WO2021060097A1 - Ｃｎｔ分散ｃｍｃ層を有する電極 - Google Patents

Ｃｎｔ分散ｃｍｃ層を有する電極 Download PDF

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Publication number
WO2021060097A1
WO2021060097A1 PCT/JP2020/035016 JP2020035016W WO2021060097A1 WO 2021060097 A1 WO2021060097 A1 WO 2021060097A1 JP 2020035016 W JP2020035016 W JP 2020035016W WO 2021060097 A1 WO2021060097 A1 WO 2021060097A1
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Prior art keywords
electrode
dispersed
item
cnt
cnts
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PCT/JP2020/035016
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English (en)
French (fr)
Japanese (ja)
Inventor
尚▲徳▼ 岩佐
辻　勝巳
圭三 米田
曽我部　敦
淳典 平塚
丈士 田中
仁志 六車
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National Institute of Advanced Industrial Science and Technology AIST
Toyobo Co Ltd
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National Institute of Advanced Industrial Science and Technology AIST
Toyobo Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
    • C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
    • 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
    • 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
    • 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
    • G01N27/416—Systems
    • 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
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • 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
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • 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
    • 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

Definitions

  • a technique relating to an electrode having a CNT-dispersed CMC layer is disclosed.
  • nanocarbon Since nanocarbon has high electrical conductivity, its application as a conductive material for electron transfer with other substances is progressing. For example, it has been proposed to mix nanocarbon with an ink composed of carbon, a resin, and an organic solvent, print it on a substrate, and use it as an electrode for a biosensor (Patent Document 1).
  • carbon nanotubes which are a type of nanocarbon, are used in sensors for measuring peroxides (Patent Document 2), or are molded into a film together with enzymes and used as electrodes for sensors and fuel cells (Patent Document 2). Patent Document 3).
  • One issue is to provide improved electrodes.
  • CNT carbon nanotubes
  • Item 1 An electrode having a structure in which a layer in which carbon nanotubes are dispersed in carboxymethyl cellulose is formed on a metal substrate.
  • Item 2 Item 2. The electrode according to Item 1, wherein the layer further contains an enzyme.
  • Item 3 Item 2. The electrode according to Item 2, wherein the enzyme is an oxidase.
  • Item 4 Item 3. The electrode according to Item 3, wherein the oxidase is uricase.
  • Item 5 A sensor provided with the electrode according to any one of Items 1 to 4.
  • Item 6 Item 5. The sensor according to Item 5, which is used for detecting hydrogen peroxide.
  • Item 7 Item 6. The sensor according to Item 6, wherein the hydrogen peroxide is derived from uric acid.
  • Item 8 A method for detecting hydrogen peroxide using the electrode according to any one of Items 1 to 4 or the sensor according to Item 5.
  • Item 9 Item 8. The method according to Item 8, wherein the hydrogen peroxide is derived from
  • Hydrogen peroxide can be detected more sensitively.
  • the cyclic voltammogram when uric acid is detected using an electrode having a layer in which a single-walled CNT is dispersed in CMC is shown.
  • the cyclic voltammogram when uric acid is detected using an electrode having a layer in which a single-walled CNT is dispersed in sodium cholicate is shown.
  • the cyclic voltammogram when uric acid is detected using an electrode having a layer in which multi-walled CNTs are dispersed in CMC is shown.
  • the cyclic voltammogram when uric acid is detected using an electrode having a layer in which multi-walled CNTs are dispersed in sodium cholic acid is shown.
  • the electrode preferably has a structure in which a layer in which carbon nanotubes are dispersed in carboxymethyl cellulose is formed on a metal substrate.
  • Carboxymethyl cellulose is commercially available and can be purchased and used.
  • CMC can also be synthesized and used. Methods for synthesizing CMC are known.
  • the CNT may be any of single-walled CNT, double-walled CNT, and multi-walled CNT. Further, the diameter and length of the CNT are also arbitrary and are not particularly limited. In one embodiment, the diameter of the CNT is preferably 0.5 to 50 nm. In one embodiment, the length of the CNTs is preferably 0.1 to 1000 ⁇ m. Commercially available CNTs may be purchased and used, or they may be synthesized and used. Methods for synthesizing CNTs are known.
  • the metal substrate is not particularly limited as long as it can be used as an electrode.
  • the metal electrode is preferably one in which a metal film is fixed to an insulating substrate.
  • the metal film is preferably a metal film selected from the group consisting of gold, platinum, titanium, and carbon. Such metal electrodes are known.
  • the formation of a layer in which CNTs are dispersed in CMC on a metal substrate can be obtained, for example, by dispersing CNTs in a liquid in which CMC is dissolved, dropping the CNTs on the metal substrate, and drying the layers.
  • the solution in which CMC is dissolved can be obtained, for example, by dissolving CMC in a suitable solvent such as water.
  • the concentration of CMC in the solvent is not particularly limited, but can be, for example, 0.01 to 2% (w / v).
  • the amount of CNTs dispersed in the solution in which CMC is dissolved is arbitrary and is not particularly limited, but is, for example, about 0.001 to 1% (w / v).
  • the dispersed state of CNTs is preferably a state in which the CNTs are not bundled and the CNTs form a network having many contacts.
  • the concentration ratio (CNT / CMC) of CNTs and CMCs is 0.1 to 1.0 in the case of single-walled CNTs and 0.5 to 5 in the case of multi-walled CNTs. It is preferably 0.0.
  • the layer in which CNTs are dispersed in the CMC formed on the metal substrate further contains an enzyme.
  • the type of enzyme can be selected according to the purpose and is not particularly limited.
  • preferred enzymes are oxidases such as uricase, glucose oxidase, lactate oxidase, cholesterol oxidase, alcohol oxidase, sarcosine oxidase, fructosylamine oxidase, pyruvate oxidase, glycerol oxidase, glycerol-3-phosphate oxidase.
  • the preferred enzyme is uricase.
  • the uricase is preferably from the genus Bacillus or from the genus Candida.
  • the method of incorporating the enzyme into the layer in which the CNTs are dispersed in the CMC is arbitrary.
  • the enzyme can be contained in the layer by dropping the solution in which the enzyme is dissolved onto the layer and drying it. It is also possible to disperse CNTs in a solution in which CMC is dissolved, prepare a solution in which an enzyme is further dissolved, drop the solution on a metal substrate, and dry the solution.
  • the amount of the enzyme contained in the layer is arbitrary and can be set according to the purpose, but can be, for example, 0.1 to 100 U / mm 2 .
  • pH buffers eg phosphate buffers, citrate buffers, and Good buffers
  • sugars sucrose, lactose, etc.
  • salts phosphates, ammonium sulfate, etc.
  • amino acids glycine, alanine, etc.
  • Serin, etc. other enzyme stabilizers
  • the sensor preferably includes the above electrodes.
  • the electrode is usually a working electrode.
  • the sensor preferably further includes a counter electrode and a reference electrode.
  • the configuration of such a sensor is known in the art. Further, the sensor may be provided with a configuration usually provided by a biosensor such as a potentiatory stat and a current detection circuit.
  • Hydrogen peroxide can be detected accurately using the above-mentioned electrode or a sensor equipped with it.
  • Hydrogen peroxide can be any substance, and in one embodiment hydrogen peroxide is preferably derived from uric acid. That is, uric acid in the sample can be detected using the electrode or the sensor. In one embodiment, the uric acid in the sample is oxidized by uricase, and the uric acid in the sample can be detected by detecting the hydrogen peroxide produced at that time.
  • FIG. 1 An electrode chip having a working electrode portion of 9 mm 2 was produced using a sheet in which gold was vapor-deposited on a PET substrate (FIG. 1).
  • FIG. 1 is a PET film
  • “2” is an adhesive sheet
  • "3” is a gold-deposited PET film
  • "4" is a working electrode site. 5 ⁇ L of the aqueous dispersion of any of the following (1) to (4) was added dropwise to the working electrode site and dried.
  • Multi-walled carbon nanotubes (NC7000: Nanocyl) in a 0.05% (w / v) carboxymethyl cellulose aqueous solution (diameter: 10 nm (median), 5 to 15 nm (measurement method: TEM), length: 1.5 ⁇ m ( A solution in which (average) (measurement method: TEM)) is dispersed at 0.1% (w / v).
  • NC7000 Nanocyl
  • FIG. 2 is the single-walled carbon nanotube dispersion liquid of the above (1)
  • FIG. 3 is the single-walled carbon nanotube dispersion liquid of the above (2)
  • FIG. 4 is the multilayer carbon nanotube dispersion liquid of the above (3)
  • FIG. This is the case where the multi-walled carbon nanotube dispersion liquid of 4) is used.
  • Table 1 shows the current value of + 0.4V when sweeping from -0.8V to + 0.8V in this cyclic voltammogram.
  • CNT indicates carbon nanotube
  • CMC indicates carboxymethyl cellulose
  • SC indicates sodium cholic acid
  • uric acid can be detected more sensitively at a lower voltage than when dispersed in sodium cholic acid.
  • the voltage required for detecting uric acid can be lowered, so that uric acid can be detected while avoiding the detection of reducing substances that may be present in the biological sample.

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  • Chemical & Material Sciences (AREA)
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  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
  • Apparatus Associated With Microorganisms And Enzymes (AREA)
PCT/JP2020/035016 2019-09-26 2020-09-16 Ｃｎｔ分散ｃｍｃ層を有する電極 Ceased WO2021060097A1 (ja)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025023893A1 (en) * 2023-07-27 2025-01-30 Nanyang Technological University Electrode device, method of forming the same, and signal collection platform

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006292495A (ja) * 2005-04-08 2006-10-26 Toray Ind Inc カーボンナノチューブ組成物、バイオセンサーおよびそれらの製造方法
WO2018043050A1 (ja) * 2016-08-29 2018-03-08 国立研究開発法人産業技術総合研究所 グルコースセンサ用試薬、グルコースセンサ、グルコースセンサの製造方法、および、グルコース測定装置
JP2018036061A (ja) * 2016-08-29 2018-03-08 東レ株式会社 積層体
JP2018169220A (ja) * 2017-03-29 2018-11-01 東レ株式会社 積層体
JP2020085759A (ja) * 2018-11-29 2020-06-04 東洋紡株式会社 グルコースセンサ用試薬

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006292495A (ja) * 2005-04-08 2006-10-26 Toray Ind Inc カーボンナノチューブ組成物、バイオセンサーおよびそれらの製造方法
WO2018043050A1 (ja) * 2016-08-29 2018-03-08 国立研究開発法人産業技術総合研究所 グルコースセンサ用試薬、グルコースセンサ、グルコースセンサの製造方法、および、グルコース測定装置
JP2018036061A (ja) * 2016-08-29 2018-03-08 東レ株式会社 積層体
JP2018169220A (ja) * 2017-03-29 2018-11-01 東レ株式会社 積層体
JP2020085759A (ja) * 2018-11-29 2020-06-04 東洋紡株式会社 グルコースセンサ用試薬

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025023893A1 (en) * 2023-07-27 2025-01-30 Nanyang Technological University Electrode device, method of forming the same, and signal collection platform

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