Redox polymers

• US 10,219,730 B2
• Filed: 04/20/2016
• Issued: 03/05/2019
• Est. Priority Date: 11/15/1999
• Status: Expired due to Fees

• Current Assignee: Abbott Diabetes Care Incorporated (Abbott Laboratories Incorporated)
• Original Assignee: Abbott Diabetes Care Incorporated (Abbott Laboratories Incorporated)
• Inventors: Mao, Fei, Heller, Adam
• Primary Examiner(s): Kessel, Maris R
• Application Number:
  US15/134,116
• Publication Number:
  US 20160296147A1
• Time in Patent Office: 1,049 Days
• CPC Class Codes: A61B 5/14532 for measuring glucose, e.g. by tissue impedance measurement
• CPC Class Codes: A61B 5/1477 non-invasive
• CPC Class Codes: A61B 5/1486 using enzyme electrodes, e.g. with immobilised oxidase
• CPC Class Codes: C07F 15/0026 without a metal-carbon linkage
• CPC Class Codes: C07F 15/0053 without a metal-carbon linkage
• CPC Class Codes: C07F 15/025 without a metal-carbon linkage
• CPC Class Codes: C07F 15/065 without a metal-carbon linkage
• CPC Class Codes: C07F 9/005 Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
• CPC Class Codes: C08F 8/42 Introducing metal atoms or metal-containing groups
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: C09B 57/10 Metal complexes of organic compounds not being dyes in uncomplexed form
• CPC Class Codes: C12Q 1/004 mediator-assisted

Abstract

Novel transition metal complexes of iron, cobalt, ruthenium, osmium, and vanadium are described. The transition metal complexes can be used as redox mediators in enzyme based electrochemical sensors. In such instances, transition metal complexes accept electrons from, or transfer electrons to, enzymes at a high rate and also exchange electrons rapidly with the sensor. The transition metal complexes include at least one substituted or unsubstituted biimidazole ligand and may further include a second substituted or unsubstituted biimidazole ligand or a substituted or unsubstituted bipyridine or pyridylimidazole ligand. Transition metal complexes attached to polymeric backbones are also described.

Claims

1. An analyte sensor comprising:

a substrate comprising a non-conductive base material, wherein the substrate comprises a first surface and a second surface that is opposite the first surface;

a counter electrode disposed on the first surface of the substrate;

a working electrode comprising a conductive layer disposed on the second surface of the substrate; and

a reagent positioned on the working electrode, the reagent comprising;

an analyte responsive enzyme; and

a mediator comprising a plurality of polymeric transition metal complexes, each transition metal complex having the formula;

2. The analyte sensor of claim 1, wherein the analyte-responsive enzyme is an enzyme selected from the group consisting of glucose oxidase and glucose dehydrogenase.

3. The analyte sensor of claim 1, wherein the polymer backbone comprises a nitrogen containing heterocyclic ring.

4. The analyte sensor of claim 1, wherein the nitrogen-containing heterocycle comprises a substituted or unsubstituted pyridine, imidazole, 2,2′

-bipyridine, 2-(2-pyridyl)imidazole, or 2,2′

-biimidazole.

5. The analyte sensor of claim 1, wherein at least two of L¹, L², L³, L⁴, L⁵, and L⁶ are combined to form at least one multidentate ligand.

6. The analyte sensor of claim 1, wherein at least four of L¹, L², L³, L⁴, L⁵, and L⁶ are combined to form at least two multidentate ligands.

7. The analyte sensor of claim 1, wherein at least four of L¹, L², L³, L⁴, L⁵, and L⁶ are combined to form at least two multidentate ligands selected from the group consisting of substituted and unsubstituted 2,2′

-bipyridines, 2-(2-pyridyl)imidazoles, and 2,2′

-biimidazoles.

8. The analyte sensor of claim 7, wherein the mediator comprises at least one substituted or unsubstituted 2,2′

-biimidazole or 2-(2-pyridyl)imidazole.

9. The analyte sensor of claim 1, wherein the mediator has the formula:

10. The analyte sensor of claim 1, wherein the mediator has the formula:

11. The analyte sensor of claim 1, wherein the mediator has the formula:

12. The analyte sensor of claim 1, wherein the analyte-responsive enzyme further comprises an enzyme cofactor.

13. The analyte sensor unit of claim 12, wherein the enzyme cofactor is flavin adenine dinucleotide.

14. The analyte sensor of claim 1, wherein the polymer is crosslinked.

15. The analyte sensor of claim 1, wherein the spacer comprises —

C(O)O—

or —

S(O)₂NR^k—

, wherein R^k, is hydrogen or substituted or unsubstituted alkyl.

16. The analyte sensor of claim 1, wherein the spacer comprises —

C(O)NR^t—

.

17. The analyte sensor of claim 1, wherein the spacer comprises —

(CR^rR^s)—

, wherein R^r and R^s are independently hydrogen, chlorine, fluorine, or substituted or unsubstituted alkyl, alkoxy, alkenyl, or alkynyl.

18. The analyte sensor of claim 1, wherein the spacer comprises —

O—

or —

S—

.

19. The analyte sensor of claim 1, wherein the spacer comprises —

CR^v═

N—

O—

or —

CR^w═

NNR^x—

, wherein R^v, is hydrogen or substituted or unsubstituted alkyl and wherein R^w and R^x are independently hydrogen or substituted or unsubstituted alkyl.

20. The analyte sensor of claim 1, wherein the spacer comprises —

(SiR^yR^z)—

, wherein R^y and R^z are independently hydrogen or substituted or unsubstituted alkyl.