Polyvinyl alcohol copolymers comprising biomolecules

• US 7,772,286 B2
• Filed: 02/27/2004
• Issued: 08/10/2010
• Est. Priority Date: 02/28/2003
• Status: Active Grant

• Current Assignee: EyeSense AG
• Original Assignee: EyeSense AG
• Inventors: Schmieder, Roland, Schmid, Katharina, Muller, Achim
• Primary Examiner(s): EGWIM, KELECHI CHIDI
• Application Number:
  US10/544,725
• Publication Number:
  US 20060148983A1
• Time in Patent Office: 2,356 Days
• Field of Search: 514/738, 524/56, 524/57
• US Class Current: 514/738
• CPC Class Codes: C08F 16/06 Polyvinyl alcohol ; Vinyl alcohol
• CPC Class Codes: C08F 2810/30 leading to the formation or introduction of aliphatic or alicyclic unsaturated groups
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08F 8/48 Isomerisation; Cyclisation
• CPC Class Codes: C08L 29/04 Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
• CPC Class Codes: G02B 1/043 Contact lenses

Abstract

The present invention relates to a copolymer, which is the reaction product of (a) a first prepolymer, comprising a bioactive moiety and at least one radically polymerizable group, and (b) a second prepolymer which is a polyvinyl alcohol having a weight average molecular weight of at least about 2000 that, based on the number of hydroxy groups of the polyvinyl alcohol, comprises from 0.5 to 80% structural units of formula (I) wherein: R is alkylene having up to 8 carbon atoms, R¹ is hydrogen or alkyl having up to seven carbon atoms, and R² is an olefinically unsaturated, electron-attracting copolymerizable radical.

Claims

1. A copolymer, which is the reaction product of

(a) a first prepolymer comprising a bioactive moiety B and at least one radically polymerizable group, being

(i) a polyvinyl alcohol having a weight average molecular weight of at least 500 that, based on the number of hydroxyl groups of the polyvinyl alcohol, comprises

(i-a) from 0.5 to 80% structural units of formula (1);

2. The copolymer according to claim 1, wherein B is the radical of a protein, of a peptide or an antibody.

3. The copolymer according to claim 1, wherein, in (a), B is a Concanavalin A radical.

4. The copolymer according to claim 1, wherein in formula (3) T is —

CH₂—

O—

—

CH₂—

CH(OH)—

CH₂—

;

X is —

S—

or —

NH—

; and

B is a Concanavalin A radical.

5. The copolymer according to claim 1, wherein T is —

C₁—

C₁₀-alkylene-NH—

C(O)—

(CH₂)₃;

X is —

S—

or —

NH—

; and

B is a Concanavalin A radical.

6. The copolymer according to claim 1, wherein in formula (2) X is —

NH—

or —

S—

;

g and n are zero;

i is 1;

L² is —

C(O)—

;

Q is —

C(CH₃)═

CH₂ or —

CH₂═

CH₂;

s is an integer from 1 to 6; and

m is from 1 to 20.

7. The copolymer according to claim 1, wherein in formula (2) X is —

NH—

, or —

S—

;

g, n and i are 1;

L¹ is —

C(O)—

;

(spacer) is a radical of a polyethylene glycol having a weight average molecular weight of up to 20,000;

L² is —

OC(O)—

;

Q is —

C(CH₃)═

CH₂ or —

CH═

CH₂; and

m is from 1 to 20.

8. The copolymer according to claim 1, wherein, in formula (1) of the first prepolymer and/or of the second prepolymer, R is methylene, R¹ is hydrogen and R² is acryloyl.

9. A copolymer, which is the reaction product of

(a) a first prepolymer comprising a bioactive moiety B and at least one radically polymerizable group, being

(i) a polyvinyl alcohol having a weight average molecular weight of at least 500 that, based on the number of hydroxyl groups of the polyvinyl alcohol, comprises

(i-a) from 0.5 to 80% structural units of formula (1);

10. The copolymer according to claim 9, wherein B is the radical of a protein, of a peptide or an antibody.

11. The copolymer according to claim 9, wherein, in (a), B is a Concanavalin A radical.

12. The copolymer according to claim 9, wherein in formula (3) T is —

CH₂—

O—

CH₂—

CH(OH)—

CH₂—

;

X is —

S—

or —

NH—

; and

B is a Concanavalin A radical.

13. The copolymer according to claim 9, wherein T is —

C₁-C₁₀-alkylene-NH—

C(O)—

(CH₂)₃;

X is —

S—

or —

NH—

; and

B is a Concanavalin A radical.

14. The copolymer according to claim 9, wherein in formula (2) X is —

NH—

or —

S—

;

g and n are zero;

i is 1;

L² is —

C(O)—

;

Q is —

C(CH₃)═

CH₂ or —

CH₂═

CH₂;

s is an integer from 1 to 6; and

m is from 1 to 20.

15. The copolymer according to claim 9, wherein in formula (2) X is —

NH—

, or —

S—

;

g, n and i are 1;

L¹ is —

C(O)—

;

(spacer) is a radical of a polyethylene glycol having a weight average molecular weight of up to 20,000;

L² is —

OC(O)—

;

Q is —

C(CH₃)═

CH₂ or —

CH═

CH₂; and

m is from 1 to 20.

16. The copolymer according to claim 9, wherein, in formula (1) of the first prepolymer and/or of the second prepolymer, R is methylene, R¹ is hydrogen and R² is acryloyl.

17. A copolymer, which is the reaction product of

(a) a first prepolymer comprising a bioactive moiety B and at least one radically polymerizable group, being

(i) a polyvinyl alcohol having a weight average molecular weight of at least 500 that, based on the number of hydroxyl groups of the polyvinyl alcohol, comprises

(i-a) from 0.5 to 80% structural units of formula (1);

18. The copolymer according to claim 17, wherein B is the radical of a protein, of a peptide or an antibody.

19. The copolymer according to claim 17, wherein, in (a), B is a Concanavalin A radical.

20. The copolymer according to claim 17, wherein in formula (3) T is —

CH₂—

O—

CH₂—

CH(OH)—

CH₂—

;

X is —

S—

or —

NH—

; and

B is a Concanavalin A radical.

21. The copolymer according to claim 17, wherein T is —

C₁-C₁₀-alkylene-NH—

C(O)—

(CH₂)₃;

X is —

S—

or —

NH—

; and

B is a Concanavalin A radical.

22. The copolymer according to claim 17, wherein in formula (2) X is —

NH—

or —

S—

;

g and n are zero;

i is 1;

L² is —

C(O)—

;

Q is —

C(CH₃)═

CH₂ or —

CH₂═

CH₂;

s is an integer from 1 to 6; and

m is from 1 to 20.

23. The copolymer according to claim 17, wherein in formula (2) X is —

NH—

, or —

S—

;

g, n and i are 1;

L¹ is —

C(O)—

;

(spacer) is a radical of a polyethylene glycol having a weight average molecular weight of up to 20,000;

L² is —

OC(O)—

;

Q is —

C(CH₃)═

CH₂ or —

CH═

CH₂; and

m is from 1 to 20.

24. The copolymer according to claim 17, wherein, in formula (1) of the first prepolymer and/or of the second prepolymer, R is methylene, R¹ is hydrogen and R² is acryloyl.