US8415059B2
Active / In Force
US
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Direct electron transfer using enzymes in bioanodes, biocathodes, and biofuel cells
Assignee: Saint Louis University
•
Filing: 2006-11-02
•
Granted: 2013-04-09
•
Expires: 2026-11-02
Abstract
Abstract Bioanodes, biocathodes, and biofuel cells comprising an electron conductor, at least one anode enzyme or cathode enzyme, and an enzyme immobilization material. The anode enzyme is capable of reacting with a fuel fluid to produce an oxidized form of the fuel fluid, and capable of releasing electrons to the electron conductor. The cathode enzyme is capable of reacting with an oxidant to produce water, and capable of gaining electrons from the electron conductor. The enzyme immobilization material for both the anode enzyme and the cathode enzyme is capable of immobilizing and stabilizing the enzyme, and is permeable to the fuel fluid and/or the oxidant.
Inventors
- 👤 Shelley D. Minteer
- 👤 Becky L. Treu
- 👤 Rodica Duma
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 16:05
CPC Classifications
H; H01; H01M; H01M4/00; H01M4/86; H01M4/90; H01M8/00; H01M8/16; C; C12; C12N; C12N11/00; C12N11/02; C12N11/04; C12N11/08; C12N11/082; C12N11/089; C12N11/14; Y; Y02; Y02E; Y02E60/00; Y02E60/30; Y02E60/50
Claims Analysis
Total Claims: 33
Claim 1
Independent Claim
96 words
A bioanode consisting essentially of (a) an electron conductor; (b) at least one anode enzyme capable of reacting with a fuel fluid to produce an oxidized form of the fuel fluid, the anode enzyme being capable-of directly releasing electrons to the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the fuel fluid; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days.
Claim 2
Dependent Claim
96 words
A bioanode consisting essentially of (a) an electron conductor; (b) at least one anode enzyme capable of reacting with a fuel fluid to produce an oxidized form of the fuel fluid, the anode enzyme being capable-of directly releasing electrons to the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the fuel fluid; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days.
Claim 3
Dependent Claim
17 words
The bioanode of claim 1 wherein the enzyme immobilization material comprises a micellar or inverted micellar structure.
Claim 4
Dependent Claim
47 words
The bioanode of claim 1 wherein the enzyme immobilization material comprises either (a) a modified perfluoro sulfonic acid-PTFE copolymer or a hydrophobically modified alginate wherein the enzyme immobilization material is modified with a hydrophobic cation larger than NH 4 + ; or (b) a hydrophobically modified polysaccharide.
Claim 5
Dependent Claim
58 words
The bioanode of claim 3 wherein the hydrophobic cation comprises a quaternary ammonium ion represented by Formula 4 wherein R 1 , R 2 , R 3 and R 4 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or heterocyclo wherein at least one of R 1 , R 2 , R 3 and R 4 is other than hydrogen.
Claim 6
Dependent Claim
38 words
The bioanode of claim 3 wherein said hydrophobically modified polysaccharide corresponds to Formula 1 wherein n is an integer; R 10 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl; and R 11 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl.
Claim 7
Dependent Claim
21 words
The bioanode of claim 5 wherein R 10 is independently hydrogen or alkyl and R 11 is independently hydrogen or alkyl.
Claim 8
Dependent Claim
62 words
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 or polycrystalline graphite.
Claim 9
Dependent Claim
16 words
The bioanode of claim 1 wherein the anode enzyme comprises a PQQ-dependent dehydrogenase or a lipoxygenase.
Claim 10
Dependent Claim
89 words
A biocathode consisting essentially of: (a) an electron conductor; (b) at least one cathode enzyme capable of reacting with an oxidant to produce water, the cathode enzyme being capable of directly gaining electrons from the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the oxidant; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days.
Claim 11
Dependent Claim
89 words
A biocathode consisting essentially of: (a) an electron conductor; (b) at least one cathode enzyme capable of reacting with an oxidant to produce water, the cathode enzyme being capable of directly gaining electrons from the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the oxidant; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days.
Claim 12
Dependent Claim
17 words
The biocathode of claim 9 wherein the enzyme immobilization material comprises a micellar or inverted micellar structure.
Claim 13
Dependent Claim
47 words
The biocathode of claims 9 wherein the enzyme immobilization material comprises either (a) a modified perfluoro sulfonic acid-PTFE copolymer or a hydrophobically modified alginate wherein the enzyme immobilization material is modified with a hydrophobic cation larger than NH 4 + ; or (b) a hydrophobically modified polysaccharide.
Claim 14
Dependent Claim
58 words
The biocathode of claim 11 wherein the hydrophobic cation comprises a quaternary ammonium ion represented by Formula 4 wherein R 1 , R 2 , R 3 and R 4 are independently hydrogen, hydrocarbyl, substituted hydrocarbyl or heterocyclo wherein at least one of R 1 , R 2 , R 3 and R 4 is other than hydrogen.
Claim 15
Dependent Claim
38 words
The biocathode of claim 11 wherein said hydrophobically modified polysaccharide corresponds to Formula 1 wherein n is an integer; R 10 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl; and R 11 is independently hydrogen, hydrocarbyl, or substituted hydrocarbyl.
Claim 16
Dependent Claim
21 words
The biocathode of claim 13 wherein R 10 is independently hydrogen or alkyl and R 11 is independently hydrogen or alkyl.
Claim 17
Dependent Claim
62 words
The biocathode of claim 9 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.
Claim 18
Dependent Claim
15 words
The biocathode of claim 9 wherein the cathode enzyme comprises bilirubin oxidase or superoxide dismutase.
Claim 19
Dependent Claim
19 words
A biofuel cell for generating electricity comprising: a fuel fluid; a bioanode of claim 1 ; and a cathode.
Claim 20
Dependent Claim
19 words
A biofuel cell for generating electricity comprising: a fuel fluid; an anode; and a biocathode of claim 9 .
Claim 21
Dependent Claim
16 words
The biofuel cell of claim 17 wherein the cathode comprises a biocathode of claim 9 .
Claim 22
Dependent Claim
13 words
The biofuel cell of claim 18 wherein the oxidant comprises oxygen or peroxide.
Claim 23
Dependent Claim
100 words
The biofuel cell of claim 17 wherein the fuel fluid comprises ammonia, methanol, ethanol, propanol, isobutanol, butanol, isopropanol, an allyl alcohol, an aryl alcohol, glycerol, propanediol, mannitol, glucuronate, aldehyde, a carbohydrate, 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, a fatty acid, a lipid, phosphoglycerate, retinal, estradiol, cyclopentanol, hexadecanol, a long-chain alcohol, coniferyl-alcohol, cinnamyl-alcohol, formate, a long-chain aldehyde, pyruvate, butanal, acyl-CoA, a steroid, an amino acid, flavin, NADH, NADH 2 , NADPH, NADPH 2 or hydrogen.
Claim 24
Dependent Claim
103 words
A bioanode comprising (a) an electron conductor; (b) at least one anode enzyme capable of reacting with a fuel fluid to produce an oxidized form of the fuel fluid, the anode enzyme capable of directly releasing electrons to the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the fuel fluid; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days and the bioanode does not contain an electron mediator.
Claim 25
Dependent Claim
103 words
A bioanode comprising (a) an electron conductor; (b) at least one anode enzyme capable of reacting with a fuel fluid to produce an oxidized form of the fuel fluid, the anode enzyme capable of directly releasing electrons to the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the fuel fluid; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days and the bioanode does not contain an electron mediator.
Claim 26
Dependent Claim
15 words
The bioanode of claim 22 wherein the anode enzyme comprises more than one redox center.
Claim 27
Dependent Claim
16 words
The bioanode of claim 23 wherein the anode enzyme comprises a PQQ-dependent dehydrogenase or a lipoxygenase.
Claim 28
Dependent Claim
96 words
A biocathode comprising: (a) an electron conductor; (b) at least one cathode enzyme capable of reacting with an oxidant to produce water, the cathode enzyme being capable of directly gaining electrons from the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the oxidant; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days and the biocathode does not contain an electron mediator.
Claim 29
Dependent Claim
96 words
A biocathode comprising: (a) an electron conductor; (b) at least one cathode enzyme capable of reacting with an oxidant to produce water, the cathode enzyme being capable of directly gaining electrons from the electron conductor; and (c) an enzyme immobilization material immobilizing and stabilizing the enzyme, the material being permeable to the oxidant; wherein the enzyme is stabilized when it retains at least about 75% of its initial catalytic activity upon continuous operation in a biofuel cell for at least about 7 days to about 730 days and the biocathode does not contain an electron mediator.
Claim 30
Dependent Claim
15 words
The biocathode of claim 25 wherein the cathode enzyme comprises more than one redox center.
Claim 31
Dependent Claim
15 words
The biocathode of claim 26 wherein the cathode enzyme comprises bilirubin oxidase or superoxide dismutase.
Claim 32
Dependent Claim
15 words
The bioanode of claim 1 wherein the anode enzyme comprises more than one redox center.
Claim 33
Dependent Claim
15 words
The biocathode of claim 9 wherein the cathode enzyme comprises more than one redox center.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 2016-04-08 | 2016-10-08 | 2017-04-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2020-04-08 | 2020-10-08 | 2021-04-09 | $3760.00 | Window Closed / Lapsed |
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