US5916585A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Materials and method for the immobilization of bioactive species onto biodegradable polymers
Assignee: W.L. Gore and Associates Inc
•
Filing: 1997-05-30
•
Granted: 1999-06-29
•
Expires: 2017-05-30
Abstract
Abstract The present invention is directed to hydrophobic biodegradable polymeric materials having at least one surface thereof rendered more hydrophilic by attachment of at least one layer of a hydrophilic polymer thereto. The hydrophilic polymer layer is cross-linked together on the surface of the biodegradable material with a cross-linking agent or scheme that is biodegradable. Bioactive species are immobilized to chemically functional groups of the components of the first layer or to unreacted chemically functional groups of the cross-linking agent. Optionally, the bioactive species may be reversibly immobilized through chemically functional linkages that are degradable. The result is an implantable construction with immobilized bioactive species having structural components that are all subject to degradation in the body of a recipient.
Inventors
- 👤 Alonzo D. Cook
- 👤 Paul D. Drumheller
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 15:59
CPC Classifications
A; A61; A61L; A61L31/00; A61L31/14; A61L31/148; A61L27/00; A61L27/28; A61L27/34; A61L27/36; A61L27/38; A61L27/50; A61L27/54; A61L27/58; A61L31/08; A61L31/10; A61L31/16; A61L2300/00; A61L2300/40; A61L2300/412; A61L2300/414; A61L2300/60; A61L2300/602; A61L2300/604; A61L2300/64; Y; Y10; Y10S; Y10S977/00; Y10S977/70; Y10S977/788; Y10S977/902; Y10S977/904; Y10S977/931
Claims Analysis
Total Claims: 80
Claim 1
Independent Claim
70 words
A biodegradable material for immobilization of bioactive species thereon, the material comprising: a porous hydrophobic biodegradable support member; a first layer comprised of at least one species of a polymeric surfactant, wherein the polymeric surfactant is adsorbed to the support member, and wherein the surfactant is cross-linked to itself with a cross-linking agent that forms covalent bonds that are subject to enzymatic cleavage or non-enzymatic hydrolysis under in vivo conditions.
Claim 2
Dependent Claim
70 words
A biodegradable material for immobilization of bioactive species thereon, the material comprising: a porous hydrophobic biodegradable support member; a first layer comprised of at least one species of a polymeric surfactant, wherein the polymeric surfactant is adsorbed to the support member, and wherein the surfactant is cross-linked to itself with a cross-linking agent that forms covalent bonds that are subject to enzymatic cleavage or non-enzymatic hydrolysis under in vivo conditions.
Claim 3
Dependent Claim
20 words
The biodegradable material of claim 1 further comprising at least one type of bioactive species attached to the first layer.
Claim 4
Dependent Claim
17 words
The biodegradable material of claim 2 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 5
Dependent Claim
82 words
The biodegradable material of claim 1 wherein the support member is selected from a member of the groups consisting of polyglycolide (PGA), copolymers of glycolide, glycolide/L-lactide copolymers (PGA/PLLA), lactide/trimethylene carbonate copolymers (PLA/TMC), glycolide/trimethylene carbonate copolymers (PGA/TMC), polylactides (PLA), stereo-copolymers of PLA, poly-L-lactide (PLLA), poly-DL-lactide (PDLLA), L-lactide/DL-lactide copolymers, copolymers of PLA, lactide/tetramethylglycolide copolymers, lactide/α-valerolactone copolymers, lactide/ε-caprolactone copolymers, PLA/polyethylene oxide copolymers, poly-βhydroxybutyrate (PHBA), PHBA/βhydroxyvalerate copolymers (PHBA/HVA), poly-p-dioxanone (PDS), poly-α-valerolactone, poly-ε-caprolactone, methylmethacrylate-N-vinyl-pyrrolidone copolymers, polyesters of oxalic acid, polyalkyl-2-cyanoacrylates, polyurethanes, and blends of the aforementioned polymers.
Claim 6
Dependent Claim
35 words
The biodegradable material of claim 1 wherein the support member is selected from a member of the groups consisting of polybutylene oxalate, polyethylene adipate, polyethylene carbonate, and polybutylene carbonate, and blends of the aforementioned polymers.
Claim 7
Dependent Claim
30 words
The biodegradable material of claim 1 wherein the support member is selected from a member of the groups consisting of polyesters containing silyl ethers and blends of the aforementioned polymers.
Claim 8
Dependent Claim
54 words
The biodegradable material of claim 1 wherein the polymeric surfactant is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polypropylene glycol, dextran, agarose, alginate, polyacrylamide, polyglycidol, polyvinyl alcohol-co-polyethylene, poly(vinyl acetate-co-vinyl alcohol), polyacrylic acid, polyamide, polypeptides, poly-lysine, polyethyleneimine, poly-β-malic acid, hyaluronic acid, derivatives of hyaluronic acid, and polyvinyl pyrrolidone, alone or in combination.
Claim 9
Dependent Claim
13 words
The biodegradable material of claim 1 wherein the polymeric surfactant comprises a polysaccharide.
Claim 10
Dependent Claim
50 words
The biodegradable material of claim 1 wherein the cross-linking agent comprises a compound having at least two chemically functional groups selected from the group consisting of aldehydes, epoxides, acyl halides, alkyl halides, isocyanates, amines, anhydrides, acids, alcohols, haloacetals, aryl carbonates, thiols, esters, imides, vinyls, azides, nitros, peroxides, sulfones, and maleimides.
Claim 11
Dependent Claim
31 words
The biodegradable material of claim 1 wherein the cross-linking agent is selected from the group consisting of poly(acrylic acid), vinyl sulfone, succinyl chloride, polyanhydrides, succinimidyl succinate-polyethylene glycol, and succinimidyl succinamide-polyethylene glycol.
Claim 12
Dependent Claim
25 words
The biodegradable material of claim 1 further comprising: a second layer comprised of at least one species of a surfactant attached to the first layer.
Claim 13
Dependent Claim
20 words
The biodegradable material of claim 11 further comprising at least one type of bioactive species attached to the second layer.
Claim 14
Dependent Claim
17 words
The biodegradable material of claim 12 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 15
Dependent Claim
53 words
The biodegradable material of claim 1 wherein the surfactant of the second layer is selected from the group consisting of polyvinyl alcohol, polylysine, poly(acrylonitrile-co-acrylic acid-acrylamidine), polyacrylic acid, polyhydroxyethylmethacrylate, polyvinylpyrrolidone, polyethylene glycol, alginate, agarose, poly-β-malic acid, hyaluronic acid, derivatives of hyaluronic acid, polyacrolein, polyethyleneimine, polyallylamine, polyornithine, and their copolymers, either alone or in combination.
Claim 16
Dependent Claim
20 words
The biodegradable material of claim 2 wherein a spacer compound is interposed between the first layer and the bioactive species.
Claim 17
Dependent Claim
28 words
The biodegradable material of claim 15 wherein the spacer compound is selected from the group consisting of succinic acid, diaminohexane, glyoxylic acid, short chain polyethylene glycol, and glycine.
Claim 18
Dependent Claim
12 words
The biodegradable material of claim 15 wherein the spacer compound is cleavable.
Claim 19
Dependent Claim
25 words
The biodegradable material of claim 17 wherein the cleavable spacer compound is selected from the group consisting of polyhydroxyacids, polyanhydrides, polyamino acids, tartarates, and cysteine-linkers.
Claim 20
Dependent Claim
76 words
A biodegradable material having bioactive species immobilized thereon, the material comprising: a porous hydrophobic biodegradable support member; a first layer comprised of at least one species of a polymeric surfactant, wherein the polymeric surfactant is adsorbed to the support member, wherein the surfactant is cross-linked to itself through acid-base coacervation, carboxyic acid-ether complexation, ion complexation, ionic interactions, metal complexation, or alcoholic hydrogen bonding, and wherein the cross-linked surfactant is subject to degradation under in vivo conditions.
Claim 21
Dependent Claim
76 words
A biodegradable material having bioactive species immobilized thereon, the material comprising: a porous hydrophobic biodegradable support member; a first layer comprised of at least one species of a polymeric surfactant, wherein the polymeric surfactant is adsorbed to the support member, wherein the surfactant is cross-linked to itself through acid-base coacervation, carboxyic acid-ether complexation, ion complexation, ionic interactions, metal complexation, or alcoholic hydrogen bonding, and wherein the cross-linked surfactant is subject to degradation under in vivo conditions.
Claim 22
Dependent Claim
20 words
The biodegradable material of claim 19 further comprising at least one type of bioactive species attached to the first layer.
Claim 23
Dependent Claim
17 words
The biodegradable material of claim 20 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 24
Dependent Claim
82 words
The biodegradable material of claim 19 wherein the support member is selected from a member of the groups consisting of polyglycolide (PGA), copolymers of glycolide, glycolide/L-lactide copolymers (PGA/PLLA), lactide/trimethylene carbonate copolymers (PLA/TMC), glycolide/trimethylene carbonate copolymers (PGA/TMC), polylactides (PLA), stereo-copolymers of PLA, poly-L-lactide (PLLA), poly-DL-lactide (PDLLA), L-lactide/DL-lactide copolymers, copolymers of PLA, lactide/tetramethylglycolide copolymers, lactide/(α-valerolactone copolymers, lactide/ε-caprolactone copolymers, PLA/polyethylene oxide copolymers, poly-βhydroxybutyrate (PHBA), PHBA/βhydroxyvalerate copolymers (PHBA/HVA), poly-p-dioxanone (PDS), poly-α-valerolactone, poly-ε-caprolactone, methylmethacrylate-N-vinyl-pyrrolidone copolymers, polyesters of oxalic acid, polyalkyl-2-cyanoacrylates, polyurethanes, and blends of the aforementioned polymers.
Claim 25
Dependent Claim
35 words
The biodegradable material of claim 19 wherein the support member is selected from a member of the groups consisting of polybutylene oxalate, polyethylene adipate, polyethylene carbonate, and polybutylene carbonate, and blends of the aforementioned polymers.
Claim 26
Dependent Claim
30 words
The biodegradable material of claim 19 wherein the support member is selected from a member of the groups consisting of polyesters containing silyl ethers and blends of the aforementioned polymers.
Claim 27
Dependent Claim
54 words
The biodegradable material of claim 19 wherein the polymeric surfactant is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polypropylene glycol, dextran, agarose, alginate, polyacrylamide, polyglycidol, polyvinyl alcohol-co-polyethylene, poly(ethyleneglycol-co-propyleneglycol), poly(vinyl acetate-co-vinyl alcohol), polyacrylic acid, polypeptides, poly-lysine, polyethyleneimine, poly-β-malic acid, hyaluronic acid, derivatives of hyaluronic acid, and polyvinyl pyrrolidone, alone or in combination.
Claim 28
Dependent Claim
13 words
The biodegradable material of claim 19 wherein the polymeric surfactant comprises a polysaccharide.
Claim 29
Dependent Claim
25 words
The biodegradable material of claim 19 further comprising: a second layer comprised of at least one species of a surfactant attached to the first layer.
Claim 30
Dependent Claim
20 words
The biodegradable material of claim 27 further comprising at least one type of bioactive species attached to the second layer.
Claim 31
Dependent Claim
17 words
The biodegradable material of claim 28 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 32
Dependent Claim
49 words
The biodegradable material of claim 27 wherein the surfactant of the second layer is selected from the group consisting of polyvinyl alcohol, polylysine, polyacrylic acid, polyvinylpyrrolidone, polyethylene glycol, alginate, agarose, poly-β-malic acid, hyaluronic acid, derivatives of hyaluronic acid, polyethyleneimine, polyallylamine, polyornithine, and their copolymers, either alone or in combination.
Claim 33
Dependent Claim
20 words
The biodegradable material of claim 28 wherein a spacer compound is interposed between the first layer and the bioactive species.
Claim 34
Dependent Claim
28 words
The biodegradable material of claim 31 wherein the spacer compound is selected from the group consisting of succinic acid, diaminohexane, glyoxylic acid, short chain polyethylene glycol, and glycine.
Claim 35
Dependent Claim
12 words
The biodegradable material of claim 31 wherein the spacer compound is cleavable.
Claim 36
Dependent Claim
25 words
The biodegradable material of claim 33 wherein the cleavable spacer compound is selected from the group consisting of polyhydroxyacids, polyanhydrides, polyamino acids, tartarates, and cysteine-linkers.
Claim 37
Independent Claim
58 words
A method of making a material for the immobilization of bioactive species thereon, the method comprising: providing a porous hydrophobic biodegradable support member; adsorbing a first layer comprised of at least one type of polymeric surfactant to the support member; and cross-linking the polymeric surfactant to itself with chemical bonds that are subject to degradation in a recipient.
Claim 38
Independent Claim
58 words
A method of making a material for the immobilization of bioactive species thereon, the method comprising: providing a porous hydrophobic biodegradable support member; adsorbing a first layer comprised of at least one type of polymeric surfactant to the support member; and cross-linking the polymeric surfactant to itself with chemical bonds that are subject to degradation in a recipient.
Claim 39
Dependent Claim
19 words
The method of claim 35 further comprising attaching at least one type of bioactive species to the first layer.
Claim 40
Dependent Claim
17 words
The biodegradable material of claim 36 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 41
Dependent Claim
15 words
The method of claim 35 wherein the polymeric surfactant is cross-linked with a cross-linking agent.
Claim 42
Dependent Claim
14 words
The method of claim 35 wherein the polymeric surfactant is cross-linked with non-covalent bonds.
Claim 43
Dependent Claim
15 words
The method of claim 39 wherein the polymeric surfactant is cross-linked via cyano polar interactions.
Claim 44
Dependent Claim
14 words
The method of claim 39 wherein the polymeric surfactant is cross-linked by acid-base coacervation.
Claim 45
Dependent Claim
15 words
The method of claim 39 wherein the polymeric surfactant is cross-linked by carboxylic acid-ether complexation.
Claim 46
Dependent Claim
14 words
The method of claim 39 wherein the polymeric surfactant is cross-linked by ion complexation.
Claim 47
Dependent Claim
14 words
The method of claim 39 wherein the polymeric surfactant is cross-linked by metal complexation.
Claim 48
Dependent Claim
15 words
The method of claim 39 wherein the polymeric surfactant is cross-linked by alcoholic hydrogen bonding.
Claim 49
Dependent Claim
23 words
The method of claim 35 further comprising: attaching a second layer comprised of at least one type of surfactant to the first layer.
Claim 50
Dependent Claim
19 words
The method of claim 46 further comprising attaching at least one type of bioactive species to the first layer.
Claim 51
Dependent Claim
17 words
The biodegradable material of claim 47 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 52
Dependent Claim
66 words
The method of claim 35 wherein the polymeric surfactants are selected from a member of the group consisting of polyvinyl alcohol, polyethylene glycol, polypropylene glycol, dextran, agarose, alginate, polyacrylamide, polyglycidol, polyvinyl alcohol-co-polyethylene, poly(ethyleneglycol-co-propyleneglycol), poly(vinyl acetate-co-vinyl alcohol), poly(tetrafluoroethylene-co-vinyl alcohol), poly(acrylonitrile-co-acrylamide), poly(acrylonitrile-co-acrylic acid-acrylamidine), polyacrylic acid, poly-lysine, polyethyleneimine, polyvinyl pyrrolidone, poly-b-malic acid, hyaluronic acid, derivatives of hyaluronic acid, polyhydroxyethylmethacrylate, and polysaccharides, and their copolymers, either alone or in combination.
Claim 53
Dependent Claim
52 words
The method of claim 46 wherein the surfactant of the second layer is selected from the group consisting of polyvinyl alcohol, polylysine, poly(acrylonitrile-co-acrylic acid-acrylamidine), polyacrylic acid, polyhydroxyethylmethacrylate polyvinylpyrrolidone, polyethylene glycol, alginate, agarose, poly-β-malic acid, hyaluronic acid, derivatives of hyaluronic acid, polyacrolein, polyethyleneimine, polyallylamine, polyornithine, and their copolymers, either alone or in combination.
Claim 54
Dependent Claim
38 words
The method of claim 38 wherein the cross-linking agent is selected from a member of the group consisting of vinyls, imidazoles, carbamates, aldehydes, epoxides, acyl halides, akyl halides, isocyanates, amines, anhydrides, acids, alcohols, thiols, esters, imides, and maleimides.
Claim 55
Dependent Claim
31 words
The method of claim 38 further comprising: using a sufficient amount of cross-linking agent when cross-linking the polymeric surfactants so that unreacted chemically reactive groups of the cross-linking agent are present.
Claim 56
Dependent Claim
26 words
The method of claim 38 further comprising: cross-linking the polymeric surfactants with a cross-linking agent under conditions that do not produce polymerization of the cross-linking agent.
Claim 57
Dependent Claim
23 words
The method of claim 38 further comprising: using a catalyst with the cross-linking agent that evolves as a gas following the cross-linking step.
Claim 58
Dependent Claim
58 words
The biodegradable material of claim 1 wherein the material is produced through the following process: providing a porous hydrophobic biodegradable support member; adsorbing a first layer comprised of at least one species of a polymeric surfactant to the support member; and cross-linking the polymeric surfactant to itself with chemical bonds that are subject to degradation in a recipient.
Claim 59
Dependent Claim
19 words
The method of claim 55 further comprising attaching at least one type of bioactive species to the first layer.
Claim 60
Dependent Claim
17 words
The biodegradable material of claim 56 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 61
Dependent Claim
24 words
The biodegradable material of claim 55 further comprising: attaching a second layer comprised of at least one type of surfactant to the first layer.
Claim 62
Dependent Claim
19 words
The method of claim 55 further comprising attaching at least one type of bioactive species to the first layer.
Claim 63
Dependent Claim
17 words
The biodegradable material of claim 59 wherein the bioactive species is recombinant human bone morphogenetic protein-2 (rhBMP-2).
Claim 64
Dependent Claim
104 words
The material of claim 55 wherein the porous support member is selected from a member of the group consisting of porous polyglycolide (PGA), porous copolymers of glycolide, porous glycolide/L-lactide copolymers (PGA/PLLA), porous lactide/trimethylene carbonate copolymers (PLA/TMC), porous glycolide/trimethylene carbonate copolymers (PGA/TMC), porous polylactides (PLA), porous stereo-copolymers of PLA, porous poly-L-lactide (PLLA), porous poly-DL-lactide (PDLLA), porous L-lactide/DL-lactide copolymers, porous copolymers of PLA, porous lactide/tetramethylglycolide copolymers, porous lactide/α-valerolactone copolymers, porous lactide/ε-caprolactone copolymers, porous PLA/polyethylene oxide copolymers, porous poly-βhydroxybutyrate (PHBA), porous PHBA/βhydroxyvalerate copolymers (PHBA/HVA), porous poly-p-dioxanone (PDS), porous poly-α-valerolactone, porous poly-ε-caprolactone, porous methylmethacrylate-N-vinyl-pyrrolidone copolymers, porous polyesters of oxalic acid, porous polyalkyl-2-cyanoacrylates, and blends of the aforementioned polymers.
Claim 65
Dependent Claim
40 words
The material of claim 55 wherein the polymeric surfactant comprises a multifunctional copolymer comprised of at least one domain having a physicochemical affinity for the support member and at least one domain that is chemically reactive with a cross-linking agent.
Claim 66
Dependent Claim
52 words
The method of claim 58 wherein the surfactant of the second layer is selected from the group consisting of polyvinyl alcohol, polylysine, poly(acrylonitrile-co-acrylic acid-acrylamidine), polyacrylic acid, polyhydroxymethylmethacrylate polyvinylpyrrolidone, polyethylene glycol, alginate, agarose, poly-β-malic acid, hyaluronic acid, derivatives of hyaluronic acid, polyacrolein, polyethyleneimine, polyallylamine, polyornithine, and their copolymers, either alone or in combination.
Claim 67
Dependent Claim
19 words
The material of claim 55 wherein a spacer compound is interposed between the first layer and the bioactive species.
Claim 68
Dependent Claim
30 words
The material of claim 64 wherein the spacer compound is selected from a member of a group consisting of succinic acid, diaminohexane, glyoxylic acid, short chain polyethylene glycol, and glycine.
Claim 69
Dependent Claim
11 words
The material of claim 64 wherein the spacer compound is cleavable.
Claim 70
Dependent Claim
24 words
The material of claim 66 wherein the cleavable spacer compound is selected from the group consisting of polyhydroxyacids, polyanhydrides, polyamino acids, tartarates, and cysteine-linkers.
Claim 71
Dependent Claim
53 words
A biodegradable material for immobilization of bioactive species thereon, the material comprising: a support member comprising poly(glycolic acid); and a first layer comprising poly(ethyleneimine) adsorbed to the support member, wherein the poly(ethyleneimine) is cross-linked to itself with a cross-linking agent that forms covalent bonds that are subject to enzymatic cleavage or non-enzymatic hydrolysis.
Claim 72
Dependent Claim
53 words
A biodegradable material for immobilization of bioactive species thereon, the material comprising: a support member comprising poly(glycolic acid); and a first layer comprising poly(ethyleneimine) adsorbed to the support member, wherein the poly(ethyleneimine) is cross-linked to itself with a cross-linking agent that forms covalent bonds that are subject to enzymatic cleavage or non-enzymatic hydrolysis.
Claim 73
Dependent Claim
18 words
The biodegradable material of claim 68 further comprising a second layer comprising poly(ethyleneimine) attached to the first layer.
Claim 74
Dependent Claim
33 words
The biodegradable material of claim 68 further comprising a bioactive species attached to the first layer, the bioactive species comprising a polypeptide having an amino acid sequence comprising arginine, glycine, and aspartic acid.
Claim 75
Dependent Claim
33 words
The biodegradable material of claim 69 further comprising a bioactive species attached to the second layer, the bioactive species comprising a polypeptide having an amino acid sequence comprising arginine, glycine, and aspartic acid.
Claim 76
Dependent Claim
58 words
A biodegradable material for immobilization of bioactive species thereon, the material comprising: a support member comprising a copolymer of glycolide and trimethylene carbonate; and a first layer comprising poly(ethyleneimine) adsorbed to the support member, wherein the poly(ethyleneimine) is cross-linked to itself with a cross-linking agent that forms covalent bonds that are subject to enzymatic cleavage or non-enzymatic hydrolysis.
Claim 77
Dependent Claim
58 words
A biodegradable material for immobilization of bioactive species thereon, the material comprising: a support member comprising a copolymer of glycolide and trimethylene carbonate; and a first layer comprising poly(ethyleneimine) adsorbed to the support member, wherein the poly(ethyleneimine) is cross-linked to itself with a cross-linking agent that forms covalent bonds that are subject to enzymatic cleavage or non-enzymatic hydrolysis.
Claim 78
Dependent Claim
18 words
The biodegradable material of claim 72 further comprising a second layer comprising poly(ethyleneimine) attached to the first layer.
Claim 79
Dependent Claim
33 words
The biodegradable material of claim 72 further comprising a bioactive species attached to the first layer, the bioactive species comprising a polypeptide having an amino acid sequence comprising arginine, glycine, and aspartic acid.
Claim 80
Dependent Claim
33 words
The biodegradable material of claim 73 further comprising a bioactive species attached to the second layer, the bioactive species comprising a polypeptide having an amino acid sequence comprising arginine, glycine, and aspartic acid.
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