Zwitterionically modified polymers and hydrogels

1. A monomer of Formula (I):

wherein

A is selected from a saccharide containing unit and a polyvinyl alcohol containing unit;

X is selected from the group consisting of O, NH, NR′, C(O), and C 1-20 alkylene, wherein C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy;

Q is absent or is a linker;

Y is

Z is

m 1 is 0 to 50;

m 2 is 0 to 50;

m 3 is 0 to 50;

R is C 1-20 alkyl; and

R′ is —C(O)—C 1-6 alkene.

2. The monomer of claim 1 , wherein A is selected from the group consisting of a monosaccharide, disaccharide, trisaccharide, and oligosaccharide.

3. The monomer of claim 1 , wherein A is selected from the group consisting of:

wherein

is the point of attachment of A to X.

4. The monomer of claim 1 , wherein Q is present and is selected from the group consisting of C 1-20 alkylene, C 3-20 cycloalkylene, arylene, heteroarylene, heterocyclene, —O—C 1-20 alkylene, poly(ethylene glycol), and polypeptide; wherein C 1-20 alkylene, C 3-20 cycloalkylene, arylene, heteroarylene, heterocyclylene, or —O—C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of —OH, halogen, cyano, —CF 3 , C 1-6 alkyl, and C 1-6 alkoxy; and wherein C 1-20 alkylene is optionally interrupted by one or more heteroatoms selected from the group consisting of oxygen, sulfur, and nitrogen.

5. A polymer of Formula (IV):

wherein,

A is independently selected from a saccharide containing unit and a polyvinyl alcohol containing unit for each monomer unit of the polymer;

X is selected from the group consisting of O, NH, NR′, C(O), and C 1-20 alkylene, wherein C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy;

Q is absent or is a linker;

Y is

Z is

m 1 is 0 to 50;

m 2 is 0 to 50;

m 3 is 0 to 50;

R is C 1-20 alkyl;

R′ is —C(O)—C 1-6 alkene;

k 1 is any integer; and

k 2 is independently selected for each monomer unit from 0 or 1, with the proviso that at least one k 2 is 1;

wherein the monomers units of the polymer are the same or different.

6. The polymer of claim 5 , wherein A is a saccharide independently selected at each occurrence from a monosaccharide, disaccharide, or oligosaccharide containing unit.

7. The polymer of claim 5 , wherein A is selected from the group consisting of:

wherein

is the point of attachment of A to X.

8. The polymer of claim 5 , wherein Q is present and is selected from the group consisting of C 1-20 alkylene, C 3-20 cycloalkylene, arylene, heteroarylene, heterocyclene, —O—C 1-20 alkylene, poly(ethylene glycol), and polypeptide; wherein C 1-20 alkylene, C 3-20 cycloalkylene, arylene, heteroarylene, heterocyclylene, or —O—C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of —OH, halogen, cyano, —CF 3 , C 1-6 alkyl, and C 1-6 alkoxy; and wherein C 1-20 alkylene is optionally interrupted by one or more heteroatoms selected from the group consisting of oxygen, sulfur, and nitrogen.

9. The polymer of claim 5 having Formula (IVc):

10. The polymer of claim 5 , wherein one or more monomer units of the polymer is independently selected from the group consisting of:

11. The polymer of claim 5 , wherein said polymer comprises one or more monomer units of Formula (I):

and further comprises

one or more monomer units of Formula (II):

A-L 1 -L 2 -L 3 -R 4   (II),

wherein

L 1 is selected from the group consisting of O, NH, NR′, C(O), and C 1-20 alkylene, wherein C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy;

L 2 is absent or is C 1-20 alkylene, wherein C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy;

L 3 is selected from the group consisting of C 1-20 alkylene, C 1-20 alkenylene, C 3-12 cycloalkenylene, and arylene, wherein arylene is optionally substituted from 1 to 3 times with a substituent selected independently at each occurrence thereof from the group consisting of heteroarylene and heterocyclylene; and

R 4 is selected from the group consisting of SH, N 3 , C 2-20 alkenyl, C 2-20 alkynyl, C 3-12 cycloalkenyl, C 3-12 cycloalkynyl, heteroaryl, and heterocyclyl, wherein C 2-20 alkenyl, C 2-20 alkynyl, C 3-12 cycloalkenyl, C 3-12 cycloalkynyl, heteroaryl, and heterocyclyl is optionally substituted from 1 to 3 times with a substituent selected independently at each occurrence thereof from the group consisting of H, OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy.

12. A zwitterionic polymer of Formula (IIa):

wherein

A is independently selected from a saccharide containing unit and a polyvinyl alcohol containing unit for each monomer unit of the polymer;

X is selected from the group consisting of O, NH, NR′, C(O), and C 1-20 alkylene, wherein C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy;

Q is absent or is a linker;

Y is selected from the group consisting of

Z is selected from the group consisting of

m 1 is 0 to 50;

m 2 is 0 to 50;

m 3 is 0 to 50;

R is C 1-20 alkyl;

R′ is —C(O)—C 1-6 alkene;

R 1 is C 1-20 alkyl;

R 2 is C 1-20 alkyl;

R 3 is C 1-20 alkyl;

L 1 is selected from the group consisting of O, NH, NR′, C(O), and C 1-20 alkylene, wherein C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy;

L 2 is absent or is C 1-20 alkylene, wherein C 1-20 alkylene is optionally substituted from 1 to 20 times with a substituent selected independently at each occurrence thereof from the group consisting of OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy;

L 3 is selected from the group consisting of C 1-20 alkylene, C 1-20 alkenylene, C 3-12 cycloalkenylene, and arylene, wherein arylene is optionally substituted from 1 to 3 times with a substituent selected independently at each occurrence thereof from the group consisting of heteroarylene and heterocyclylene;

R 4 is selected from the group consisting of SH, N 3 , C 2-20 alkenyl, C 2-20 alkynyl, C 3-12 cycloalkenyl, C 3-12 cycloalkynyl, heteroaryl, and heterocyclyl, wherein C 2-20 alkenyl, C 2-20 alkynyl, C 3-12 cycloalkenyl, C 3-12 cycloalkynyl, heteroaryl, and heterocyclyl is optionally substituted from 1 to 3 times with a substituent selected independently at each occurrence thereof from the group consisting of H, OH, halogen, cyano, —CF 3 , and C 1-6 alkoxy; and

n 1 , n 2 , and n 3 are any integer.

13. The polymer of claim 12 , selected from the group consisting of:

where n 1 , n 2 and n 3 are any integer.

14. A hydrogel comprising the polymer of claim 5 .

15. A capsule comprising:

the hydrogel of claim 14 and

a therapeutic agent encapsulated in said hydrogel.

16. A method of delivering a therapeutic agent to a subject, said method comprising:

administering the capsule according to claim 15 to the subject.

17. A method of treating a diabetic subject, said method comprising:

implanting the capsule according to claim 15 into a subject with diabetes.

18. A hydrogel comprising the polymer of claim 13 .

19. A capsule comprising:

the hydrogel of claim 18 and

a therapeutic agent encapsulated in said hydrogel.

20. A method of delivering a therapeutic agent to a subject, said method comprising administering the capsule according to claim 19 to the subject.