Degradable thiol-ene polymers

Abstract

A thiol-ene polymeric material is disclosed. The material is produced by the photopolymerization of reactants having thiol and olefin moieties. The material can incorporate encapsulated components, including cells. Additionally, the material can be derivatized by reacting the polymeric material with components such as proteins.

1 - 15 . (canceled) 
     
     
         16 . A composition comprising:
 (a) a photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer comprising a thiol component and an ene component; and   (b) a cell, tissue, tissue aggregate, protein, pharmacologically active agent, or agricultural chemical.   
     
     
         17 . The composition of  claim 16 , wherein the thiol component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from a thiol compound comprising a polymeric moiety selected from the group consisting of poly(lactic acid) (PLA); polyglycolide (PGA); a copolymer of PLA and PGA (PLGA); poly(vinyl alcohol) (PVA); poly(ethylene glycol) (PEG); poly(ethylene oxide); a poly(ethylene oxide)-co-poly(propylene oxide) block copolymer; a poloxamine; a polyanhydride; a polyorthoester; a poly(hydroxy acids); a polydioxanone; a polycarbonate; a polyaminocarbonate; a poly(vinyl pyrrolidone); a poly(ethyl oxazoline); a carboxymethyl cellulose; a hydroxyalkylated cellulose; a polypeptide; a polysaccharide; a carbohydrate; heparan sulfate; chondroitin sulfate; heparin, alginate; and a combination thereof. 
     
     
         18 . The composition of  claim 17 , wherein the thiol component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from a thiol compound comprising a polymeric moiety selected from the group consisting of polypeptide, poly(lactic acid) (PLA), poly(vinyl alcohol) (PVA), and poly(ethylene glycol) (PEG), and a combination thereof. 
     
     
         19 . The composition of  claim 16 , wherein the ene component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from an ene compound comprising a polymeric moiety selected from the group consisting of poly(lactic acid) (PLA); polyglycolide (PGA); a copolymer of PLA and PGA (PLGA); poly(vinyl alcohol) (PVA); poly(ethylene glycol) (PEG); poly(ethylene oxide); a poly(ethylene oxide)-co-poly(propylene oxide) block copolymer; a poloxamine; a polyanhydride; a polyorthoester; a poly(hydroxy acids); a polydioxanone; a polycarbonate; a polyaminocarbonate; a poly(vinyl pyrrolidone); a poly(ethyl oxazoline); a carboxymethyl cellulose; a hydroxyalkylated cellulose; a polypeptide; a polysaccharide; a carbohydrate; heparan sulfate; chondroitin sulfate; heparin, alginate; and a combination thereof. 
     
     
         20 . The composition of  claim 19 , wherein the ene component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from an ene compound comprising a polymeric moiety selected from the group consisting of polypeptide, poly(lactic acid) (PLA), poly(vinyl alcohol) (PVA), and poly(ethylene glycol) (PEG), and a combination thereof. 
     
     
         21 . The composition of  claim 16 , wherein the thiol component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from a thiol compound having a molecular weight of from about 30 Da to about 50 kDa. 
     
     
         22 . The composition of  claim 16 , wherein the ene component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from an ene compound having a molecular weight of from about 30 Da to about 50 kDa. 
     
     
         23 . The composition of  claim 16 , wherein the ene component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from an ene compound comprising an olefin moiety selected from the group consisting of a vinyl moiety, an acetyl moiety, a vinyl ether moiety, an allyl moiety, an acrylate moiety, a methacrylate moiety, a maleimide moiety, and a norbornene moiety. 
     
     
         24 . The composition of  claim 16 , wherein the ene component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from a norbornene moiety. 
     
     
         25 . The composition of  claim 24 , wherein the thiol component of the photopolymerized biocompatible cross-linked degradable thiol-ene hydrogel polymer is derived from a thiol compound comprising a polymeric moiety selected from the group consisting of poly(lactic acid) (PLA); polyglycolide (PGA); a copolymer of PLA and PGA (PLGA); poly(vinyl alcohol) (PVA); poly(ethylene glycol) (PEG); poly(ethylene oxide); a poly(ethylene oxide)-co-poly(propylene oxide) block copolymer; a poloxamine; a polyanhydride; a polyorthoester; a poly(hydroxy acids); a polydioxanone; a polycarbonate; a polyaminocarbonate; a poly(vinyl pyrrolidone); a poly(ethyl oxazoline); a carboxymethyl cellulose; a hydroxyalkylated cellulose; a polypeptide; a polysaccharide; a carbohydrate; heparan sulfate; chondroitin sulfate; heparin, alginate; and a combination thereof. 
     
     
         26 . The composition of  claim 16 , wherein the cell, tissue, or tissue aggregate is encapsulated within the polymer. 
     
     
         27 . The composition of  claim 26 , wherein the cell is selected from the group consisting of a chondrocyte, immortalized cell line, stem cell, hormone-producing cell, fibroblast, and a combination thereof. 
     
     
         28 . The composition of  claim 16 , wherein the protein, pharmacologically active agent, or agricultural chemical is encapsulated within the polymer or chemically bound to the polymer. 
     
     
         29 . The composition of  claim 28 , wherein the protein, pharmacologically active agent, or agricultural chemical is encapsulated within the polymer. 
     
     
         30 . The composition of  claim 28 , wherein the protein, pharmacologically active agent, or agricultural chemical is chemically bound to the polymer. 
     
     
         31 . The composition of  claim 28 , wherein the protein is selected from the group consisting of an adhesion peptide, growth factor, hormone, antihormone, signaling compound, enzyme, serum protein, albumin, macroglobulin, globulin, agglutinin, lectin, extracellular matrix protein, antibody, antigen, and a combination thereof. 
     
     
         32 . The composition of  claim 28 , wherein the pharmacologically active agent is selected from the group consisting of an analgesic, antipyretic, nonsteriodal antiinflammatory drug, antiallergic, antibacterial drug, antianemia drug, cytotoxic drug, antihypertensive drug, dermatological drug, psychotherapeutic drug, vitamin, mineral, anorexiant, dietetic, antiadiposity drug, carbohydrate metabolism drug, protein metabolism drug, thyroid drug, antithyroid drug, coenzymes, and a combination thereof. 
     
     
         33 . The composition of  claim 28 , wherein the agricultural chemical is selected from the group consisting of a fungicide, herbicide, fertilizer, pesticide, carbohydrate, nucleic acid, organic molecule, inorganic biologically active molecule, and a combination thereof. 
     
     
         34 . A method for producing a polymeric material comprising (a) a biocompatible cross-linked degradable thiol-ene hydrogel polymer; and (b) a cell, tissue, tissue aggregate, protein, pharmacologically active agent, or agricultural chemical, the method comprising:
 subjecting a polymerization reaction mixture comprising a thiol compound and an olefin compound to a radical polymerization reaction under conditions sufficient to produce a biocompatible cross-linked degradable thiol-ene hydrogel polymer, wherein the thiol compound comprises m number of reactive thiol groups, and the olefin compound comprises n number of reactive ene groups, and wherein each of n and m is an integer of at least 2, provided the sum of n+m is at least 5;   and wherein (i) the polymerization reaction mixture further comprises a cell, tissue, tissue aggregate, protein, pharmacologically active agent, or agricultural chemical for encapsulation within the polymer, or (ii) the method further comprising derivatizing the thiol compound, the ene compound or the polymer with a protein, pharmacologically active agent, or agricultural chemical.   
     
     
         35 . The method of  claim 34 , wherein the thiol compound comprises a polymeric moiety selected from the group consisting of poly(lactic acid) (PLA); polyglycolide (PGA); a copolymer of PLA and PGA (PLGA); poly(vinyl alcohol) (PVA); poly(ethylene glycol) (PEG); poly(ethylene oxide); a poly(ethylene oxide)-co-poly(propylene oxide) block copolymer; a poloxamine; a polyanhydride; a polyorthoester; a poly(hydroxy acids); a polydioxanone; a polycarbonate; a polyaminocarbonate; a poly(vinyl pyrrolidone); a poly(ethyl oxazoline); a carboxymethyl cellulose; a hydroxyalkylated cellulose; a polypeptide; a polysaccharide; a carbohydrate; heparan sulfate; chondroitin sulfate; heparin, alginate; and a combination thereof. 
     
     
         36 . The method of  claim 35 , wherein the thiol compound comprises a polymeric moiety selected from the group consisting of polypeptide, poly(lactic acid) (PLA), poly(vinyl alcohol) (PVA), and poly(ethylene glycol) (PEG), and a combination thereof. 
     
     
         37 . The method of  claim 34 , wherein the ene compound comprises a polymeric moiety selected from the group consisting of poly(lactic acid) (PLA); polyglycolide (PGA); a copolymer of PLA and PGA (PLGA); poly(vinyl alcohol) (PVA); poly(ethylene glycol) (PEG); poly(ethylene oxide); a poly(ethylene oxide)-co-poly(propylene oxide) block copolymer; a poloxamine; a polyanhydride; a polyorthoester; a poly(hydroxy acids); a polydioxanone; a polycarbonate; a polyaminocarbonate; a poly(vinyl pyrrolidone); a poly(ethyl oxazoline); a carboxymethyl cellulose; a hydroxyalkylated cellulose; a polypeptide; a polysaccharide; a carbohydrate; heparan sulfate; chondroitin sulfate; heparin, alginate; and a combination thereof. 
     
     
         38 . The method of  claim 37 , wherein the ene compound comprises a polymeric moiety selected from the group consisting of polypeptide, poly(lactic acid) (PLA), poly(vinyl alcohol) (PVA), and poly(ethylene glycol) (PEG), and a combination thereof. 
     
     
         39 . The method of  claim 34 , wherein the molecular weight of the thiol compound is from about 30 Da to about 50 kDa. 
     
     
         40 . The method of  claim 34 , wherein the molecular weight of the ene compound is from about 30 Da to about 50 kDa. 
     
     
         41 . The method of  claim 34 , wherein the ene compound comprises an olefin moiety selected from the group consisting of a vinyl moiety, an acetyl moiety, a vinyl ether moiety, an allyl moiety, an acrylate moiety, a methacrylate moiety, a maleimide moiety, and a norbornene moiety. 
     
     
         42 . The method of  claim 34 , wherein the polymerization reaction mixture further comprises a chemical initiator. 
     
     
         43 . The method of  claim 34 , wherein the radical polymerization reaction is photoinitiated radical polymerization reaction. 
     
     
         44 . The method of  claim 34 , wherein the method further comprising encapsulating a cell, tissue, tissue aggregate, protein, pharmacologically active agent, or agricultural chemical within the polymer. 
     
     
         45 . The method of  claim 34 , wherein the method further comprising derivatizing the thiol compound, the ene compound or the polymer with a protein, pharmacologically active agent, or agricultural chemical.