Electrode arrangement with improved electron transfer rates for redox of molecules

• US 10,281,424 B2
• Filed: 06/27/2016
• Issued: 05/07/2019
• Est. Priority Date: 06/27/2016
• Status: Active Grant

• Current Assignee: Robert Bosch GmbH
• Original Assignee: Robert Bosch GmbH
• Inventors: Fomina, Nadezda, Maruniak, Autumn, Johnson, Christopher, Ahmad, Habib, Kavusi, Sam
• Primary Examiner(s): Noguerola, Alexander S
• Application Number:
  US15/194,290
• Publication Number:
  US 20170370870A1
• Time in Patent Office: 1,044 Days
• CPC Class Codes: B05D 1/60 Deposition of organic layers from vapour phase vapour phase deposition in general C23C14/00, C23C16/00
• CPC Class Codes: C12Q 1/004 mediator-assisted
• CPC Class Codes: C25D 3/48 of gold
• CPC Class Codes: C25D 7/00 Electroplating characterised by the article coated
• CPC Class Codes: C25D 9/08 by cathodic processes
• CPC Class Codes: G01N 27/305 optically transparent or photoresponsive electrodes
• CPC Class Codes: G01N 27/307 Disposable laminated or multilayered electrodes G01N27/3272 takes precedence
• CPC Class Codes: G01N 27/327 Biochemical electrodes , e.g. electrical or mechanical details for in vitro measurements
• CPC Class Codes: G01N 27/3277 being a redox reaction, e.g. detection by cyclic voltammetry voltammetry per se G01N27/42, G01N27/48

Abstract

A coated electrode includes an electrode, a coating configured to immobilize biomolecules, and a coating configured to improve electron transfer rate. Methods of making the coated electrode are also provided. A biosensor comprises a plurality of electrodes, each electrode including the coated electrode.

Claims

1. A coated electrode comprising:

(a) an electrode;

(b) a coating configured to immobilize biomolecules; and

(c) a coating configured to improve electron transfer rate;

wherein one or both of the following;

(1) the coated electrode further comprises (d) a quinone that the electrode is configured to trigger to regulate or sense a pH level in a region local to the coated electrode; and

(2) the coating configured to immobilize biomolecules comprises poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers.

2. The coated electrode of claim 1, wherein the electrode is an indium tin oxide electrode.

3. The coated electrode of claim 1, wherein the coated electrode is configured to activate a quinone to regulate or sense a pH level in a region local to the coated electrode.

4. The coated electrode of claim 1, wherein the coated electrode further comprises the quinone that the electrode is configured to trigger to regulate or sense the pH level in the region local to the coated electrode.

5. The coated electrode of claim 1, wherein the coating configured to immobilize biomolecules comprises the poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers.

6. The coated electrode of claim 5, wherein the coating configured to immobilize biomolecules contains gaps in between each of the poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers.

7. The coated electrode of claim 6, wherein the coating configured to improve electron transfer rate is deposited in the gaps in between each of the poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers, such that the two coatings are interspersed among each other.

8. The coated electrode of claim 7, wherein a thickness of the coating configured to improve electron transfer rate is less than a thickness of the coating configured to immobilize biomolecules.

9. The coated electrode of claim 1, wherein the coating configured to improve electron transfer rate contains one or more chemical handles, and wherein the one or more chemical handles are configured to bind the coating configured to immobilize biomolecules to the coating configured to improve electron transfer rate.

10. The coated electrode of claim 9, wherein the one or more chemical handles are selected from a group consisting of carboxylates, amines, and thiols.

11. The coated electrode of claim 1, wherein the coating configured to improve electron transfer rate is made entirely or substantially of conductive organic polymers.

12. The coated electrode of claim 11, wherein the conductive organic polymers are selected from a group consisting of polyanilines, polythiophenes, polypyrroles, polyindoles, and polyphenylenes.

13. The coated electrode of claim 1, wherein the coating configured to improve electron transfer rate is made entirely or substantially of an inorganic conductive material.

14. The coated electrode of claim 13, wherein the inorganic conductive material comprises nanoparticles.

15. The coated electrode of claim 13, wherein the inorganic conductive material is selected from a group consisting of gold, platinum, and palladium.

16. The coated electrode of claim 13, wherein the coating configured to improve electron transfer rate is less than 100 nanometers.

17. The coated electrode of claim 1, wherein the coating configured to improve electron transfer rate is made entirely or substantially of graphene.

18. A biosensor comprising a plurality of electrodes, wherein:

each of the plurality of electrodes comprises a coated electrode that includes;

(a) an electrode;

(b) a coating configured to immobilize biomolecules; and

(c) a coating configured to improve electron transfer rate; and

one or both of the following;

(1) the coated electrode further comprises (d) a quinone that the electrode is configured to trigger to regulate or sense a pH level in a region local to the coated electrode; and

(2) the coating configured to immobilize biomolecules comprises poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers.

19. A method of modifying an electrode, the method comprising:

(a) providing an electrode with a coating configured to immobilize biomolecules via one or more chemical groups; and

(b) applying to the electrode a coating configured to improve electron transfer rate;

wherein one or both of the following;

(1) the method further comprises (c) applying to the electrode a quinone that the electrode is configured to trigger to regulate or sense a pH level in a region local to the electrode; and

(2) the coating configured to immobilize biomolecules comprises poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers.

20. The method of claim 19, wherein the coating configured to immobilize biomolecules comprises the poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers.

21. The method of claim 19, wherein the electrode is an indium tin oxide electrode.

22. The method of claim 19, wherein the coating configured to improve electron transfer rate is made entirely or substantially of conductive organic polymers.

23. The method of claim 22, wherein the conductive organic polymers are selected from a group consisting of polyanilines, polythiophenes, polypyrroles, polyindoles, and polyphenylenes.

24. The method of claim 22, further comprising:

inactivating the one or more chemical groups of the coating configured to immobilize biomolecules prior to applying the coating configured to improve electron transfer rate; and

reactivating the one or more chemical groups subsequent to applying the coating configured to improve electron transfer rate.

25. The method of claim 24, wherein the one or more chemical groups are deactivated using hydrolysis.

26. The method of claim 22, wherein the coating configured to improve electron transfer rate is applied using electropolymerization.

27. The method of claim 19, wherein the coating configured to improve electron transfer rate is made entirely or substantially of an inorganic conductive material.

28. The method of claim 27, wherein the inorganic conductive material comprises nanoparticles.

29. The method of claim 27, wherein the inorganic conductive material is selected from a group consisting of gold, platinum, and palladium.

30. The method of claim 27, wherein the coating configured to improve electron transfer rate is applied using a technique selected from a group consisting of vapor-phase deposition, electroplating, electrodeposition, and solution-phase deposition.

31. The method of claim 27, wherein the coating configured to improve electron transfer rate is less than 100 nanometers.

32. The method of claim 19, wherein the coating configured to improve electron transfer rate is made entirely or substantially of graphene.

33. The method of claim 32, wherein the coating configured to improve electron transfer rate is applied using electrodeposition or covalent attachment.

34. A method of modifying an electrode, the method comprising:

(a) providing an electrode;

(b) applying to the electrode a coating configured to improve electron transfer rate;

(c) incorporating one or more chemical handles onto the coating configured to improve electron transfer rate; and

(d) applying to the electrode a coating configured to immobilize biomolecules via one or more chemical groups, wherein the one or more chemical handles are configured to bind the coating configured to immobilize biomolecules to the coating configured to improve electron transfer rate;

wherein one or both of the following;

(1) the method further comprises (c) applying to the electrode a quinone that the electrode is configured to trigger to regulate or sense a pH level in a region local to the electrode; and

(2) the coating configured to immobilize biomolecules comprises poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymers.

35. The method of claim 34, wherein the coating configured to immobilize biomolecules comprises the poly(ethylene glycol) carboxymethyl succinimidyl ester (PEG-NHS) polymer.

36. The method of claim 34, wherein the electrode is an indium tin oxide electrode.

37. The method of claim 34, wherein the one or more chemical handles is selected from a group consisting of carboxylates, amines, and thiols.

38. The method of claim 34, wherein the coating configured to improve electron transfer rate is made entirely or substantially of a conductive organic polymer.

39. The method of claim 38, wherein the conductive organic polymer is selected from a group consisting of polyanilines, polythiophenes, polypyrroles, polyindoles, and polyphenylenes.

40. The method of claim 38, wherein the coating configured to improve electron transfer rate is made entirely or substantially of an inorganic conductive material.

41. The method of claim 40, wherein the inorganic conductive material is platinum or palladium.

42. The method of claim 34, wherein the coating configured to improve electron transfer rate is made entirely or substantially of graphene.

43. A method comprising:

contacting a coated electrode with a solution that includes a quinone, wherein the coated electrode includes (a) an electrode, (b) a coating configured to immobilize biomolecules, and (c) a coating configured to improve electron transfer rate;

measuring a pH level of a region local to the coated electrode; and

adjusting the pH level;

wherein the measuring and adjusting of the pH level includes applying a charge to the coated electrode to activate the quinone.