# Patent

## Title
Devices and methods for the delivery of molecular sieve materials for the formation of blood clots

## Abstract

An apparatus for promoting the clotting of blood and controlling bleeding comprises a receptacle for retaining molecular sieve material in particulate form therein. A pad for controlling bleeding comprises a mesh structure and a rigid or semi-rigid support attached to the mesh structure to facilitate the application of pressure to the pad and the wound. A bandage applicable to a bleeding wound comprises a mesh structure and a flexible substrate attached to the mesh structure, the substrate being a cloth or plastic member that may be adhesively attached to cover a wound. In any embodiment, at least a portion of the receptacle or mesh structure is defined by a mesh having openings therein, and at least a portion of the particulate molecular sieve material is in direct contact with blood.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. patent application Ser. No. 12/555,876, entitled “Devices and methods for the delivery of molecular sieve materials for the formation of blood clots,” filed Sep. 9, 2009, which is continuation of U.S. patent application Ser. No. 11/054,918, entitled “Devices and methods for the delivery of molecular sieve materials for the formation of blood clots,” filed Feb. 9, 2005. The contents of all the above-referenced applications are incorporated herein by reference in their entireties.


BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to blood clotting devices and, more particularly, to blood clotting materials, devices incorporating such materials, and methods for the delivery of such materials for use as bleeding control devices.
2. Description of the Related Art
Blood is a liquid tissue that includes red cells, white cells, corpuscles, and platelets dispersed in a liquid phase. The liquid phase is plasma, which includes acids, lipids, solublized electrolytes, and proteins. The proteins are suspended in the liquid phase and can be separated out of the liquid phase by any of a variety of methods such as filtration, centrifugation, electrophoresis, and immunochemical techniques. One particular protein suspended in the liquid phase is fibrinogen. When bleeding occurs, the fibrinogen reacts with water and thrombin (an enzyme) to form fibrin, which is insoluble in blood and polymerizes to form clots.
In a wide variety of circumstances, animals, including humans, can be wounded. Often bleeding is associated with such wounds. In some circumstances, the wound and the bleeding are minor, and normal blood clotting functions in addition to the application of simple first aid are all that is required. Unfortunately, however, in other circumstances substantial bleeding can occur. These situations usually require specialized equipment and materials as well as personnel trained to administer appropriate aid. If such aid is not readily available, excessive blood loss can occur. When bleeding is severe, sometimes the immediate availability of equipment and trained personnel is still insufficient to stanch the flow of blood in a timely manner.
Moreover, severe wounds can often be inflicted in remote areas or in situations, such as on a battlefield, where adequate medical assistance is not immediately available. In these instances, it is important to stop bleeding, even in less severe wounds, long enough to allow the injured person or animal to receive medical attention.
In an effort to address the above-described problems, materials have been developed for controlling excessive bleeding in situations where conventional aid is unavailable or less than optimally effective. Although these materials have been shown to be somewhat successful, they are sometimes not effective enough for traumatic wounds and tend to be expensive. Furthermore, these materials are sometimes ineffective in some situations and can be difficult to apply as well as remove from a wound.
Additionally, or alternatively, the previously developed materials can produce undesirable side effects. For example, prior art blood clotting material is generally a powder or a fine particulate in which the surface area of the material often produces an exothermic reaction upon the application of the material to blood. Oftentimes excess material is unnecessarily poured onto a wound, which can exacerbate the exothermic effects. Depending upon the specific attributes of the material, the resulting exothermia may be sufficient to cause discomfort to or even burn the patient. Although some prior art patents specifically recite the resulting exothermia as being a desirable feature that can provide clotting effects to the wound that are similar to cauterization, there exists the possibility that the tissue at and around the wound site may be undesirably impacted.
Furthermore, to remove such materials from wounds, irrigation of the wound is often required. If an amount of material is administered that causes discomfort or burning, the wound may require immediate flushing. In instances where a wounded person or animal has not yet been transported to a facility capable of providing the needed irrigation, undesirable effects or over-treatment of the wound may result.
Bleeding can also be a problem during surgical procedures. Apart from suturing or stapling an incision or internally bleeding area, bleeding is often controlled using a sponge or other material used to exert pressure against the bleed site and/or absorb the blood. However, when the bleeding becomes excessive, these measures may not be sufficient to stop the flow of blood. Moreover, any highly exothermic bleed-control material may damage the tissue surrounding the bleed site and may not be configured for easy removal after use.
Based on the foregoing, it is a general object of the present invention to provide devices for controlling bleeding and methods of their use that overcome or improve upon the prior art.
SUMMARY OF THE INVENTION
According to one aspect, the present invention resides in an apparatus for promoting the clotting of blood, thereby controlling bleeding. The apparatus comprises a receptacle for retaining molecular sieve material in particulate form therein. At least a portion of the receptacle is defined by a mesh having openings therein such that when the apparatus is applied to a bleed site, the particulate molecular sieve material comes into contact with blood through the openings.
Other aspects of the present invention include a pad for controlling bleeding and a bandage applicable to a bleeding wound. In both the pad and the bandage, there is a mesh structure and particles of molecular sieve material retained therein. In the pad embodiment, there is a rigid or semi-rigid support attached to the mesh structure to facilitate the application of pressure to the pad and the wound. In the bandage, there is a flexible substrate attached to the mesh structure, the substrate being a cloth or plastic member that may be adhesively attached to cover a wound. In any embodiment, the mesh structure may be defined by a plurality of members (strands, filaments, or strips of synthetic or natural material) interconnected and arranged to define openings. The openings are sized to allow contact to be maintained between the particles of the molecular sieve material and blood.
In yet another aspect of the present invention, a method of dressing a bleeding wound includes providing a molecular sieve material in particle form and retaining the material in a mesh structure, placing the mesh structure on a bleeding wound such that the molecular sieve material comes into contact with blood flowing from the wound, applying pressure to the mesh structure to ensure contact of the material with the blood, and removing the mesh structure from the wound.
An advantage of the present invention is that upon completion of the application of any of the devices of the present invention to a bleeding wound, the devices can be easily removed. In particular, because the zeolite material is in granule, bead, or pellet form and encased in a pouch or mesh structure, the material can be cleanly pulled away from the treated wound and disposed of. Accordingly, little or no irrigation of the wound is required to flush away remaining zeolite. In devices in which the pouch containing zeolite material is incorporated into an adhesive bandage, the device can be left on the wound for the amount of time necessary to cause clotting.
Another advantage is that the particlized form of the zeolite material allows the material to react less exothermically with blood. As the particle size increases (e.g., from fine to coarse), the surface area of the particles that the blood can come into contact with decreases. The porous nature of the material still allows liquid blood constituents to be wicked away to cause thickening of the blood, thereby facilitating the formation of clots. Because the particle surface area exposed to the blood is reduced, a less aggressive drawing of moisture from the blood is realized, which thereby tempers the exothermic effects experienced at the wound site.
Still another advantage of the present invention is that the proper dose of molecular sieve material can be readily applied to an open wound. Particularly when the device is a porous pouch containing zeolite material, the device can be readily removed from sterilized packaging and held directly at the points from which blood emanates to facilitate clotting of the blood without spilling powder or pellets outside the wound area. Guesswork, estimation, or calculation of the amounts of molecular sieve material for application to a bleeding wound is eliminated. Accordingly, little or no molecular sieve material is wasted.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a blood clotting device of the present invention.
FIG. 2 is a side view of the blood clotting device of FIG. 1 illustrating the retaining of molecular sieve particles in a mesh container.
FIG. 3 is a side view of a pressure pad incorporating the molecular sieve particles encapsulated in a mesh container for pressure application to a bleeding wound.
FIG. 4 is a perspective view of a bandage incorporating the molecular sieve particles in a mesh container for application to a bleeding wound.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Disclosed herein are devices and methods for delivering materials to wounds to promote the clotting of blood and the dressing of the wounds. The devices generally comprise expedients or apparatuses that can be applied to bleeding wounds such that the materials contact the tissue of the wound to minimize or stop a flow of blood by absorbing at least portions of the liquid phases of the blood, thereby promoting clotting. One apparatus comprises a receptacle for retaining molecular sieve material in particulate form therein. At least a portion of the receptacle is defined by a mesh having openings therein, and at least a portion of the particulate molecular sieve material is in direct contact with blood through the openings.
The molecular sieve material used in the present invention may be a synthetic polymer gel, cellulosic material, porous silica gel, porous glass, alumina, hydroxyapatite, calcium silicate, zirconia, zeolite, or the like. Exemplary synthetic polymers include, but are not limited to, stylene-divinylbenzene copolymer, cross-linked polyvinyl alcohol, cross-linked polyacrylate, cross-linked vinyl ether-maleic anhydride copolymer, cross-linked stylene-maleic anhydride copolymer or cross-linked polyamide, and combinations thereof.
The molecular sieve material is preferably a zeolite. Other molecular sieve materials that may be used include, but are not limited to, faujasite. As used herein, the term “zeolite” refers to a crystalline form of aluminosilicate having the ability to be dehydrated without experiencing significant changes in the crystalline structure. The zeolite may include one or more ionic species such as, for example, calcium and sodium moieties. Typically, the zeolite is a friable material that is about 90% by weight calcium and about 10% by weight sodium. The calcium portion contains crystals that are about 5 angstroms in size, and the sodium portion contains crystals that are about 4 angstroms in size. The preferred molecular structure of the zeolite is an “A-type” crystal, namely, one having a cubic crystalline structure that defines round or substantially round openings.
The zeolite may be mixed with or otherwise used in conjunction with other materials having the ability to be dehydrated without significant changes in crystalline structure. Such materials include, but are not limited to, magnesium sulfate, sodium metaphosphate, calcium chloride, dextrin, a polysaccharide, combinations of the foregoing materials, and hydrates of the foregoing materials.
Zeolites for use in the disclosed applications may be naturally occurring or synthetically produced. Numerous varieties of naturally occurring zeolites are found as deposits in sedimentary environments as well as in other places. Naturally occurring zeolites that may be applicable to the compositions described herein include, but are not limited to, analcite, chabazite, heulandite, natrolite, stilbite, and thomosonite. Synthetically produced zeolites that may also find use in the compositions and methods described herein are generally produced by processes in which rare earth oxides are substituted by silicates, alumina, or alumina in combination with alkali or alkaline earth metal oxides.
Various materials may be mixed with, associated with, or incorporated into the zeolites to maintain an antiseptic environment at the wound site or to provide functions that are supplemental to the clotting functions of the zeolites. Exemplary materials that can be used include, but are not limited to, pharmaceutically-active compositions such as antibiotics, antifungal agents, antimicrobial agents, anti-inflammatory agents, analgesics (e.g., cimetidine, chloropheniramine maleate, diphenhydramine hydrochloride, and promethazine hydrochloride), bacteriostatics, compounds containing silver ions, and the like. Other materials that can be incorporated to provide additional hemostatic functions include ascorbic acid, tranexamic acid, rutin, and thrombin. Botanical agents having desirable effects on the wound site may also be added.
In one embodiment of the present invention, a device for facilitating the clotting of blood directly at a wound site is shown with reference to FIG. 1. The device is a permeable pouch that allows liquid to enter to contact blood clotting zeolite (or other molecular sieve) material retained therein. Sealed packaging (not shown) provides a sterile environment for storing the device until it can be used. The device, which is shown generally at 10 and is hereinafter referred to as “pouch 10,” comprises a screen or mesh 12 and zeolite particles 14 retained therein by the screen or mesh. The mesh 12 is closed on all sides and defines openings that are capable of retaining the zeolite particles 14 therein while allowing liquid to flow through. As illustrated, the mesh 12 is shown as being flattened out, and only a few zeolite particles 14 are shown.
The zeolite particles 14 are substantially spherical or irregular in shape (e.g., balls, beads, pellets, or the like) and about 0.2 millimeters (mm) to about 10 mm in diameter, preferably about 1 mm to about 7 mm in diameter, and more preferably about 2 mm to about 5 mm in diameter. In any embodiment (balls, beads, pellets, etc.), less particle surface area is available to be contacted by blood as the particle size is increased. Therefore, the rate of clotting can be controlled by varying the particle size. Furthermore, the adsorption of moisture (which also has an effect on the exothermic effects of the zeolite) can also be controlled.
The mesh 12 is defined by interconnected strands, filaments, or strips of material. The strands, filaments, or strips can be interconnected in any one or a combination of manners including, but not limited to, being woven into a gauze, intertwined, integrally-formed, and the like. Preferably, the interconnection is such that the mesh can flex while substantially maintaining the dimensions of the openings defined thereby. The material from which the strands, filaments or strips are fabricated may be a polymer (e.g., nylon, polyethylene, polypropylene, polyester, or the like), metal, fiberglass, or an organic substance (e.g., cotton, wool, silk, or the like).
Referring now to FIG. 2, the openings defined by the mesh 12 are dimensioned to retain the zeolite particles 14 but to accommodate the flow of blood therethrough. Because the mesh 12 may be pulled tight around the zeolite particles 14, the particles may extend through the openings by a distance d. If the zeolite particles 14 extend through the openings, the particles are able to directly contact tissue to which the pouch 10 is applied. Thus, blood emanating from the tissue immediately contacts the zeolite particles 14, and the water phase thereof is wicked into the zeolite material, thereby facilitating the clotting of the blood. However, it is not a requirement of the present invention that the zeolite particles protrude through the mesh.
To apply the pouch 10 to a bleeding wound, the pouch is removed from the packaging and placed on the bleeding wound. The zeolite particles 14 in the mesh 12 contact the tissue of the wound and/or the blood, and at least a portion of the liquid phase of the blood is adsorbed by the zeolite material, thereby promoting the clotting of the blood.
Another embodiment of the present invention is a pad which is shown at 20 with reference to FIG. 3 and is hereinafter referred to as “pad 20.” The pad 20 comprises the mesh 12, zeolite (or other molecular sieve) particles 14 retained therein by the mesh 12, and a support 22 to which pressure may be applied in the application of the pad 20 to a bleeding wound. The mesh 12, as above, has openings that are capable of retaining the zeolite particles 14 therein while allowing the flow of blood therethrough.
The mesh 12 is stitched, glued, clamped, or otherwise mounted to the support 22. The support 22 comprises an undersurface 24 against which the zeolite particles 14 are held by the container 12 and a top surface 26. The undersurface 24 is impermeable to the zeolite particles 14 (migration of the particles into the support 22 is prevented) and is further resistant to the absorption of water or other fluids. The top surface 26 is capable of having a pressure exerted thereon by a person applying the pad 20 to a bleeding wound or by a weight supported on the top surface 26. The entire support 22 is rigid or semi-rigid so as to allow the application of pressure while minimizing discomfort to the patient.
To apply the pad 20 to a bleeding wound, the pad 20 is removed from its packaging and placed on the bleeding wound. As with the pouch of the embodiment of FIGS. 1 and 2, the zeolite particles 14 are either in direct contact with the tissue of the wound or are in direct contact with the blood. Pressure may be applied to the wound by pressing on the top surface 26 with a hand or by placing a weight on the surface, thereby facilitating the contact between the zeolite particles 14 and the wound and promoting the adsorption of the liquid phase of the blood. The pad 20 (with or without a weight) may also be held onto the wound using a strapping device such as a belt, an elastic device, hook-and-loop material, combinations of the foregoing devices and materials, and the like.
Referring now to FIG. 4, another embodiment of the present invention is a bandage, shown at 50, which comprises zeolite particles 14 (or some other molecular sieve material) retained in a mesh 12 and mounted to a flexible substrate 52 that can be applied to a wound (for example, using a pressure-sensitive adhesive to adhere the bandage 50 to the skin of a wearer). The mesh 12 is stitched, glued, or otherwise mounted to a substrate 52 to form the bandage 50.
The substrate 52 is a plastic or a cloth member that is conducive to being retained on the skin of an injured person or animal on or proximate a bleeding wound. An adhesive 54 is disposed on a surface of the substrate 52 that engages the skin of the injured person or animal. Particularly if the substrate 52 is a non-breathable plastic material, the substrate may include holes 56 to allow for the dissipation of moisture evaporating from the skin surface.
In the preparation of zeolite material for the devices of the present invention (i.e., formation of the material into particle form), an initial level of hydration of the zeolite may be controlled by the application of heat to the zeolite material either before or after the material is formed into particles. However, it has also surprisingly been found that as the particle size of the zeolite is increased, the moisture content has less of a correlative effect on any exothermia produced as the result of mixing the particlized zeolite in blood. As such, formation of the zeolite material into the zeolite particles (shown at 14 in FIGS. 1-4), may be by extrusion, milling, casting, or the like.
Although this invention has been shown and described with respect to the detailed embodiments thereof, it will be understood by those of skill in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed in the above detailed description, but that the invention will include all embodiments falling within the scope of the appended claims.

## Claims

1. A device for promoting the clotting of blood comprising:
a pouch that is closed on all sides; and
a molecular sieve in particle form which is retained in the pouch;
wherein the pouch is composed of a mesh comprising a plurality of openings;
wherein the molecular sieve particles are configured to produce a diminished exothermic reaction upon contact with blood; and
wherein the molecular sieve particles are:
sufficiently large to be retained by the mesh; and
sufficiently small so that at least a portion of the particles can protrude through at least a portion of the openings of the mesh to make direct contact with blood outside of the pouch.

2. The device of claim 1, wherein configuring the molecular sieve particles to produce a diminished exothermic reaction comprises controlling the initial level of hydration of the molecular sieve particles.

3. The device of claim 1, wherein configuring the molecular sieve particles to produce a diminished exothermic reaction comprises controlling the particle size of the molecular sieve particles.

4. The device of claim 1, wherein the molecular sieve comprises a zeolite.

5. The device of claim 4, wherein the molecular sieve comprises an A-type zeolite.

6. The device of claim 1, wherein the mesh comprises at least one of polyester, cotton, wool, or silk.

7. The device of claim 1, wherein the particles have a diameter from about 2 mm to about 5 mm.

8. The device of claim 1, further comprising at least one of the following materials or agents mixed with, associated with or incorporated into the molecular sieve: a pharmaceutically-active composition, an analgesic, an antibiotic, or an anti-inflammatory agent.

9. The device of claim 1, further comprising sterile packaging within which the pouch is stored until the pouch is used.

10. The device of claim 1, further comprising magnesium sulfate, sodium metaphosphate, calcium chloride, dextrin, a polysaccharide, silver ions or a compound containing silver ions, combinations of the foregoing materials, or hydrates of the foregoing materials.

11. The device of claim 1, wherein the mesh is woven.

12. A method of accelerating the clotting of blood in a bleeding wound comprising:
providing an apparatus comprising:
providing a pouch that is closed on all sides;
providing a molecular sieve in particle form which is retained in the pouch; and
wherein the pouch is composed of a mesh comprising a plurality of openings;
wherein the molecular sieve particles are configured to produce a diminished exothermic reaction upon contact with blood; and
wherein the molecular sieve particles are:
sufficiently large to be retained by the mesh; and
sufficiently small so that at least a portion of the particles can protrude through at least a portion of the openings of the mesh to make direct contact with blood outside of the pouch;


applying the apparatus to the bleeding wound; and
maintaining the apparatus at the bleeding wound at least until blood from the wound begins to clot.

13. The method of claim 12, wherein configuring the molecular sieve particles to produce a diminished exothermic reaction comprises controlling the initial level of hydration of the molecular sieve particles.

14. The method of claim 12, wherein configuring the molecular sieve particles to produce a diminished exothermic reaction comprises controlling the particle size of the molecular sieve particles.

15. The method of claim 12, further comprising applying pressure to the apparatus while the apparatus is applied to the bleeding wound.

16. The method of claim 12, wherein the molecular sieve comprises an A-type zeolite.

17. The method of claim 12, wherein the mesh comprises at least one of polyester, cotton, wool, or silk.

18. The method of claim 16, further comprising at least one of the following materials or agents mixed with, associated with or incorporated into the molecular sieve: a pharmaceutically-active composition, an analgesic, an antibiotic, or an anti-inflammatory agent.

19. A method of manufacturing a hemostatic device, the method comprising:
providing a pouch that is closed on all sides; and
providing a molecular sieve in particle form which is retained in the pouch;
wherein the pouch is composed of a mesh comprising a plurality of openings;
wherein the molecular sieve particles are configured to produce a diminished exothermic reaction upon contact with blood ; and
wherein the molecular sieve particles are:
sufficiently large to be retained by the mesh; and
sufficiently small so that at least a portion of the particles can protrude through at least a portion of the openings of the mesh to make direct contact with blood outside of the pouch.

20. The method of claim 19, wherein configuring the molecular sieve particles to produce a diminished exothermic reaction comprises controlling the initial level of hydration of the molecular sieve particles.

21. The method of claim 19, wherein configuring the molecular sieve particles to produce a diminished exothermic reaction comprises controlling the particle size of the molecular sieve particles.