Integrated zwitterionic conjugated polymers for bioelectronics, biosensing, regenerative medicine, and energy applications

Patent metadata

Field	Value
Publication number	US-10407537-B2
Application number	US-201715600080-A
Country	US
Kind code	B2
Filing date	May 19, 2017
Priority date	Oct 9, 2013
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

The present invention is directed to a versatile and high performance zwitterionic CP platform, which integrates all desired functions into one material. This zwitterionic CP consists of the conducting backbone and multifunctional zwitterionic side chains. Non-conducting zwitterionic materials gain electronic conductivity through the conducting backbone and CPs obtain excellent biocompatibility, sensitivity to environmental stimuli and controllable antifouling properties via multifunctional zwitterionic side chains. Unique properties from two distinct materials (conducting materials and zwitterionic materials) are integrated into one material without sacrificing any properties. This platform can potentially be adapted for a range of applications (e.g. bioelectronics, tissue engineering, wound healing, robotic prostheses, biofuel cell, etc.), which all require high performance conducting materials with excellent antifouling/biocompatibility at complex biointerfaces. This conducting material platform will significantly advance the development of conducting polymers in the field of biomedicine and biotechnology.

First claim

What is claimed is:

1. A conjugated polymer comprising a conjugated polymer backbone having one or more zwitterionic side chains wherein said zwitterionic side chains further comprise a carboxybetaine group, a sulfobetaine group, a phosphobetaine group or combinations thereof and said conjugated polymer backbone is selected from the group consisting of poly(phenylene)s, poly(pyrene)s, poly(azulene)s, poly(naphthalene)s, poly(pyrrole)s, poly(carbazole)s, poly(indole)s, poly(azepine)s, poly(aniline)s, poly(p-phenylene sulfide)s, poly(p-phenylene vinylene)s, and combinations thereof.

2. The conjugated polymer of claim 1 wherein said zwitterionic side chains comprises a carboxybetaine group.

3. The conjugated polymer of claim 1 wherein said zwitterionic side chains comprises a sulfobetaine group.

4. The conjugated polymer of claim 1 wherein said zwitterionic side chains comprises a phosphobetaine group.

5. The conjugated polymer of claim 1 wherein said zwitterionic side chains further comprise a carboxybetaine group having at least one ethanol, propanol, butanol or pentanol group bonded to the nitrogen atom of said carboxybetaine group.

6. The conjugated polymer of claim 1 wherein said one or more zwitterionic side chains have a formula selected from:

wherein R 1 is —O—, —NH—, —C(O)NH—, —CH 2 C(O)NH—, —CH 2 CH 2 C(O)NH—, —(CH 2 ) m C(O)NH—, —NHC(O)—, —NHC(O)CH 2 —, —NHC(O)CH 2 CH 2 —, —NHC(O)(CH 2 ) m —, —(CH 2 ) m NHC(O)(CH 2 ) n —, —(CH 2 ) m NHC(O)O(CH 2 ) n —, —(CH 2 ) m OC(O)NH(CH 2 ) n —, —(CH 2 ) m C(O)NH(CH 2 ) n —, —NHC(O)(CH 2 ) m C(O)NH—, OC(O)(CH 2 ) m C(O)NH—, —O(CH 2 ) m C(O)NH—, —NHC(O)(CH 2 ) m O—, —NHC(O)(CH 2 ) m C(O)O—, —C(O)O—, —CH 2 C(O)O—, —CH 2 CH 2 C(O)O—, —(CH 2 ) m C(O)O—, OC(O)—, —OC(O)CH 2 —, —OC(O)CH 2 CH 2 —, —OC(O)(CH 2 ) m —, —OC(O)(CH 2 ) m C(O)O—, —OC(O)(CH 2 ) m O—, —O(CH 2 ) m C(O)O—, —(CH 2 ) m OC(O)(CH 2 ) n —, —(CH 2 ) m C(O)O(CH 2 ) n —, —CH 2 O—, —CH 2 CH 2 O—, —CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O—, —(CH 2 ) m O—, —O(CH 2 ) m O—, —O(CH 2 ) m —, —(CH 2 ) m —, —O(CH 2 CH 2 O) m , —(OCH 2 CH 2 ) m — or —(CH 2 CH 2 O) m —; R 2 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, or —(CH 2 ) x —; R 3 is H, —CH 3 , CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 OH, or —CH 2 CH 2 CH 2 CH 2 CH 2 OH; R 4 is H, —CH 3 , CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 OH, or —CH 2 CH 2 CH 2 CH 2 CH 2 OH; R 5 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, or —(CH 2 ) y ; m, n, x and y are an integer from 1 to 20; is the conjugated polymer backbone.

7. The conjugated polymer of claim 1 wherein said one or more zwitterionic side chains have the formula:

wherein R 1 is —O—, —NH—, —C(O)NH—, —CH 2 C(O)NH—, —CH 2 CH 2 C(O)NH—, —(CH 2 ) m C(O)NH—, —NHC(O)—, —NHC(O)CH 2 —, —NHC(O)CH 2 CH 2 —, —NHC(O)(CH 2 ) m —, —(CH 2 ) m NHC(O)(CH 2 ) n —, —(CH 2 ) m NHC(O)O(CH 2 ) n —, —(CH 2 ) m OC(O)NH(CH 2 ) n —, —(CH 2 ) m C(O)NH(CH 2 ) n —, —NHC(O)(CH 2 ) m C(O)NH—, OC(O)(CH 2 ) m C(O)NH—, —O(CH 2 ) m C(O)NH—, —NHC(O)(CH 2 ) m O—, —NHC(O)(CH 2 ) m C(O)O—, —C(O)O—, —CH 2 C(O)O—, —CH 2 CH 2 C(O)O—, —(CH 2 ) m C(O)O—, OC(O)—, —OC(O)CH 2 —, —OC(O)CH 2 CH 2 —, —OC(O)(CH 2 ) m —, —OC(O)(CH 2 ) m C(O)O—, —OC(O)(CH 2 ) m O—, —O(CH 2 ) m C(O)O—, —(CH 2 ) m OC(O)(CH 2 ) n —, —(CH 2 ) m C(O)O(CH 2 ) n —, —CH 2 O—, —CH 2 CH 2 O—, —CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O—, —(CH 2 ) m O—, —O(CH 2 ) m O—, —O(CH 2 ) m —, —(CH 2 ) m —, —O(CH 2 CH 2 O) m , —(OCH 2 CH 2 ) m — or —(CH 2 CH 2 O) m —; R 2 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —(CH 2 ) x —, —NHC(O)—, —C(O)NH—, —NHC(O)O—, —NHC(O)CH 2 —, —NHC(O)CH 2 CH 2 —, NHC(O)(CH 2 ) x —, NHC(O)O(CH 2 ) x —, OC(O)NH(CH 2 ) x , OC(O)NH(CH 2 ) x —, —OC(O)—, —OC(O)CH 2 —, —OC(O)CH 2 CH 2 — or —OC(O)(CH 2 ) x —; R 3 is —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, or —(CH 2 ) y —; R 4 is H, —CH 3 , CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 OH, or —CH 2 CH 2 CH 2 CH 2 CH 2 OH; R 5 is H, —CH 3 , CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 OH, or —CH 2 CH 2 CH 2 CH 2 CH 2 OH; R 6 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 — or —(CH 2 ) z ; m, n, x, y and z are an integer from 1 to 20 and is the conjugated polymer backbone.

8. The conjugated polymer of claim 1 wherein said one or more zwitterionic side chains have the formula:

wherein R 1 is —O—, —NH—, —C(O)NH—, —CH 2 C(O)NH—, —CH 2 CH 2 C(O)NH—, —(CH 2 ) m C(O)NH—, —NHC(O)—, —NHC(O)CH 2 —, —NHC(O)CH 2 CH 2 —, —NHC(O)(CH 2 ) m —, —(CH 2 ) m NHC(O)(CH 2 ) n —, —(CH 2 ) m NHC(O)O(CH 2 ) n —, —(CH 2 ) m OC(O)NH(CH 2 ) n —, —(CH 2 ) m C(O)NH(CH 2 ) n —, —NHC(O)(CH 2 ) m C(O)NH—, OC(O)(CH 2 ) m C(O)NH—, —O(CH 2 ) m C(O)NH—, —NHC(O)(CH 2 ) m O—, —NHC(O)(CH 2 ) m C(O)O—, —C(O)O—, —CH 2 C(O)O—, —CH 2 CH 2 C(O)O—, —(CH 2 ) m C(O)O—, OC(O)—, —OC(O)CH 2 —, —OC(O)CH 2 CH 2 —, —OC(O)(CH 2 ) m —, —OC(O)(CH 2 ) m C(O)O—, —OC(O)(CH 2 ) m O—, —O(CH 2 ) m C(O)O—, —(CH 2 ) m OC(O) (CH 2 ) n —, —(CH 2 ) m C(O)O(CH 2 ) n —, —CH 2 O—, —CH 2 CH 2 O—, —CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 CH 2 O—, —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 O—, —(CH 2 ) m O—, —O(CH 2 ) m O—, —O(CH 2 ) m —, —(CH 2 ) m —, —O(CH 2 CH 2 O) m , —(OCH 2 CH 2 ) m — or —(CH 2 CH 2 O) m —; R 2 is —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —, —(CH 2 ) x —, —NHC(O)—, —NHC(O)CH 2 —, —NHC(O)CH 2 CH 2 —, NHC(O)(CH 2 ) x —, —OC(O)—, —OC(O)CH 2 —, —OC(O)CH 2 CH 2 — or —OC(O))(CH 2 ) x —; R 3 is —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 — or —(CH 2 ) y —; R 4 is —H, —CH 3 , CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 OH, or —CH 2 CH 2 CH 2 CH 2 CH 2 OH; R 5 is H, —CH 3 , CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 CH 2 OH; R 6 is H, —CH 3 , CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH 2 OH, —CH 2 CH 2 CH 2 OH, —CH 2 CH 2 CH 2 CH 2 OH, or —CH 2 CH 2 CH 2 CH 2 CH 2 OH; m, n, x and y are an integer from 1 to 20 and the conjugated polymer backbone.

9. The conjugated polymer of claim 1 wherein said one or more zwitterionic side chains have a formula:

wherein R 1 is —O—, —NH—, —C(O)NH—, —CH 2 C(O)NH—, —CH 2 CH 2 C(O)NH—, —(CH 2 ) m C(O)NH—, —NHC(O)—, —NHC(O)CH 2 —, —NHC(O)CH 2 CH 2 —, —NHC(O)(CH 2 ) m —, —(CH 2 ) m NHC(O)(CH 2 ) n —, —(CH 2 ) m NHC(O)O(CH 2 ) n —, —(CH 2 ) m OC(O)NH(CH 2 ) n —, —C(O)NH(CH 2 ) n —, —NHC(O)(CH 2 ) n —, —(CH 2 ) m C(O)NH(CH 2 ) n —, —NHC(O)(CH 2 ) m C(O)NH—, OC(O)(CH 2 ) m C(O)NH—, —O(CH 2 ) m C(O)NH—, —NHC(O)(CH 2 ) m O—, —CH 2 C(O)O—, —OC(O)CH 2 —, —OC(O)CH 2 CH 2 —, —OC(O)(CH 2 ) m —, —OC(O)(CH 2 ) m O—, —(CH 2 ) m OC(O) (CH 2 ) n —, —(CH 2 ) m C(O)O

Assignees

• Univ Akron

Inventors

• Cheng Gang

Classifications

• C09D5/16

  Antifouling paints; Underwater paints · CPC title

• C08G2261/522

  fluorescent · CPC title

• C08G2261/51

  Charge transport · CPC title

• C08G2261/147

  Side-chains with other heteroatoms in the side-chain · CPC title

• C08G2261/1452

  containing sulfonyl or sulfonate-groups · CPC title