RENEWABLE BIOELECTRONIC INTERFACE FOR ELECTROBIOCATALYTIC REACTOR

• US 20100314248A1
• Filed: 04/23/2010
• Published: 12/16/2010
• Est. Priority Date: 05/10/2005
• Status: Active Grant

• Current Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Original Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Inventors: Worden, Robert M., Hassler, Brian L., Lee, Ilsoon, Drzal, Lawrence T.
• Granted Patent: US 9,406,959 B2
• Time in Patent Office: Days
• US Class Current: 204/403.14
• 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: C25B 11/051 Electrodes formed of electrocatalysts on a substrate or carrier
• CPC Class Codes: C25B 11/057 consisting of a single element or compound
• CPC Class Codes: C25B 11/095 at least one of the compounds being organic
• CPC Class Codes: G01N 27/3272 Test elements therefor, i.e. disposable laminated substrates with electrodes, reagent and channels optical biosensors G01N33/52
• CPC Class Codes: H01M 4/9008 Organic or organo-metallic compounds
• CPC Class Codes: H01M 8/16 Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

An inexpensive, easily renewable bioelectronic device useful for bioreactors, biosensors, and biofuel cells includes an electrically conductive carbon electrode and a bioelectronic interface bonded to a surface of the electrically conductive carbon electrode, wherein the bioelectronic interface includes catalytically active material that is electrostatically bound directly or indirectly to the electrically conductive carbon electrode to facilitate easy removal upon a change in pH, thereby allowing easy regeneration of the bioelectronic interface.

Claims

1. A bioelectronic device comprising:

an electrically conductive carbon electrode; and

a bioelectronic interface bonded to a surface of the electrically conductive carbon electrode, the bioelectronic interface including a catalytically active material that facilitates electron transfer, the catalytically active material electrostatically bound directly or indirectly to the electrically conductive carbon electrode.

2. The device of claim 1, in which the catalytically active material includes an enzyme that is bound directly or indirectly to a polyelectrolyte.

3. The device of claim 2, in which the enzyme is an oxidoreductase.

4. The device of claim 2, in which the enzyme is a dehydrogenase.

5. The device of claim 2, in which the enzyme is a secondary alcohol dehydrogenase.

6. The device of claim 2, in which the enzyme is a mannitol dehydrogenase.

7. The device of claim 2, in which a polyelectrolyte is electrostatically bound directly to the surface of the electrically conductive carbon electrode.

8. The device of claim 2, in which a polyelectrolyte is electrostatically bound to an ionic linker that is covalently bound to the surface of the electrically conductive carbon electrode.

9. The device of claim 8, in which the ionic linker that is covalently bound to a carbon atom at the surface of the electrically conductive carbon electrode is glycine.

10. The device of claim 8, in which the polyelectrolyte that is covalently bound to a carbon atom at the surface of the electrically conductive carbon electrode is comprised of a compound that includes a linking moiety covalently bound to the carbon atom at the surface of the electrically conductive carbon electrode, and further includes at least one ionized moiety for achieving the direct or indirect electrostatic bonding of the catalytically active material to the electrically conductive carbon electrode.

11. The device of claim 1, in which the electrically conductive carbon electrode is a glassy carbon electrode.

12. The device of claim 1, in which the electrically conductive carbon electrode is a reticulated vitreous carbon electrode.

13. The device of claim 1, in which the bioelectronic interface further comprises a redox cofactor that facilitates or enhances activity of the catalytically active material.

14. The device of claim 13, in which the bioelectronic interface includes an electron mediator that reduces the electrical potential needed to transfer electrons during a chemical reaction.

15. The device of claim 14, in which the electron mediator is toluidine blue O.

16. The device of claim 14, in which the electron mediator is neutral red.

17. The device of claim 14, in which the electron mediator is Nile blue A.

18. The device of claim 13, in which the redox cofactor is covalently bound to a polyelectrolyte that is electrostatically bound directly or indirectly to the surface of the electrically conductive carbon electrode.

19. The device of claim 13, in which the redox cofactor is selected from the group consisting of nicotinamide adenine dinucleotide (NAD), nicotinamide adenine dinucleotide phosphate (NADP), flavin adenine dinucleotide (FAD), and flavin mononucleotide (FMN).

20. The device of claim 13, in which a boronate linkage is used to bind the redox cofactor to the polyelectrolyte that is electrostatically bound directly or indirectly to the surface of the electrically conductive carbon electrode.

21. The device of claim 1, in which the polyelectrolyte is polyethyleneimine.

22. The device of claim 1, in which the exfoliated graphite nanoplatelets are incorporated as a component of the bioelectronic interface.

23. The device of claim 1, in which carbon nanotubes are incorporated as a component of the bioelectronic interface.

24. The device of claim 1, in which fullerenes are incorporated as a component of the bioelectronic interface.

25. The bioelectronic device of claim 1, in which the catalytically active material is associated with multiple layers that are bound together by alternating layers of oppositely charged polyelectrolytes.

26. The device of claim 25, in which a redox cofactor is associated with multiple layers that are bound together by alternating layers of oppositely charged polyelectrolytes.

27. The device of claim 25, in which a redox cofactor and an electron mediator is associated with multiple layers that are bound together by alternating layers of oppositely charged polyelectrolytes.

28. The device of claim 25, in which the oppositely charged polyelectrolytes are polyethyleneimine (PEI) and polyacrylic acid (PAA).

29. The device of claim 1, wherein a polyelectrolyte ionically bonds a dehydrogenase enzyme and a redox cofactor to an ionically functionalized, electrically conductive carbon electrode to which an electron mediator is bound.

30. The device of claim 1, in which the catalytically active material includes at least two different catalytically active components.

31. The device of claim 30, in which the catalytically active components are enzymes that catalyze different reactions.

32. The device of claim 30, in which one of the two enzymes is a xylose isomerase and the other enzyme is a mannitol dehydrogenase.

33. The device of claim 30, in which a branched heterotrifunctional linking molecule and polyelectrolytes are used to couple the enzymes, and optionally couple a redox cofactor for one or both of the enzymes, and optionally couple an electron mediator for one or both of the redox cofactors.

35. A process for reconstituting a bioelectronic interface of a bioelectronic device, comprising the steps of:

providing a bioelectronic device comprising an electrically conductive carbon electrode and a bioelectronic interface having catalytically active material electrostatically bound directly or indirectly to a surface of the electrically conductive carbon electrode;

exposing the bioelectronic interface to an aqueous medium having a first pH that releases the catalytically active material from the surface of the electrically conductive carbon electrode;

exposing the electrically conductive carbon electrode to an aqueous medium having a second pH that facilitates electrostatic bonding of a catalytically active material to the surface of the electrically conductive carbon electrode; and

introducing catalytically active material to the aqueous medium, and electrostatically bonding the catalytically active material to the surface of the electrically conductive carbon electrode, so that the bioelectronic interface'"'"'s catalytic activity is restored.

36. The process of claim 35, wherein the steps are performed on a bioelectronic device installed in a bioreactor, thereby facilitating in situ reconstitution of the bioelectric interface without removal of the bioelectric device from the bioreactor.

37. An electrobiocatalytic reactor comprising:

a cathode compartment containing a first electrolytic solution and an anode compartment containing a second electrolytic solution, the anode compartment and cathode compartments being separated by a proton permeable membrane;

a cathode located at the cathode compartment and in contact with the first electrolyte, and an anode located at the anode compartment and in contact with the second electrolyte, at least one of the anode and cathode being an electrically conductive carbon electrode; and

a bioelectronic interface bonded to a surface of at least one electrically conductive carbon electrode, the bioelectronic interface including a catalytically active material that facilitates electron transfer, the catalytically active material electrostatically bound directly or indirectly to the electrically conductive carbon electrode.

38. The reactor of claim 37, wherein the cathode is an electrically conductive carbon electrode having a bioelectronic interface comprising xylose isomerase and mannitol dehydrogenase bound to the surface of the cathode, wherein the anode is an electrically conductive carbon electrode having a bioelectronic interface comprising glycerol dehydrogenase, whereby the reactor is configured to produce mannitol from glucose and simultaneously produce dihydroxyacetone from glycerol.