Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
  • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
  • G01N27/28—Electrolytic cell components
  • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
  • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
  • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
  • G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
  • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
  • G01N27/28—Electrolytic cell components
  • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
  • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
  • G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
  • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
  • G01N27/28—Electrolytic cell components
  • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
  • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
  • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
  • G01N27/3277—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction being a redox reaction, e.g. detection by cyclic voltammetry
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/88—Processes of manufacture
  • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
  • H01M4/8896—Pressing, rolling, calendering
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
  • H01M4/9008—Organic or organo-metallic compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
  • H01M4/90—Selection of catalytic material
  • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
  • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/16—Biochemical fuel cells, i.e. cells in which microorganisms function as catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49002—Electrical device making

Definitions

• the present invention relates to bioelectrodes adapted to biofuels (in English biofuel cells) or biosensors, for example of the sugar-oxygen type, for example glucose-oxygen.
• a biosensor has the same structure as a biopile but is used to detect the content of one of the components of the enzymatic reaction, for example glucose.
• each electrode, anode and cathode, of the biopile corresponds to an enclosure containing a liquid medium into which an electrode wire is immersed.
• the anode and cathode enclosures are delimited by membranes that can be traversed by hydrogen and oxygen but avoiding the circulation of other heavier elements.
• the anode comprises in a solution an enzyme and a redox mediator.
• the enzyme is capable of catalyzing the oxidation of sugar and is for example glucose oxidase if the sugar is glucose.
• the redox mediator has a low redox potential tible to exchange electrons with the anode enzyme and is for example ubiquinone (UQ).
• the cathode also comprises in a solution an enzyme and a redox mediator.
• the enzyme is capable of catalyzing the reduction of oxygen and is for example polyphenol oxidase (PPO).
• PPO polyphenol oxidase
• the redox mediator has a high redox potential capable of exchanging electrons with the cathode enzyme and is, for example, hydroquinone (QHD).
• biocells function well but require anode and cathode conductors to be immersed in enclosures containing appropriate liquids, which is a practical disadvantage in many cases and makes it particularly difficult or impossible to implant such biocells into living beings, in particular to feed various actuators, such as pacemakers, artificial sphincters, or even artificial hearts.
• Solid electrode biopiles have been proposed.
• the unpublished French patent application 10/52657 of April 8, 2010 describes such a biopile.
• this biopile comprises an anode body A and a cathode body K.
• the anode body consists of a solid body comprising a conductive material associated with an enzyme and a redox mediator. anode appropriate.
• the anode body is secured to anode wire 1.
• the cathode consists of a solid body formed of a conductor associated with an enzyme and a mediator of cathode appropriate.
• the cathode body is secured to a cathode wire 3.
• the anode and cathode wires for example platinum, are shown as penetrating into the anode and cathode bodies; they can simply be stuck to these bodies.
• the anode body and the cathode body are formed by compressing powdered graphite mixed with the appropriate redox enzyme and mediator.
• Redox chemical mediators provide an electrical connection between the enzyme and the electrode by electron jumps between the redox mediators positioned between the surface of the electrode and the prosthetic center or active center of the enzyme.
• the redox mediators are generally soluble in aqueous medium, it is necessary to fix them on the surface of the electrode
• a main disadvantage of the use of these mediators is the fact that they greatly reduce poten ⁇ tiel provided by the biopile.
• these mediators must have a potential greater than that of the redox center of the enzyme catalyzing the oxidation of glucose in order to react with it, in particular with its reduced form in order to oxidize it.
• the redox mediators dedicated to the connection of the oxygen-reducing enzyme must have a lower potential ⁇ than the active center of this enzyme in order to react with its oxidized form.
• the potential difference between the active sites of the enzyme catalyzing the oxidation of glucose and that catalyzing the reduction of oxygen is necessarily greater than the potential difference between the redox mediators involved in these two reactions.
• a biofuel cell glucose / oxygen should provide a potential of 1 V, or the use of media ⁇ tors redox leads to biofuel cells having significantly lower potentials.
• the potential of the battery is also limited by kinetic limitation problems and ohmic drops. A direct electrical connection was so tempted to do (without using mediators) enzymes to elec ⁇ trodes. However, the electron transfer remains very weak and sometimes requires modification of the enzyme. In addition, the performance of these batteries remains low.
• bioelectrodes that are simple to handle for applications in the field of biopiles and biosensors, and in particular that can be implanted in a living animal or human being.
• an embodiment of the present invention provides a biopile or biosensor electrode to be immersed in a liquid medium containing a target and an oxidant, respectively a reducing agent, wherein the anode comprises an enzyme capable of catalyzing the oxidation of a target, and the cathode comprises an enzyme capable of catalyzing the reduction of the oxidant, and wherein each of the anode and cathode electrodes is made of a chipboard ⁇ solid carbon nanotubes mixed with Mérat the enzyme, and is integral with an electrode wire.
• the electrode is surrounded by a semipermeable membrane allowing the oxidant and the target to pass and not allowing the enzyme to pass.
• the membrane is of the dialysis membrane type.
• the target is glucose
• One embodiment of the present invention provides a method of manufacturing a biopile or biosensor, wherein the anode and the cathode are formed by compressing a solution mixture comprising carbon nanotubes and an enzyme.
• the carbon nanotubes are of the multi-sheet type.
• FIG. 1 very schematically represents a biopile with solid electrodes
• FIG. 2 illustrates the current and power performance as a function of the voltage of a glucose / oxygen biofuel made of bioelectrodes manufactured according to the present invention
• FIGS. 3A and 3B respectively illustrate the electrochemical response of a biosensor to glucose injections and the current response of this biosensor as a function of the glucose concentration.
• the present invention relates to a new type of solid electrolyte containing electri cally connected ⁇ enzymes.
• the invention provides for the electrical connection of a large density of enzymes by compression in the form of a compact block, for example a disk, a mixture of carbon nanotubes, enzymes, water required for solubilization enzymes and glycerol as a binder between the different constituents.
• Carbon nanotubes are of the mono- or multi-layer type.
• the conductivity of the nanotubes and their very small diameter allows electrical communication with the enzyme which retains its catalytic activity.
• These bioelectrodes can be used in the fields of biopiles and biosensors.
• the anode consists, for example, of a compression of carbon nanotubes containing an oxidase such as glucose oxidase (GOX) capable of catalyzing the oxidation of a fuel, for example sugar.
• an oxidase such as glucose oxidase (GOX) capable of catalyzing the oxidation of a fuel, for example sugar.
• the cathode is for example constituted by a compres ⁇ carbon nanotube sion containing an enzyme such as laccase or bilirubin oxidase capable of catalyzing the reduction ⁇ an oxidant such as oxygen.
• the fuel is glucose
• the anode enzyme is glucose oxidase (GOX)
• the oxidant is oxygen
• the cathode enzyme is laccase.
• an anode was prepared by Mélan ⁇ giant 150 mg of carbon nanotubes, 30 mg of glucose oxidase and 30 mg of catalase (the role of the catalase is to eliminate 3 ⁇ 402 (a noxious product) formed by glucose oxidase in the presence of
• these anode and cathode bodies are arranged in a fluid containing oxygen and a sugar, for example glucose.
• This biopile has a zero current potential of 1 V, a maximum power of 1800 and a maximum current of 8 mA. These performances are far superior to those obtained for known biocells with direct enzyme connection (maximum power 5 and maximum potential at zero current 0.73 V). In addition, this biopile gives the possibility of having a high power at a high enough potential to operate devices: 800 ⁇ 0.8 V.
• FIG. 2 represents power and electric current curves as a function of the potential of a biopile as described by way of example above.
• Figure 3A illustrates the electrochemical response of a biosensor constituted as the cell described above to the presence of glucose and Figure 3B shows the measured current as a function of glucose concentration.
• the electrode is immersed in an aqueous liquid and glucose is added.
• An electric potential for example 0.1 V, is applied between the bioelectrode and a reference electrode both immersed in the liquid analysis medium and the electric current is measured between the bioelectrode and an auxiliary electrode also immersed in this medium.
• the detection and quantification of glucose present in the liquid is done by measuring the glucose oxidation current catalyzed by the enzyme.
• the performances of the biosensor maintained at the potential of 0.1 V are 17 mA / M / cm 2 and 685 AU / cm 2 for sensitivity and maximum current density, respectively.
• this system In addition to working potential to overcome the anodic interfer ⁇ ences, this system has the highest density maximum current so far described even for conventional glucose biosensors.
• each of the anode and cathode bodies may be surrounded by a microperforated membrane such as membranes commonly used in dialysis, which allows glucose and oxygen to pass and prohibits the passage of the enzyme. and carbon nanotubes of higher molecular weight.
• the set of anode and cathode electrodes may be surrounded by a semipermeable membrane permitting glucose and oxygen to pass through and impervious to enzymes and carbon nanotubes, in particular to allow their implantation in an animal or human body. .
• Any sugar-oxygen biopile can be modi ⁇ fied according to the present invention, and more generally any biopile whose anode comprises an enzyme capable of catalyzing the oxidation of a target, and whose cathode comprises an enzyme capable of catalyzing the oxidation of a target. reduction of the oxidant.

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• Inert Electrodes (AREA)
• Apparatus Associated With Microorganisms And Enzymes (AREA)
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• 2010
  • 2010-08-19 FR FR1056672A patent/FR2963989B1/fr not_active Expired - Fee Related
• 2011
  • 2011-08-18 US US13/817,536 patent/US20130284596A1/en not_active Abandoned
  • 2011-08-18 CA CA2808869A patent/CA2808869A1/fr not_active Abandoned
  • 2011-08-18 JP JP2013525336A patent/JP5833123B2/ja not_active Expired - Fee Related
  • 2011-08-18 WO PCT/FR2011/051931 patent/WO2012022921A1/fr active Application Filing
  • 2011-08-18 EP EP11758521.6A patent/EP2606527A1/de not_active Withdrawn

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