WO2003015837A1 - Porous vascular graft prostheses with luminal sealing layer - Google Patents
Porous vascular graft prostheses with luminal sealing layer Download PDFInfo
- Publication number
- WO2003015837A1 WO2003015837A1 PCT/US2002/027113 US0227113W WO03015837A1 WO 2003015837 A1 WO2003015837 A1 WO 2003015837A1 US 0227113 W US0227113 W US 0227113W WO 03015837 A1 WO03015837 A1 WO 03015837A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wall
- graft
- tissue
- vascular graft
- ingrowth
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/34—Macromolecular materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
- A61L27/44—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
- A61L27/48—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix with macromolecular fillers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/0077—Special surfaces of prostheses, e.g. for improving ingrowth
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/04—Hollow or tubular parts of organs, e.g. bladders, tracheae, bronchi or bile ducts
- A61F2/06—Blood vessels
Definitions
- This invention relates to improved structures for vascular graft prostheses.
- a range of vascular grafts are utilized within the medical arts fields, but often such grafts do not permit sufficient healing due to many reasons.
- small diameter conventional vascular grafts do not permit sufficient tissue ingrowth or transmural endothelialization that would allow for proper healing and satisfactory long-term outcomes.
- Larger bore grafts often are too stiff and do not have proper ingrowth of surrounding tissue.
- This invention is designed to provide solutions to these serious and long misunderstood problems.
- a vascular graft prosthesis has a polymeric tubular structure.
- the structure has a porous wall with interstices arranged to permit transmural ingrowth of tissue substantially through the full thickness of the wall.
- a thin film or layer of sealant material is on a portion of the wall forming a lumenal wall surface which promotes rather than inhibits transmural tissue growth.
- Figure 1 is a sectional schematic view of a segment of a hybrid graft model illustrating fibrin buildup.
- Figure 2 is a sectional schematic view of a segment of an ePTFE graft model illustrating fibrin buildup.
- Figure 3 is a sectional schematic view of a segment of a polyurethane graft model illustrating fibrin buildup.
- Figure 4 is a sectional schematic view of a segment of a polyethylene terephthalate (e.g. Dacron) graft model illustrating fibrin buildup.
- a polyethylene terephthalate e.g. Dacron
- Figure 5 is a sectional schematic view of a test segment of a graft model.
- Figure 6 is a sectional schematic view of a segment of a hybrid graft model illustrating the lack of fibrin buildup due to a first embodiment lumenal sealant.
- Figure 7 is a sectional schematic view of a segment of an ePTFE graft model illustrating a first embodiment lumenal sealant.
- Figure 8 is a sectional schematic view of a segment of a polyurethane graft model illustrating a first embodiment lumenal sealant.
- Figure 9 is a sectional schematic view of a segment of a polyethylene terephthalate (e.g. Dacron) graft model illustrating a first embodiment lumenal sealant.
- a polyethylene terephthalate e.g. Dacron
- Figure 10 is an exemplary unit cell of a porous foam-type material of a graft structure.
- Figure 11 is a sectional schematic view of a segment of a graft model illustrating a second embodiment lumenal sealant.
- Figure 12 is a sectional schematic view of a segment of a graft model illustrating a third embodiment lumenal sealant.
- Figure 13 is a sectional schematic view of a segment of a graft model illustrating a third embodiment lumenal sealant.
- a 30 ⁇ m expanded polytetrafluoroethylene (ePTFE) graft has been shown to not support full transmural healing due to the fact that the capillaries (10-15 ⁇ m in diameter), the smallest vessels required to sustain tissue in the graft wall, simply are not able to grow in to the full extent of the wall. This is due to the tight packing of intemodular fibrils.
- the internodular distance may be 30 ⁇ m, the actual ingrowth dimensions are much lower (probably in the range of 5-10 ⁇ m).
- the lack of defined channels (interconnections between "pores") of sufficient porosity results in the "tapering down" of ingrowth spaces as one progresses into the wall.
- the first factor is the physical structure of the graft wall material. Typically, there is inadequate spacing for capillaries to grow transmurally into the graft beyond only one outer portion.
- the second factor is the filling of the inner lumenal portion of the graft wall by either blood products or artificial sealant materials. In either case, the clogging of the inner portion of the wall structure creates a growth- prohibitive environment that prevents desired healing.
- a pure capillary ingrowth with the goal of surface endothelialization (with a space requirement of greater than about lO ⁇ in continuity) is one type.
- a second type is arteriole ingrowth with a goal of surface endothelialization plus arterialization of the prosthetic vessel wall (with a space requirement of about 23 ⁇ in continuity).
- the population of the pores by smooth muscle cells and other desirable cell and extracellular matrix tissues is required for long-term healing and other performance characteristics, such as flexibility and compliance.
- This invention discloses short- and long-term strategies to overcome this healing problem, for both large and small diameter grafts.
- One short-term strategy includes use of a permanent sealant or film on a very high porosity graft material, such as highly porous expanded polytetrafluoroethylene (ePTFE).
- One long-term solution includes use of a temporary sealant on porous polyurethane grafts with angiopermissive porosity. It is recognized that other combinations of short-term and long-term solutions are contemplated and possible within this invention. Overall, however, the lack of healing in commercial grafts can be ascribed to the insufficient size of the ingrowth spaces.
- sealants have been used in vascular prostheses, and possibly without appreciating the adverse effects these sealants have on the healing process. These include, for example, hemostatic impregnation of the graft wall with collagen, fibrin or gelatin in order to prevent excessive blood flow through the wall during implantation, and coating of the surfaces of grafts with elastomers or growth inhibitors, etc., for reasons other than to improve transmural healing and in manners adverse to healing.
- high porosity polyurethane grafts as well as ePTFE grafts with very high internodular distances (100-150 ⁇ m), and high porosity Polyethylene terephthalate (e.g. Dacron) or similar grafts, may all allow for the improved ingrowth of tissue and cells, the level of healing that is desired throughout the graft wall is not observed. This has been shown to be due to the chronic deposition of impenetrable blood products, such as fibrin, onto/into the lumenal surface portion, thereby limiting ingrowth and healing to only the ablumenal or outer portions of the graft wall.
- impenetrable blood products such as fibrin
- achievement of spontaneous healing of ePTFE, polyurethane, or other vascular prostheses by providing very high, angiopermissive porosities (for example, ⁇ 150 ⁇ m IND/pore size) and a permanent or degradable lumenal film to limit or control fibrin deposition and compaction is one goal.
- angiopermissive porosities for example, ⁇ 150 ⁇ m IND/pore size
- a permanent or degradable lumenal film to limit or control fibrin deposition and compaction
- graft model 12 comprises any of a plurality of materials, including for example, ePTFE 15, polyurethane 19, or Polyethylene terephthalate (e.g. Dacron) 22. As shown, these materials form a lumenal wall 28 (which is shown having multiple different material constructions for illustration only) having an ablumenal outer portion 33, outer surface 36, lumenal inner portion 40 and lumenal surface 44.
- model graft 120 uses isolating segments 133 of low porosity (30 ⁇ m) ePTFE around a high porosity material such as, for example, high porosity ePTFE, Polyethylene terephthalate (e.g.
- a sealant or film material 149 is placed between isolating and test segments to prevent tissue ingrowth between the two graft segments.
- This test demonstrated that the film material prevented or facilitated the prevention of unwanted growth via any anastomotic approach (arrows T or transmural approach (T 2 ), while promoting the desired transmural ingrowth through the test segment as shown by arrows G.
- This test also demonstrated the inability of tissue to grow transmurally through a low porosity material (T 2 ).
- FIGS. 6-9 illustrate sections of a schematic model graft 75 formed of any of the graft materials noted above, and further described below.
- model graft 75 (which is shown having multiple different material constructions for illustration only) illustrates two different types of graft wall material, ePTFE 81 and polyurethane 84- although other materials are possible if the configuration of the material allows for transmural tissue ingrowth.
- a thin film of permanent or degradable sealant material 88 is placed on a lumenal portion 90, which may include the lumenal surface 94, of the graft wall 96. This placement of film material 88 must functionally prevent the buildup of blood products, e.g. fibrin, without clogging the pores or other interstitial growth spaces within the graft wall structure.
- FIGS 7, 8, and 9 show graft walls 96 made of either high porosity ePTFE 81 (Figure 7), high porosity polyurethane 84 (Figure 8), or Polyethylene terephthalate (e.g. Dacron) 99 ( Figure 9).
- a preferred ePTFE material includes pore sizes having an internodular distance (IND) of greater than about 60 ⁇ m and more preferably about 60 to about 200 ⁇ m.
- a preferred porous foam-type of material includes a polyurethane material having spheroid interconnected pores formed as unit cells resembling dodecahedra, although various shapes may provide the desired characteristics.
- Figure 10 shows a representation of one embodiment of a 50-250 ⁇ m diameter pore 100 having 20-150 ⁇ m diameter interconnecting windows 105, as shown by diameter line 108.
- a preferred Polyethylene terephthalate (e.g. Dacron), or other material, should be constructed (i.e. knitted, felt, or other technique) so that the porosity between fibers permits transmural growth substantially through to an inner lumenal portion.
- the wall thickness of grafts made according to this invention may be about 0.2-2 mm, with a preferred range of about 0.3- 0.7 mm, and an overall graft diameter of between about 2-25 mm.
- the thickness of a solid sealant or film material may be in the range of 10-200 ⁇ m, with a preferred range of thickness of about 20-50 ⁇ m. Examples of suitable graft materials and constructions are shown in co-pending and commonly owned patent applications: U.S. Serial No. 09/434,649; International Patent Applications PCT US97/27629 and WO 01/05333, each of which is incorporated by reference for such teaching.
- the film material should span each pore of the surface of the graft wall lumenal portion, or at a selected depth-rather than filling each pore it contacts.
- the film should function as if it were a thin piece of paper laying atop a sponge to prevent material penetration into the sponge pores below the paper.
- the film of sealant material acts as a spanning film rather than a filling sealant, so as to separate the blood from the tissue with as little thickness as possible or desired.
- Figure 11 shows another embodiment of improved graft prostheses 121 combining angio-permissive graft wall material 125 with a preferred film 129 at a lumenal portion of the wall structure, as described herein.
- Another material referred to herein as an additional porous layer 134, provides either a porous structure or a surface having increased roughness as compared to film material 129.
- Layer 134 is designed to improve graft patency by creating a more anti-thrombogenic effect within the lumen 142.
- Tissue ingrowth lines 150 illustrate the depth to which transmural ingrowth occurs when this combination of ingrowth-permissive wall material and a preferred film is utilized.
- Figure 12 shows a graft prosthesis 161 formed substantially similar to that of Figure 11, except that wall structure 125 has a film material 129 that is covered or substantially coated with a thin anti-thrombotic surface 167, rather than a thicker porous structure as shown by structure 134 in Figure 11.
- the sealant or film material may be a permanent, semi-permanent or intentionally degradable material.
- a permanent film or a film having a degree of permanence which extends over considerable time in order to permit rapid and continuous muscle-like tissue ingrowth transmurally through the graft.
- a permanent film might best facilitate such rapid transmural tissue ingrowth.
- graft prosthesis 183 comprises a graft wall material 186 which is an ingrowth-permissive material, such as those mentioned herein, and which has a film 190 which defines regions 194 of degradation over time which allow for the degradation of these areas to form communications between the ablumenal and lumenal surfaces and thereby promote full transmural ingrowth by tissue.
- regions 194 are shown in a representative fashion only for illustration of this concept, and may comprise various patterns or area configurations. Such regions 194 may also prevent the sloughing off of large pieces of degradable material as it naturally degrades over the desired time.
- preferred degradation times will vary according to the recipient of the graft prosthesis and the type of material within the graft.
- the material which forms the film of Applicants is preferably a polymeric film which is deposited in as thin a structure as possible, but strong enough to withstand the rigors of the biological system within which the graft is placed.
- the film is designed to obstruct rather than clog the pores of the lumenal portion of the graft, and by not necessarily penetrating the pores the film permits rapid and effective transmural ingrowth of tissue to promote healing throughout the width of the graft wall.
- the graft wall is made of ingrowth-prohibitive material or the lumenal portion of the graft wall is sealed off or clogged by either a sealant material (unlike that preferably described herein as a film) or by blood products such as compacted fibrin or the like, then the graft prosthesis will fail to demonstrate the advantageous results and characteristics as described by Applicants.
- a graft wall material which is ingrowth-permissive so that a complete transgression from the outer wall into the lumen of the graft is permitted for capillaries, and the type of film described herein is provided at a lumenal portion, to facilitate and encourage rapid ingrowth of the capillaries and tissue transmurally, then the combination will result in improved outcomes and higher acceptance of the graft by the recipient or host body.
- the permanent or semi-permanent sealants or films of this invention include medical grade polyurethanes, such as for example those known by the names Pellethane, M48, Elast-Eon, Bionate, or other medical grade polyurethanes marketed under various trade names.
- the method of application of the material includes application of the polymer solution to a lumenal portion or surface and then solidification of the polymer by evaporation and/or precipitation. Anti-thrombogenicity may be enhanced by the covalent immobilization of heparin onto the lumenal surface after placement of the material.
- a 150 ⁇ m polyurethane and 150 ⁇ m internodular diameter ePTFE with plus or minus ⁇ 50 ⁇ m polyurethane lumenal film skin was provided.
- Acrylic acid/acrylamide hydrogel and ethylene diamine (EDA) bridge and a periodate oxidized heparin was provided as well.
- EDA ethylene diamine
- the ingrowing vessels occupied the full extent of the graft wall thickness (up to the ablumenal side of the lumenal film) of grafts provided with a lumenal film.
- Medical grade polysiloxanes for example that known as PDMS (trade name NuSil) or other branded medical grade polysiloxanes are also useful as a film.
- Application of the monomer or prepolymer to the lumenal portion or surface is accomplished. Then, solidification of the polymer by reaction with an initiator occurs.
- Silicone films are permeable to oxidation and carbon dioxide and may be used (when compared to essentially oxygen-impermeable materials e.g. polyurethanes) to determine the effect of hypoxia on the healing of sub-sealant regions. Hypoxia is one of the possible mechanisms which are involved with the advancements of this invention.
- degradable films or sealants discussed herein include degradable polyurethanes, polyethylene oxide-polylactic acid copolymers and degradable hydrogels. Although most polyurethanes are designed to be biostable, i.e. to resist chemical degradation in vivo, there are instances for this application where biodegradability may be desired.
- One class of such materials include the polyesters (polyglycolic acid, polylactic acid, polycaprolactone, polyhydroxybuterate, polyortoesters, etc.), polyanhydrides (poly (sebasic acid-hexadecanoic acid anhydride)), and polyiminocarbonates.
- degradable materials include synthetic hydrogels, which may be simply non-degradable hydrogel monomers incorporating degradable sites in their chains and/or using degradable crosslinkers.
- synthetic hydrogels such as polyethyleneglycol, etc.
- hydrolytically or enzymatically cleavable compounds in such a way that cleavage of the crosslinker results in the degradation of the crosslinked polymer.
- biodegradable polymers includes the biologically derived hydrogels such as polyamino acids and polysaccharides.
- Synthetic hydrogels include a number of other water soluble polymers which may be used to form hydrogel films by a wide range of crosslinking reactions. These materials include polyethyleneglycol (PEG), polyvinyl alcohol
- Crosslinking may be effected by: inclusion of a di or multi-vinyl compounds during polymerization and reaction of di-or multifunctional compounds with side groups of preformed linear polymers.
- Another class of degradable polymers are of biologic origin. When they occur in their hydrated insoluble state, these materials may also be classified as hydrogels.
- Both carbohydrates hyaluronic acid, cellulose, alginates
- proteins collagen, gelatin
- ePTFE polyurethane
- Polyethylene terephthalate e.g. Dacron
- other vascular prostheses by providing very high angiopermissive porosities ( ⁇ 150 ⁇ m IND/pore size) and permanent or degradable lumenal portion films to better control the deposition and compaction of blood products.
- the film would initially inhibit, prevent, or control the deposition of impenetrable fibrin or other products in the pores of the wall structure, thereby allowing uninterrupted tissue ingrowth from the ablumenal surface. Any degradable film material would be dissolved or otherwise eliminated through biologic action, while allowing the population and proper healing of the lumenal surface by transmural tissue ingrowth.
- this novel and non-obvious lumenal sealant or film having possible degradation features designed therein, provides a temporary shield against plasma insituization as well as a temporary modality to create controlled hypoxia during the healing process, thus permitting proper penetration of desired tissues in the desired manner, and obviating creation of undesirable barriers to such healing.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60211176T DE60211176T2 (en) | 2001-08-17 | 2002-08-18 | Film with highly porous vascular graft prostheses |
EP02763527A EP1418955B1 (en) | 2001-08-17 | 2002-08-18 | Porous vascular graft prostheses with luminal sealing layer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US31307501P | 2001-08-17 | 2001-08-17 | |
US60/313,075 | 2001-08-17 |
Publications (1)
Publication Number | Publication Date |
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WO2003015837A1 true WO2003015837A1 (en) | 2003-02-27 |
Family
ID=23214271
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2002/027113 WO2003015837A1 (en) | 2001-08-17 | 2002-08-18 | Porous vascular graft prostheses with luminal sealing layer |
Country Status (5)
Country | Link |
---|---|
US (1) | US7022135B2 (en) |
EP (1) | EP1418955B1 (en) |
DE (1) | DE60211176T2 (en) |
WO (1) | WO2003015837A1 (en) |
ZA (1) | ZA200401013B (en) |
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US8906087B2 (en) | 2004-11-29 | 2014-12-09 | W. L. Gore & Associates, Inc. | Method of making implantable devices with reduced needle puncture site leakage |
US9814560B2 (en) | 2013-12-05 | 2017-11-14 | W. L. Gore & Associates, Inc. | Tapered implantable device and methods for making such devices |
US9867727B2 (en) | 1998-02-09 | 2018-01-16 | Trivascular, Inc. | Endovascular graft |
CN109009561A (en) * | 2018-08-13 | 2018-12-18 | 哈尔滨工业大学(威海) | A kind of artificial blood vessel and preparation method thereof |
WO2019086874A1 (en) * | 2017-10-31 | 2019-05-09 | Hothouse Medical Limited | Textile products having a sealant or coating and method of manufacture |
US10357385B2 (en) | 2015-06-05 | 2019-07-23 | W. L. Gore & Associates, Inc. | Low bleed implantable prosthesis with a taper |
KR20210067658A (en) * | 2019-11-29 | 2021-06-08 | 서울대학교병원 | Composition for filing internal prosthesis comprising metal-organic framework and gel |
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US11577003B2 (en) | 2017-10-31 | 2023-02-14 | Hothouse Medical Limited | Textile products having selectively applied sealant or coating with visual indicator and method of detecting the same |
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US20050119762A1 (en) * | 2003-11-03 | 2005-06-02 | Peter Zilla | Hydrogel providing cell-specific ingrowth |
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Also Published As
Publication number | Publication date |
---|---|
ZA200401013B (en) | 2004-10-18 |
EP1418955A1 (en) | 2004-05-19 |
EP1418955B1 (en) | 2006-05-03 |
DE60211176T2 (en) | 2006-09-14 |
DE60211176D1 (en) | 2006-06-08 |
US7022135B2 (en) | 2006-04-04 |
US20030045927A1 (en) | 2003-03-06 |
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