WO1995026762A1 - Intravascular polymeric stent - Google Patents

Intravascular polymeric stent Download PDF

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Publication number
WO1995026762A1
WO1995026762A1 PCT/NL1995/000122 NL9500122W WO9526762A1 WO 1995026762 A1 WO1995026762 A1 WO 1995026762A1 NL 9500122 W NL9500122 W NL 9500122W WO 9526762 A1 WO9526762 A1 WO 9526762A1
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WO
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Application
Patent type
Prior art keywords
manufactured
stent
polymer
cross
linked
Prior art date
Application number
PCT/NL1995/000122
Other languages
French (fr)
Inventor
Peter Bruin
Theo Albert Cornelus Flipsen
Atze Jan Nijenhuis
Albert Johan Pennings
Original Assignee
Rijksuniversiteit Te Groningen
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • C08G18/3278Hydroxyamines containing at least three hydroxy groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/04Macromolecular materials
    • A61L31/06Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS 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
    • A61F2/00Filters 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
    • A61F2/82Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents

Abstract

The invention relates to an intravascular polymeric stent manufactured from an amorphous, biocompatible polymer.

Description

Title: Intravascular polymeric stent

The invention relates to an intravascular polymeric stent, more particularly to a stent which is manufactured from a biocompatible, non-thrombogenic material. Stents are (spiral) bodies suitable for maintaining the patency of veins in the human body, more particularly veins which have undergone a so-called Dotter treatment.

In the 1960s Charles Dotter introduced a technique for treating obstruction of coronary arteries (stenosis), which is generally the result of atherosclerosis. This treatment is presently known as the so-called Dotter therapy, a promising and widely accepted alternative to bypass surgery. Important disadvantages of this technique are acute collapse, chronic complete occlusion and restenosis of the affected vessels.

In order to obviate these problems, an intravascular stent can be plac in the treated segment of the vessels in order to maintain patency. The first stents were described in 1969 and consisted of a tubular stainless steel coil spring. Thereafter a large number of other designs, substantially consisting of metal, were developed. The metal stents currently in use can be divided into two types, based on the manner of placement, viz. self- expanding or balloon-expanding.

These metal stents have been particularly successful in preventing restenosis, but it is to be expected that complications can occur in the long term. Metal stents are far from ideal, since metals are relatively thrombogenic and non- degradable. Moreover, metal stents may perforate the walls of the blood vessel.

An ideal stent, on the other hand, would be compatible in the biological system, i.e. compatible with blood, non- thrombogenic, not inducing any rejection reactions, and biodegradable, while any decomposition products would not be toxic.

The literature describes degradable intravascular stents which are manufactured from poly(L-lactide) . Poly(L- lactide) is a hydrolytically labile semi-crystalline aliphatic polyester which is used in a large number of biomedical applications since the degradation product thereof, L-lactic acid, possesses a very minor toxicity. Recent developments, however, have shown that implantation of semi-crystalline poly(L-lactide) may eventually lead to a late tissue reaction because of the presence of small highly crystalline low- molecular poly(L-lactide) particles which are hydrolytically rather stable. These particles can be found at the site of implantation up to 5 years after implantation. The object of the invention is to provide an intravascular stent suitable for use in blood vessels after a Dotter therapy, which does not have the disadvantages of the above-described materials.

According to the invention, such an intravascular stent is manufactured from an amorphous, biocompatible polymer. Surprisingly, it has been found that amorphous biocompatible polymers are highly suitable for the manufacture of stents, without possessing the disadvantages of, for instance, the semi-crystalline pol (L-lactide) . A next advantage of such a polymeric stent resides in the fact that the material, after the cure of the blood vessel, which takes about three weeks, is absorbed by the body, since the material has no further function anymore.

The stent can be implanted in the blood vessel by a catheter as an elongated spiral of slight diameter. The stent is then thermally expanded to its original spiral shape. To make this possible, the polymeric material should have a glass transition temperature just below the body temperature. The material of the stents should therefore have a so-called thermal shape memory. A suitable stent can be manufactured by the in situ polymerization of suitable starting materials in a spiral-shaped matrix, for instance manufactured from PTFE. After polymerization, the spiral obtained can be stretched to any desired shape above the glass transition temperature of the material. This shape can be frozen after cooling to a temperature below the glass transition temperature. This makes it possible to introduce the stent into the blood vessel via a catheter. After the stent has been introduced into the blood vessel, it can expand freely to the original spiral shape at body temperature. The closer to the body temperature the Tg of the polymeric material is, the faster the material wil l resume its original shape again. The expanding spiral then anchors itself in the blood vessel by exerting pressure on the wall of the blood vessel. It is therefore preferred to use a material which has a Tg between 0°C and 37°C.

In such situations, creep resistance is a particularly important property because it should be possible for the elongated spiral to expand completely to its original dimensions upon heating. A permanent deformation as a result of the elongation of the coil spring is undesirable. It has been found, however, that the use of polymeric (amorphous) networks as stent material gives an article of sufficient creep resistance. In practice this means that the creep of the material at body temperature is nil.

According to the invention, a large number of plastics are suitable for th> manufacture of the polymeric stent. The common feature of these polymers is that they are amorphous, cross-linked biologically active polymers, which are preferably also biodegradable. Examples of suitable groups of polymers are the amorphous non-crystallizable polylactic acid networks, the highly cross-linked polyurethane networks, which also includes the conversion products of star prepolyesters, for instance based on lactic acid copolymers, with diisocyanate. The extent of cross-linking should be such that the maximum gel content is obtained. Preferably, no unreacted low-molecular components are present. These polymers moreover have in common that they are sterilizable in the conventional manner with steam and that they meet the biocompatibility requirements given in the introduction (compatible with blood, non-thrombogenic, not causing any rejection reactions, biodegradable, while any decomposition products are non-toxic) .

The first group of polymers, amorphous non- crystallizable polylactic acid networks, comprises inter alia the amorphous copolymers of lactides and glycolides, which have been converted to a network with suitable cross-linking agents. In view of the nature of the materials, cross-linking for the purpose of forming a network is preferably effected with a tetra- or higher functional cyclic ester, preferably with a tetrafunctional cyclic cross-linking agent such as biscaprolactone.

The second group of polymers, highly cross-linked polyurethane networks, is described inter alia in International patent application PCT/NL93/00203 filed 13 October 1993.

This group of polymers consists of cross-linked polyurethane networks obtainable by reacting one or more low- molecular polyols with a functionality of three or more and one or more polyisocyanates with a functionality of two or more in the absence of a solvent.

For obtaining suitable materials it is of importance that the polyols are low-molecular. In practice this means that the equivalent weight of the polyol is preferably 125 at a maximum. 'Equivalent weight' in this case is understood to mean the molecular weight per hydroxyl group. In general, the starting material is 3 or 4 functional polyols, although higher functionalities can be used as well. Practically, an upper limit lies at a functionality of 8. It is also possible, however, to include a minor amount of diols in the mixture.

However, since diols do not give rise to cross-linking, either the amount thereof should be kept low or one should work with substantially 3 or higher functional isocyanates . In general, the number of hydroxyl groups coming from a diol will be less than about 10% of the total number of hydroxyl groups. Preferred polyols are selected from the group consisting of triethanolamine (TEA), tri-isopropanolamine, 1,1,1, -trimethylol-propane (TMP) , N,N,N' ,N' -tetrakis (2- hydroxypropy1) -ethylenediamine (Quadrol) , octakis(2- hydroxypropyl) penta-erytrytyltetra-amine, tetrakis{β- hydroxyethyl}methane, 1,1,1 trihydroxyethylpropane, 1,1,1 trihydroxyethylethane and other polyols. It is also possible to use modified or unmodified pentaerytritol or inositol.

The polyisocyanates which can be used according to this embodiment of the invention are the conventional diisocyanates and higher isocyanates, for instance selected from the group consisting of butanediisocyanate, hexamethylene diisocyanate, dodecane diisocyanate, trans 1,4-cyclohexane diisocyanate, methylene dicyclohexane diisocyanate, lysine di- or triisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, methylene diphenyl diisocyanate, triphenyl- methanetriisocyanate, thiophosphoric acid tris(4-isocyanati- phenyl ester), polymeric methylene diphenyl diisocyanate as well as trimerization products and adducts of these isocyanates, for instance based on polyols. Examples of suitable polyols have been given hereinabove.

The third product group comprises the conversion products of star prepolyesters and a di-isocyanate, preferably a di-isocyanate based on an L-lysine derivative or on 1,4-diisocyanatobutane. A number of these products are described inter alia in International patent application PCT/NL 88/00060, incorporated herei* y reference.

According to this variant oi the invention, as diisocyanate, preferably a lysine derivative is used having one of the formulae 1-3 of the sheet of formulae, or 1,4-diisocyanatobutane. These isocyanates are reacted with suitable polyols, such as polyester polyols based on lactide, glycolide, and/or lactones such as ε-caprolactone or δ-valerolactone. Such a polyester can be initiated with a suitable low-molecular polyol, such as glycol, pentaerytritol, myo-inositol and the like.

In the case where it is desirable that the material of the polymeric stent is broker down in the body, it is preferred to manufacture the polymer from polymers whose decomposition products are not toxic. Although the three groups of polymers described hereinabove are highly suitable as such, it may be desirable, in order to obtain the desirable strength properties, that a second phase be incorporated into the material, for instance by the introduction of one or more fillers, fibers and/or a second polymeric phase. In particular by incorporating a second polymeric phase, in the form of a separate rubber phase, materials are obtained which possess a particularly good combination of mechanical properties.

The invention will now be elucidated in and by a few examples which should not be construed as limiting.

Example 1

Cross-linked poly(lactide-ε-caprolactone;80/20 mole ratio) was manufactured by in situ polymerization in a spiral- shaped PTFE mold. The monomer mixture, the cross-linking agent (5, 5 ' -bis(oxepan-2-one) ) and the catalyst, tin octoate

(monomer-catalyst ratio 1000 based on weight) were introduced into a silanized glass ampoule and melted and homogenized at 130°C. Then the mold, also disposed in the ampoule, was filled with the molten mixture by allowing it to fill up under the influence of gravity. The polymerization was carried out at

130°C for 90 hours. Upon completion of the polymerization the stent obtained could easily be removed from the mold.

Example 2

A stent was manufactured from a highly cross-linked polyurethane network, using a PTFE mold. The starting materials, triethanolamine, tetrakis(2-hydroxypropyl) - ethylenediamine and hexamethylenediisocyanate, were purified by distillation at reduced pressure. The components were then mixed and degassed a number of times. With a syringe the mixture was introduced into the mold and gelled at room temperature. Then curing was allowed to take place for 24 hours at about 100°C, whereafter the stent was removed from the mold. Re s ults

The mechanical properties of a number of stents manufactured according to Examples 1 and 2 are included in the following table and figures.

Table 1 mechanical properties of polyester and polyurethane networks at different temperatures

T Tensile Young's elongation toughness Tg strength modulus at break

°C MPa MPa % MPa °C

1 40 21 21 450 25 32

2 40 17 57 96 7 23

3 24 60* 1200 26 14 70

4 80 10 21 50 2 70

5 80 10 21 50 2 73

1: poly(lactide-co-ε-caprolactone) , 80/20 mole %, cross- linked with 5,5' -bis(oxepan-2-one)

2: TEA/Quadrol(40: 60)/HDI PU network after water uptake

3,4: TEA/Quadrol(40:60)/HDI PU network

5: TEA/Quadrol(20:80)/HDI PU network *: Yield stress:71 MPa

Claims

C IMS
1. A polymeric stent manufactured from an amorphous, biocompatible and cross-linked polymer.
2. A stent according to claim 1, manufactured from a polymer having a shape memory at body temperature.
3. A stent according to claim 1 or 2, manufactured from a polymer selected from the group consisting of amorphous, non-crystallizable polylactic acid networks, highly cross- linked polyurethane networks and conversion products of star prepolyesters and di-isocyanate.
4. A stent according to claim 2, manufactured from polylactide copolyester cross-linked with a di-functional cyclic ester.
5. A stent according to claim 4, manufactured from a pol (lactide-ε-caprolactone) cross-linked with biscaprolactone.
6. A stent according to claim 3, manufactured from a polyurethane network obtained by polymerizing a suitable polyol, preferably a triol or a tetra-ol and a suitable polyisocyanate, preferably a diisocyanate, in the absence of solvents.
7. A stent according to claims 1-6, manufactured from a polyphase polymer.
8. A stent according to claim 7, manufactured from a polymer comprising one or more fillers, fibers and/or a second, preferably amorphous, polymeric phase.
9. A biomedical aid manufactured from an amorphous, biocompatible and cross-linked polymer having a shape memory at body temperature.
10. A method for manufacturing a stent or a biomedical aid according to claims 1-9, comprising polymerizing the starting materials for the polymer in a spiral-shaped mold, followed by removing the obtained article from the mold.
11. A method according to claim 10, wherein the mold is manufactured from polytetrafluoroethene.
PCT/NL1995/000122 1994-03-31 1995-03-30 Intravascular polymeric stent WO1995026762A1 (en)

Priority Applications (2)

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NL9400519 1994-03-31
NL9400519A NL9400519A (en) 1994-03-31 1994-03-31 Intravascular polymeric stent.

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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011725A1 (en) * 1995-09-27 1997-04-03 Biocon Oy Under tissue conditions degradable material and a method for its manufacturing
US5962007A (en) * 1997-12-19 1999-10-05 Indigo Medical, Inc. Use of a multi-component coil medical construct
US6001117A (en) * 1998-03-19 1999-12-14 Indigo Medical, Inc. Bellows medical construct and apparatus and method for using same
US6206883B1 (en) 1999-03-05 2001-03-27 Stryker Technologies Corporation Bioabsorbable materials and medical devices made therefrom
WO2002041929A1 (en) * 2000-11-21 2002-05-30 Schering Ag Tubular vascular implants (stents) and methods for producing the same
US6747121B2 (en) 2001-09-05 2004-06-08 Synthes (Usa) Poly(L-lactide-co-glycolide) copolymers, methods for making and using same, and devices containing same
US7087078B2 (en) 2000-11-21 2006-08-08 Schering Ag Tubular vascular implants (stents) and methods for producing the same
US7091297B2 (en) 2002-10-11 2006-08-15 The University Of Connecticut Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments
WO2006098757A3 (en) * 2004-08-16 2006-11-16 Jane P Bearinger Shape memory polymers
US7173096B2 (en) 2002-10-11 2007-02-06 University Of Connecticut Crosslinked polycyclooctene
US7208550B2 (en) 2002-10-11 2007-04-24 The University Of Connecticut Blends of amorphous and semicrystalline polymers having shape memory properties
US7524914B2 (en) 2002-10-11 2009-04-28 The University Of Connecticut Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments
US8048980B2 (en) 2007-09-17 2011-11-01 Bezwada Biomedical, Llc Hydrolysable linkers and cross-linkers for absorbable polymers
WO2012109535A2 (en) 2011-02-11 2012-08-16 Bezwada Biomedical, Llc Amino acid derivatives and absorbable polymers therefrom
US8367747B2 (en) 2008-05-23 2013-02-05 Bezwada Biomedical, Llc Bioabsorbable polymers from bioabsorbable polyisocyanates and uses thereof
US8449903B2 (en) 2009-06-08 2013-05-28 Boston Scientific Scimed, Inc. Crosslinked bioabsorbable medical devices
US9034356B2 (en) 2006-01-19 2015-05-19 Warsaw Orthopedic, Inc. Porous osteoimplant
US9115245B2 (en) 2002-10-11 2015-08-25 Boston Scientific Scimed, Inc. Implantable medical devices
US9173973B2 (en) 2006-07-20 2015-11-03 G. Lawrence Thatcher Bioabsorbable polymeric composition for a medical device
US9211205B2 (en) 2006-10-20 2015-12-15 Orbusneich Medical, Inc. Bioabsorbable medical device with coating
US9328192B2 (en) 2014-03-12 2016-05-03 Bezwada Biomedical, Llc Bio-based monomers and polymers
US9724864B2 (en) 2006-10-20 2017-08-08 Orbusneich Medical, Inc. Bioabsorbable polymeric composition and medical device
US9745402B2 (en) 2004-08-16 2017-08-29 Lawrence Livermore National Security, Llc Shape memory polymers

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EP0326426A2 (en) * 1988-01-28 1989-08-02 JMS Co., Ltd. Plastic molded articles with shape memory property
EP0420541A2 (en) * 1989-09-27 1991-04-03 Bristol-Myers Squibb Company Biodegradable stent
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Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011725A1 (en) * 1995-09-27 1997-04-03 Biocon Oy Under tissue conditions degradable material and a method for its manufacturing
US6503278B1 (en) 1995-09-27 2003-01-07 Bionx Implants Oy Under tissue conditions degradable material and a method for its manufacturing
US5962007A (en) * 1997-12-19 1999-10-05 Indigo Medical, Inc. Use of a multi-component coil medical construct
US6001117A (en) * 1998-03-19 1999-12-14 Indigo Medical, Inc. Bellows medical construct and apparatus and method for using same
US6206883B1 (en) 1999-03-05 2001-03-27 Stryker Technologies Corporation Bioabsorbable materials and medical devices made therefrom
US6716957B2 (en) 1999-03-05 2004-04-06 Stryker Technologies Corporation Bioabsorbable materials and medical devices made therefrom
WO2002041929A1 (en) * 2000-11-21 2002-05-30 Schering Ag Tubular vascular implants (stents) and methods for producing the same
US7087078B2 (en) 2000-11-21 2006-08-08 Schering Ag Tubular vascular implants (stents) and methods for producing the same
US6747121B2 (en) 2001-09-05 2004-06-08 Synthes (Usa) Poly(L-lactide-co-glycolide) copolymers, methods for making and using same, and devices containing same
US7091297B2 (en) 2002-10-11 2006-08-15 The University Of Connecticut Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments
US9115245B2 (en) 2002-10-11 2015-08-25 Boston Scientific Scimed, Inc. Implantable medical devices
US7173096B2 (en) 2002-10-11 2007-02-06 University Of Connecticut Crosslinked polycyclooctene
US7208550B2 (en) 2002-10-11 2007-04-24 The University Of Connecticut Blends of amorphous and semicrystalline polymers having shape memory properties
US7371799B2 (en) 2002-10-11 2008-05-13 University Of Connecticut Blends of amorphous and semicrystalline polymers having shape memory properties
US7524914B2 (en) 2002-10-11 2009-04-28 The University Of Connecticut Shape memory polymers based on semicrystalline thermoplastic polyurethanes bearing nanostructured hard segments
US7563848B2 (en) 2002-10-11 2009-07-21 University Of Connecticut Crosslinked polycyclooctene
US7705098B2 (en) 2002-10-11 2010-04-27 University Of Connecticut Crosslinked polycyclooctene
US7906573B2 (en) 2002-10-11 2011-03-15 University Of Connecticut Crosslinked polycyclooctene
US7795350B2 (en) 2002-10-11 2010-09-14 Connecticut, University Of Blends of amorphous and semicrystalline polymers having shape memory properties
WO2006098757A3 (en) * 2004-08-16 2006-11-16 Jane P Bearinger Shape memory polymers
US9745402B2 (en) 2004-08-16 2017-08-29 Lawrence Livermore National Security, Llc Shape memory polymers
US9034356B2 (en) 2006-01-19 2015-05-19 Warsaw Orthopedic, Inc. Porous osteoimplant
US9173973B2 (en) 2006-07-20 2015-11-03 G. Lawrence Thatcher Bioabsorbable polymeric composition for a medical device
US9211205B2 (en) 2006-10-20 2015-12-15 Orbusneich Medical, Inc. Bioabsorbable medical device with coating
US9724864B2 (en) 2006-10-20 2017-08-08 Orbusneich Medical, Inc. Bioabsorbable polymeric composition and medical device
US9174924B2 (en) 2007-09-17 2015-11-03 Bezwada Biomedical, Llc Hydrolysable linkers and cross-linkers for absorbable polymers
US8664429B2 (en) 2007-09-17 2014-03-04 Bezwada Biomedical, Llc Hydrolysable linkers and cross-linkers for absorbable polymers
US9045396B2 (en) 2007-09-17 2015-06-02 Bezwada Biomedical, Llc Hydrolysable linkers and cross-linkers for absorbable polymers
US8048980B2 (en) 2007-09-17 2011-11-01 Bezwada Biomedical, Llc Hydrolysable linkers and cross-linkers for absorbable polymers
US8551519B2 (en) 2008-05-23 2013-10-08 Bezwada Biomedical, Llc Bioabsorbable surgical articales or components thereof
US8367747B2 (en) 2008-05-23 2013-02-05 Bezwada Biomedical, Llc Bioabsorbable polymers from bioabsorbable polyisocyanates and uses thereof
US8449903B2 (en) 2009-06-08 2013-05-28 Boston Scientific Scimed, Inc. Crosslinked bioabsorbable medical devices
WO2012109535A2 (en) 2011-02-11 2012-08-16 Bezwada Biomedical, Llc Amino acid derivatives and absorbable polymers therefrom
US9328192B2 (en) 2014-03-12 2016-05-03 Bezwada Biomedical, Llc Bio-based monomers and polymers

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