초록 ▼

Disclosed are bioanodes comprising a quaternary ammonium treated Nafion® polymer membrane and a dehydrogenase incorporated within the treated Nafion® polymer. The dehydrogenase catalyzes the oxidation of an organic fuel and reduces an adenine dinucleotide. The ion conducting polymer membrane lies ju

Disclosed are bioanodes comprising a quaternary ammonium treated Nafion® polymer membrane and a dehydrogenase incorporated within the treated Nafion® polymer. The dehydrogenase catalyzes the oxidation of an organic fuel and reduces an adenine dinucleotide. The ion conducting polymer membrane lies juxtaposed to a polymethylene green redox polymer membrane, which serves to electro-oxidize the reduced adenine dinucleotide. The bioanode is used in a fuel cell to produce high power densities.

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What is claimed is: 1. A bioanode comprising (a) an electron conductor; (b) at least one enzyme capable of reacting with an oxidized form of an electron mediator and a fuel fluid to produce an oxidized form of the fuel fluid and a reduced form of the electron mediator, the reduced form of the elect

What is claimed is: 1. A bioanode comprising (a) an electron conductor; (b) at least one enzyme capable of reacting with an oxidized form of an electron mediator and a fuel fluid to produce an oxidized form of the fuel fluid and a reduced form of the electron mediator, the reduced form of the electron mediator being capable of releasing electrons to the electron conductor; and (c) an enzyme immobilization material comprising the electron mediator, the enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the fuel fluid, the stabilized enzyme retaining at least about 75% of its initial catalytic activity for at least about 30 days; wherein the enzyme is entrapped within the enzyme immobilization material. 2. The bioanode of claim 1 wherein the enzyme immobilization material comprises a micellar or inverted micellar structure, the material being permeable to the fuel fluid. 3. The bioanode of claim 1 wherein the enzyme immobilization material comprises an alkylammonium salt extracted perfluoro sulfonic acid-PTFE copolymer, the material being permeable to the fuel fluid. 4. The bioanode of claim 1 wherein the enzyme immobilization material comprises a perfluoro sulfonic acid-PTFE copolymer, modified with a hydrophobic cation larger than NH4+ wherein the hydrophobic cation exchanges for protons as the counterion to the--SO3- groups of the perfluoro sulfonic acid-PTFE copolymer, the material being permeable to the fuel fluid. 5. The bioanode of claim 4 wherein the hydrophobic cation comprises an ammonium-based cation, quatemary ammonium cation, alkyltrimethylammonium cation, organic cation, phosphonium cation, triphenylphosphonium, pyridinium cation, imidazolium cation, hexdecylpyridinium, ethidium, viologen, methyl viologen, benzyl viologen, bis(triphenylphosphine)iminium, metal complex, bipyridyl metal complex, phenanthroline-based metal complex, [Ru(bipyridine)3]2+ or [Fe(phenanthroline)3]3+. 6. The bioanode of claim 4 wherein the hydrophobic cation comprises a quatemary ammonium cation represented by formula 1 wherein R1, R2, R3 and R4 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or heterocyclo wherein at least one of R1, R2, R3 and R4 is other than hydrogen. 7. The bioanode of claim 6 wherein R1, R2, R3 and R4 are independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl wherein at least one of R1, R2, R3 and R4 is other than hydrogen. 8. The bioanode of claim 6 wherein R1, R2, R3 and R4 are the same and are methyl, ethyl, propyl, butyl, pentyl or hexyl. 9. The bioanode of claim 6 wherein R1, R2, R3 and R4 are butyl. 10. The bioanode of claim 1 wherein the electron conductor comprises a carbon-based material, a metallic conductor, a semiconductor, a metal oxide or a modified conductor. 11. The bioanode of claim 10 wherein the electron conductor comprises a carbon-based material. 12. The bioanode of claim 11 wherein the electron conductor comprises carbon cloth, carbon paper, carbon screen printed electrodes, carbon black, carbon powder, carbon fiber, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube arrays, diamond-coated conductors, glass carbon, mesoporous carbon, graphite, uncompressed graphite worms, delaminated purified flake graphite, high performance graphite, highly ordered pyrolytic graphite, pyrolytic graphite or polycrystalline graphite. 13. The bioanode of claim 1 wherein the electron conductor comprises carbon cloth, carbon paper, carbon screen printed electrodes, carbon black, carbon powder, carbon fiber, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube arrays, diamond-coated conductors, glass carbon, mesoporous carbon, graphite, uncompressed graphite worms, delaminated purified flake graphite, high performance graphite, highly ordered pyrolytic graphite, pyrolytic graphite, polycrystalline graphite, gold, platinum, iron, nickel, copper, silver, stainless steel, mercury, tungsten, nanoparticles made of cobalt or diamond, silver-plated nickel screen printed electrodes, metal oxides, metal sulfides, nanoporous titanium oxide, tin oxide coated glass, cerium oxide particles, molybdenum sulfide, boron nitride nanotubes, aerogels modified with carbon, solgels modified with carbon, ruthenium carbon aerogels and mesoporous silicas modified with carbon; silicon or germanium, which can be doped with phosphorus, boron, gallium, arsenic, indium or antimony. 14. The bioanode of claim 1 wherein the enzyme comprises an oxidoreductase. 15. The bioanode of claim 1 wherein the enzyme comprises a dehydrogenase. 16. The bioanode of claim 1 wherein the enzyme comprises an alcohol dehydrogenase, aldehyde dehydrogenase, formate dehydrogenase, formaldehyde dehydrogenase, glucose dehydrogenase, glucose oxidase, lactatic dehydrogenase, lactose dehydrogenase or pyruvate dehydrogenase. 17. The bioanode of claim 16 wherein the enzyme comprises an alcohol dehydrogenase. 18. The bioanode of claim 1 wherein the enzyme immobilization material comprises periluoro sulfonic acid-polytetrafluoro ethylene (PTFE) copolymer, modified perfluoro sulfonic acid-polytetrafluoro ethylene (PTFE) copolymer, polysulfone, micellar polymers, poly(ethylene oxide) based block copolymers, polymers formed from microemulsion, polymers formed from micellar polymerization, copolymers of alkyl methacrylates, alkyl acrylates and styrenes, ceramics, sodium bis(2-ethylhexyl)sulfosuccinate, sodium dioctylsulfonsuccinate, lipids, phospholipids, sodium dodecyl sulfate, decyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, (4-[(2-hydroxyl-1-naphthalenyl)azo]benzenesulfonic acid monosodium salt), linoleic acids, linolenic acids, colloids, liposomes or micelle networks. 19. The bioanode of claim 18 wherein the enzyme immobilization material comprises a perfluoro sulfonic acid-polytetrafluoro ethylene (PTFE) copolymer. 20. The bioanode of claim 18 wherein the enzyme immobilization material comprises a modified perfluoro sulfonic acid-polytetrafluoro ethylene (PTFE) copolymer. 21. The bioanode of claim 1 wherein the electron mediator comprises pyrroloquinoline quinone, phenazine methosulfate, dichlorophenol indophenol, short chain ubiquinones or potassium ferricyanide. 22. The bioanode of claim 4 wherein the electron conductor comprises an uncompressed graphite worm treated with poly(methylene green), the modified perfluoro sulfonic acid-PTFE copolymer is modified with a tetrabutylammonium ion, the enzyme comprises an alcohol dehydrogenase and further comprises a solution containing ethanol and NAD+. 23. A biofuel cell for generating electricity comprising: a fuel fluid; a cathode capable of reducing an oxidant in the presence of electrons to form water; and a bioanode of claim 1. 24. The biofuel cell of claim 23 wherein the bioanode and the cathode are separated by a salt bridge or a polymer electrolyte membrane. 25. The biofuel cell of claim 24 wherein the bioanode and the cathode are separated by a polymer electrolyte membrane wherein the bioanode, polymer electrolyte membrane and cathode are fabricated into a membrane electrode assembly. 26. The biofuel cell of claim 25 wherein the polymer electrolyte membrane comprises a perfluoro sulfonic acid-polytetrafluoro ethylene (PTFE) copolymer. 27. The biofuel cell of claim 23 further comprising a solution of a fuel fluid. 28. The biofuel cell of claim 27 wherein the fuel fluid comprises ammonia, methanol, ethanol, propanol, isobutanol, butanol and isopropanol, allyl alcohols, aryl alcohols, glycerol, propanediol, mannitol, glucuronate, aldehyde, carbohydrates, glucose, glucose-1, D-glucose, L-glucose, glucose-6-phosphate, lactate, lactate-6-phosphate, D-lactate, L-lactate, fructose, galactose-1, galactose, aldose, sorbose, mannose, glycerate, coenzyme A, acetyl Co-A, malate, isocitrate, formaldehyde, acetaldehyde, acetate, citrate, L-gluconate, beta-hydroxysteroid, alpha-hydroxysteroid, lactaldehyde, testosterone, gluconate, fatty acids, lipids, phosphoglycerate, retinal, estradiol, cyclopentanol, hexadecanol, long-chain alcohols, coniferyl-alcohol, cinnamyl-alcohol, formate, long-chain aldehydes, pyruvate, butanal, acyl-CoA, steroids, amino acids, flavin, NADH, NADH2, NADPH, NADPH2 or hydrogen. 29. The biofuel cell of claim 28 wherein the fuel fluid comprises methanol, ethanol or propanol. 30. The biofuel cell of claim 29 wherein the fuel fluid comprises ethanol. 31. The biofuel cell of claim 23 wherein the electron mediator is in solution. 32. The biofuel cell of claim 23 wherein the cathode comprises a biocathode. 33. A method of generating electricity using the biofuel cell of claim 23 comprising (a) oxidizing the fuel fluid at the bioanode and reducing the oxidant at the cathode; (b) reducing the oxidized form of the electron mediator during the oxidization of the fuel fluid at the bioanode; and (c) oxidizing the electron mediator at the electron conductor. 34. The method of claim 33 wherein the fuel fluid comprises ammonia, methanol, ethanol, propanol, isobutanol, butanol and isopropanol, allyl alcohols, aryl alcohols, glycerol, propanediol, mannitol, glucuronate, aldehyde, carbohydrates, glucose, glucose-1, D-glucose, L-glucose, glucose-6-phosphate, lactate, lactate-6-phosphate, D-lactate, L-lactate, fructose, galactose-1, galactose, aldose, sorbose, mannose, glycerate, coenzyme A, acetyl Co-A, malate, isocitrate, formaldehyde, acetaldehyde, acetate, citrate, L-gluconate, beta-hydroxysteroid, alpha-hydroxysteroid, lactaldehyde, testosterone, gluconate, fatty acids, lipids, phosphoglycerate, retinal, estradiol, cyclopentanol, hexadecanol, long-chain alcohols, coniferyl-alcohol, cinnamyl-alcohol, formate, long-chain aldehydes, pyruvate, butanal, acyl-CoA, steroids, amino acids, flavin, NADH, NADH2, NADPH, NADPH2 or hydrogen. 35. The method of claim 33 wherein the fuel fluid comprises methanol, ethanol or propanol. 36. The method of claim 34 wherein the fuel fluid comprises ethanol. 37. The method of claim 33 wherein the electron mediator comprises pyrroloquinoline quinone, phenazine methosulfate, dichlorophenol indophenol, short chain ubiquinones or potassium ferricyanide. 38. The method of claim 37 wherein the electron mediator comprises pyrroloquinoline quinone (PQQ). 39. The method of claim 33 wherein the electron conductor comprises carbon cloth, the modified perfluoro sulfonic acid-PTFE copolymer is modified with a tetrabutylammonium ion, the enzyme comprises an alcohol dehydrogenase, the fuel fluid comprises ethanol and the electron mediator comprises PQQ. 40. The biofuel cell of claim 23 wherein the electron conductor comprises a carbon-based material, a metallic conductor, a semiconductor, a metal oxide or a modified conductor. 41. The biofuel cell of claim 40 wherein the electron conductor comprises carbon cloth, carbon paper, carbon screen printed electrodes, carbon black, carbon powder, carbon fiber, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube arrays, diamond-coated conductors, glass carbon, mesoporous carbon, graphite, uncompressed graphite worms, delaminated purified flake graphite, high performance graphite, highly ordered pyrolytic graphite, pyrolytic graphite, polycrystalline graphite, gold, platinum, iron, nickel, copper, silver, stainless steel, mercury, tungsten, nanoparticles made of cobalt or diamond, silver-plated nickel screen printed electrodes, metal oxides, metal sulfides, nanoporous titanium oxide, tin oxide coated glass, cerium oxide particles, molybdenum sulfide, boron nitride nanotubes, aerogels modified with carbon, solgels modified with carbon, ruthenium carbon aerogels and mesoporous silicas modified with carbon; silicon or germanium, which can be doped with phosphorus, boron, gallium, arsenic, indium or antimony. 42. The biofuel cell of claim 41 wherein the electron conductor comprises a carbon-based material. 43. The biofuel cell of claim 42 wherein the electron conductor comprises carbon cloth, carbon paper, carbon screen printed electrodes, carbon black, carbon powder, carbon fiber, single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube arrays, diamond-coated conductors, glass carbon, mesoporous carbon, graphite, uncompressed graphite worms, delaminated purified flake graphite, high performance graphite, highly ordered pyrolytic graphite, pyrolytic graphite or polycrystalline graphite. 44. The biofuel cell of claim 23 wherein the enzyme immobilization material is modified with a hydrophobic cation larger than NH4+. 45. The biofuel cell of claim 44 wherein the hydrophobic cation comprises an ammonium-based cation, quatemary ammonium cation, alkyltrimethylammonium cation, organic cation, phosphonium cation, triphenylphosphonium, pyridinium cation, imidazolium cation, hexdecylpyridinium, ethidium, viologen, methyl viologen, benzyl viologen, bis(triphenylphosphine)iminium, metal complex, bipyridyl metal complex, phenanthroline-based metal complex, [Ru(bipyridine)3]2+ or [Fe(phenanthroline)3]3+. 46. The biofuel cell of claim 44 wherein the hydrophobic cation comprises a quatemary ammonium cation represented by formula 1 wherein R1, R2, R3 and R4 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or heterocyclo wherein at least one of R1, R2, R3 and R4 is other than hydrogen. 47. The biofuel cell of claim 46 wherein R1, R2, R3 and R4 are independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl wherein at least one of R1, R2, R3 and R4 is other than hydrogen. 48. The biofuel cell of claim 46 wherein R1, R2, R3 and R4 are the same and are methyl, ethyl, propyl, butyl, pentyl or hexyl. 49. The biofuel cell of claim 46 wherein R1, R2, R3 and R4 are butyl. 50. The biofuel cell of claim 23 wherein the enzyme comprises an oxidoreductase. 51. The biofuel cell of claim 23 wherein the enzyme comprises a dehydrogenase. 52. The biofuel cell of claim 23 wherein the enzyme comprises an alcohol dehydrogenase, aldehyde dehydrogenase, formate dehydrogenase, formaldehyde dehydrogenase, glucose dehydrogenase, glucose oxidase, lactatic dehydrogenase, lactose dehydrogenase or pyruvate dehydrogenase. 53. The biofuel cell of claim 52 wherein the enzyme comprises an alcohol dehydrogenase.