Electron conducting crosslinked polyaniline-based redox hydrogel, and method of making

• US 9,303,279 B2
• Filed: 04/08/2014
• Issued: 04/05/2016
• Est. Priority Date: 05/03/2007
• Status: Expired due to Fees

• Current Assignee: Abbott Diabetes Care Incorporated (Abbott Laboratories Incorporated)
• Original Assignee: Abbott Diabetes Care Incorporated (Abbott Laboratories Incorporated)
• Inventors: Heller, Adam, Feldman, Benjamin J., Mano, Nicolas, Loo, Yueh-Lin
• Primary Examiner(s): Claytor, Renee
• Assistant Examiner(s): Fernandez, Susan E
• Application Number:
  US14/248,005
• Publication Number:
  US 20140216931A1
• Time in Patent Office: 728 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C12Q 1/001 Enzyme electrodes
• CPC Class Codes: C12Q 1/005 involving specific analytes or enzymes including groups of enzymes, e.g. oxydases; C12Q1/004 takes precedence
• CPC Class Codes: C12Q 1/006 for glucose
• CPC Class Codes: C12Q 1/26 involving oxidoreductase
• CPC Class Codes: G01N 27/327 Biochemical electrodes , e.g. electrical or mechanical details for in vitro measurements
• CPC Class Codes: G01N 27/3271 Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood amperometry per se G01N27/49; aspects concerning the enzyme reagent C12Q1/001

Abstract

A polymer matrix that may coated on an electrode is created by co-crosslinking (1) an adduct of a polyaniline formed by templated oxidative polymerization on a polymer acid; (2) a water-soluble crosslinker; and (3) a redox enzyme. The polymer matrix may be hydrated, and the absorbed water may make it permeable to, for example, glucose. The polyaniline may be polyaniline itself or a substituted polyaniline; the water-soluble crosslinker may be poly(ethylene glycol)diglycidyl ether, and the redox enzyme may be glucose oxidase. The polymer matrix may be produced by co-crosslinking (1) an adduct of an electrically conductive polymer and a polymer acid; (2) a water-soluble crosslinker; and (3) a redox enzyme in a single step at an about neutral pH, curing by drying. After hydration, the crosslinked polymer matrix may form a 3-dimensional glucose-permeable bioelectrocatalyst, catalyzing the electrooxidation of glucose.

Claims

1. An electrode, comprising:

a conductive substrate and a crosslinked polymeric matrix deposited thereon comprising a polyaniline crosslinked with a polymer acid and a redox enzyme through a crosslinker.

2. The electrode according to claim 1, wherein the polyaniline is a ring-substituted polyaniline.

3. The electrode according to claim 2, wherein the ring-substituted polyaniline is a compound selected from the group consisting of poly-meta-toluidine, poly-ortho-toluidine, poly-ortho-fluoroaniline, poly-ortho-methoxyaniline and poly-ortho,ortho′

-dimethylaniline.

4. The electrode according to claim 1, wherein the polymer acid is poly(2-acrylamido-2-methyl-propane sulfonic acid) (PAAMSA).

5. The electrode according to claim 4, wherein the polyaniline and PAAMSA are present in a molar ratio of from about 1:

0.7 to about 1;

0.99.

6. The electrode according to claim 1, wherein the crosslinker is a water soluble crosslinker.

7. The electrode according to claim 6, wherein the water soluble crosslinker comprises poly(ethylene glycol) diglycidyl ether.

8. The electrode according to claim 7, wherein the conductive substrate comprises carbon.

9. The electrode according to claim 8, wherein the conductive substrate comprises a corrosion resistant conductor surface.

10. The electrode according to claim 6, wherein the water-soluble crosslinker is present in an amount of from about 2 weight % to about 30 weight %, based upon the dry weight of the polymer matrix.

11. The electrode according to claim 1, wherein the crosslinked polymeric matrix is a hydrogel.

12. The electrode according to claim 11, wherein the hydrogel further comprises water.

13. The electrode according to claim 1, wherein the redox enzyme is selected from the group consisting of a flavoenzyme, a heme enzyme, and a PQQ enzyme.

14. The electrode according to claim 1, wherein the redox enzyme is selected from the group consisting of glucose oxidase, glucose dehydrogenase, and peroxidase.

15. The electrode sensor according to claim 1, wherein the redox enzyme of the crosslinked polymer matrix has an apparent Michaelis-constant obtained from an Edi-Hofstee plot of greater than 10 mM glucose.

16. The electrode according to claim 1, wherein the crosslinked polymer matrix comprises two enzymes, wherein a first enzyme is an enzyme which catalyzes a reaction to form a substrate for the redox enzyme.

17. The electrode according to claim 1, wherein the redox enzyme is present in an amount of from greater than 0 weight % to about 60 weight %, based upon the dry weight of the polymer matrix.