetrahydrofuran (300 ml) under a nitrogen atmosphere. The temperature was maintained at 20° to 25° C. The dark maroon solution was stirred for 1 hour, then refluxed for 7 hours. Water (500 ml) and diethyl ether (400 ml) were added. The mixture was shaken and the organic phase separated. The ethereal extracts were washed with 10% sulphuric acid (3×100 ml) and then with saturated aqueous sodium hydrogen carbonate (1×150 ml). The extracts were dried over anhydrous magnesium sulphate, filtered and evaporated at reduced pressure to give a crude brown oil. Vacuum distillation provided diheptafluorobutyl fumarate as a colorless liquid that crystallized on cooling. Yield: 42.89 g (75%); b.p. 82°-92° C. (0.4 torr).
Diheptafluorobutyl fumarate (12.60 g, 0.026 mol) was dissolved in ethanol (200 ml). Water (50 ml) and sodium metabisulphite (5.50 g, 0.029 mol) were added and the mixture refluxed for a total of 5 hours. During the first hour, sodium sulphite (3.00 g, 0.024 mol) was added in portions. The resulting solution was cooled and the ethanol removed at reduced pressure. Water (200 ml) was added and the aqueous emulsion extracted with ethyl acetate (3×150 ml). The extracts were dried over anhydrous magnesium sulphate, filtered, and evaporated under reduced pressure to give a white solid. Yield 10.1 g (66%).
Analytical and spectroscopic data showed that the solid was sodium diheptafluorobutyl sulfosuccinate.
The invention is further illustrated by the following Examples.
______________________________________ ##STR4##
______________________________________Compound 1 (invention): R = C.sub.3 F.sub.7 CH.sub.2Compound 2 (Comparison): R = H(CF.sub.2).sub.4 CH.sub.2Compound 3 (Comparison): R = CF.sub.3 (CF.sub.2).sub.3 (CH.sub.2).sub.2Compound 4 (Comparison): R = C.sub.2 F.sub.5 CH.sub.2Compound 5 (Comparison): R = H(CF.sub.2).sub.2 CH.sub.2______________________________________
EXAMPLE 1
The ability of a coating aid to control repellencies caused by an impurity often found in hydrophilic colloid coating compositions was tested as follows.
Two gelatin layers, the uppermost of which contained sodium diheptafluorobutyl sulfosuccinate as a coating aid, were coated onto a polyethylene terephthalate film base subbed to give good adhesion to gelatin. The bottom layer consisted of a 4% by weight solution of lime-processed bone gelatin in water coated at 85.4 ml/m 2 . The top layer consisted of a 7% by weight solution of lime-processed bone gelatin in water containing a colored dye marker, 1 ppm oleic acid emulsified in small droplet form to induce repellency sodium diheptafluorobutyl sulfocuccinate of concentrations indicated in Table I. The top layer was applied at a coverage of 14.2 ml/m 2 . Both layers were applied simultaneously at a temperature of 40° C. using a conventional double slide hopper with applied suction and a linear coating speed of 15.25 m/min. In a separate series of experiments, the coatings were repeated using a linear coating speed of 30.5 m/min.
For each series of experiments, the coating aid was used in amounts ranging from 0.01 to 0.20% by weight. In each case, the coating was uniform and free from repellencies.
For comparison, the experiment was repeated using compounds 3 and 4, which fall outside the scope of the invention.
The results are summarized in Table I below.
TABLE I______________________________________ ConcnCoating Aid (wt. %) Coating Result______________________________________1 (invention 0.02 No repellenciesR═C.sub.3 F.sub.7 CH.sub.2) 0.05 No repellencies3 (comparison 0.02 Many repellenciesR═C.sub.4 F.sub.9 (CH.sub.2).sub.2) 0.05 Many repellencies4 (comparison 0.02 Many repellenciesR═C.sub.2 F.sub.5 CH.sub.2) 0.05 Many repellencies______________________________________
The results in Table I show the superiority of the compound used in the invention for controlling repellencies over the comparison compounds.
EXAMPLE 2
The ability of a coating aid to control repellencies caused by surface active material of the type often introduced by an external source during the coating process was tested as follows. In this Example, the coating comprised two layers and the coating aid material was present at the same concentration throughout the coating.
The gelatin layers were coated following the procedure of Example 1. The layers had the same composition as described in Example 1 except no oleic acid was added and an amount of sodium heptafluorobutyl sulfosuccinate or comparison compound equal to the amount present in the top layer was added to the lower layer.
A small amount of a non-ionic surface active agent solution (25% by weight in water) representing a contaminant was introduced directly onto the top layer by touching it onto the surface using a platinum loop-shaped wire. A series of non-ionic surface active agent solutions, each having a slightly different surface activity measured independently with a surface tensioniometer by the Wilhelmy plate method, was applied to the surface of the top layer.
By examining which surface active contaminants produced repellencies in the coating and which did not, a measure was obtained of the extent to which the coating aid provided protection against repellencies from an external source.
In this Example, the solutions of compounds representing the contaminant were applied to the coated layers at approximately 15 cm from where the layers were applied to the support. For comparison, a compound similar in structure to those suitable for use in the present invention was also tested. The results are shown in Table II.
TABLE II______________________________________ Concn. Surface Tension Minimum (mN/m) (wt. produced by ContaminantCoating Aid %) 18 22 24 26.5 29 31 43 46.5______________________________________1 (invention 0.05 R C C C C C -- --R═C.sub.3 H.sub.7 CH.sub.2) 0.10 R C C C C C -- --2 (comparison 0.05 R R R R R R -- --R═H(CF.sub.2).sub.4 CH.sub.2) 0.10 R R R R C C -- --5 (comparison 0.05 -- -- -- -- -- -- R RR═H(CF.sub.2).sub.2 CH.sub.2) 0.10 -- -- -- -- -- -- R R______________________________________
In Table II, R denotes that the surface-active contaminant produces a repellency while C denotes that no repellency is produced, i.e., repellency formation has been controlled.
The above results clearly demonstrate the extra protection against external sources of repellency provided by a coating aid used in the invention relative to the comparison compounds. Compound 2 required higher concentrations than the compound of the invention to control the formation of repellencies. Compound 5 did not control repellancies even when used at higher concentrations than the compound of the invention.
EXAMPLE 3
The ability of a coating aid to control repellencies arising from surface active material introduced by an external source during the coating process was tested as follows. In this Example, the coating comprises two layers and the coating aid was present in the top layer of the coating only.
Two gelatin layers were coated following the procedure of Example 1. Then a series of non-ionic surface active agent solutions were applied to the surface of the coating in the same manner as described in Example 2. The results of the experiments are presented in Table III.
TABLE III______________________________________ Concn. Surface tension minimum pro- (wt. duced by contaminant (mN/m)Coating Aid %) 24 26.5 29 31 34 36 43 46.5______________________________________1 (invention 0.13 R C C C C C -- --R═C.sub.3 H.sub.7 CH.sub.2)2 (comparison 0.13 R R R R R C -- --R═H(CF.sub.2).sub.4 CH.sub.2)5 (comparison 0.13 -- -- -- -- -- -- R RR═H(CF.sub.2).sub.2 CH.sub.2)______________________________________
As before, R denotes that the surface active contaminant produces a repellency while C denotes that no repellency is produced.
These results clearly demonstrate the extra protection against external sources of repellency provided by a coating aid used in the invention relative to the comparison compounds. Compound 2 required higher concentrations than the compound of the invention to control the formation of repellencies. Compound 5 did not control repellencies even when used at higher concentrations than the compound of the invention.
EXAMPLE 4
The ability of a coating aid to control repellencies arising from a surface-active lubricant and a surface-active antifoam agent arriving at the surface during coating was tested as follows.
Two gelatin layers were coated following the procedure of Example 1. The layers had the same composition as described in Example 1 except that in some cases the coating aid was added to the bottom layer such that its concentration matched that of the top layer.
A small amount of a lubricant WD40®, sold by the WD40 Co., Ltd., United Kingdom and an antifoam agent, Nalco 2341®, sold by the Nalco Chemical Co., Illinois, were introduced individually onto the top layer using the same method as that employed in Example 2. By examining which coatings exhibited repellency and which did not, a measure was obtained of the relative ability of the coating aid to provide protection against the two surface-active contaminants.
Results of the experiments performed are shown in Table IV.
TABLE IV______________________________________ Concentration of Coating Aid (wt. %) Contaminant bottom top NalcoCoating Aid layer layer WD40 ® 2341 ®______________________________________1 0.05 0.05 C C(invention 0.10 0.10 C CR═C.sub.3 F.sub.7 CH.sub.2) 0 0.13 C C 0 0.20 C C 0 0.25 C C2 0 0.13 R R(comparison 0 0.20 R RR═H(CF.sub.2).sub.4 CH.sub.2) 0 0.25 R R5 0.05 0.5 R R(comparison 0.10 0.10 R RR═H(CF.sub.2).sub.2 CH.sub.2) 0 0.13 R R 0 0.20 R R 0 0.25 R R______________________________________
As in the previous Examples, these results clearly demonstrate the extra protection afforded by a coating aid of this invention relative to the comparison compounds.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention. | Fluoroalkyl surface active agents are provided as effective coating aids for hydrophilic colloid coating compositions for photographic materials. These coating aids are of the formula: ##STR1## where M is a cation,
x and y are each independently 0 or an integer of from 1 to 6 such that the sum of x and y is an integer of from 2 to 6, and
p and q are each independently 1 or 2, with the proviso that when the sum of x and y is 6, p and q are each 1, and when the sum of x and y is 2, p and q are each 2. | 2 |
FIELD OF THE INVENTION
The present invention relates generally to filtration systems. More particularly, the present invention relates to a hydrogen purge gas economizer system having an improved membrane filter for the removal of air, oil, and particulates from a hydrogen stream.
BACKGROUND OF THE INVENTION
Generally, large generators are filled with pressurized hydrogen to cool the generator. The purity of the hydrogen dictates its effectiveness in cooling the generator; the higher the purity, the more efficiently the hydrogen cools the generator. Typically, the hydrogen has purity levels in excess of 95%. When purity levels fall below this level of purity, the cooling characteristics of the hydrogen are significantly reduced.
A significant source of contaminants in the hydrogen stream is oil which enters the hydrogen from the lubrication oil and exists in the hydrogen in the form of small droplets and gaseous molecules. Air is often trapped in the oil droplets and is thereby also suspended in the hydrogen stream. Impurities may also comprise styrene, anomine, and various other gases which emanate from the epoxies which are used throughout the generator. Solid particulates generated by the heating of non-metallic components might also be suspended in the hydrogen.
In addition to adversely effecting the cooling qualities of the hydrogen, impurities can adversely effect the electrical quality of the insulating components of the generator. Also, these impurities increase the density of the mixture of gases in the generator and thereby add to windage loss. Further, it should be noted that hydrogen has a greater tendency to explode when found in purity levels of 4 to 74%; thus, lower purity levels increase the possibility of explosion.
A significant and sometimes primary cause for the existence of oil mist and air within the cooling hydrogen of a turbine generator is the leakage of oil-laden gas from the generator's defoaming tanks into the generator's stator housing through the generator rotor's labyrinth seals. Many types of electrical generators utilize gland seals to contain hydrogen within the generator's frame. These gland seals operate by surrounding a portion of the generator rotor, with a very small gap between the stationary gland seal and the rotating rotor, and injecting a stream of oil in the interface therebetween. The passage of oil in an inboard axial direction prevents hydrogen gas from escaping from within the generator frame through this interface. Upon leaving this interface region of the gland seal, the oil is collected in a defoaming tank and recirculated within the oil system of the generator. These gland seals are located at both the turbine and exciter end of the rotor shaft and are provided with a deflector which prevents the oil from splashing directly against the labyrinth seals as it is ejected from the gland seals. Although the deflectors are generally successful in this function, it is possible that a quantity of oil can be ejected from the gland seals with sufficient velocity to enter the labyrinth seals.
A more severe cause of oil contamination of the hydrogen coolant is the defoaming tank itself. The defoaming tank contains oil in both liquid and vapor form, i.e. oil particles suspended in the hydrogen gas. The defoaming tank contains a quantity of liquid oil at its bottom portion which will eventually be recirculated through the generator's oil system. Above this liquid oil is a mixture of hydrogen gas with oil mist dispersed throughout it and with gaseous oil molecules mixed therethrough. This contaminated gas within the defoaming tank is separated from the cooling hydrogen which exists within the generator's frame by the above-mentioned labyrinth seals. However, if the pressure within the defoaming tank exceeds that of the hydrogen gas on the opposite side of the labyrinth seal, the contaminated gas from above the oil in the defoaming tank can flow through the labyrinth seal into the cooling region of the generator frame and contaminate the much purer quantity of hydrogen used to cool the generator.
Although the pressure of the defoaming tank is intended to be kept at a value less than that of the hydrogen within the generator frame. various factors, including a rise of the oil temperature within the defoaming tank, can cause the pressure within the defoaming tank to exceed that of the hydrogen gas located within the generator. As described above, this increase in gas pressure within the defoaming tank can trigger the harmful flow of contaminated gas through the labyrinth seal and into the generator frame causing contamination of the generator's hydrogen cooling system.
Various methods have been developed to address the problems associated with impurities in the cooling hydrogen stream. Some have proposed vacuum treating the sealing oil to remove impurities. In such systems, a vacuum maintains hydrogen purity by removing gases including hydrogen from the oil prior to the oil entering the seal ring. The major drawback of such systems is the amount of hydrogen that is consumed. When the de-gassed oil enters the seal ring and contacts the hydrogen atmosphere, the oil has the potential to absorb 5-7% hydrogen (by volume) prior to exiting the seal area. Because the system consumes large amounts of hydrogen, it is therefore not feasible for use on larger generators.
It has also been proposed to employ a separate sealing oil circuit in equilibrium with the generator atmosphere. This method is prevalent in today's hydrogen cooled generators. Such systems maintain high purity by utilizing two separate oil systems, one for untreated air and one for the treated hydrogen. However, employing two separate systems increases cost and operational difficulty.
One method of reducing impurities involves simply minimizing oil flow into the generator. This can be accomplished by reducing operating clearances of the seal ring and oil pressures. This method has resulted in excessive oil temperatures which has lead to thermal instability of the seal ring. Thus, reduction of clearances has not proven a viable option to maintain high hydrogen purity.
Still another suggested method of reducing impurities involves continuously purging all hydrogen from the system and replacing the hydrogen with fresh hydrogen from exterior to the system. Such systems are expensive to operate due to the costs associated with providing a constant supply of new hydrogen.
As an alternative to purging all hydrogen from the generator, it has been proposed to filter the hydrogen and recirculate the filtered hydrogen into the generator. U.S.
U.S. Pat. No. 4,531,070 ('070 Patent) entitled "Turbine Generator Hydrogen Filtration System," which is assigned to the assignee of the present invention and the contents of which are hereby incorporated by reference in their entirety, discloses such a system. The '070 patent discloses a filtration mechanism directed toward removing oil, gas-born particulates and gaseous contaminates such as styrene and anomine. The filtering mechanism disclosed in the '070 Patent comprises the following items: an air filter for removing solid particles one micron and larger from the gaseous stream; a coalescing oil filter tank which operates to coalesce very small particles of oil into larger particles or droplets; and a gaseous contaminant removing means for removing the oil droplets as well as gaseous contaminates such as styrene and anomine from the hydrogen stream. Thus, the filtering mechanism of the '070 Patent comprises three different filtering devices directed at removing oil, gas-borne particles, and gases such as styrene and anomine.
Although the filter of the '070 Patent is effective at removing most oil, air-borne particles, as well as styrene and anomine, it does not operate to remove air from the hydrogen stream. Air has the same deleterious effects as other contaminants and therefore optimally should be removed from the hydrogen stream. Further, the filtering mechanism of the '070 Patent comprises three different devices and therefore represents an inefficient filtering method.
Additionally, the coalescing filter of the '070 Patent cannot maintain adequate purity levels without employing additional treatment systems such as the vacuum system or separate sealing oil circuit described above.
It is therefore desirable to provide a more compact and efficient system that filters not only oil, particulates, and various gases, but also removes air from the hydrogen stream without the use of additional treatment systems.
SUMMARY OF THE INVENTION
Accordingly, there is disclosed a hydrogen cooled generator system having a hydrogen gas economizer, and a membrane filter for removing contaminants such as oil and gases including air from a hydrogen stream. The membrane filter comprises a membrane having palladium therein for removing air as well as other contaminants from the hydrogen stream.
According to one embodiment, the membrane filter may comprise the following elements: a first layer of palladium alloy for separating hydrogen from other gases such as air; a second layer integrally formed with said first layer for eliminating hydrogen flux; and a third layer of base metal for mechanical support.
According to another embodiment, the membrane filter has a membrane comprising the following elements: a first layer of palladium alloy for disassociating molecular hydrogen; a layer of refractory, body-centered cubic metal for mechanical support; and a second layer of palladium alloy for reassociating molecular hydrogen.
Additional features and advantages of the present invention will become evident hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing summary, as well as the following detailed description of the preferred embodiment, is better understood when read in conjunction with the appended drawings. For the purpose of illustrating the invention, there is shown in the drawings an embodiment that is presently preferred, it being understood, however, that the invention is not limited to the specific methods and instrumentalities disclosed.
In the drawings:
FIG. 1 is a schematic diagram of a generator hydrogen purge gas economizer in accordance with the present invention;
FIG. 2a illustrates the operation of a membrane employed in a hydrogen filter for use in the gas economizer of FIG. 1;
FIG. 2b illustrates an alternative operation of a membrane employed in a hydrogen filter for use in the gas economizer of FIG. 1;
FIG. 3 depicts the layered composition of a membrane employed in a hydrogen filter for use in the gas economizer of FIG. 1; and
FIG. 4 depicts an alternative membrane employed in a hydrogen filter for use in the gas economizer of FIG. 1.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A turbine generator hydrogen purge gas economizer with the above-mentioned beneficial features in accordance with a presently preferred exemplary embodiment of the invention will be described below with reference to FIGS. 1 through 4. It will be appreciated by those of ordinary skill in the art that the description given herein with respect to those figures is for illustrative purposes only and is not intended in any way to limit the scope of the invention. All questions regarding the scope of the invention may be resolved by referring to the appended claims.
The present invention provides a generator hydrogen purge gas economizer having a membrane filter for removal of contaminant gases and particulates. The hydrogen economizer system can process hydrogen contaminated with up to 10% air and oil vapor. FIG. 1 provides a schematic diagram of a generator hydrogen gas economizer system in accordance with the present invention. A hydrogen atmosphere of approximately 30 to 75 psig is maintained in generator 100 via use of a bronze seal ring which floats on pressurized oil. The oil pressure is maintained at about 8 to 12 psig above the pressure of the hydrogen atmosphere pressure. Although a seal can be maintained at 3 psig over gas pressure, 8-12 psig is employed to maintain a seal and provide a margin of safety.
As shown, seal ring areas 110 interact with defoaming tanks 112 via conduits 114. A hydrogen gas mixture is purged from seal ring areas 110 and settles in defoaming tanks 112. The purged hydrogen gas mixture contains impurities such as air and oil. As noted above, contaminated hydrogen mixture fills the area above the condensed liquid oil in the defoaming tank. The pressure of the contaminated hydrogen in the defoaming tank is in the range of about 30 to 75 psig with a dew-point as high as 60° F. The hydrogen gas mixture is evacuated via conduits 118. Control valves 120 control the flow of hydrogen gas mixture through conduits 118. Flowmeters 122 measure the flow of hydrogen gas mixture out of the defoaming tanks and through conduits 118. The hydrogen gas mixture is evacuated from defoaming tanks 112 at a rate of up to 1000 standard cubic feet per day (SCFD) at about from 32 to 250° F. The hydrogen gas mixture is compressed and heated in heater device 124. Thereafter, the hydrogen gas mixture enters hydrogen purification filter 126. A purified hydrogen stream exits filter 126 and enters compressor 128. The compressed hydrogen is released into generator 100. Compression of the purified hydrogen stream is necessary to maintain flow into generator 100. The impurities removed by filter 126 are released into the atmosphere.
The filter employed in the above described system is a membrane type filter, i.e. a membrane operates to allow certain components of a gas stream to permeate while other components of the gas stream do not permeate the membrane. FIGS. 2a and 2b illustrate alternative embodiments of the membrane filter. As shown in FIG. 2a, membrane 140 may be employed to pass hydrogen through the membrane while impurities are filtered out. Alternatively, as illustrated in FIG. 2b, the contaminants may be allowed to pass through the membrane while the hydrogen is filtered out. In either embodiment, nearly pure hydrogen is filtered from the air, oil, and particulate contaminants.
Various membranes have been developed which may be employed in a filter for use in the above described economizer invention. One such membrane is shown in FIG. 3. As shown, the membrane consists of thin layer 210 of platinum or palladium alloy, intermediate layer 212, and base-metal layer 214. Palladium alloy layer 210 separates hydrogen from other gases such as air. Intermediate layer 212, which may be composed of SiO 2 or Al 2 O 3 eliminates the rapid hydrogen-flux decline exhibited by earlier metal-on-metal membranes and the mechanical failure typical of metal-on-metal ceramic membranes. Thus, intermediate layer 212 prevents intermetallic diffusion. Base metal layer 214 simply provides mechanical support. A membrane filter in accordance with that described can be purchased from Bend Research, Inc. of Bend Oregon.
Membrane filters employing a membrane such as that described with reference to FIG. 3 provide the following benefits: exceptionally high selectivity for hydrogen; high hydrogen fluxes; excellent stability at high temperatures; and attractive economics for many applications due to excellent membrane performance and minimal use of expensive noble metals.
A second membrane for use in a filter to be employed in a hydrogen economizer of the preferred embodiment is shown in FIG. 4. As shown, thin layer 310 of refractory, body-centered cubic (bcc) metal is coated on both sides with layers 312 and 314 of a face-centered cubic (fcc) metal, preferably palladium. First layer 312 of palladium operates to disassemble molecular hydrogen. The disassociated hydrogen is transported through refractory metal bulk layer 310, which is typically composed of a Group V metal, and reassociated by layer 314 of palladium.
A membrane such as that depicted in FIG. 4 has several advantages. First, because bulk diffusion is not limited by the face centered cubic structure of palladium, the membrane of FIG. 4 provides greater overall hydrogen fluxes. As a consequence, the membrane structure can be thicker, yielding improved mechanical stability while still providing acceptable gas fluxes. Second, because refractory metals are significantly cheaper than palladium and only a surface layer of palladium is required, these structures are much more economical. Finally, while the Group V metals are also subject to embrittlement, this only becomes a problem at well below room temperature. Further, should the surface palladium layer develop defects, this would not render the membrane useless since it would merely expose a small area of the refractory metal.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. For example, the membrane filter may be one of several palladium based membranes. Further, the number and types of defoaming tanks, control valves, and flow meters may vary. Accordingly, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention. | A turbine generator hydrogen filtration system having an improved membrane filter for the removal of gases and particulates is provided. The system comprises a membrane filter operably connected with defoaming tanks. The hydrogen stream is routed through an improved membrane filter where air and other contaminants such as oil are removed. The hydrogen is recirculated into the hydrogen cooled generator. The membrane filter employed in the system is one of several palladium based membrane filters which effectively remove air and other contaminants and provide high hydrogen through-put. | 2 |
TECHNICAL FIELD OF THE INVENTION
This invention relates in general to the field of health care devices and facial protective devices. More particularly, the present invention relates to a disposable face shield.
BACKGROUND OF THE INVENTION
Medical and dental care professionals are exposed to hazardous infectious pathogens on a daily basis. With the spread of acquired immune deficiency syndrome (AIDS) and other deadly and presently incurable diseases, the protection of these professionals from nasal and oral emissions, blood, and other bodily fluids has become more vital than ever. Because the eyes, nose and mouth include regions of thin and penetrable membranes, the face is an area requiring appropriate protection from flying contaminants and particulates.
Several requirements must be met by a facial protection device of this type. It must be light weight and easily worn and removed. It must adequately shield the vital areas of the face yet not obstruct vision. It must provide ample ventilation as not to hamper breathing and to further avoid fogging and accumulation of moisture. In addition, it should be disposable for adequate and safe disposition of contaminants. Because such face protection is disposable and a large number of them may be used, ease of packaging and storage is also an important criteria.
SUMMARY OF THE INVENTION
In accordance with the present invention, a disposable face shield is provided to protect the wearer against air borne particles and droplets possibly containing infectious pathogens.
In one aspect of the present invention, the disposable face shield includes a transparent plastic shield and a stretchable or elastic cord attached to the transparent plastic shield for securing the shield about the wearer's face. A crescent-shaped foam member is affixed to the transparent plastic shield at an upper-central spot. The foam member further defines at least one gap between the foam member and the transparent plastic shield to provide ventilation.
In another aspect of the present invention, the foam member is affixed to the transparent shield at one spot so that the disposable face shield has a generally flat profile for ease of storage and packaging.
In yet another aspect of the present invention, a liquid-impervious film is applied to the foam member to close off its open cell structure.
In another aspect of the present invention, an anti-glare strip is provided along an upper edge or the entire outer edge of the transparent shield to improve the wearer's vision by reducing glare.
In yet another aspect of the invention, a method for fabricating a disposable face shield provides the steps of forming a transparent plastic shield and attaching a cord to the transparent plastic shield for securing the shield about a wearer's face. A foam member is shaped into a generally crescent shape and attached to the transparent plastic shield at an upper-central spot. The foam member is further shaped to define at least one ventilation gap between the foam member and the transparent plastic shield.
Technical advantages of the present invention include the disposable nature of the face shield. Once used where it may have come into contact with harmful pathogens, it may be properly disposed. Furthermore, since it is disposable and a large quantity of them may be used, the ease of packaging and storage provided by its flat profile is tremendously valuable.
Because emergency response vehicles have limited storage space for medical devices and equipment, the flat profile of the disposable face shield allows emergency response personnel to have access to a plentiful supply of the protective face shields.
The anti-glare strip further improves the wearer's vision by reducing the amount of glare striking the wearer's eyes. The attachment of the transparent shield to the foam member at one central location rather than along the entire surface of the foam member reduces the amount of bonding agent required. Additionally, the attachment of the elastic headband to the transparent shield obviates the need to reinforce the somewhat weaker foam member ends. These features contribute to a lowered manufacturing cost of the disposable face shield.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of the present invention, reference may be made to the accompanying drawings, in which:
FIG. 1 is a perspective view of a disposable face shield according to the teachings of the invention being worn about a person's face;
FIG. 2 is a top view of a disposable face shield in use;
FIG. 3 is a perspective view of a disposable face shield lying flat for ease of packaging and storage; and
FIG. 4 is a cross-sectional view of the foam member along line 4--4 in FIG. 3.
DETAILED DESCRIPTION OF THE INVENTION
The preferred embodiment of the present invention and its advantages are best understood by referring to FIGS. 1-4 of the drawings, like numerals being used for like and corresponding parts of the various drawings.
Disposable face shield 10 is shown in FIGS. 1 and 2 as being worn about the face of a person to protect against flying particulates, liquid spray and bodily fluids. Disposable face shield 10 includes a transparent shield 12 of an appropriate size to protect substantially the entire facial region of an average adult. Preferably, the length of transparent shield 12 enables it to extend to or beyond the wearer's chin and the width thereof is sufficient to substantially enclose the wearer's face. Naturally, disposable face shield 10 may include transparent shields 12 of smaller or larger sizes when necessary to serve different purposes. Transparent shield 12 may be constructed of any transparent, liquid-impermeable and light-weight material, such as polyester, polycarbonate, and the like.
Transparent shield 12 may incorporate a non-reflective or darkened strip 14 positioned along an upper edge thereof to reduce the amount of glare reflecting off transparent shield 12 and into the wearer's eyes. Additionally, darkened strip 14 may also reduce the amount of overhead light shinning directly into the wearer's eyes. Darkened strip 14 may be fabricated by printing a dark color onto the desired location of transparent shield 12 by known processes. Darkened strip 14 also may be formed by laminating or otherwise affixing a dark colored strip of vinyl thereon. The resultant darkened strip 14 may be opaque or remain slightly transparent. Alternatively, the non-reflective surface may be formed by mechanical or chemical etching. Referring also to FIG. 3, a non-reflective or darkened strip 16 is further provided along the lower and side outer regions of transparent shield 12 to further improve the wearer's vision by reducing the amount of reflected glare that may strike the wearer's eyes. Darkened strips 14 and 16 may be integrated into one strip.
Transparent shield 12 is attached to a foam member 20 acting as a spacer between transparent shield 12 and the wearer's face. Foam member 20 has a central region 22, two tapering ends 24 and 25, a forehead-engaging surface 28, a top surface 30, and a forward surface 32 facing and contacting transparent shield 12. Central region 22 of foam member 20 has a thickness appropriate for establishing the spacing between transparent shield 12 and the face. Two ends 24 and 25 curve inwardly to form about the wearer's forehead have a tapering thickness. In effect, the spacing between transparent shield 12 and the wearer's face is at a maximum at or near the wearer's nose and mouth, and at a minimum near the sides of the wearer's face.
Foam member 20 is preferably attached to transparent shield 12 at one central spot on forward surface 32, so that when face shield 10 is not in use, transparent shield 12 is able to lie flat, as shown in FIG. 3. Any suitable adhesive, glue, bonding agent or bonding process may be used for securely affixing foam member 20 to transparent shield 12. Since face Shield 10 is disposable, a large quantity may need to be stored and used. The flat profile of disposable face shield 10 therefore facilitates bulk packaging and storage.
In a preferred embodiment, foam member 20 may be fabricated from a number of light-weight and flexible materials including polyester foam, polyurethane foam, latex foam, neoprene sponge, PVC blends, and the like. These materials provide flexibility and some rigidity so that foam member 20 may form closely and comfortably to the contours of the wearer's forehead. In addition, top surface 30 of foam member 20 may include a liquid-impermeable skin or film 40 to close off the open cells in foam member 20. Foam member film 40 may be formed by applying a liquid which dries into a solid film or by affixing a solid film of appropriate size and shape. Alternatively, foam material having a natural film surface 40 may be used to form foam member 20. A liquid-impervious polyurethane or polyethylene, such as one manufactured by Tuftain Corporation, may be used. By closing off the open foam cells at top surface 30 of foam member 20, the likelihood of any flying contaminants and liquids coming into contact with the wearer's face becomes even more remote.
In FIGS. 2 and 3, it may be easily seen that tapered ends 24 and 25 of foam member 20 are specially formed to leave ventilation gaps 42 and 44 between transparent shield 12 and the wearer's forehead or temple region. In particular, tapered ends 24 and 25 are fashioned so that small portions thereof are removed, leaving a discontinuous surface 46 in the curvature of forward surface 32. Since the intended purpose of gaps 42 and 44 is to provide ventilation, the shape thereof may vary. Therefore, gaps 42 and 44 may be triangular, curved, or straight. However, the size of ventilation gaps 42 and 44 is preferably small so that airborne contaminants do not easily gain access to the wearer's face.
Disposable face shield 10 further includes a headband 50 for securely positioning the shield over the wearer's face. Headband 50 is of a construction that adapts to a varying circumferences of heads and provides adjustable tension around the wearer's head, such as tieable cords or an elastic band. Headband 50 has two ends 52 and 54, which are attached to the upper and outer edges of transparent shield 12. Preferably, headband 50 is fabricated from a heat-bondable elastic material, including LYCRA™, GLOSPAN™, polyurethane elastomeric tape, or any elastic material surrounded by a heat-bondable cover or carrier made of polyester, polypropylene, nylon, or any combination thereof. When non-heat bondable elastic material is used, such as natural rubber, a heat-bondable carrier should be used if the intended method of affixing headband 50 to transparent shield 12 is by heat bonding. Other known methods of attachment are also contemplated, including ultrasound bonding and like techniques.
Note that since headband 50 is attached to transparent shield 12 rather than foam member 20, affixing foam member 20 to transparent shield 12 at one central location is possible because the tension of headband 50 pulls and forms transparent shield 12 over foam member 20 and the wearer's face. In addition, since headband 50 may experience varying degrees of tension as disposable shield 10 is being put on, worn, and removed, its attachment to transparent shield 12 obviates the need to reinforce weaker tapered ends 24 and 25 of foam member 20 if headband 50 were affixed thereto. Recall that the central spot attachment of foam member 20 to transparent shield 12 also provides the flat profile for ease of packaging and storage and reduced manufacturing cost. The darkened or non-reflective strip along the edge of transparent shield 12 further advantageously blocks glaring light from the wearer's eyes.
Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims. | The disposable face shield (10) protects the wearer against airborne particles and droplets possibly containing pathogens. The disposable face shield (10) includes a transparent plastic shield (12) and a cord (50) attached to the transparent plastic shield (12) for securing the shield about the wearer's face. A crescent-shaped foam member (20) is affixed to the transparent plastic shield (12) at an upper-central spot. The foam member further defines at least one gap between the foam member and the transparent plastic shield to provide ventilation. When not in use, the disposable face shield has a generally flat profile for ease of storage and packaging. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a steering control apparatus for turning steered wheels in accordance with rotation of a steering wheel. More particularly, the invention concerns a steering control apparatus wherein a steering shaft connected to the steering wheel is mechanically separated from a turning mechanism for turning the steered wheels and wherein the turning mechanism is controlled by an electric control device.
2. Related Background Art
An example of such steering control apparatus is described in Japanese Laid-open Patent Application No. Hei 2-85059 and the general configuration thereof is shown in FIG. 4. Steering angle sensor 103 provided on steering shaft 101 detects a steering angle of steering wheel 102 and reaction force mechanism 104, a main element of which is a motor, exerts steering reaction force on the steering shaft 101. Rotation of motor 105 for turning the tires is transmitted through reducing unit 106 to pinion 107 to axially displace rack shaft 108 in mesh with the pinion 107, thereby turning the tires 109. A displacement amount of the rack shaft 108 is detected by turning angle sensor 110 and is supplied, together with a detection signal of the steering angle sensor 103, to controller 100.
The controller 100 of the steering control apparatus constructed in the above structure performs such feedback control of motor 105 that a real steering angle obtained from the detection result of turning angle sensor 110 can be coincident with a target steering angle obtained based on the steering angle detected.
Gains in this feedback control are so set as to be always constant, regardless of the running status of vehicle. This sometimes resulted in failing to perform proper steering control, depending upon the running status of vehicle. For example, if a small gain was set despite circumstances requiring a larger gain (e.g., during running at low speed), the response of control would be slow; conversely, if a large gain was set despite circumstances requiring a smaller gain (e.g., during running at high speed), the sensitivity could be so high as to degrade stability.
SUMMARY OF THE INVENTION
The present invention has been accomplished to solve the problems described above and an object of the invention is to provide a steering control apparatus that can carry out the turning control with proper response according to the running status of vehicle.
For achieving this object, a steering control apparatus of the present invention is arranged to comprise: a steering shaft on which a steering effort is exerted through a steering wheel; steering angle detecting means for detecting an angle of rotation of the steering shaft; turning means for turning a steered wheel, the turning means being mechanically separated from the steering shaft; target control amount calculating means for calculating a target control amount as a target of turning control, based on a detection result of the steering angle detecting means; turning control means for outputting a turning control signal according to the target control amount to the turning means and controlling drive of the turning means so that a turning amount of the steered wheel becomes the target control amount; and correction means for correcting the turning control signal outputted, based on a running status of a vehicle.
The correction means corrects the steering control signal in accordance with the running status of the vehicle represented by a vehicle speed, a steering angle (rotational angle of the steering shaft), a road friction coefficient μ, or the like. This permits the turning control means to control the drive of the turning means with proper response according to the running status.
The present invention will be more fully understood from the detailed description given hereinbelow and the accompanying drawings, which are given by way of illustration only and are not to be considered as limiting the present invention.
Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will be apparent to those skilled in the art from this detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram to show the structure of a steering control apparatus according to an embodiment of the present invention;
FIG. 2 is a flowchart to show a control process carried out by a turning shaft motor control circuit;
FIG. 3A is a graph to show the relationship between road friction coefficient μ and gain coefficient Gs1;
FIG. 3B is a graph to show the relationship between vehicle speed V and gain coefficient Gs2;
FIG. 3C is a graph to show the relationship between steering angle Θ and gain coefficient Gs3; and
FIG. 4 is a structural drawing to schematically show a conventional steering control apparatus.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An embodiment of the present invention will be described by reference to the accompanying drawings.
FIG. 1 schematically shows the structure of the steering control apparatus according to the present embodiment. This steering control apparatus is composed of master section A to be manipulated by a driver, slave section B for turning the steered wheels, and control section C for electrically controlling the master section A and slave section B.
The master section A has steering shaft 2 on which steering wheel 1 is mounted, and steering shaft motor 3 for rotating the steering shaft 2, and the steering shaft 2 is provided with steering angle sensor 4 for detecting the steering angle Θ of the steering shaft 2 and steering effort sensor 5 for detecting steering effort T.
The slave section B has turning shaft motor 11 as a drive source for displacing turning shaft 13, and converter 12 for axially displacing the turning shaft 13 by converting rotational motion of the turning shaft motor 11 into rectilinear motion is provided between the turning shaft motor 11 and the turning shaft 13. Each of the two ends of the turning shaft 13 is connected through tie rod 15a, 15b and knuckle arm 16a, 16b to steered wheel 14a, 14b, thereby composing a mechanism for axially displacing the turning shaft 13 to turn each steered wheel 14a, 14b according to an amount and a direction of the displacement.
Each tie rod 15a, 15b is equipped with turning reaction force sensor 18a, 18b for detecting axial force (turning reaction force) exerted on each tie rod 15a, 15b by the left or right steered wheel 14a, 14b. The turning shaft 13 is provided with turning displacement amount sensor 17 for detecting a displacement amount of this turning shaft 13. A real turning amount of the steered wheels 14a, 14b can be detected by detecting the displacement amount of turning shaft 13 by the turning displacement amount sensor 17.
The control section C has steering shaft motor control circuit 21 for controlling the drive of steering shaft motor 3 and turning shaft motor control circuit 26 for controlling the drive of turning shaft motor 11 and performs the drive controls of the two motors, based on arithmetic results from respective arithmetic units and other data.
The steering shaft motor control circuit 21 receives arithmetic results of steering effort arithmetic unit 23 and turning reaction force arithmetic unit 24. The steering effort arithmetic unit 23 calculates the steering effort T exerted on the steering shaft 2, based on the detection result of steering effort sensor 5 and also calculates a control amount aT (where "a" is a coefficient corresponding to a gear ratio of steering effort) for rotating the steering shaft 2 in the direction of exertion of the steering effort T.
The turning reaction force arithmetic unit 24 calculates the turning reaction force F exerted on the turning shaft 13, based on the detection results of the turning reaction force sensors 18a, 18b. The steering shaft motor control circuit 21 calculates a rotation control amount Mm of the steering shaft 2 according to Eq. (1) below, based on the arithmetic results of these steering effort arithmetic unit 23 and turning reaction force arithmetic unit 24, and outputs a drive control signal according to the steering shaft rotation control amount Mm to the steering shaft motor 3. In Eq. (1) Gm is a gain coefficient indicating a gain of output signal.
Mm=Gm×(aT-F) (1)
The turning shaft motor control circuit 26 calculates a control displacement amount Ms of the turning shaft 13 according to Eq. (2) below and outputs a turning control signal according to the control displacement amount Ms to the turning shaft motor 11 to control the drive of turning shaft motor 11. In Eq. (2) Gs is a gain coefficient indicating a gain of the turning control signal and, as described hereinafter, this Gs is adjusted according to the running status of vehicle.
Ms=GsX(θ-bX) (2)
The turning shaft motor control circuit 26 receives arithmetic results of turning displacement amount arithmetic unit 22 and target control amount arithmetic unit 25 and also receives the gain coefficient Gs set by gain coefficient setting circuit 28.
The turning displacement amount arithmetic unit 22 obtains a displacement amount of the turning shaft 13 as a turning displacement amount X, based on the detection result of the turning displacement amount sensor 17, and outputs a control amount bX (where "b" is a coefficient corresponding to a gear ratio of turning displacement) proportional to the turning displacement amount X.
The target control amount arithmetic unit 25 calculates from the steering angle Θ detected by the steering angle sensor 4 a target control amount θ which is a target in the turning control, i.e., in turning the steered wheels 14a, 14b in correspondence to the steering angle.
The gain coefficient setting circuit 28 receives the information indicating the running status of vehicle, including the speed V detected by speed sensor 27 and the steering angle Θ detected by the steering angle sensor 4, and also receives the turning reaction force F and turning displacement amount X for calculation of road friction coefficient μ. Then the gain coefficient Gs is set based on the road friction coefficient μ, calculated from the turning reaction force F and turning displacement amount X, the speed V, and the steering angle Θ.
Based on the arithmetic results of the turning displacement amount arithmetic unit 22 and target control amount arithmetic unit 25 and the gain coefficient Gs set by the gain coefficient setting circuit 28, the turning shaft motor control circuit 26 controls the drive of the turning shaft motor 11 so that a turning amount of the steered wheels 14a, 14b becomes equal to the target control amount Θ. Namely, the control displacement amount Ms of the turning shaft 13 is calculated according to Eq. (2) and the turning control signal according to the control displacement amount Ms is outputted to the turning shaft motor 11.
The operation of the steering control apparatus constructed in the above structure will be schematically described below. Let us suppose that during straight-ahead driving of the vehicle the steering wheel 1 is so manipulated as to exert, for example, counterclockwise torque on the steering shaft 2. Since the steering shaft motor 3 is not rotating the steering shaft 2 yet at the start of rotation of steering wheel 1, torsion appears in the steering shaft 2. This torsion in the steering shaft 2 is detected by the steering effort sensor 5 and the steering effort arithmetic unit 23 calculates the steering effort T from this detection result and outputs the control amount aT obtained by multiplying the steering effort T by the coefficient a.
The steering shaft motor control circuit 21 puts the control amount aT from the steering effort arithmetic unit 23 and the turning reaction force F from the turning reaction force arithmetic unit 24 into above Eq. (1) to calculate the steering shaft rotation control amount Mm and outputs a drive control signal indicating it. Since the turning reaction force F of the turning shaft 13 is zero at the start of rotation of the steering wheel 1, the steering shaft motor 3 receives the drive control signal of Mm=Gm×aT. In response to this drive control signal, the steering shaft motor 3 rotates the steering shaft 2 counterclockwise.
This rotation causes the steering angle Θ from the steering angle sensor 4 to be supplied to the target control amount arithmetic unit 25, and the target control amount arithmetic unit 25 calculates the target control amount θ, based on the steering angle Θ, and outputs the arithmetic result to the turning shaft motor control circuit 26. At this time, since the turning displacement amount X of the turning shaft 13 is still zero, the turning shaft motor control circuit 26 outputs the control signal indicating the control displacement amount Ms=Gs×θ obtained from above Eq. (2) to the turning shaft motor 11 to start displacing the turning shaft 13 to the right and to start turning the left and right steered wheels 14a, 14b to the left.
As this displacement of the turning shaft 13 increases values of turning displacement amount X, values of control displacement amount Ms according to above Eq. (2) decrease. When the control amount bX proportional to the turning shaft displacement amount X becomes nearly equal to the target control amount θ, the motion of the turning shaft 13 stops.
On the other hand, the left and right steered wheels 14a, 14b receive rightward turning reaction force from the road surface when turned to the left. The turning reaction force sensors 18a, 18b detect force according to this turning reaction force and supply detection results to the turning reaction force arithmetic unit 24. The turning reaction force arithmetic unit 24 calculates the turning reaction force F, based on the signals from the turning reaction force sensors 18a, 18b, and outputs it to the steering shaft motor control circuit 21.
The steering shaft motor control circuit 21 calculates the rotation control amount Mm of the steering shaft 2 according to Eq. (1), based on the arithmetic results of the steering effort arithmetic unit 23 and turning reaction force arithmetic unit 24, as described previously, and outputs the drive control signal according to the steering shaft rotation control amount Mm to the steering shaft motor 3. Accordingly, an increase in the turning reaction force F due to the turning will decrease values of steering shaft rotation control amount Mm; when the turning reaction force F becomes nearly equal to the control amount aT proportional to the steering effort T, the steering shaft 2 stops at a rotational position at that time.
If the driver intends to further rotate the steering wheel 1 counterclockwise, the steering shaft motor 3 will rotate the steering shaft 2 counterclockwise and the turning shaft motor 11 will turn the steered wheels 14a, 14b to the left. Conversely, if the driver relaxes the steering effort, the control amount aT will become smaller than the turning reaction force F and values of steering shaft rotation control amount Mm will become negative. Then the steering shaft motor 3 will rotate the steering shaft 2 clockwise. Since this decreases the target control amount θ, values of turning control displacement amount Ms become negative and the turning shaft motor 11 turns the steered wheels 14a, 14b to the right.
The above operation permits proper turning of the steered wheels according to the steering operation to be carried out without degrading the preferred steering feeling.
Although the above description was given with the example of operation where the wheels are turned to the left from straight-ahead driving, the proper turning according to the steering operation can also be carried out similarly in the operation where the wheels are turned to the right from straight-ahead driving, by controlling the steering shaft motor 3 and turning shaft motor 11, based on Eqs. (1) and (2).
The fundamental steering control is performed as described above, and the control process carried out by the turning shaft motor control circuit 26 will be described in further detail herein. This turning shaft motor control circuit 26 outputs the turning control signal according to the control displacement amount Ms to the turning shaft motor 11, as described previously, and the gain coefficient Gs indicating the gain of this drive control signal is a variable coefficient. The gain coefficient Gs is set according to the running status of vehicle represented by the speed V, steering angle Θ, road friction coefficient μ, or the like. This is from the following reason.
Among the turning reaction force F, reaction force from the tires attached to the steered wheels 14a, 14b (tire reaction force) differs even at the same turning angle, depending upon the running status of vehicle represented by the speed V, steering angle Θ, road friction coefficient μ, or the like. The control displacement amount Ms of the turning shaft motor 11 is thus also changed according to these running conditions, thereby enhancing the response and stability of control.
The control process carried out by the turning shaft motor control circuit 26 will be described referring to the flowchart of FIG. 2. This control process is started by turning on the ignition switch.
In step 100 ("step" will be represented hereinafter by "S"), the coefficient b corresponding to the steering displacement gear ratio, preliminarily stored in ROM, is first read and in S102 the steering angle Θ, turning displacement amount X, speed V, and turning reaction force F are read.
In S104 the value of road friction coefficient μ is retrieved from a map of relationships between turning displacement amount X corresponding to the turning angle of steered wheels 14a, 14b and axial force (turning reaction force F) of the turning shaft 13 and thereafter a gain coefficient Gsl according to the road friction coefficient μ thus retrieved is set based on the graph of FIG. 3A.
When values of road friction coefficient μ are small, divergence of the tires, i.e., divergence of the feedback system based on Eq. (2) is likely to occur, degrading stability. Thus, small values of gain coefficient Gsl are set as shown in the graph of FIG. 3A. When values of road friction coefficient μ are large, the tire reaction force is large. Thus, large values of gain coefficient Gsl are set, thereby enhancing the response of control. This adjustment of gain coefficient Gsl permits the harmonious control of response and stability to be carried out, based on the same displacement deviation amount, even with change in the road friction coefficient μ.
In next step S106 a gain coefficient Gs2 according to the speed V is set based on the graph of FIG. 3B. As shown in the graph of FIG. 3B, since the divergence of tires is easier to occur with large values of speed V, the gain coefficient Gs2 is set to small values in order to enhance the stability; with small values of speed V the gain coefficient Gs2 is set to large values in order to enhance the response.
In S108 a gain coefficient Gs3 according to the steering angle Θ is set based on the graph of FIG. 3C. As shown in the graph of FIG. 3C, since the divergence of tires is easier to occur with small steering angles Θ, the gain coefficient Gs3 is set to small values; with large steering angles Θ the gain coefficient Gs3 is set to large values, because the tire reaction force is also strong. This adjustment permits the harmonious control of response and stability to be carried out, based on the same displacement deviation amount, regardless of magnitudes of steering angle Θ.
In S110, based on the gain coefficients Gs1, Gs2, and Gs3 set in S104 to S108, the gain coefficient Gs in Eq. (2) is calculated by Gs=Gs1×Gs2×Gs3. In this way the gain coefficient Gs is set, taking account of the running status of vehicle represented by the road friction coefficient μ, speed V, and steering angle Θ.
In S112, using the gain coefficient Gs calculated in S110, the displacement control amount Ms is calculated according to Eq. (2) and in S114 a turning control signal according to this displacement control amount Ms is outputted to the turning shaft motor 11.
After that, it is determined in S116 whether the ignition switch is off. When the ignition switch is on, the flow returns to S102 to repeat the same process operation; if the ignition switch is off, this control process of the turning shaft motor control circuit 26 is terminated.
The embodiment described above was the example wherein in setting the gain coefficient Gs, the velocity V, steering angle Θ, and road friction coefficient μ all are taken into account as values representing the running status of a vehicle, but the gain coefficient Gs may be set based on either one or two values of them, for example, based on the speed V and steering angle Θ.
The present embodiment was the example wherein the drive control of the turning shaft motor 11 was carried out by feeding the output of turning displacement amount sensor 17 back, but the invention is not limited to the cases for carrying out such feedback control. For example, it can be contemplated that the turning shaft motor 11 is a step motor, a rotation amount of this step motor is calculated according to the target control amount θ, and rotation of the step motor is controlled based on this calculation result. In this case the feedback control is not necessary.
As described above, the steering control apparatus according to the present invention is arranged so that the correction means corrects the turning control signal outputted from the turning control means in accordance with the running status of vehicle, whereby the turning control can be carried out with proper response according to the running status of vehicle.
From the invention thus described, it will be obvious that the invention may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended for inclusion within the scope of the following claims. | A steering control apparatus of the present invention comprises: a steering shaft on which a steering effort is exerted through a steering wheel; a steering angle detecting device for detecting an angle of rotation of the steering shaft; a turning device for turning a steered wheel, the turning device being mechanically separated from the steering shaft; a target control amount calculating device for calculating a target control amount as a target of turning control, based on a detection result of the steering angle detecting device; a turning control device for outputting a turning control signal according to the target control amount to the turning device and controlling drive of the turning device so that a turning amount of the steered wheel becomes the target control amount; and a correction device for correcting the turning control signal outputted, based on a running status of a vehicle. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 14/181,901, filed on Feb. 17, 2014.
STATEMENT REGARDING FEDERALLY-SPONSORED RESEARCH OR DEVELOPMENT
Not Applicable.
BACKGROUND OF THE INVENTION
1. Field of Invention
The present invention relates generally to the field of seating and chairs including moveable and stackable seating. More specifically, this invention relates to stackable chairs having a flexible back support with an improved spring assembly.
2. Description of the Related Art
Prior chairs having a flexible backrest frame have provided frame members with spring members connected internal of seat tube members for control of movement of the backrest frame of the chair. A typical flexible backrest is illustrated in U.S. Pat. No. 5,039,163, issued to Tolleson, which discloses a chair including depending leg members and a hollow support frame having members with open ends terminating beneath the seat assembly of the chair. The chair includes a pair of hollow backrest frame members having open frame ends extending beneath the seat assembly for alignment with respective open ends of the support frame members. Each open end of the respective frame members includes at least one flexible spring member inserted therein. Prior configurations of spring members allow insertion of opposed spring member ends into opposed and aligned open frame ends, with each spring member being aligned with the frame ends and extended to fill any gap between the respective back frame members and support frame members. Therefore, replacement of the spring member required full disassembly of the chair frame and removal of each inserted spring member end. In order to prevent each spring element from excessive flexing during reclining movements of the chair backrest, the spring member ends have been typically enclosed by pairs of U-shaped brackets of metal that limit the range of angular movement of each enclosed spring member, thereby limiting the reclining movements of the chair backrest. Additional pairs of spring members and U-shaped brackets have been required to be added for rigorous use. The additional pairs of spring members are typically positioned parallel to each first set of spring members with associated enclosure by U-shaped brackets of greater width or depth, thereby requiring an increased width or depth of the support frame members to accommodate the additional spring members and brackets.
Another example of a prior art chair having a flexible backrest frame is illustrated in U.S. Pat. No. 6,896,327, issued to Barile, which discloses a stackable chair with a seat assembly and flexible back support having a seat spring system attached there between. The seat assembly includes seat sides having spaced apart rear portions. The back support includes lower ends curved forwardly and disposed in registry with and separated by right and left gaps from respective seat side rear portions. Right and left spring members are disposed inwardly adjacent to bridge each gap. Each spring member includes forward ends connected to respective right and left front support members extended inbound from respective seat sides, and includes rear ends connected to opposed ends of a frame rear cross-member. The spring members allow limited reclining movement of the back frame. A limit to excessive forward movement of the back support is provided by pairs of fixation plates positioned in aligned and abutting relationship on upper surfaces of each respective forward and rear ends of each spring member.
The prior art leaf springs are securely fastened to the frame of the chair making replacement of the spring difficult and labor intensive. What is missing from the art is a stackable chair with a flexible back support frame employing a spring assembly attached directly to the rear cross support member of the seat assembly that allows for easily replacing the spring, or compression, member allowing for ease of adjustment of flex tension, thus eliminating elongated, or leaf, spring members and their attendant support members.
BRIEF SUMMARY OF THE INVENTION
The present invention provides an improved spring assembly for a chair frame for a stackable chair having a flexible back member. While described herein in terms of a stackable chair, it will be appreciated that the present invention has utility with non-stackable chairs as well. The chair frame comprises a seat support portion for supporting a chair seat, and a pair of leg assemblies oppositely disposed on either side of the seat support portion. Each leg assembly includes a front leg and a rear leg, and an upper support member. Each leg assembly also includes a stacking bar extending between the front leg and the rear leg, the stacking bar being disposed below, and being selectively spaced from the upper support member. The stacking bar of each leg assembly has a lower surface configured to closely engage at least a portion of the upper surface of the upper support member of another chair frame of the present invention to facilitate the stacking of the chair frame on such other chair frame.
The back support frame includes frame lower ends curved forwardly and positioned in registry with and spaced apart by a gap separation from the rear portions of the seat assembly. Right and left spring can assemblies are carried by the rear cross support member. This improved spring can assembly dispenses with the need for the prior art elongated springs and their attendant support components that were previously required.
During reclining movement of the back support frame, the back support frame member compresses the compression member downwardly to a compressed position. When reclining pressure is released from the back support frame member, the spring member biases the back support frame member to a non-reclined position, thereby returning the back support to a substantially upright position when not reclined by a seat occupant.
BRIEF DESCRIPTION OF THE DRAWINGS
The above-mentioned and additional features of the invention will become more clearly understood from the following detailed description of the invention read together with the drawings in which:
FIG. 1 illustrates a perspective view of a chair constructed in accordance with the present invention.
FIGS. 2A and 2B illustrate a partial rear elevation view of the chair illustrated in FIG. 1 .
FIG. 3 illustrates an exploded view of the compression member, and plunger of the present invention. In FIGS. 3A and 3B , the compression member is illustrated as a helical coil spring. In FIG. 3C , the compression member is illustrated as a crest-to-crest wave spring.
FIGS. 4A and 4B illustrates the hinge member of the present invention; FIG. 4A is an assembled perspective view; while FIG. 4B is an exploded perspective view.
FIG. 5 is a partial perspective view of the chair illustrated in FIG. 1 .
FIGS. 6A, 6B and 6C are partial elevation views showing the interaction of the back frame member and the spring assembly during assembly of the chair and during reclining of the back frame member.
FIG. 7 is a side elevation view of the chair illustrated in FIG. 1 showing a seat cushion.
FIG. 8 illustrates an exploded view of a further embodiment of the can member, plastic insulator member, compression member, and plunger of the present invention.
FIGS. 9A and 9B illustrate an additional embodiment of the hinge member of the present invention.
FIG. 10A illustrates a top view of the additional embodiment hinge member illustrated in FIGS. 9A and 9B .
FIG. 10B illustrates a cross-sectional view of the hinge member illustrated in FIG. 9A taken at cut-line 10 B in FIG. 10A .
DETAILED DESCRIPTION OF THE INVENTION
A chair frame for a stackable chair incorporating various features of the present invention is illustrated generally at 10 in FIGS. 1-7 . While the chair frames 10 , constructed in accordance with the present invention may be stacked, one upon another, to facilitate the storage of a plurality of chairs, it will be appreciated that the present invention is not limited to stackable chairs but rather could be utilized with non-stacking chairs or other seating structures, such as benches, that include a back support frame.
The chair frame 10 includes a seat support portion 15 which in the preferred illustrated embodiment defines a generally U-shaped frame portion 20 and a rear cross support member 25 which extends across, and is secured at its opposite ends to, the right and left leg assemblies 35 , 40 . The seat support portion 15 is used to support the seat portion of a chair utilizing the frame 10 , such as the seat cushion 30 .
The right and left leg assemblies 35 and 40 are disposed on opposite sides of, and attached to, the seat support portion 15 . Each of the leg assemblies 35 and 40 includes a front leg 45 and a rear leg 50 . The leg assemblies 35 and 40 also include an upper support member 55 which is disposed between the upper ends of the front leg 45 and the rear leg 50 . As will be understood by those skilled in the art, the upper support members 55 serve to support another chair utilizing a chair frame 10 which is stacked above. In the preferred embodiment, the support members 55 extend between, and serve to support, the associated leg members 45 and 50 . Each of the leg assemblies 35 and 40 are also provided with a stacking bar 60 which extends between the front leg 45 and the rear leg 50 , and which is selectively spaced below the upper support member 55 .
In the preferred embodiment the chair frame 10 also includes a back support frame member 65 for supporting a seat back member (not shown), which can be a cushion or a rigid member for supporting the back of an occupant of the chair. The back support frame member 65 includes an upper portion 70 joined at opposed ends to right and left frame side members 75 and 80 which are spaced apart by a sufficient width to accept a seat back member (not shown). Each frame side member 75 and 80 extends downwardly and is bent forwardly to form respective frame lower ends 75 ′, 80 ′ that extend forwardly to a generally horizontal orientation in aligned registry with and spaced apart from the seat member rear portions 90 and 95 . In order to facilitate the preferred hinged attachment of the frame lower ends 75 ′, and 80 ′ with the seat member rear portions 90 and 95 , a gap is preferably provided there between.
As best illustrated in FIGS. 4A and 4B , the chair frame 10 includes hinge assembly 100 defined by cooperating hinge members 105 and 110 for connecting the lower ends 75 ′ and 80 ′ of the back support frame member 65 to the rear portions 90 and 95 of the seat assembly 15 respectively. In the preferred embodiment, each hinge member 105 and 110 includes at least one knuckle 115 which are connected hingedly by a pin 120 . In one embodiment, hinge member 105 defines a tenon which is releasably received by the tubular end of either of the lower ends 75 ′ and 80 ′, in mortise and tenon manner. Similarly, hinge member 110 defines a tenon which is releasably received by the tubular end of the rear portions 90 and 95 of the seat assembly 15 . In this regard, a rivet, a combination of a nut and bolt, or other known means of securement, could be used to releasably secure hinge members 105 and 110 to the tubular portions of the lower ends 75 ′ and 80 ′ of the back support frame member 65 and the rear portions 90 and 95 of the seat assembly 15 respectively. Whereas the figures, specifically FIGS. 4A and 4B depict a tenon and mortise configuration for the knuckles 115 of the hinge members 105 and 110 , it will be appreciated by those skilled in the art, that the hinge members 105 could include a plurality of knuckles for receiving hinge pin 120 . It will be appreciated that the present invention does not intend to limit the number or configuration of the knuckles of hinge assembly 100 . Rather, it should be appreciated that, regardless of the configuration and number of knuckles of the hinge assembly 100 , hinge assembly 100 is configured so as to provide pivotal motion of the lower ends 75 ′ and 80 ′ with respect to rear portions 90 and 95 . Further, while one type of hinge member has been shown, those skilled in the art will appreciate that various types of hinge members could be utilized. Further, it will be recognized that frame lower ends 75 ′ and 80 ′ could be pivotally secured to a portion of the chair frame in a manner that allows for pivotal motion of the back frame support 65 and maintains the substantial horizontal plane alignment with the seat member rear portions 90 and 95 when the back frame support 65 is in the non-reclined position.
In order to provide a back support frame 65 that repetitively reclines and rebounds to a generally vertical position relative to the seat assembly 15 , the rear cross support member 25 includes distal ends 125 which are secured to the rear legs 50 . A recess 130 is provided at each distal end 125 . Further, at least one compression member 140 is carried by at least one distal end 125 . In the preferred embodiment, a cylindrical can member 135 is carried by recess 130 . The compression member 140 is received within the can member 135 . Further, a plunger member 145 is received within the can member 135 and engages the compression member 140 such that the compression member biases the plunger 145 upward when the plunger 145 engages and compresses compression member 140 . In this regard, the can 135 is positioned such that the lower surface of each lower end 75 ′ and 80 ′ of the back support frame member 65 engages the plunger 145 . As a reclining force is applied to the back support frame member 65 by an occupant of the chair 10 , the lower ends 75 ′ and 80 ′ compress the plunger 145 against the biasing force of the compression member 140 . The can member 135 serves as a stop to limit the extent of reclining motion for the back support frame member. The fully reclined position is illustrated in FIG. 6C .
The compression member 140 of the improved spring can assembly biases the back frame support member 65 to return to the non-reclined position shown in FIG. 6B , after the reclining force is released. Whereas in one embodiment, illustrated in FIGS. 3A and 3B , compression member 140 is defined by a helical coil spring, it will be appreciated that other compression members could be utilized. For instance, as illustrated in FIG. 3C , compression member 140 ′ could be defined by a crest-to-crest wave spring. Those skilled in the art will recognize that other known compression members could be utilized for biasing the plunger 145 upward upon release of the reclining pressure applied to the back support frame member 65 . In the preferred embodiment, the range of compression of the plunger member 145 and compression member 140 is limited to approximately ⅜″. Further, while the can member 135 is illustrated as being a separate component carried by recess 130 , it will be appreciated that the can member 135 and the recess 130 could be integrally formed.
In one embodiment, as the chair 10 is being assembled, it will be appreciated that the frame members will be fully assembled prior to the attachment of either the seat cushion 30 or the supporting seat back member (not shown) are attached. With the back frame support member 65 tilted forward, as illustrated in FIG. 6A , compression member 140 and plunger member 145 are inserted within can 135 . The back frame support member 65 is then returned to a neutral, i.e. non-reclined position. The seat cushion 30 is then secured to the seat support 15 . The back portion of the seat cushion 30 extends over the frame lower ends 75 ′ and 80 ′. In this position, the frame lower ends 75 ′ and 80 ′ will engage the lower surface of the seat cushion 30 if the back frame support member is flexed substantially forward, thereby retaining compression member 140 and plunger 145 within the can member 135 . It will be appreciated by those skilled in the art that the spring can assembly of the present invention allows the compression member to be readily and easily changed, thus providing the ability to easily adjust the flex tension of the back support member.
In another embodiment, illustrated in FIG. 8 , the can member 135 ′ is adapted to receive a plastic insulator member 150 is adapted so as to substantially prevent the plastic insulator member from rotating within can member 135 ′. In the embodiment illustrated can member 135 ′ has a substantially square “footprint” with beveled corners. And, the illustrated embodiment of the plastic insulator member 150 has a footprint, and area, adapted to be tightly received within can member 135 ′. The plastic insulator member has a cylindrical hole member 155 provided therein adapted for receiving compression member 140 and the cooperating plunger member 145 . As described above, as the chair 10 is being assembled, it will be appreciated that the frame members will be fully assembled prior to the attachment of either the seat cushion 30 or the supporting seat back member (not shown) are attached. With the back frame support member 65 tilted forward, as illustrated in FIG. 6A , compression member 140 and plunger member 145 are inserted within the hole member 155 disposed in plastic insulator member 150 which, is received by can 135 ′. The back frame support member 65 is then returned to a neutral, i.e. non-reclined position. The seat cushion 30 is then secured to the seat support 15 . The back portion of the seat cushion 30 extends over the frame lower ends 75 ′ and 80 ′. In this position, the frame lower ends 75 ′ and 80 ′ will engage the lower surface of the seat cushion 30 if the back frame support member is flexed substantially forward, thereby retaining compression member 140 and plunger 145 within the plastic insulator member 150 .
In a further embodiment, illustrated in FIGS. 9A-10B , a one piece hinge assembly 100 ′ is provided for connecting the lower ends 75 ′ and 80 ′ of the back support frame member 65 to the rear portions 90 and 95 of the seat assembly 15 respectively. In this embodiment, hinge assembly 100 ′ includes two molded inserts 105 ′, defining tenons which are releasably received by, and secured to, the tubular end of the rear portions 90 and 95 of the seat assembly 15 and the tubular ends of the frame lower ends 75 ′ and 80 ′. Molded within the molded inserts 105 ′ is a flexible metal hinge strip 108 .
While the present invention has been illustrated by description of some embodiments, and while the illustrative embodiments have been described in detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept. | Disclosed is a chair containing a flexible back support frame mechanism that includes an improved spring assembly designed to allow reclining movement of a back support frame relative to a seat assembly. The spring can assembly of the present invention is, preferably, carried by a rear cross support member thereby eliminating the need for cumbersome elongated springs and their attendant support members. Further, the spring can assembly of the present invention allows the compression member to be readily and easily changed, thus providing the ability to easily adjust the flex tension of the back support member. | 0 |
This application is a divisional of U.S. patent application Ser. No. 11/761,099, filed Jun. 11, 2007, now abandoned which claims the benefit of U.S. Provisional Patent Application No. 60/804,431, filed Jun. 10, 2006, both of which are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates generally to a dunnage converter for converting a sheet stock material into a dunnage product, and various improvements thereof.
BACKGROUND
Dunnage conversion machines, also referred to as converters, generally convert a sheet stock material into a strip of dunnage. The dunnage is then placed in a container with one or more objects for shipment.
Some converters produce a dunnage product primarily to provide cushioning in a packaging container to prevent or minimize damage to the contents during shipment. U.S. Pat. No. 5,674,172, for example, which is hereby incorporated herein by reference, discloses a cushioning conversion machine for converting a sheet stock material into a cushioning dunnage product. The cushioning conversion machine includes a forming assembly that causes inward rolling of the lateral edges of the sheet stock material to form a strip having a three-dimensional shape with lateral pillow-like portions separated by a thin central band. The forming assembly includes a shaping member over which the sheet stock material is drawn and a converging chute cooperative with the shaping member to roll the edges of the stock material inward to form the lateral pillow-like portions. A feed mechanism downstream of the forming assembly pulls the stock material through the forming assembly. The feed mechanism also connects overlapping layers of stock material along the thin central band. The feed mechanism has a pair of rotating gear-like members that engage and pull the stock material over the shaping member, through the converging chute, and connect, by coining, the overlapping layers in the thin central band to maintain the three-dimensional shape of the strip. The conversion machine further includes a cutting mechanism for cutting the strip into cut sections, or pads, of a desired length for use as a protective cushioning dunnage product.
Other converters produce a dunnage product primarily to fill voids in a packaging container to prevent or minimize shifting of the contents during shipment. These machines typically operate at relatively high speeds. An exemplary dunnage converter is disclosed in International Patent Application No. PCT/US2001/018678, published under Publication No. WO 01/094107 on Dec. 13, 2001, and International Patent Application No. PCT/US2003/012301, filed on Apr. 22, 2003, and published under Publication No. WO 03/089163 on Oct. 30, 2003, both of which are hereby incorporated herein by reference.
An exemplary machine of this type includes a forming assembly for shaping a sheet stock material into a continuous strip of dunnage and a pulling assembly for advancing the sheet material through the forming assembly. The forming assembly includes a funnel portion, similar to a converging chute, through which the sheet stock material passes for shaping the sheet stock material into the strip of dunnage and directing the formed strip to the pulling assembly. The pulling assembly includes at least two opposed grippers, at least one of which is moveable through a dunnage transfer region in opposition to the other gripper. The grippers are cooperative to define an aperture therebetween and to grip the sheet stock material therein and advance it through the transfer region. The moving gripper includes a plurality of paddles that aid in defining the aperture and in engaging the sheet stock material. The grippers can help to crease the crumpled folds in the strip to help it maintain its shape. Due to the aperture between the grippers, however, the grippers generally cannot coin or stitch together the layers of stock material passing therebetween, in contrast to the gear-like members in the aforementioned cushioning conversion machine.
SUMMARY
A compact dunnage conversion machine includes a converging chute with a restricted inlet, a powered feed assembly with a sealed gearbox, a plurality of interchangeable power supplies, and a restricted outlet chute. The converter can convert a sheet stock material into dunnage for use in packaging one or more objects in a container. The restricted inlet and outlet make it more difficult for foreign objects to enter the converter and disrupt the conversion process. The sealed gearbox interposed between the driving elements of the feed assembly and an electric motor facilitates maintenance and repair of the feed assembly, while also protecting the gears therein. Finally, the power supplies provide electrical power to the motor and can include an electrical storage device, such as a battery, or an alternating-current-to-direct-current converter which is connectable to a source of electricity for supplying that electricity to the motor in an acceptable form.
Accordingly, a dunnage converter for converting a stock material into a relatively less dense dunnage product comprises a powered feed assembly and at least two power supplies. The feed assembly has at least one rotatable member for engaging and feeding stock material, and an electric direct current motor for driving the at least one rotatable member. The power supplies are interchangeably connectable to the motor. A first power supply has a battery, and a second power supply is connectable to a source of alternating current and has an alternating-current-to-direct-current converter for supplying direct current to the motor. In a packaging system, the converter may be mounted on a stand, which also may support a power supply and/or a supply of sheet stock material.
Another dunnage converter for converting a sheet stock material into a relatively less dense dunnage product comprises a powered feed assembly for feeding the stock material that has at least one rotatable member, a motor for driving the at least one rotatable member and a gear box interposed between the at least one rotatable member and the motor for transferring rotational motion from the motor to the at least one rotatable member. The gear box includes a housing that encloses at least one gear, and the housing has a first opening therein for receipt of a shaft of the motor and a second opening for receipt of a shaft for each rotatable member. The motor shaft may pass through one side of the housing and the shaft for the rotatable member may pass through an opposing side of the housing. The motor may be mounted to the gear box housing.
Still another dunnage converter for converting a sheet stock material into a relatively less dense dunnage product, comprises a converging chute having a first pair of opposed side walls that generally converge towards each other in a downstream direction and a second pair of opposed top and bottom walls that interconnect the side walls. The top and bottom walls define a constriction adjacent an upstream end of the chute where the top and bottom walls gradually converge toward each other to define a minimum distance therebetween of no more than about 30 mm.
Another dunnage converter for converting a stock material into a relatively less dense dunnage product comprises a powered feed assembly for feeding a stock material and an output chute downstream of the feed assembly that guides the stock material to an outlet opening thereof that is spaced from the feed assembly. The output chute has a pair of opposed walls that have a minimum distance therebetween of no more than about 32 mm adjacent the outlet opening. The output chute may have a length of about 150 mm to about 200 mm.
The foregoing and other features of the invention are hereinafter fully described and particularly pointed out in the claims, the following description and the annexed drawings setting forth in detail one or more illustrative embodiments of the invention. These embodiments, however, are but a few of the various ways in which the principles of the invention can be employed. Other objects, advantages and features of the invention will become apparent from the following detailed description of the invention when considered in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an exemplary dunnage conversion machine provided in accordance with the present invention, looking from above and toward an upstream end of the conversion machine.
FIG. 2 is a perspective view of a stand for supporting the conversion machine and a supply of sheet stock material at an elevated position.
FIG. 3 is a side view of the conversion machine of FIG. 1 .
FIG. 4 is a top view of the conversion machine of FIG. 1 .
FIG. 5 is a bottom view of the conversion machine of FIG. 1 .
FIG. 6 is a front view of the conversion machine of FIG. 1 , looking from the downstream end toward the upstream end of the conversion machine.
FIG. 7 is a rear view of the conversion machine of FIG. 1 , looking from the upstream end toward the downstream end of the conversion machine.
FIG. 8 is a perspective view of the conversion machine of FIG. 1 , as seen from below and looking toward the upstream end of the conversion machine.
FIG. 9 is an exploded view of the conversion machine shown in FIG. 1 .
FIG. 10 is a schematic diagram of a powered portion of a conversion machine provided in accordance with the present invention.
FIG. 11 is a perspective view of a power supply for the converter shown in FIG. 1 , with a battery.
FIG. 12 is a perspective view of a power supply for the converter shown in FIG. 1 , with an AC-to-DC converter.
FIG. 13 is a perspective view of an exemplary strip of dunnage.
DETAILED DESCRIPTION
Referring now in detail to the drawings, and initially FIGS. 1-9 , FIG. 1 shows an exemplary compact dunnage conversion machine (i.e., converter) 20 for converting a sheet stock material 22 ( FIG. 3 ) into a strip 24 ( FIG. 13 ) of dunnage. The converter 20 is part of a packaging system 26 that also includes an adjustable stand 40 , shown in FIG. 2 , on which the converter 20 is mountable at an elevated location.
The stand 40 shown in FIG. 2 includes a base 42 and a telescopically adjustable upright 44 to which the converter 20 can be secured. The base 42 includes wheels 46 so that the stand 40 may be moved easily. The base 42 of the stand 40 can have a different configuration, however, such as a clamp for mounting on a table.
Referring now to FIG. 9 as well, the converter 20 is mountable to the stand 40 via a pair of rotating guide plates 50 pivotally rotatable through a pivot shaft 52 passing therethrough to the arms of a generally U-shape bracket 54 , the base of which can be secured to the stand at “A” in FIGS. 1 and 2 . The stand 40 and the converter mounting bracket 54 cooperate to allow a packer to orient the converter 20 so that the converter 20 discharges dunnage products exactly where the packer wants them. Specifically, the stand 40 and the converter mounting bracket 54 operate to allow the packer both to rotate the converter 30 about a substantially vertical axis and to pivot the converter 20 about a substantially horizontal axis. The illustrated stand 40 also allows the packer to raise and lower the height of the converter 20 . This adjustability provides several advantages. Rotating the converter 20 , for example, allows multiple packers, spaced around the vertical rotation axis of the stand 40 at separate packing stations, to use the same converter 20 . That is, the converter 20 can be swung back and forth between the two packing stations as needed. Pivoting the converter 20 about a horizontal axis allows the packer to change the angle at which the dunnage exits the converter 20 relative to the stand 40 or a packing surface (not shown). In addition, adjusting the height of the stand may be desirable to accommodate different ranges of box sizes, or packers of different heights, for example.
The stand 40 also includes a support, such as the illustrated tray 60 mounted to the upright, for supporting a supply 62 of sheet stock material 22 , such as that shown in FIG. 3 . The supply 62 supplies the converter 20 with one or more plies of sheet stock material, which typically consists of paper, particularly kraft paper, and typically about fifteen inch (about thirty-eight centimeters) wide to about thirty inch (about seventy-six centimeters) wide kraft paper. A common width in twenty-two and a half inches (about fifty-seven centimeters). A paper dunnage product is an environmentally responsible protective packaging material; paper is recyclable, reusable and composed of a renewable resource. Other sheet materials may be suitable alternatives to paper, however.
The stock material preferably is perforated or otherwise weakened in regions that extend across its width and are spaced apart along the length of the stock material. The stock material typically is supplied as a continuous fan-folded stack that is perforated at the folds. These weakened regions make it easier to separate dunnage products from the strip of dunnage, for example by tearing, so that a desired length of dunnage can be torn from the strip as it emerges from the converter.
The converter 20 includes a housing 70 that encloses a conversion assembly 72 for converting the stock material into a dunnage product. The conversion assembly 72 includes a converging chute 74 and a powered feed assembly 76 downstream of the converging chute 74 . The sheet stock material 22 is fed into an upstream end 80 of the converter housing 70 and the feed assembly 76 pulls the stock material from the supply (not shown) and through the converging chute 74 . The converging chute 74 inwardly gathers and crumples the stock material into the shape of a crumpled strip or rope 24 ( FIG. 13 ) having a generally round cross-sectional shape, typically with one or more longitudinally-extending crumpled lobes. The converted stock material exits the housing 70 at a downstream end 82 of the converter 20 as the completed dunnage strip. The terms “upstream” and “downstream” are used herein to refer to the flow of the stock material through the converter 20 , from the upstream end 80 of the converter to the downstream end 82 .
In the illustrated embodiment, the housing 70 has a relatively planar bottom portion 90 that forms the bottom wall and a top portion 92 having a generally U-shape cross-section that forms the side and top walls. The bottom portion 90 in the illustrated embodiment has a hollow shape that is about seventeen millimeters thick with one or more stiffening brackets 94 mounted thereto to provide additional support and to increase the rigidity of the converter housing 70 . The top portion 92 of the converter housing 70 includes an upstream section 96 that provides the top of the converging chute 74 , and a downstream section 98 that covers the feed assembly 76 . The downstream section 98 also helps to form an outlet chute 100 downstream of the feed assembly 76 that terminates at an outlet opening 102 . The illustrated housing 70 , with its two readily removable upper sections 96 and 98 , simplifies maintenance and operation of the converter 20 . The housing 70 and components of the conversion assembly 72 therein generally define the path of the stock material through the converter 20 in a substantially upstream to downstream direction.
One of those components of the conversion assembly 72 that defines the path of the stock material through the converter 20 is the converging chute 74 , best seen in FIGS. 4 and 7 . The converging chute 74 has a first pair of opposed side walls 110 that generally converge towards each other in a downstream direction and second pair of opposed top and bottom walls 112 and 114 that interconnect the side walls 110 . The converging walls 110 of the chute 74 define a progressively smaller cross-sectional area in the downstream direction whereby the stock material is turned in on itself and crumpled to form a strip of dunnage.
The top and bottom walls 112 and 114 also define a constriction 120 adjacent an upstream end of the chute 74 where the top and bottom walls 112 and 114 gradually converge towards each other to define a minimum distance therebetween of no more than about thirty millimeters.
In the illustrated embodiment, the top wall 112 includes an upper protrusion 122 that gradually curves to form a hemi-cylindrical shape. The protrusion 122 extends across the path of the stock material in the upstream-to-downstream direction. Other curved shapes also may be suitable. The bottom wall 114 also includes a corresponding cylindrical lower protrusion 124 generally aligned with the upper protrusion 122 to define the constriction 120 . The longitudinal axis of either or both protrusions 122 and 124 may be straight or curved. The lower protrusion 124 also defines the lower upstream edge of the converter 20 , and also presents a gradually curving surface to guide the stock material into the converging chute 74 . The lower protrusion 124 , which in the illustrated embodiment is bowed in the middle in an upstream direction, generally provides a relatively constant entry point for the stock material entering the converging chute 74 .
The constriction 120 at the upstream end of the converging chute 74 limits the ability for foreign objects to enter the converging chute 74 that could interfere with the conversion process. The constriction 120 generally has a width that is about as wide as the stock material expected to be used with the converter 20 . In an exemplary converter 20 , the side walls 110 typically are spaced apart about eighty centimeters at the constriction 120 .
The powered feed assembly 76 is similar to that disclosed in U.S. patent application Ser. No. 10/887,220, filed Jul. 8, 2004, and published under Publication No. 2005-0181924 on Aug. 18, 2005, which is hereby incorporated herein by reference. The feed assembly 76 has at least one rotatable member 130 , and in the illustrated embodiment it includes a pair of rotatable members 130 , for engaging and feeding stock material from a supply thereof through the converging chute 74 in a downstream direction. The rotatable members 130 further crumple the stock material and help to fix the crumpled stock material in its crumpled state.
The opposing rotatable members each have a plurality of paddles 132 uniformly circumferentially spaced apart. Each paddle 132 has a somewhat V-shape or outwardly opening cavity or indentation in the side thereof such that rotation of the rotatable members 130 causes the paddles 132 to sweep through a generally hourglass-shape volume. The opposing sets of paddles 132 together form a through-gap or channel 136 that gradually narrows as the paddles 132 progressively move toward each other as the rotatable members 130 rotate. The hourglass-shape volumes of the opposing rotatable members 130 can overlap one another as alternating paddles 132 move through the overlapping regions. In other words, the opposing paddles 132 sequentially move transversely toward or “close in” on each other as the rotatable members rotate to grip the stock material therebetween.
Once the opposing paddles 132 engage the strip of dunnage, they maintain a grip on the strip for the duration of their travel along the path of the stock material through the feed assembly 76 . At the downstream end of the feed assembly 76 , the opposing sets of paddles 132 gradually diverge away from each other to release the strip of dunnage.
The converter 20 also includes one or more guide members 140 that direct the gathered strip from the converging chute 74 and through the feed assembly 76 without significantly impairing the operation of the feed assembly 76 or the crumpling of the strip as it is fed therethrough. The guide members 140 extend from a position upstream of the feed assembly 76 , through the gap 136 between the opposing rotatable members 130 , to a position downstream of the feed assembly 76 to guide the stock material past the rotatable members 130 . The guide members 140 typically are secured at an upstream end, such as to a portion of the housing 70 that defines the converging chute 74 , and are free at a downstream end. Each guide member 140 generally has sufficient flexibility to move out of the way as the strip passes thereby, substantially between the guide members 140 . The guide members 140 can be formed of nylon, such as nylon cable ties, also referred to as tie-wraps.
The feed assembly 76 feeds the stock material downstream and through the output chute 100 which guides the stock material to the outlet opening 102 thereof that is spaced from the feed assembly 76 , and thus out of the converter 20 . The output chute 100 provides a continuous path from the feed assembly 76 to the outlet opening 102 . The output chute 100 has a pair of opposed walls 144 that have a minimum distance therebetween of no more than about thirty-two millimeters adjacent the outlet opening 102 . The output chute 100 generally provides a rectangular passage for the stock material although it may have other shapes, including a trapezoid, for example, with a width near the top of the outlet opening 102 of about twenty-five millimeters and a width near the bottom of the outlet opening 102 of about thirty-two millimeters, and a height of about eighty-seven millimeters. The output chute 100 has a length of about one hundred fifty millimeters to about two hundred millimeters from the feed assembly 76 to the outlet opening 102 . The narrow width of the output chute 100 restricts or limits or prevents entry into the output chute 100 by foreign objects that could interfere with the conversion process, as well as guiding the stock material and perhaps contributing to its formation into a strip of dunnage.
The feed assembly 76 is powered by a motor 150 . In an exemplary embodiment, the rotatable members 130 of the feed assembly 76 are driven by a rotary electric motor 150 , and at least one gear, and typically at least two gears in a gear train, for transferring rotational motion from the motor 150 to the rotatable members 130 . The rotatable members 130 can be keyed or otherwise secured to respective shafts 152 for rotation therewith. The axes of the rotatable members 130 generally extend in a direction that is parallel to an axis of the shaft 154 of the motor 150 . In the illustrated embodiment, the gear train includes a pinion gear 156 secured to the shaft of the motor 150 and a spur gear 156 and 158 secured to each shaft 152 of the rotatable members 130 . The gears 156 and 158 thus transfer the rotational motion from the shaft of the motor 150 to the shafts 152 of the rotatable members 130 .
A gear box 160 is interposed between the rotatable members 130 and the motor 150 . The gear box 160 includes a housing 162 , which includes a generally tubular portion 164 that has a generally rectangular cross-sectional shape and a pair of end covers 166 that close and seal the open ends of the tubular portion 164 and thereby enclosing at least one gear within the gear box 160 . The gear box housing 162 has a first opening 170 therein through one side of the housing 162 for receipt of the shaft of the motor 150 , and a pair of second openings 172 in another side of the housing 162 , the opposing side, for example, for receipt of the shafts 152 of the rotatable members 130 . The shafts 152 of the rotatable members 130 are mounted in the gear box housing 162 with bushings 176 in aligned openings in opposing sides of the gear box 160 and extend through the converter housing 70 to the rotatable members 130 enclosed therein on an opposite side of the bottom portion 90 of the converter housing 70 .
The gear box housing 160 is mounted to the housing 70 of the converter and the motor 150 is mounted to the opposing side of the gear box 160 with the shaft 154 of the motor 150 entering the gear box housing 162 from an opposite side of the gear box housing 162 from the openings 172 through which the shafts 152 of the rotatable members 130 extend.
The motor 150 is typically a direct current (DC) motor. An exemplary DC motor is a twenty-four volt DC motor, such as one which can rotate its shaft at about 2,300 revolutions per minute, and provides approximately one hundred to one hundred and fifty watts of power. The power cord for the motor includes a quick disconnect connection for connection to a power supply.
Turning to FIGS. 10-12 , the dunnage converter 20 also includes at least two power supplies 200 and 202 interchangeably connectable to the motor 150 , and thus the powered feed assembly 76 , to supply electrical power thereto. A controller 203 may be provided separately from the power supplies 200 and 202 , or a controller may be incorporated in each power supply 200 and 202 to provide the necessary control functions. In an exemplary converter 20 , each power supply 200 and 202 has a housing 204 that has the same dimensions as the other power supply or supplies. Consequently, the housing 204 for each power supply typically is substantially identical such that the power supplies 200 and 202 are readily swappable, one for another. Each power supply 200 and 202 can include an indicator light 206 to provide a visual output to indicate that the power supply 200 or 202 is operational, an emergency stop button 208 that can disconnect the power supply 200 or 202 in an emergency, and one or more fuses 210 that are accessible from outside the housing 204 . A first power supply 200 has a battery 212 and a second power supply 202 is connectable to a source of alternating current (AC) and has an AC-to-DC converter 214 for supplying the direct current to the motor 150 .
An exemplary power supply provides a 24 volt DC output with a current of no more than about six and a half amperes and provides approximately one hundred to one hundred fifty watts of power to the motor 150 . The AC power supply 202 can be provided in 110 volt or 220 volt alternating current versions for converting that voltage into a direct current for provision to the motor 150 . The AC power supply 202 includes a power cord 215 for connection to an outlet or other supply of alternating current, and the battery power supply 200 includes a connection 217 for a battery charger 216 . A connection 219 is provided for connecting the power supply to the motor, and this connection also may provide a connection for recharging the battery.
In the illustrated embodiment, the stand 48 shown in FIG. 2 also includes a bracket 220 for mounting the power supply 200 or 202 to the upright 44 . The power supply mounting bracket 220 has a pair of key slots 222 for receipt of a corresponding pair of screws (not shown) protruding from a back side of the power supply housing 204 . Other mechanisms for mounting the power supply 200 or 202 and connecting the power supply 200 or 202 to the motor 150 are possible.
An input device, such as one or more foot pedals 230 , is connectable to the power supply 200 and 202 to control the supply of power from the power supply 200 or 202 to the motor 150 . For example, to produce dunnage a packer may press on the foot pedal until a desired length of dunnage is produced, and then release the foot pedal 230 to stop the converter. The packer can then tear the dunnage along a line of perforations at or downstream of the feed assembly 76 . Alternatively, the packer can press the foot pedal 230 once to start the motor 150 , and then press the foot pedal a second time to stop it. Other means for signaling the converter 20 and the feed assembly 76 to start and stop also may be employed.
Each power supply 200 and 202 also may include multiple connections for multiple foot pedals or other type of switch so that the converter can be used by multiple packers at various stations around the dunnage converter 20 . For example, the converter 20 may be shared by two different packers at stations approximately ninety degrees apart from each other and the converter 20 may be rotated about the axis of the stand 40 for pointing the outlet opening 102 at the respective packer whereby the packer can use the nearest foot pedal 230 to control the supply of power and thus the conversion of stock material into a dunnage product.
Although the invention has been shown and described with respect to certain exemplary embodiments, it is obvious that equivalent alterations and modifications will occur to others skilled in the art upon the reading and understanding of this specification and the annexed drawings. In particular regard to the various functions performed by the above described components, the terms (including a reference to a “means”) used to describe such components are intended to correspond, unless otherwise indicated, to any component which performs the specified function of the described component (i.e., that is functionally equivalent), even though not structurally equivalent to the disclosed structure which performs the function in the herein illustrated exemplary embodiments of the invention. In addition, while a particular feature of the invention can have been disclosed with respect to only one of the several embodiments, such feature can be combined with one or more other features of the other embodiments as may be desired and advantageous for any given or particular application. | A compact dunnage conversion machine includes a converging chute with a restricted inlet, a powered feed assembly with a sealed gearbox, a plurality of interchangeable power supplies, and a restricted outlet chute. The converter can convert a sheet stock material into dunnage for use in packaging one or more objects in a container. The restricted inlet and outlet make it more difficult for foreign objects to enter the converter and disrupt the conversion process. The sealed gearbox interposed between the driving elements of the feed assembly and an electric motor facilitates maintenance and repair of the feed assembly, while also protecting the gears therein. Finally, the power supplies provide electrical power to the motor and can include an electrical storage device, such as a battery, or an alternating-current-to-direct-current converter which is connectable to a source of electricity for supplying that electricity to the motor in an acceptable form. | 1 |
RELATED APPLICATION
This is a continuation application of U.S. patent application Ser. No. 09/749,021, filed on Dec. 27, 2000 and published Sep. 5, 2002. U.S. 2002/01 22777A1; now U.S. Pat. No. 6,485,710 B2, dated Nov. 26, 2002.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to toothpaste and, more particularly, to a formulation of an appetite suppressant oral composition in the form of a toothpaste comprising ingredients which co-act to control the appetite and permit reduction in body weight by brushing the teeth of a user with the composition.
It has been found that the combination of about 5.50-22.0% by weight natural herbs functions as an appetite suppressant agent in a standard toothpaste formulation. This unexpected result from the novel toothpaste composition of the present invention to suppress appetite and promote weight loss provides a new secondary benefit to the promoting intraoral cleanliness with toothpaste.
2. Description of the Prior Art
Numerous types of appetite suppressants have been provided in the prior art. Current products to suppress appetite and control weight are generally drugs with undesirable side effects, often with a propensity to be addictive; whereas the instant novel appetite suppressant toothpaste provides a non-pharmacological means to suppress the appetite of a user by adding natural herbs to a standard toothpaste formulation.
There are many appetite suppressant products on the market, both prescription items and over the counter products. Most of these products act as central nervous system stimulants, such as amphetamines, or have a similar mechanism of action. Many of the over the counter products, such as Acutrim, Dexatrim, Appedrine, etc. contain Phenylpropanolamine HCl+Caffeine. Ayds, another well known appetite suppressant product, is a caramel candy containing Benzocaine.
Oral compositions which contain natural herbs for temporary relief of pain in the oral cavity are well known products. Such products are readily found on the market and include Anbesol gel, a liquid comprising phenol, alcohol and Benzocaine; Chloroseptic losengers containing menthol-benzocaine, corn syrup, glycerine, sucrose and flavor for temporary relief of sore throat pain; and Hurricane Topical anesthetic aerosol spray for controlling oral pain.
For example, U.S. Pat. Nos. 3,856,942 and 4,913,894 are illustrative of such prior art. However, none of the above cited prior art disclose an appetite suppressant toothpaste formulation for controlling weight, comprising a suppressing agent containing natural herbs. These prior art references also do not provide an appetite suppressant in a dental vehicle which may be in the form of a toothpaste, dental cream or mouth spray. The concept of a toothpaste formulation containing an appetite suppressing agent is novel. While these units may be suitable for the particular purpose to which they address, they would not be as suitable for the purposes of the present invention as heretofore described.
This patent discloses an appetite control composition which is readily ingested, comprising a candy base of sucrose and maltose, caffeine, Natural herbs, vitamins and optionally flavors including quinine to reduce the sweetness of the sucrose and maltose. This composition is preferably a slow-dissolving hard candy or tablet, but may also be in the form of gum drops, chocolate bars or drops, cotton candy, lozenges or gelatin desserts, all of which are ingestible.
This patent discloses an appetite suppressant oral composition containing benzocaine, high impact flavor and a sweetening agent, in the form of a toothpaste. A novel method of reducing appetite and thereby intended for controlling weight of consumers, which comprises applying to the oral cavity a high impact flavor in a toothpaste.
SUMMARY OF THE PRESENT INVENTION
The present invention relates to toothpaste and, more particularly, to a formulation of an appetite suppressant oral composition in the form of a toothpaste comprising ingredients which co-act to control the appetite and permit reduction in body weight by brushing the teeth of a user with the composition.
A primary object of the present invention is to provide an appetite suppressant toothpaste that will overcome the shortcomings of prior art devices.
The present invention provides an appetite suppressant toothpaste intended to effect weight control. The toothpaste is formulated by adding an appetite suppressing agent comprising about 5.50-22.00% by weight natural herbs to a standard dentifrice or toothpaste. Appetite suppression and weight control can be obtained by brushing the teeth, before and/or after each meal, preferably before, on a regular basis such as three times/day with the appetite suppressant toothpaste of the present invention.
Accordingly, another object of present invention is to provide an appetite suppressant toothpaste formulation by the incorporation of an appetite suppressant agent comprising natural herbs.
A further object of the present invention is to provide an appetite suppressant toothpaste which is able to reduce the appetite of a user alter brushing the teeth of the user with the toothpaste
A yet further object of this invention is to provide an appetite suppressant toothpaste in the form of a dental cream or mouthspray for use preferably prior to meals, to promote weight loss.
Still another object of present invention is to provide an appetite suppressant toothpaste for promoting weight loss as well as good dental hygiene.
Another object of present invention is to provide an appetite suppressant toothpaste formed from a novel essentially non-ingested composition containing safe natural herbs able to suppress the appetite and promote weight loss of the user.
Another object of the present invention is to provide an appetite suppressant toothpaste that is simple and easy to use.
A still further object of the present invention is to provide an appetite suppressant toothpaste that is economical in cost to manufacture
Additional objects, advantages and novel features of the invention will be set forth in part in the description which follows, and in part will become apparent to those skilled in the art upon examination of the following or may be learned by practice of the invention.
Additional objects of the present invention will appear as the description proceeds.
An appetite suppressant toothpaste formulations which simultaneously suppresses the users appetite while promoting intraoral cleanliness is disclosed by the present invention. The toothpaste composition includes toothpaste base ingredients; and at least one of appetite suppressant and appetite depressant herbs. The toothpaste base ingredients include a combination of known amounts of Vegetable Glycerin; Sorbitol, Hydrated Silica; Purified Water; Xylitol; Carrageenan; Sodium Lauryl Sulfate; and Titanium Dioxide and a flavoring agent. The appetite suppressing and depressing herbs include at least one of Garcinia Cambogia; Gymnema Sylvestre; Kola Nut; Citrus Aurantium; Yerba Mate; and Griffonia Simplicifolia and comprise a range of substantially 5.5% to substantially 22% by weight of the composition. The appetite suppressing and depressing herbs may further include at least one of Guarana, Green Tea, myrrh, guggul Lipid and black current seed oil. Alternatively, the toothpaste composition may be in the form of a dental cream or mouthspray.
To the accomplishment of the above and related objects, this invention may be embodied in the form illustrated in the accompanying drawings, attention being called to the fact, however, that the drawings are illustrative only, and that changes may be made in the specific construction illustrated and described within the scope of the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
To achieve the foregoing and other objects in accordance with the present invention, as embodied and broadly described herein, the appetite suppressant toothpaste comprises about 5.50-22.0% by weight natural herbs. The amount of natural herbs effective in minimizing the desire for food and suppress appetite of a user is about 5.50 to 22.00 wt %.
Another component in the appetite suppressant toothpaste composition is a high impact flavor which is an intense flavor including, but not limited to, any or all of oil of wintergreen, chocolate, cherry, strawberry, grape and other hunger minimizing flavors. The high impact flavor is a blend of a number of components so that the resultant mixture is a well-rounded, smooth flavor with an intense immediate initial impact, a lasting pleasant aftertaste (e.g. preferably at least about 45-60 seconds) and a prolonged pleasantly smelling impact on the breath of the user. Other food grade artificial flavors may be used provided they are intense flavors of high initial impact with a lasting pleasant aftertaste.
The standard toothpaste base of the instant invention preferably comprises substantially from 10-30% Vegetable Glycerin; substantially from 10-30% Sorbitol; substantially from 10-30% Hydrated Silica; substantially from 10-30% Purified Water; substantially from 10-30% Xylitol; substantially from 1-3% Carrageenan; substantially from 1-3% Sodium Lauryl Sulfate; substantially from 1-3% Titanium Dioxide; and substantially from 0.30-1% Oil of Wintergreen. Sorbitol is the major humectant ingredient because of its sweet taste. Minimal amounts of polyethylene are used due to its bitter taste. A mixture of sorbitol and glycerin is preferred. In the toothpaste, dental gel or dental cream, the humectant constitutes about 65-75% by weight of the composition and the water content is about 10-30% by weight of the toothpaste.
It is preferred to use a gelling agent in dental creams or gels, such as the natural and synthetic gums and gum like materials, for example Carrageenan, Irish moss, gum tragacanth, cellulose gums such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxmethyl cellulose, polyvinylpyrrolidone, hydrophilic colloidal carboxyvinyl polymers, such as those sold under the trademark Carbopol 934 and 940 and synthetic silicated clays such as those sold under the trademark Laponite CP and Laponite SP. These grades of Laponite have the formula (Si 8 Mg 5 Li 0.6 O 24 ) 0.6 −Na 0.6+ . The gelling agent constitutes about 1.0-3.0% by weight of the toothpaste formulation.
The toothpaste formulations will generally also include a dentally acceptable, substantially water insoluble polishing agent of the type commonly employed in dental creams. Representative polishing agents include, for example, dicalcium phosphate, tricalcium phosphate, insoluble sodium metaphosphate, aluminum hydroxide, including hydrated alumina, colloidal silica, hydrated silica, precipitated silica and magnesium carbonate, calcium carbonate, calcium pyrophosphate, and bentonite, including suitable mixtures thereof. It is preferred to use silica-containing polishing agents such as amorphous hydrated silicon dioxide (SiO 2 H 2 O), known as Zeodent/Zeofree/Zeosyl/Zeothix obtainable from J.M. Huber Corporation, which is in the form of a white, odorless powder having an average particle size of 8-10 micrometers and a density of 2 g/ml. at 25° C. Amorphous silica, also called silica gel and silicic acid, is also obtainable from W.R. Grace & Co. as Sylodent 704 which is a dry white powder having an average particle size of 4 microns and a specific gravity of 2.1. Sylox® is another amorphous silica provided by W.R. Grace & Co., in the form of a dry white powder having an average size of 1.5-12 microns. The preferred siliceous containing polishing agent constitutes about 10-30% by weight of the dental cream formulations.
When the toothpaste is a visually clear gel or opacified gel, a polishing agent of colloidal silica, such as those sold under the trademark Syloid as Syloid 72 and Syloid 74 or under the trademark Santocel as Santocel 100 and synthetic alkali metal aluminosilicate complexes (including silica containing combined alumina) may be particularly useful. They have refractive indices close to the refractive indices of gelling agents-liquid systems commonly used in toothpaste (which generally include humectants such as glycerine and sorbitol).
Organic surface-active agents are preferably used in the composition of the present invention to assist in achieving thorough and complete dispersion of the compositions of the present invention throughout the oral cavity and render the said compositions more cosmetically acceptable. The organic surface-active agent material may be anionic or nonionic, in nature, and it is preferred to employ as the surface-active agent a detersive material which imparts to the composition detersive and foaming properties. Suitable anionic surfactants include water-soluble salts of higher fatty acid monoglyceride monosulfates, such as the sodium salt of the monosulfated monoglyceride of hydrogenated coconut oil fatty acids, higher alkyl sulfates, such as sodium lauryl sulfate, alkyl aryl sulfonates, such as sodium dodecyl benzene sulfonate, higher alkyl sulfoacetates, higher fatty acid esters of 1,2-dihydroxy propane sulfonates, olefin sulfonates and the like.
Other particularly suitable surface active materials include nonionic agents such as condensates of sorbitan monostearate with approximately 20 moles of ethylene oxide; condensates of ethylene oxide with propylene oxide; condensates of propylene glycol (Pluronics); condensation products of an alpha-olefin oxide containing 10 to 20 carbon atoms; a polyhydric alcohol containing 2 to 10 carbons; and 2 to 6 hydroxyl groups and either ethylene oxide or a heteric mixture of ethylene oxide and propylene oxide. The resultant detergents are heteric polymers having a molecular weight in the range of 400 to 1600 and containing 40% to 80% by weight of ethylene oxide, with an alpha-olefin oxide to polyhydric alcohol mole ratio in the range of 1:1 to 1:3. The amount of anionic or nonionic surfacant constitutes about 1-3% by weight of the toothpaste formulation.
The toothpaste of this invention may also contain conventional additional ingredients such as coloring or whitening agents and preservatives. These additional ingredients may each be added to the toothpaste in minimal amounts of up to 5% by weight, and preferably up to 1%, provided they do not interfere with the appetite suppressant and compatibility properties of the finished product.
The toothpaste of this invention is prepared by conventional methods of making toothpaste and/or dental creams or dental gels. More specifically, the gelling agent such as a cellulose gum is dispersed in glycerine, to which is added an aqueous solution containing the sweetening agent such as xylitol, followed by the addition of sorbitol and mixing for a period of about 20 minutes to hydrate the gum, mixing the gum mixture with the polishing agent in a mixer under a vacuum of 28-30 inches of pressure. Lastly, the flavor, the surfactant and natural herbs are added to the vacuum mixer, mixed for a period of about 15 minutes, and the final mixture is placed in a tube. In the practice of this invention to suppress appetite, control weight and simultaneously promote oral hygiene, the toothpaste according to this invention is applied regularly to the oral cavity by brushing the teeth or spraying the mouth for 30-90 seconds, at least three times a day either after or before meals, preferably prior to eating meals.
The toothpaste composition of the present invention has a molecule size which is small enough to be absorbed through the mucous membrane of the mouth. The composition is also water soluble, and is absorbed into the person's blood stream to act as an appetite suppressant.
The following embodiments are further illustrative of the nature of the present invention, but it is understood that the invention is not limited thereto. The compositions are prepared in the usual manner and all amounts and proportions referred to herein and in the appended claims are by weight unless otherwise indicated.
The preferred embodiment of the appetite suppressant toothpaste is:
EMBODIMENT 1
APPETITE SUPPRESSANT TOOTHPASTE
INGREDIENTS
Percent %
Vegetable Glycerin
10.00-30.00
Sorbitol
10.00-30.00
(Basic
Hydrated Silica
10.00-30.00
Toothpaste
Purified Water
10.00-30.00
Base)
Xylitol
10.00-30.00
Carraqeenan
1.00-3.00
Sodium Lauryl Sulfate
1.00-3.00
Titanium Dioxide
1.00-3.00
Oil of Wintergreen
0.30-1.00
Garcinia cambogia
1.00-2.00
Gymnema Sylvestre
(All have
1.00-2.00
Kola Nut
common
1.00-2.00
Citrus Aurantium
function &/or
1.00-2.00
Yerba Mate
compliment
1.00-2.00
Griffonia Simplicifolia
each other)
0.40-2.00
Further embodiments of the appetite suppressant toothpaste according to the present invention are as follows:
APPETITE SUPRESSANT TOOTHPASTE
INGREDIENTS
Percent %
EMBODIMENT 2
Vegetable Glycerin
10.00-30.00
Sorbitol
10.00-30.00
(Basic
Hydrated Silica
10.00-30.00
Toothpaste
Purified Water
10.00-30.00
Base)
Xylitol
10.00-30.00
Carraqeenan
1.00-3.00
Sodium Lauryl Sulfate
1.00-3.00
Titanium Dioxide
1.00-3.00
Oil of Wintergreen
0.30-1.00
Garcinia cambogia
1.00-2.00
Gymnema Sylvestre
(All have
1.00-2.00
Kola Nut
common
1.00-2.00
Citrus Aurantium
function &/or
1.00-2.00
Yerba Mate
compliment
1.00-2.00
Griffonia Simplicifolia
each other)
0.40-2.00
Guarana
1.00-2.00
Green Tea
1.00-2.00
EMBODIMENT 3
Vegetable Glycerin
10.00-30.00
Sorbitol
10.00-30.00
(Basic
Hydrated Silica
10.00-30.00
Toothpaste
Purified Water
10.00-30.00
Base)
Xylitol
10.00-30.00
Carraqeenan
1.00-3.00
Sodium Lauryl Sulfate
1.00-3.00
Titanium Dioxide
1.00-3.00
Oil of Wintergreen
0.30-1.00
Garcinia cambogia
1.00-2.00
Gymnema Sylvestre
(All have
1.00-2.00
Kola Nut
common
1.00-2.00
Citrus Aurantium
function &/or
1.00-2.00
Yerba Mate
compliment
1.00-2.00
Griffonia Simplicifolia
each other)
0.40-2.00
Myrrh
1.00-2.00
EMBODIMENT 4
Vegetable Glycerin
10.00-30.00
Sorbitol
10.00-30.00
(Basic
Hydrated Silica
10.00-30.00
Toothpaste
Purified Water
10.00-30.00
Base)
Xylitol
10.00-30.00
Carraqeenan
1.00-3.00
Sodium Lauryl Sulfate
1.00-3.00
Titanium Dioxide
1.00-3.00
Oil of Wintergreen
0.30-1.00
Garcinia cambogia
1.00-2.00
Gymnema Sylvestre
(All have
1.00-2.00
Kola Nut
common
1.00-2.00
Citrus Aurantium
function &/or
1.00-2.00
Yerba Mate
compliment
1.00-2.00
Griffonia Simplicifolia
each other)
0.40-2.00
Guarana
1.00-2.00
Green Tea
1.00-2.00
Myrrh
1.00-2.00
EMBODIMENT 5
Vegetable Glycerin
10.00-30.00
Sorbitol
10.00-30.00
(Basic
Hydratcd Silica
10.00-30.00
Toothpaste
Purified Water
10.00-30.00
Base)
Xylitol
10.00-30.00
Carraqeenan
1.00-3.00
Sodium Lauryl Sulfate
1.00-3.00
Titanium Dioxide
1.00-3.00
Oil of Wintergreen
0.30-1.00
Garcinia cambogia
1.00-2.00
Gymnema Sylvestre
(All have
1.00-2.00
Kola Nut
common
1.00-2.00
Citrus Aurantium
function &/or
1.00-2.00
Yerba Mate
compliment
1.00-2.00
Griffonia Simplicifolia
each other)
0.40-2.00
Guarana
1.00-2.00
Green Tea
1.00-2.00
Myrrh
1.00-2.00
Guggul
1.00-2.00
Black current seed oil
1.00-2.00
EMBODIMENT 6
Vegetable Glycerin
10.00-30.00
Sorbitol
10.00-30.00
(Basic)
Hydrated Silica
10.00-30.00
Toothpaste
Purified Water
10.00-30.00
Base)
Xylitol
10.00-30.00
Carraqeenan
1.00-3.00
Sodium Lauryl Sulfate
1.00-3.00
Titanium Dioxide
1.00-3.00
Oil of Wintergreen
0.30-1.00
Garcinia cambogia
1.00-2.00
Gymnema Sylvestre
(All have
1.00-2.00
Kola Nut
common
1.00-2.00
Citrus Aurantium
function &/or
1.00-2.00
Yerba Mate
compliment
1.00-2.00
Griffonia Simplicifolia
each other)
0.40-2.00
Guarana
1.00-2.00
Green Tea
1.00-2.00
Guggul
1.00-2.00
Black current seed oil
1.00-2.00
Myrrh
1.00-2.00
The toothpaste compositions illustrated above have intense flavor and suppress the appetite of the consumer after brushing their teeth therewith. This provides a harmless topical means of controlling weight without ingesting drugs, troches, lozenges, gums, or the like.
Variations in the above formulations may be made. For example, other food grade anionic or nonionic surfactants may be substituted for the sodium lauryl sulfate or polyoxyethylene sorbitan diiostearate surfactants. Similarly, other dental polishing agents may be substituted for tile specific silica polishing agent in the specific examples. Likewise, other high impact or intense flavoring composition may be used in lieu of the oil of wintergreen or cheesecake flavors, such as chocolate, mint, strawberry, grape or the like.
Since the invention is described with reference to a couple of preferred embodiments, and since numerous additional modifications and changes may become readily apparent to those skilled in the art after reading this disclosure, it should be understood that I do not wish to limit the scope of my invention to the exact composition described above, and claimed by me below.
From the above description it can be seen that the appetite suppressant toothpaste of the present invention is able to overcome the shortcomings of prior art devices by providing an appetite suppressant toothpaste by the incorporation of an appetite suppressant agent comprising natural herbs. The appetite suppressant toothpaste in preferably in the form of a dental cream and mouthspray for use preferably prior to meals, to promote weight loss as a new secondary benefit to a toothpaste. The appetite suppressant toothpaste promotes weight loss via a toothpaste formulation containing safe natural herbs. Furthermore, the appetite suppressant toothpaste of the present invention is simple and easy to use and economical in cost to manufacture.
It will be understood that each of the elements described above, or two or more together may also find a useful application in other types of methods differing from the type described above.
While certain novel features of this invention have been shown and described and are pointed out in the annexed claims, it is not intended to be limited to the details above, since it will be understood that various omissions, modifications, substitutions and changes in the forms and details of the device illustrated and in its operation can be made by those skilled in the art without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. | An appetite suppressant toothpaste formulations which simultaneously suppresses the users appetite while promoting intraoral cleanliness. The toothpaste composition includes toothpaste base ingredients; and at least one of appetite suppressant and appetite depressant herbs. The toothpaste base ingredients include a combination of known amounts of Vegetable Glycerin; Sorbitol, Hydrated Silica; Purified Water; Xylitol; Carrageenan; Sodium Lauryl Sulfate; and Titanium Dioxide and a flavoring agent. The appetite suppressing and depressing herbs include at least one of Garcinia Cambogia; Gymnema Sylvestre; Kola Nut; Citrus Aurantium; Yerba Mate; and Griffonia Simplicifolia and comprise a range of substantially 5.5% to substantially 22% by weight of the composition. The appetite suppressing and depressing herbs may further include at least one of Guarana, Green Tea, myrrh, guggul Lipid and black current seed oil. Alternatively, the toothpaste composition may be in the form of a dental cream or mouthspray. | 0 |
BACKGROUND OF THE INVENTION
[0001] Referring now to U.S. Pat. No. 4,066,243 (Johnson), a jack for the use with automobile bumpers is shown, in which a frame is provided as a support means for a vertical pipe, which has a sleeve, which moves upward and downward around said pipe. A typical floor jack provided the upward lifting force against the sleeve, where the floor jack was attached to the sleeve portion through a ring. This device required a secondary jack, and was limited to the lifting of a vehicle body parts which would comprise a bumper.
[0002] Referring now to U.S. Pat. No. 4,123,038 (Meyers), an apparatus is disclosed in which an elaborate load bearing frame is provided, where the apparatus operates using two separate hydraulic jacks. There is no realistic application of this type of device with a small tractor or riding lawn mower.
[0003] Portable jacks for small tractors are specifically exampled in U.S. Pat. No. 4,549,721 (Stone), in which a screw-scissors jack was operated to provide lifting force against a framework so as to push the framework upward. It would appear that one of the drawbacks of this invention was that the framework had a rectangular configuration, which would create a problem where a portion of the framework had to be moved under the tractor front wheels. This requirement would present a problem in a situation where the tractor was unable to move under its own power, requiring physical work to move the tractor over the framework assembly. Further, this device would not work properly at a location where the ground on which the tractor was situated was not properly leveled.
[0004] Referring now to U.S. Pat. No. 5,358,217 (Dach), the lifting apparatus is disclosed, in which a framework had a narrow front end, and avoided some of the problems inherent in the Stone patent referenced above. This system required a hydraulic cylinder to provide an upward pushing force to lift the item or vehicle. Extended arms had curved metal prongs that were referenced as lifting points. This jack was not intended for use with small tractor wheels, but rather were intended for axle assemblies.
[0005] Referring now to U.S. Pat. No. 6,330,1997 (McGaun et al.), a lifting apparatus for small vehicles is shown. The assembly uses pivoting action of its framework to first engage the wheels, and then lift the wheels by pivoting the framework so as to use a lever action to urge the wheels off of the ground.
[0006] Referring now to U.S. Pat. No. 6,474,626 (Box), a rack for securing a lawn mower to an elevated position is shown, in which a cage-like framework assembly is provided, and where a flexible webbing is used with a wheel crank to pull the entire lawn mower into an elevated position. This assembly is similar to an automobile rack, with the exception that the lifting framework is rectangular in nature, and supports all four wheels of a push mower on rack.
[0007] Further patents have disclosed jacking mechanisms with riding lawn mowers. U.S. Pat. No. 6,516,597 (Samejima et al.) discloses a lawn tractor which allows manipulation of its wheel supports into position so that they can be used to assist in raising up the front end of the lawn tractor.
[0008] Referring now to U.S. Pat. No. D 468,512 S (Hernandez), an all-terrain vehicle lift is disclosed, in which a hydraulic cylinder is used, to lift a metal framework that is disposed at the front end of the apparatus. The invention uses a rectangular frame, and a support means for the wheel is limited to a single tire, and not to two wheels, unless they are fairly close together.
SUMMARY OF THE INVENTION
[0009] From time to time, small tractors, riding lawnmowers, and other similar vehicles require maintenance requiring that one end of the vehicle be elevated. The use of hydraulic floor jacks do not always provide a single stable support structure, and jack stands are often the wrong size with regard to the elevation requirements for the small vehicles. In some situations, the angle of the vehicle necessary to accomplish the desired elevation of one end of the vehicle, makes the use of small jacks unwieldy, since small hydraulic system jacks only have a single contact point. As the contact point rotates by virtue of the elevation difference between the front and back end of the vehicle, the contact point with the hydraulic jack may become unstable. Further, the amount of elevation necessary will often exceed a hydraulic jack assembly's capability.
[0010] A complete apparatus is necessary, where the wheels of the vehicle may be used to elevate the entire end of a vehicle, rather than relying on the frame or other similar contact points available with typical hydraulic jacks for such a vehicle. A means to provide use of a jack with a stationary vehicle is desired, where the supporting structure can be moved into position on a vehicle, without requiring movement of the vehicle onto the jack means itself.
[0011] This invention comprises a small portable jack that is intended for use with small tractors, riding lawn mowers, four-wheel sport motorcycles, and other small vehicles. This small vehicle jack support system obviates the need for hydraulic systems, but instead uses a vertical jack bar with a winch system and flexible strap on top of the apparatus to provide the lifting force.
[0012] The jack itself has a base that defines a stable platform, also referred to as a support frame, that is intended to slide underneath the front end of the tractor or other vehicle. This jack may also be used on the back end of the tractor or other similar vehicle, but for purposes of discussion, the front end of the vehicle will be used as the example with the lifting method and apparatus for this invention.
[0013] The forward framework that slides under the tractor is wider at the front for maximum stability, and narrows toward the rear, with the rear portion of framework able to be attached to an axle and wheel assembly. A vertical frame bar is fixed in position where the axle and wheel assembly and rearmost ends of the framework meet. The vertical frame bar is positioned between the rear frame members, and projects upward.
[0014] A lifting frame is provided, in which a center bar is connected at its front end perpendicularly to a cross bar member, where said cross bar member has a length that is equal to or greater then the width of the support frame from side to side. The crossbar and center bar define a T-shaped structure. The crossbar sits upon the support frame, with its ends resting on crossbar rest members, where the crossbar rest members define the widest portion of the support frame.
[0015] The center bar has a rigid guide member fixed to each side of the center bar rear end, where the guide members are slightly angled rearward from a 90 degree or perpendicular setting. Each guide member is spaced apart and parallel to each other, defining a gap that is at least as wide as the width of the center bar. The center bar preferably has a width greater than the vertical frame bar. As the guide members are parallel to each other, they allow the vertical frame bar to be positioned between them.
[0016] Once the lifting frame is positioned so that the vertical frame bar is situated between the angled guide members, a top roller is placed through its receiving apertures located on the terminating ends of the guide members, so that the vertical frame bar is restrained within the guide member gap area. A bottom roller is also positioned on the opposite side of the vertical frame bar, through the side guide members. The bottom roller, the parallel guide members and top roller function as a sleeve, which fits around the vertical frame bar, allowing the lifting frame to be moved upward and downward, with the gap between the guide members allowing some limited horizontal motion of the lifting frame. This allows for easy adjustment to the position of the lifting frame.
[0017] The vertical frame bar supports a winch means on its top end, with a flexible strap providing the pulling force necessary to lift the vehicle. In instances where the apparatus is desired to have height adjustment capability, a separate extension bar is provided, which allows the vertical bar, without any top structures attached, to be inserted into the extension bar.
[0018] The extension bar is provided, when greater height is desired, than can be obtained from a standard vertical frame bar. Also, the separate extension bar is provided for the simple need of disassembly and storage when so desired. Since both situations are generally desired, a extension bar is typically used with this apparatus.
[0019] The extension bar defines an inner cavity which allows the length of the vertical frame bar to be inserted completely into the extension bar. The extension bar preferably has a width similar to the center bar, with the gap defined between the guide members sufficient to allow said guide members to move freely over the extension bar.
[0020] The extension bar supports a platform which in turn supports a geared winch system that operates a flexible strap. The end of the flexible strap defines a hook, which is able to connect to a lifting ring located on the center bar, in proximity to the guide member attachment points with the center bar.
[0021] Removable wheel supports are provided, which are defined by a horizontal shaft, with a crossmember spacer which defines prongs on each end of the spacer, with the prongs defining a horizontal extension that is able to impact against the bottom side of a wheel. The prongs are spaced apart to define a gap, with the wheel able to rest between said gap. The wheel support assembly is attached to the crossbar by sliding the shaft into the inlet of said crossbar and securing the shaft and crossbar to each other.
[0022] Once the wheels of the vehicle are secured within the gap between the wheel support spacer prongs, the handle of the winch assembly is turned, causing the flexible strapped to move upward, thus exerting a lifting force against the lift ring. The lifting frame is raised vertically. The weight of the vehicle on the cross bar maintains the orientation of the lifting frame in a fairly horizontal position. The frame is unable to angle downward due to do the top and bottom roller. The strap is withdrawn until the lifting frame has raised the vehicle to the desired level. The winch is locked in position, using the braking systems commonly associated with such winch systems.
[0023] One advantage of having a separate extension bar is that the overall height capabilities of the jack can be varied, according to the length of the extension bar. Use of the strap denies the need for any type of hydraulic system, with the winch apparatus providing sufficient force to the strap, especially if the winch apparatus has a geared ratio with regard to the handle movement.
DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a perspective view of the improved small vehicle jack, in which the wheel support means and extension bar are shown in an exploded view.
[0025] FIG. 2 is a perspective view of the improved small vehicle jack in which the vertical frame bar and comprises the vertical support for the winch system.
[0026] FIG. 3 is a perspective view from above a riding lawn mower with the improved small vehicle jack positioned underneath it, with the tires of the riding mower positioned above the wheel support means.
[0027] FIG. 4 is a perspective view of the riding mower and vehicle jack, where the jack assembly has been moved to a raised position with the front end of the riding mower shown elevated.
[0028] FIG. 5 is an enlarged view of the sleeve assembly, showing the guide members and the top and bottom roller.
[0029] FIG. 6 is a side view of the sleeve means, in which the guide member is shown, with the lower and upper rollers shown, and where the safety pin is also shown.
[0030] FIG. 7 is a perspective partial view of the cross bar and the axle hook.
DETAILED DESCRIPTION OF THE INVENTION
[0031] Referring to FIG. 1 , the improved small vehicle jack apparatus 10 is shown. Said apparatus 10 is comprised of a support frame 15 , a lifting frame 60 , a lifting means 42 , and a wheel support means 50 . The support frame 15 is comprised of two generally parallel crossbar rest members 18 and 19 , which are spaced apart by a front member 20 . These members 18 , 19 and 20 , comprise the portion of the support frame 15 that is actually intended to be moved underneath the vehicle.
[0032] The crossbar rest members 18 and 19 are attached to the front member 20 ends, with angled members 13 fixed to the crossbar rest member 18 and 19 rear ends. The angled side members 13 are angled in relation to each other so that the distance between them becomes closer toward each other along their length from the front toward the rear. The rear ends of the angled side members 13 define end portions 25 that are fixed in relation to each other and which allow a vertical frame bar 14 to be fixed in a vertical position at the rear portion of the apparatus 10 .
[0033] As FIG. 1 shows, an axle 21 is provided, which is fixed to the rear end of this apparatus 10 , and which supports wheels 22 located on either side of said support frame 15 . The wheels 22 are fixed in such a manner that the rear portion of the support frame 15 is able to rest on the ground, with the wheels 22 providing ground contact for the rear portion of the support frame 15 if the apparatus 10 is tilted backwards. It should be understood however, that wheels 22 are not required, but are shown in the figures as the preferred manner of construction, since wheels 22 provide for an ease of transportation, in which the support frame forward end is elevated, with the ground contact being borne solely by wheels 22 . This allows ease of movement of the entire apparatus 10 .
[0034] The gap between the rear end portions 25 of the support frame 15 should be wide enough so as to accommodate the center bar 16 of the lifting frame 60 , and any sleeve means utilized with said lifting frame 60 .
[0035] The fixed vertical frame bar 14 projects upward from the support frame 15 . FIG. 1 shows a separate extension bar 40 , which fits down over the vertical frame bar 14 . In one of the preferred embodiments, there is no separate extension bar 40 , but the support frame 15 and incorporated vertical frame bar 14 support the winch means 42 . As is shown in FIG. 2 , the vertical frame bar 14 is fixed to the rear ends 25 of the support frame 15 , and projects upward and supports a platform 41 - and onto which a winch means 42 is provided. The winch means 42 is comprised of a spool, 62 , a winch support 43 that fixes the position of the spool 62 , and a handle 44 , whose manipulation causes a geared assembly to cause the spool 62 to turn to take up or let out the length of the strap 45 .
[0036] A flexible strap 45 is shown in FIG. 1 and in FIG. 2 , where said strap 45 is wound about the spool 62 , with its terminating end defining a hook 46 . The flexible strap 45 is fed off of the spool 62 , and a roller 66 is preferably provided at the edge of the platform 41 which supports the winch means 42 . The flexible strap 45 is not limited to any type of specific material, but could include any type of flexible material that has durability and strength in its resistance to stretching and/or breakage. The term “strap” should be understood to include chains, cables, straps of various material, cords, in any other type of flexible straps may be used, and will all function in virtually the same manner.
[0037] As is shown in FIG. 2 , the support frame 15 and incorporated vertical frame bar 14 comprise a general L-shaped configuration, where the total height of the apparatus 10 will always be consistent with the height of the vertical frame bar 14 and winch assembly 42 .
[0038] FIG. 1 shows an embodiment of the apparatus 10 in which the vertical frame bar 14 has the same configuration, except that it is much shorter in FIG. 1 than it is in FIG. 2 . In FIG. 1 , an extension bar 40 operates as an extender of the vertical frame bar 14 . The extension bar 40 may have any overall length desired by the operator of this apparatus 10 . In this manner, the interchangeability of various extension bars 40 with a single support frame 15 and vertical frame 14 , allows for a single support frame 15 to provide possibility for an apparatus 10 that has multiple choices of overall height as to the orientation of winch assembly 42 . The winch assembly 42 as described for FIG. 2 operates in the same manner as the winch assembly 42 in FIG. 1 . The winch assembly 42 may be detachable from the extension bar 40 , so that a single winch assembly 42 and support frame 15 may be used with extension bars 40 of various lengths to create a jack apparatus 10 of varied overall heights.
[0039] The lifting frame is comprised of a center bar 16 , which is attached at its front end to a crossbar 17 , where said crossbar and center bar form a T-shaped structure. The crossbar 17 preferably has a length that is equal to or greater then the distance defined by the separation of crossbar rest members 18 and 19 . The crossbar 17 is preferentially perpendicular to the crossbar rest members 18 and 19 , with the terminating ends of the crossbar 17 able to sit on top of the respective crossbar rest members 18 and 1 9 .
[0040] Wheel support means 50 are provided, which are shown as being detachable in FIG. 1 and in FIG. 2 . It should be understood, that the detachability of the wheel support means 50 is considered to be an optional and a more advanced feature, than if the wheel support means 50 was permanently attached and made a part of the terminating ends of the crossbar 17 .
[0041] As FIG. 1 shows, the wheel support means 50 is comprised of a main shaft 52 , which supports a spacer 53 , where said spacer 53 is oriented at 90° from the shaft 52 to form a T-shaped configuration. Prongs 54 are attached at each end of the spacer 53 , and project outward away from the apparatus 10 . As FIG. 1 shows, the prongs 54 are defined and shown as L-shaped members, in which the horizontal portion of the prong 54 is lower than the spacer 53 and shaft 52 . This is a preferred embodiment, since the horizontal portion of the prongs 54 are able to rest on the ground, while the crossbar 17 of the lifting frame 60 rests on top of the support frame 15 .
[0042] The wheel support means 50 may be detachable from cross bar 17 , in which the shaft 52 of the wheel support means 50 has an outer dimension that is at least less than the dimensions defined by insert 51 , which comprises the opening into the interior of crossbar 17 . Shaft 52 is moved into insert 51 until a desired position is reached, at which time both the shaft 52 and cross bar 17 are secured to each other using a securing pin 70 , which is shown in use in FIG. 2 . Such securing pins are common in the art.
[0043] The lifting frame 60 is fixed in position with regard to the vertical frame bar 14 , or where a extension bar 40 is used, fixed in position to the extension bar 40 through a sleeve means. Referring now also to FIG. 5 , a sleeve means comprises the rear end of center bar 16 , in which guide members 31 and 32 are secured to the sides of the center bar 16 , being secured at a slight rearward angle, as compared to a vertical position, so that the guide members 31 and 32 project both upwards, and slightly toward the rear.
[0044] The gap defined between the guide members 31 and 32 allow for placement of the vertical frame bar 14 , or the extension bar 40 where one is used, with a top roller 34 placed through the respective holes 33 defined on the ends of guide members 31 and 32 . Referring now also to FIG. 6 , a bottom roller 84 is situated through the side guide members 31 and 32 , in the manner that the top roller 34 is, with the bottom roller 84 positioned above the center bar 16 , but adjacent to the vertical frame bar 14 . The rollers 34 and 84 allow the lifting frame 60 to move smoothly upward and downward along the length of the vertical bar 14 , or any extension bar 40 , where one is used. The vertical frame bar 14 , or the extension bar 40 , when so situated between the guide members 31 and 32 , will provide a guide that the lifting frame 60 can follow in a vertical manner.
[0045] Operation of the apparatus 10 is accomplished by attaching the hook 46 , which is located on the end of the strap 45 , to a lifting ring 47 , which is located on the center bar 16 . Lifting ring 47 is depicted as an inverted U-shaped member that is fixed to the top side of the center bar 16 . It should be understood that any manner of connecting the strap 45 to the center bar 16 is understood to be contained within this embodiment. The strap 45 may be tied, or use any other connector means commonly known and understand in the art.
[0046] Where the wheel support means 50 are not detachable, the apparatus 10 must be positioned and the small vehicle 81 moved over the lifting frame crossbar 17 until the wheels 80 of the vehicle are placed in between the wheel support prongs 54 . Referring now also to FIG. 3 , once the wheels 80 are in position, apparatus may be actuated so as to raise the vehicle 81 .
[0047] One clear advantage of wheel support means 50 being detachable, is that their relative position to the cross bar 17 can vary. This allows for a proper fit to a wide variety of mowers and small vehicle wheel bases, which may vary from vehicle to vehicle. By sliding the shaft 52 along the length of the insert 51 of cross bar 17 , the wheel support means 50 can position the outer side of the spacer 53 against the wheel 80 of the vehicle 81 . Since most small vehicles 81 are relatively light, the vehicle 81 is simply pushed or moved forward so that the wheels 80 are positioned between the prongs 54 . The wheel support means 50 is then adjusted as to width, to ensure the proper fit.
[0048] This apparatus 10 is also useful where the vehicle is difficult to move. Referring back again to FIG. 1 , that wheel supports 50 that are detachable, allow the wheels supports 50 to be independently placed around the wheels 80 of the vehicle 81 . Once the wheel support means 50 are jointly position, with their shafts 52 oriented toward each other, the support frame 15 and lifting frame 17 are slid underneath the front end of the vehicle 81 , until the crossbar 17 is positioned adjacent to the ends of the shafts 52 of each of the wheel support means 50 .
[0049] Shafts 52 are able to be moved into insert 51 , and may be secured using pins 70 . This is a particularly advantageous operation, since small vehicles may not be movable under their own power, and the jack assembly 10 is able to be positioned so it can support the vehicle 81 without the vehicle 81 having to be moved at all.
[0050] The lifting of the vehicle 81 is accomplished as shown in FIG. 3 and 4 . As FIG. 3 shows, the wheel support means are in the proper position, with the prongs 54 making ground contact. Other points of ground contact would likely comprise the front member 20 and wheels 22 . Activation of the winch means 42 , is accomplished by turning the handle 44 which causes the length of the strap 45 to be taken up by the spool 62 . The strap 45 conveys a pulling force through the hook means 46 to the lifting ring 47 which causes the center bar 16 to move upward.
[0051] As the center bar 16 , moves upward the weight of the vehicle 81 will be pressing downward on the wheel support means 50 . Movement of the center bar 16 will be limited to vertical movement, as a result of the restrictions applied by the guide members 31 and 32 and top roller 34 and bottom roller 84 34 . top roller 34 and bottom roller 84 will prevent the lifting frame 60 from tipping forward, as its forward movement will be prevented by the vertical frame bar 14 , or the extension bar 40 if one is used.
[0052] Removal of the apparatus 10 from the vehicle 81 involves a reverse process, where the vehicle 81 is lowered to the ground, the wheel support means 50 are slid out of the crossbar 17 , and able to be removed from the vehicle area. The support frame 15 and lifting frame 60 are then pulled out from underneath the vehicle.
[0053] Referring now also to FIG. 7 , an axle hook means 90 is shown, comprising an outer sleeve 91 which has an inner perimeter opening 93 that corresponds to the outer surface of the cross bar 17 . The axle hook means 90 defines a top surface 94 , with an upwardly projecting prong 92 , with the axle hook means 90 able to slide along the length of the cross bar 17 until it is able to be positioned so as to allow the cross bar 17 to engage the axle of a small vehicle. In this use, the wheel support means 50 may not be desired or used, and in the event that they are detachable, they can be removed during this process.
[0054] From the foregoing statements, summary and description in accordance with the present invention, it is understood that the same are not limited thereto, but are susceptible to various changes and modifications as known to those skilled in the art and we therefore do not wish to be limited to the details shown and described herein, but intend to cover all such changes and modifications which would be encompassed by the scope of the appended claims. | A small vehicle jack, having the ability to lift vehicles having a variety of wheel bases, and axle configurations. A support frame provides stability for a vertical bar, which supports a winch means. The winch means raises a lifting frame using a strap means, and the lifting frame which follows the vertical bar using an improved sleeve means, in which rollers are used on either side of the vertical bar. The jack may have adjustable and detachable wheel support means, in which the wheels of the vehicle are used as the contact points to raise the vehicle. The jack may also be used without wheel support means, but instead use hook means to attach to an axle. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISC APPENDIX
[0003] Not applicable
BACKGROUND OF THE INVENTION
[0004] Vehicle suspension and steering system variations for 4 or 3-wheel vehicle designs have been extensively researched and refined. Although many improvements have been made to date, most modern systems continue to be plagued, to some extent, by problems of bump/brake steer, alignment difficulties, inaccurate turning radius angles, alignment changes during road irregularities, anti-roll limitations, lack of adjustability, excessive driver steering strength requirements (often leading to need for power steering), weight, lack of adjustability of suspension rate, lack of adjustability of anti-roll, high unsprung weight and assembly bulkiness. Some of these drawbacks of conventional systems are described below.
[0005] Most conventional vehicle steering systems (especially automotive) use a design that includes a tie rod attaching to a pivoting arm (through ball joint or other means) to the wheel knuckle and spindle. While the vehicle is driving straight forward, the tie rod is angled 90 degrees from the steering arm pivot and maximal force is transferred from tie rod to steering arm due to this angle. As the vehicle turns (either right or left), the angle between the tie rod and steering arm pivot changes and the efficiency of transfer of force from tie rod to steering arm is diminished due to the change in angles. The end result of this loss in efficiency of transferred forces to the steering arm is an increase in the steering force needed from the driver's steering input (or increased load on the power steering unit).
[0006] The (unequal length) double wishbone (or unequal length A-arm) suspension system is considered by many, especially in the racing field, as the gold standard by which other suspension systems are measured. This type of suspension has favorable aspects including overall strength and its ability to control camber during vertical suspension movements. Drawbacks of this type suspension include bump steer (Ackerman angle and steering direction changes during bumps), brake steer (steering angle changes during braking or undesirable steering turning forces transferred to the driver or power steering unit during braking), caster changes during road bumps (causing wandering of the tire/wheel and steering angle changes), toe-in changes during road bumps (causing inaccurate Ackerman angles, steering wander, loss of traction and tire wear).
[0007] High unsprung weight is another drawback of most conventional suspension systems. Conventional suspensions often incorporate a spring and shock absorber that rest on an A-arm of the suspension, thus contributing to the unsprung weight of the vehicle. Some (usually rear-engine) racing vehicles minimize unsprung weight by using a pushrod or pullrod to transfer forces from vertical suspension movement to a spring and shock absorber mounted on the sprung portion of the vehicle.
[0008] Changing of the springs, and therefore changing of the spring rate, of conventional systems usually requires lifting of the vehicle and wheel removal. This is a cumbersome process which makes fine-tuning or frequent changes of spring rate very inconvenient and time-consuming
[0009] Conventional anti-roll systems often incorporate a torsion (anti-roll) bar that resists the tendency of the vehicle to lean during turns. These anti-roll bars are typically non-adjustable metal bars that pivot on a frame bushing and attach to the A-arms of the suspension. These anti-roll bars contribute to unsprung (and total) suspension weight.
[0010] Rod-in-sleeve (sliding) type suspensions have been designed for aircraft, bicycles, snowmobiles and, to a lesser extent, automobiles and other vehicles. The designs for automotive vehicles have been limited in number and have not been successful thus far. The lack of success of automotive rod-in-sleeve designs is likely multifactorial. Rod-in-sleeve designs may have not adequately overcome enough of the limitations of conventional suspension systems (as discussed above) to justify retooling. Other reasons for the lack of success with rod-in-sleeve designs may be the new problems encountered with some designs including bulkiness, lack of strength, lack of adequate steerability, inadequate lubrication mechanisms, difficulty integrating anti-roll mechanisms and poor durability.
[0011] As discussed above, conventional steering/suspension/anti-roll systems have many limitations which have been a challenge to overcome, even after some attempts at rod-in-sleeve designs.
BRIEF SUMMARY OF THE INVENTION
[0012] This invention is comprised of numerous components which work together to produce a system for steering, suspending, shock absorbing and maintaining anti-roll for a wheeled vehicle. This invention improves on many of the limitations of common suspension designs. Compared to most conventional suspension and steering designs, the proposed suspension system:
[0013] 1. reduces the tendency of the wheel to change its turning angle, caster or camber during a bump (bump steer) by using a rod-in-sleeve design to maintain wheel travel in a linear vertical direction, thus maintaining accurate steering angles during wheel travel.
[0014] 2. allows for more accurate control of steering angles of outside and inside wheels (Ackerman angle) during turns by allowing for use of a cam in the steering system for accurate steering angle titration.
[0015] 3. allows more efficient transmission of driver steering input forces from steering wheel to the steering knuckle by use of a steering cable pulley, thus reducing losses of steering forces often encountered in tie rod/pivoting steering arm type suspension during sharp turns (high pivot angles).
[0016] 4. allows for reduced bulkiness of suspension components near the wheel/tire since the spring/shock absorber/anti-roll assembly can be placed remotely. Force from road bumps is transferred from wheel knuckle to a cable which subsequently transfers force to the remote spring/shock absorber/anti-roll assembly.
[0017] 5. provides for the possibility of easier adjustment of suspension spring rate and anti-roll since it maintains springs, shock absorbers and the anti-roll mechanism in a common location which can be made easily accessible by appropriate vehicle design.
[0018] 6. provides sufficient lubrication to moving parts of the suspension system by using oil to provide lubrication to the rods and sleeves. Seals and scraper blades are used to prevent leakage of oil and keep oscillating shafts free of debris.
[0019] 7. allows for increased interior occupant and cargo space since spring/shock absorber/anti-roll can be mounted in an area that does not limit this interior space.
[0020] 8. eliminates the need for a separate anti-sway device by integrating the suspension and anti-roll into a distinct working unit.
[0021] 9. reduces unsprung weight by mounting the spring/shock absorber/anti-roll assembly to the sprung part of the vehicle.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0022] FIG. 1 is a frontal view of the right front wheel-based suspension assembly with a translucent wheel/tire shown for reference.
[0023] FIG. 2 is a frontal view of the right front wheel-based suspension assembly.
[0024] FIG. 3 is a lateral (viewing from right side of vehicle) view of the right front wheel-based suspension assembly.
[0025] FIG. 4 is a medial view of the right front wheel-based suspension assembly.
[0026] FIG. 5 is top view of the right front wheel-based suspension assembly. Section line for FIG. 10 is shown.
[0027] FIG. 6 is an exploded view of the right front wheel-based suspension assembly.
[0028] FIG. 7 is a close-up (magnified) exploded view of the upper portion of the right front wheel-based suspension assembly. FIGS. 7 , 8 and 9 are non-contiguous drawings with some overlapping of areas.
[0029] FIG. 8 is a close-up (magnified) exploded view of the middle portion of the right front wheel-based suspension assembly.
[0030] FIG. 9 is a close-up (magnified) exploded view of the lower portion of the right front wheel-based suspension assembly.
[0031] FIG. 10 is a front sectional view of the right front wheel-based suspension assembly with steering cables and oil reservoir/tubing removed.
[0032] FIG. 11 is a frontal view of the suspension sleeve.
[0033] FIG. 12 is a posterior view of the sleeve.
[0034] FIG. 13 is a perspective view of the sleeve.
[0035] FIG. 14 is a top view of the steering pulley.
[0036] FIG. 15 is a frontal view of the steering pulley.
[0037] FIG. 16 and FIG. 17 are perspective views of the steering pulley.
[0038] FIG. 18 is a view of the cable connection between the steering shaft pulley and the wheel-based steering pulley.
[0039] FIG. 19 is a frontal view of the right rear wheel-based suspension system. Section line for drawing in FIG. 21 is shown.
[0040] FIG. 20 is a perspective view of the right rear wheel-based suspension system.
[0041] FIG. 21 is a lateral view (viewing from right side of vehicle) of a cutaway section of the right rear wheel-based suspension system.
[0042] FIG. 22 is an exploded view of the right rear wheel-based suspension system.
[0043] FIG. 23 is a frontal view of the spring/shock absorber/anti-roll assembly.
[0044] FIG. 24 is an exploded view of the spring/shock absorber/anti-roll assembly.
[0045] FIG. 25 is a close-up (magnified) exploded view of the upper portion of the spring/shock absorber/anti-roll assembly. FIG. 25 and FIG. 26 are non-contiguous views with some overlap of areas.
[0046] FIG. 26 is a close-up (magnified) exploded view of the lower portion of the spring/shock absorber/anti-roll assembly.
[0047] FIG. 27 is a bottom view of the spring/shock absorber/anti-roll assembly.
[0048] FIG. 28 is a view of the cable connection between the right wheel-based suspension and the spring/shock absorber/anti-roll assembly.
[0049] FIG. 29 is a perspective view of the right front wheel-based suspension system mounted on the frame of the vehicle.
[0050] FIG. 30 is a perspective view of the right rear wheel-based suspension system mounted on the frame of the vehicle.
[0051] FIG. 31 is a perspective view showing examples of possible mounting locations of the suspension and spring assemblies.
[0052] FIG. 32 is a perspective view of the right front wheel-based suspension system which incorporates small wheels mounted on the steering pulley to apply pressure to the knuckle spindle support (instead of using a secondary bore of the steering pulley to apply forces to a secondary rod of the knuckle).
[0053] FIG. 33 is a perspective view of the right front wheel-based suspension system which incorporates a steering-rod type linkage to the steering pulley instead of a cable system.
[0054] FIG. 34 is a perspective view of the steering pulley with the optional rod-type steering linkage instead of a cable type linkage.
[0055] FIG. 35 is a perspective view of the right front wheel-based suspension system under no-load situation (uncompressed). Note the sleeve situated on the upper end of the main rod in this scenario.
[0056] FIG. 36 is a medial view of the right front wheel-based suspension system under full-load situation (during road bump, compressed). Note the sleeve situated on the lower end of the main rod in this scenario.
[0057] FIG. 37 is a perspective view of the right front wheel-based suspension system during a sharp left turn (32 degrees). The subframe is shown but the vehicle frame is not shown in this picture.
[0058] FIG. 38 is a medial view of the right front wheel-based suspension system during sharp left turn (32 degrees). Turn movement is limited to 32 degrees in this configuration due to large (12 inch) rim width and large positive rim offset whereby medial rim surface comes in close proximity to steering cable route. Smaller rim width or smaller rim offset will allow larger degrees of turning angle.
[0059] FIG. 39 is a perspective view of a cam that has been placed on the steering wheel column shaft to maintain proper toe-in on turns.
[0060] FIG. 40 shows a right front wheel-based suspension system that is designed to incorporate a lubricating block of PTFE or nylon on the anterior and posterior vertical surfaces of the spindle support frame of the knuckle (as opposed to using a secondary rod and steering pulley bore).
[0061] FIG. 41 shows a steering pulley designed to incorporate a contact surface for a lubricating block of PTFE or nylon that glides on the vertical surface of the spindle support frame of the knuckle.
DETAILED DESCRIPTION OF THE INVENTION
Description of Components Involved in Suspension Travel
[0062] The wheel attaches to hub 132 . During road bumps, the upward tire force is transferred to the main rod of the knuckle 111 via the wheel spindle 133 and spindle frame of the knuckle 129 . This upward force causes the knuckle assembly to move in an upward, linear direction. The knuckle assembly components move up and down in concert. The knuckle assembly components consist of the spindle support frame 129 , the upper knuckle frame 102 , the main rod 111 , the lower end cap 123 and the secondary rod 128 . The knuckle assembly moves up or down relative to the subframe 116 (and vehicle frame) while sliding in the sleeve 109 . As the knuckle assembly moves upward, the upper part of the suspension cable 106 moves upward and increases cable tension. The suspension cable contains a stop 105 at its top end. Upward movements of the knuckle assembly are transmitted to washer 151 , inner bearing race of bearing 150 , to outer bearing race of bearing 150 , to bearing cap 104 , to bearing cap pin 171 and then to the suspension cable 106 . The rotating bearing cap 104 does not rotate in relation to the subframe but rotates in relation to the steering knuckle on its bearing 150 . The pin 171 of the rotating bearing cap 104 continuously points toward the vehicle thus maintaining alignment of the cable 106 with its associated cable pulley 113 . The rotating bearing cap allows the cable 106 to travel in an up/down motion only (no rotation in relation to subframe). The suspension cable 106 connects to the bearing cap 104 on one end and to a pulley ( 310 or 305 ) of the spring/shock absorber/anti-roll assembly on the other.
[0063] Components involved in steering motion of the wheel-based steerable suspension system (front wheels):
[0064] The steering pulley 119 pivots on a bearing 155 . The bearing 155 is held in place between the steering pulley 119 and sleeve 109 by upper and lower clips. Upper inner clip 152 rests in sleeve groove 191 , contacts spacer 153 which then contacts the upper inner bearing race of the bearing 155 . Lower inner clip 157 rests in sleeve groove 192 , contacts spacer 160 which then contacts the lower inner bearing race of bearing 155 . Upper outer clip rests in the upper inner groove of the steering pulley 119 and contacts the outer bearing race of bearing 155 . Lower outer clip rests in the lower inner groove of the steering pulley 119 and contacts the lower edge of the outer bearing race of bearing 155 . The pivoting motion of the steering pulley allows for pivoting of the knuckle.
[0065] Driver steering wheel motion can be converted to steering cable motion by a variety of mechanisms. A proposed mechanism is a pulley placed on the steering wheel shaft. For accurate toe-in and toe-out on turns, a cam may be placed on the steering wheel shaft (or between steering wheel shaft and wheel-based suspension components) so that the inside wheel turns at a greater angle than the outer wheel on turns, thus adjusting for toe-in on turns (Ackerman angle).
[0066] Two cables ( 118 and 140 ) from the driver steering system attach to the steering pulley 119 . Differential input from the two steering cables causes the steering pulley 119 to rotate on the bearing 155 . The secondary bore 179 of the steering pulley 119 is lubricated by oil residing in the oil reservoir 178 which flows through oil hole 183 . The secondary bore 179 of the steering pulley 119 contains grooves towards the upper and lower portions of the inner bore for upper/lower o-rings and upper/lower scraper blades. The o-rings prevent leakage of oil and the scraper blades clean the secondary rod of debris. When differential steering input is applied, the steering pulley rotates and applies horizontal pressure to the secondary shaft of the knuckle 128 and thereby causes rotation of the knuckle about the axis (main rod 111 ). The secondary bore 179 of the steering pulley 119 acts as a sleeve for the secondary rod 128 and allows the secondary rod 128 to move up/down inside the steering pulley 119 during road bumps while also transferring turning (horizontal) forces to the secondary rod 128 . The secondary rod makes up part of the steering knuckle assembly and rotation of the secondary rod 128 causes the steering knuckle assembly and thus the wheel/tire to rotate (turn).
[0067] For camber adjustment, shims can be used between contact surfaces of upper and lower subframe and the vehicle frame. Ideally, a small amount of negative camber should be maintained for maximum tire contact patch area during turns (to compensate for mild vehicle sway). The vehicle sway can be minimized with anti-roll adjustments as described below in the paragraph regarding the spring/shock absorber/anti-roll components. When shims are placed between subframe and frame and used to place negative camber, a few degrees of steering axis inclination are introduced and this scenario can improve steering feel.
[0068] Caster can be adjusted by mounting the subframe slightly clockwise or counterclockwise (based on a lateral observer viewpoint) on the frame. The use of cables and steering pulley reduces the loss of turning force that would be have otherwise introduced by a more conventional tie rod/pivot/steering arm type steering during sharp turns. Since the steering pulley 119 remains fixed vertically and performs only pivoting movements in the horizontal plane, there are no changes in steering angle, caster, camber or steering axis inclination during suspension travel.
[0069] Description of Components Involved in Braking:
[0070] The brake caliper 101 for the right front suspension is mounted to upper part of the knuckle 102 using a caliper bracket 135 . The brake caliper applies pressure to the brake disc 131 . The rear suspension proposed is designed for use with an inboard type brake assembly (not shown), thereby reducing unsprung weight.
[0071] Description of Components Involved in Anti-Roll and Bump Absorption/Damping:
[0072] Right and left wheel-based suspension cables ( 309 and 306 ) attach to their respective pulleys ( 310 and 305 ). Tension and movement from these cables ( 309 and 306 ) cause the pulleys ( 310 and 305 ) to rotate on their respective bearings ( 313 and 328 ). Two (2) shorter cables ( 325 and 324 ) attach to the pulleys ( 310 and 305 ) on one end and to the spring compression plates ( 301 and 302 ) on the other. As the tension from cables ( 309 and 306 ) cause the pulleys ( 310 and 305 ) to rotate, the shock absorbers ( 311 and 304 ) are compressed and the smaller cables ( 325 and 324 ) pull the spring compression plates ( 301 and 302 ) downward. As the spring compression plates ( 301 and 302 ) press downward, the springs ( 312 and 303 ) compress and apply pressure on the guided spring base plate 314 which in turn applies pressure on the third spring 307 . The third spring 307 rests on center spring support plate 308 . The base plate guiding rod 317 slides in its sleeve 315 with grease lubricating the outer rod and inner sleeve surface. The posterior surface of the guided spring base plate 314 is lubricated with grease or PTFE strip and glides on the mounting plate 318 . The base plate 314 is restricted to a linear up/down motion by the guiding rod 317 and mounting plate 318 . For example, if the right wheel rises in response to a road bump, the wheel-based suspension cables (for example, right cable 309 ) will pull on the upper end of the right spring 312 and cause compression of the third spring 307 due to the linear motion of the guided spring base plate 314 . In the example, the left spring 302 will move downward to some extent, following the guided spring base plate 314 which it rests upon. This lowering of the left spring (following the downward movement of the guided spring base plate 314 will cause (through reduction of tension of its associated suspension cable) the left wheel to rise, following the rise of the right wheel and thus produce an anti-roll effect. The u-bracket 316 holds the sleeve 315 in place (fixed in relation to mounting plate 318 ). Upper ends of the shocks ( 311 and 304 ) are mounted on spacer blocks ( 329 and 323 ). Lower ends of the shocks are mounted to pulleys ( 310 and 305 ) and are compressed as the pulleys rotate, producing a damping effect to the wheel during road bumps. Bolts 330 attach the sleeve 315 to the u-bracket 316 .
PARTS LIST FOR DRAWINGS
[0000]
101 . Brake caliper, front, right
102 . Knuckle, upper portion, right wheel
103 . Bolt, rotating cable attachment site assembly
104 . Bearing cap, rotating cable attachment site assembly
105 . Cable stop
106 . Cable, vertical suspension movement transfer
107 . Oil tube
108 . Oil reservoir
109 . Sleeve for rod of steering knuckle, right
110 . Scraper seal, upper, for knuckle sleeve, right front wheel
111 . Main Rod of right knuckle
112 . Bolt, subframe to sleeve, right front wheel, upper-anterior
113 . Pulley, for redirection of cable during transfer of vertical suspension movement
114 . Bolt—subframe to pulley, right front wheel, front upper
115 . Washer—subframe to pulley, right front wheel, front
116 . Subframe assembly, right front wheel
117 . Cable, vertical suspension movement transfer
118 . Cable, steering, right front wheel, front cable
119 . Pulley, steering, right front wheel
120 . Washer, subframe to sleeve, right front wheel, front
121 . Bolt, subframe to sleeve, right front wheel, front
122 . Scraper seal lower, for knuckle sleeve, right front wheel
123 . Knuckle, lower end cap
124 . Bolt, lower end cap to main rod of knuckle, medial
125 . Bolt, lower end cap to main rod of knuckle, lateral
126 . Bolt, lower end cap to secondary rod of knuckle
127 . Bolt, lower end cap to spindle support of knuckle
128 . Secondary rod of knuckle, right front wheel
129 . Knuckle, spindle support portion
130 . Bolt, cable to steering pulley, front
131 . Brake disc, right front wheel
132 . Hub, right front wheel
133 . Spacer, spindle bearing
134 . Wheel spindle
135 . Brake caliper bracket
136 . Bolt, brake caliper bracket, upper, right front wheel
137 . Washer, subframe to sleeve, right front wheel, front upper
138 . Washer, subframe to sleeve, right front wheel, rear upper
139 . Bolt, subframe to sleeve, right front wheel, rear upper
140 . Cable, steering, right front wheel, rear cable
141 . Nut—subframe to pulley, right front wheel, rear
142 . Washer, subframe to pulley, right front wheel, rear
143 . Spacer, rear, subframe to pulley bearing
144 . Spacer, front, subframe to pulley bearing
145 . Oil reservoir cap, steering pulley reservoir
146 . Bolt, caliper bracket, posterior
147 . Bolt, caliper bracket, lower
148 . Bolt, caliper bracket, anterior
149 . Washer, upper, rotating cable attachment site assembly
150 . Bearing, rotating cable attachment site assembly
151 . Washer, lower, rotating cable attachment site assembly
152 . Retaining clip, inner, to upper sleeve groove, mates with upper bearing spacer
153 . Spacer, mates to retaining clip on upper side, mates to inner bearing race on lower side
154 . Retaining clip, outer, mates to upper surface of outer bearing race, rests in upper steering pulley groove
155 . Bearing, allows for steering pulley pivoting movement
156 . Retaining clip, outer, mates to lower surface of outer bearing race, rests in lower steering pulley groove.
157 . Retaining clip, inner, mates to lower surface of lower bearing spacer, rests in lower outer sleeve groove
158 . O-ring seal, upper, rests in inner upper o-ring sleeve groove
159 . O-ring seal, lower, rests in inner lower o-ring sleeve groove
160 . Spacer, mates to retaining clip on lower side, mates to inner bearing race on upper side
161 . Scraper seal, lower, rests in secondary (smaller) steering pulley bore
162 . O-ring, lower, rests in lower o-ring groove of secondary (smaller) steering pulley bore
163 . Bearing, posterior, rests inside of pulley bore
164 . Bearing, anterior, rests inside of pulley bore
165 . O-ring seal, upper, rests in upper o-ring groove of secondary (smaller) steering pulley bore
166 . Scraper seal, upper, rests in secondary (smaller) steering pulley bore
167 . Wheel bearing, outer
168 . Wheel bearing, inner
169 . Washer, subframe to sleeve, rear, lower
170 . Bolt, lower knuckle end cap, connects lower knuckle end cap to main rod, medial
171 . Pin, bearing cap, rotating cable attachment site assembly.
172 . Bolt, subframe to sleeve, rear lower
174 . Bolt, rear steering cable
175 . Bolt, lower knuckle end cap, connects lower knuckle end cap to main knuckle rod, lateral
176 . Bolt, lower knuckle end cap, connects lower knuckle end cap to secondary knuckle rod
177 . Bolt, lower knuckle end cap, posterior, connects lower knuckle end cap to knuckle spindle support
178 . Oil reservoir for steering pulley
179 . Secondary (smaller) bore of steering pulley
180 . Primary bore (larger) of steering pulley
181 . Threaded hole for front steering cable attachment
182 . Groove for front steering cable
183 . Oil hole for secondary bore
184 . Groove for upper scraper blade, secondary bore, steering pulley
185 . Groove for upper o-ring, secondary bore, steering pulley
187 . Threaded hole for rear steering cable attachment
188 . Groove for rear steering cable
189 . Threaded hole, lower front, for bolt that attaches subframe to sleeve
190 . Threaded hole, upper front, for bolt that attaches subframe to sleeve
191 . Retaining clip groove, upper
192 . Retaining clip groove, lower
193 . Threaded hole, lower rear, for bolt that attaches subframe to sleeve
194 . Oil hole, feeds oil from external reservoir to inner sleeve housing surface
195 . Threaded hole, upper rear, for bolt that attaches subframe to sleeve
196 . Upper scraper blade groove, sleeve
197 . Upper o-ring groove, sleeve
301 . Spring compression plate assembly, right
302 . Spring compression plate assembly, left
303 . Upper spring, left
304 . Shock, left
305 . Pulley, left
306 . Cable—attaches pulley to left rotating cable attachment site bearing cap
307 . Spring, lower center (largest)
308 . Support plate for center spring
309 . Cable—attaches pulley to right rotating cable attachment site bearing cap
310 . Pulley, right
311 . Shock absorber, right
312 . Upper spring, right
313 . Bearing for right pulley
314 . Guided spring base plate
315 . Sleeve for base plate guiding rod
316 . U-bracket for sleeve
317 . Base plate guiding rod
318 . Mounting plate
319 . Washer for bearing bolt of spring assembly
320 . Bolt for bearing of spring assembly, left
321 . Bolt for lower shock absorber, left
322 . Bolts for center spring support plate (4 total)
323 . Spacer block, left, for upper end of shock absorber of spring assembly
324 . Cable—Attaches to left spring compression plate
325 . Cable—Attaches to right spring compression plate.
327 . Bolts—for attachment of U-bracket to mounting plate
328 . Bearing for left pulley
329 . Spacer block, right, for upper end of shock absorber of spring assembly
330 . Bolts—for attachment of spring guiding rod sleeve to u-bracket, right side
331 . Bolt, for lower shock absorber, right
332 . Bolts—for attachment of spring guiding rod sleeve to u-bracket, left side
401 . Rod, anterior, right rear suspension assembly
402 . Wheel studs, right rear wheel
403 . Wheel spindle
404 . Sleeve, anterior
405 . Scraper blade, lower, anterior sleeve
406 . Bolt, mounts pulley to underside of suspension
407 . Cable, attaches to underside of hub on one end and spring assembly on other
408 . Pulley, for cable
409 . Bottom plate
410 . Universal joint
411 . Oil tube, anterior
412 . Oil reservoir, anterior
413 . Bolt, anterior, mounts upper plate to anterior rod
414 . Bolt, posterior, mounts upper plate to posterior rod
415 . Upper plate
416 . Scraper blade, upper, anterior sleeve
417 . Spindle washer
418 . Spindle nut
419 . Oil reservoir, posterior
420 . Oil tube, posterior
421 . Scraper blade, upper, posterior sleeve
422 . Sleeve, posterior
423 . Bearing, medial
424 . Rod, posterior
425 . Hub
426 . O-ring, upper, posterior sleeve
427 . O-ring, upper, anterior sleeve
428 . Bearing, outer
429 . Bolt, cable bracket, anterior
430 . Bolt, cable bracket, posterior
431 . Washer, anterior, for pulley bolt
432 . Bearing, pulley, anterior
433 . Washer, middle, used as spacer between bearings
434 . Bearing, pulley, posterior
435 . Washer, pulley, posterior
436 . Nut, for pulley bolt
437 . Scraper blade, lower, posterior sleeve
438 . O-ring, lower, posterior sleeve
439 . O-ring, lower, anterior sleeve
440 . Cable attachment plate
501 . Small wheals mounted on bearings which contact anterior and posterior vertical surfaces of knuckle spindle support.
502 . Vertical surface of spindle support frame where a PTFE or nylon lubricating strip can be applied.
503 . Vertical surface of steering pulley where a PTFE or nylon lubricating strip can be applied. | A vehicle suspension, steering, damping and anti-roll system for a wheeled vehicle. Unlike most previous vehicle suspension and steering systems, this invention uses a rod-in-sleeve design for the front and rear suspension assemblies to allow vertical linear wheel knuckle movement of the wheels. This invention is unusual by using a cable-operated steering system and also by using cables to transfer cable tension from upward wheel movement to remote spring/shock absorber assemblies. Also unique is the use of a spring/shock absorber assembly arrangement that provides both suspension and anti-roll effects for a pair of right and left wheels in the same unit. The rear suspension proposed shares some similarities to the front suspension and consists of a dual rod-in-sleeve design with cables that transfer forces from road bumps to a remote spring assembly. | 1 |
Subsets and Splits
No community queries yet
The top public SQL queries from the community will appear here once available.