Redox polymers

• US 8,795,490 B2
• Filed: 08/22/2011
• Issued: 08/05/2014
• 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): Van, Luan
• Assistant Examiner(s): Kessel, Maris R
• Application Number:
  US13/214,999
• Publication Number:
  US 20110303537A1
• Time in Patent Office: 1,079 Days
• Field of Search: 204/403.1, 204/403.04, 204/403.14, 526/161, 546/2, 548/101
• US Class Current: 204/403.14
• 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 electrochemical sensor comprising:

a working electrode and a counter electrode, wherein the working electrode comprises a polymeric transition metal complex, the polymeric transition metal complex comprising;

a transition metal complex comprising the formula;

2. The electrochemical sensor of claim 1, further comprising an analyte-responsive enzyme.

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

4. The electrochemical sensor of claim 2, wherein the analyte-responsive enzyme is covalently coupled to the polymer backbone.

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

6. The electrochemical sensor of claim 1, wherein the spacer comprises —

C(O)NR^t—

.

7. The electrochemical 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.

8. The electrochemical 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.

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

10. The electrochemical 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.

11. The electrochemical sensor of claim 8, wherein the transition metal complex comprises at least one substituted or unsubstituted 2,2′

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

12. The electrochemical sensor of claim 1, wherein the polymer is crosslinked.

13. The electrochemical sensor of claim 1, wherein the transition metal complex has the formula:

14. The electrochemical sensor of claim 1, wherein the transition metal complex has the formula:

15. The electrochemical sensor of claim 1, wherein the transition metal complex has the formula:

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

S(O)₂NR^k—

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

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

CR^v═

N—

O—

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

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

CR^w═

NNR^x—

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

19. The electrochemical 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.