WO2023053905A1 - 電極 - Google Patents

電極 Download PDF

Info

Publication number
WO2023053905A1
WO2023053905A1 PCT/JP2022/033886 JP2022033886W WO2023053905A1 WO 2023053905 A1 WO2023053905 A1 WO 2023053905A1 JP 2022033886 W JP2022033886 W JP 2022033886W WO 2023053905 A1 WO2023053905 A1 WO 2023053905A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrode
conductive carbon
layer
metal
metal layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/033886
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
結奈 須賀
基希 拝師
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to JP2023550524A priority Critical patent/JPWO2023053905A1/ja
Priority to CN202280060335.5A priority patent/CN117957440A/zh
Priority to US18/696,709 priority patent/US20250012753A1/en
Publication of WO2023053905A1 publication Critical patent/WO2023053905A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • G01N27/3271—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

Definitions

  • the present invention relates to electrodes.
  • An electrode that includes a carbon substrate and a noble metal layer covering one surface of the carbon substrate in a sea-island pattern (see, for example, Patent Document 1 below).
  • the electrode of Patent Document 1 is used for detecting physiologically active substances including glucose.
  • the signal-background ratio is the ratio of signal intensity to background (noise) intensity.
  • the electrode described in Patent Document 1 there is a limit to increasing the signal-background ratio.
  • the present invention provides an electrode with a high signal-background ratio.
  • a substrate, a conductive carbon layer, and a metal layer are sequentially provided toward one side in the thickness direction, and the conductive carbon layer has sp 2- bonded atoms and sp 3- bonded atoms. and atoms, wherein the metal layer is arranged on one side of the conductive carbon layer in the thickness direction, and the area ratio of the metal layer on the one side of the conductive carbon layer is 95% or less. including.
  • the present invention (2) includes the electrode according to (1), wherein the metal layer is a gold layer.
  • the present invention (3) includes the electrode according to (1) or (2), wherein the metal layer has an island structure.
  • the present invention (4) provides any one of (1) to (3), wherein the ratio of the number of sp 3- bonded atoms to the sum of the number of sp 3- bonded atoms and the number of sp 2 -bonded atoms is 0.30 or more.
  • the present invention (5) includes the electrode according to any one of (1) to (4), wherein the area ratio is 70% or more.
  • the present invention (6) further comprises a metal underlayer, wherein the substrate, the metal underlayer, the conductive carbon layer, and the metal layer are arranged in order toward one side in the thickness direction. comprising an electrode according to any one of (1) to (5), wherein
  • the present invention (7) includes the electrode according to any one of (1) to (6), wherein the substrate is a flexible film.
  • the electrode of the present invention has a high signal-background ratio.
  • FIG. 1 is a cross-sectional view of one embodiment of an electrode of the present invention.
  • Electrode 1 has a thickness. Electrode 1 extends in the plane direction. The plane direction is perpendicular to the thickness direction. Specifically, the electrode 1 has a sheet shape.
  • the electrode 1 includes a substrate 2, a metal underlayer 3, a conductive carbon layer 4, and a metal layer 5 in order toward one side in the thickness direction. In this embodiment, electrode 1 preferably comprises only substrate 2 , metal underlayer 3 , conductive carbon layer 4 and metal layer 5 .
  • the base material 2 forms the other surface of the electrode 1 in the thickness direction.
  • Materials for the substrate 2 include, for example, inorganic materials and organic materials.
  • Inorganic materials include, for example, silicon and glass.
  • Organic materials include, for example, polyesters, polyolefins, acrylics, and polycarbonates. Polyesters include, for example, polyethylene terephthalate (PET) and polyethylene naphthalate.
  • the material of the base material 2 is preferably an organic material, more preferably polyester, and still more preferably PET.
  • the base material 2 will be a flexible film. If the base material 2 is a flexible film, the electrode 1 will be excellent in handleability.
  • the thickness of the base material 2 is, for example, 2 ⁇ m or more, preferably 20 ⁇ m or more, and is, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less.
  • the metal underlayer 3 is arranged on one surface of the base material 2 in the thickness direction. Specifically, the metal underlayer 3 is in contact with one surface of the base material 2 in the thickness direction. The metal underlayer 3 extends in the planar direction.
  • Materials for the metal underlayer 3 include, for example, Group 4 metal elements (titanium and zirconium), Group 5 metal elements (vanadium, niobium and tantalum), Group 6 metal elements (chromium, molybdenum and , tungsten), Group 7 metal elements (manganese), Group 8 metal elements (iron), Group 9 metal elements (cobalt), Group 10 metal elements (nickel and platinum), Group 11 metal elements ( gold), Group 12 metallic elements (zinc), Group 13 metallic elements (aluminum and gallium), and Group 14 metallic elements (germanium and tin). These materials can be used alone or in combination.
  • a preferred material for the metal underlayer 3 is titanium.
  • the thickness of the metal underlayer 3 is 50 nm or less, preferably 35 nm or less, and is, for example, 1 nm or more, preferably 3 nm or more.
  • Conductive carbon layer 4 The conductive carbon layer 4 is arranged on one surface of the metal underlayer 3 in the thickness direction. Specifically, the conductive carbon layer 4 is in contact with one surface of the metal underlayer 3 in the thickness direction. The conductive carbon layer 4 extends in the planar direction. The conductive carbon layer 4 has conductivity.
  • the conductive carbon layer 4 includes sp 2- bonded atoms and sp 3- bonded atoms. Specifically, the conductive carbon layer 4 contains carbon with sp 2 bonds and carbon with sp 3 bonds. That is, the conductive carbon layer 4 has a graphite structure and a diamond structure. This allows the conductive carbon layer 4 to have good conductivity and a high signal-to-background ratio.
  • the signal-to-background ratio cannot be sufficiently increased.
  • the ratio of the number of sp 3- bonded atoms to the sum of the number of sp 3- bonded atoms and the number of sp 2 -bonded atoms is not limited.
  • the ratio of the number of sp 3- bonded atoms to the sum of the number of sp 3- bonded atoms and the number of sp 2 -bonded atoms is, for example, 0.05 or more, preferably is 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more, particularly preferably 0.25 or more, most preferably 0.30 or more, and, for example, 0 0.90 or less, preferably 0.75 or less, more preferably 0.50 or less, and still more preferably 0.40 or less.
  • the signal-to-background ratio can be increased. It is presumed that this is because the amount of functional groups on the one surface 41 of the conductive carbon layer 4 is reduced, thereby reducing the background current.
  • the ratio of sp 3 bonded atoms is measured using X-ray photoelectron spectroscopy.
  • the conductive carbon layer 4 is allowed to contain a small amount of unavoidable impurities other than oxygen.
  • the thickness of the conductive carbon layer 4 is, for example, 0.1 nm or more, preferably 1 nm or more, and 100 nm or less, preferably 50 nm or less.
  • the metal layer 5 is arranged on part of one surface 41 of the conductive carbon layer 4 in the thickness direction.
  • the metal layer 5 forms one surface of the electrode 1 in the thickness direction together with the conductive carbon layer 4 described above. Also, the metal layer 5 exposes the remainder of the one surface 41 of the conductive carbon layer 4 .
  • the metal layer 5 forms one surface of the electrode 1 in the thickness direction together with the conductive carbon layer 4 .
  • the area ratio of the metal layer 5 on the one surface 41 of the conductive carbon layer 4 is 95% or less.
  • the metal layer 5 on the one surface 41 of the conductive carbon layer 4 exceeds 95%, the metal layer 5 has a continuous film structure continuous in the plane direction, and the electrode 1 has a high signal- Unable to obtain background ratio.
  • the metal layer 5 in the one surface 41 of the conductive carbon layer 4 is 95% or less, the metal layer 5 has an island structure, and the electrode 1 has a high signal-back ground ratio can be obtained.
  • Materials for the metal layer 5 include, for example, gold, copper, platinum, iron, tin, and silver.
  • a preferred material for the metal layer 5 is gold.
  • the metal layer 5 is a gold layer. If the metal layer 5 is a gold layer, the signal-to-background ratio can be even higher.
  • the area ratio of the metal layer 5 on one surface 41 of the conductive carbon layer 4 is preferably 94% or less, more preferably 93% or less.
  • the area ratio of the metal layer 5 on the one surface 41 of the conductive carbon layer 4 is, for example, 10% or more, preferably more than 50%, more preferably 70% or more, further preferably 75% or more, especially Preferably, it is 90% or more.
  • the electrode 1 can obtain a higher signal-background ratio.
  • the area ratio of the metal layer 5 on one surface 41 of the conductive carbon layer 4 is calculated from a phase image obtained by Tapping mode measurement with an atomic force microscope. A method for measuring the area ratio of the metal layer 5 on the one surface 41 of the conductive carbon layer 4 will be described in detail later in Examples.
  • the method for setting the area ratio of the metal layer 5 on the one surface 41 of the conductive carbon layer 4 to the range described above is not limited.
  • the sputtering (described later) time is adjusted.
  • the metal layer 5 described above has, for example, an island structure when viewed from one side in the thickness direction. Specifically, in the metal layer 5, a large number of mutually independent spherical gold particles are dispersed. In this case, the electrode 1 has a sea-island structure when viewed from one side in the thickness direction.
  • the thickness of the metal layer 5 is, for example, 0.05 nm or more, preferably 0.1 nm or more, more preferably 0.3 nm or more, still more preferably 0.7 nm or more, particularly preferably 1 nm or more, and most preferably , 1.5 nm or more, more preferably 2 nm or more, and for example, 5 nm or less.
  • the thickness of the electrode 1 is, for example, 2 ⁇ m or more, preferably 20 ⁇ m or more, and is, for example, 1000 ⁇ m or less, preferably 500 ⁇ m or less.
  • Electrode 1 Next, a method for manufacturing the electrode 1 will be described. In this method, first, the base material 2 is prepared, and then the metal underlayer 3, the conductive carbon layer 4, and the metal layer 5 are sequentially formed toward one side of the base material 2 in the thickness direction. do.
  • a dry method preferably sputtering
  • sputtering for example, the above-described metals are used as targets.
  • a target has a face.
  • a noble gas preferably argon
  • the sputtering gas is used as the sputtering gas.
  • the power applied to the target and the pressure of the sputtering gas are appropriately set. Specifically, the power density applied to the target is, for example, 1 W/cm 2 or more, preferably 2 W/cm 2 or more, and for example, 5 W/cm 2 or less.
  • a dry method preferably sputtering
  • sputtering for example, carbon is used as a target.
  • a target has a face.
  • a noble gas preferably argon
  • the sputtering gas is used as the sputtering gas.
  • the power applied to the target and the pressure of the sputtering gas are appropriately set. Specifically, the power density applied to the target is, for example, 1 W/cm 2 or more, preferably 2 W/cm 2 or more, and for example, 5 W/cm 2 or less.
  • a dry method preferably sputtering
  • sputtering for example, the above metal (preferably gold) is used as a target.
  • a target has a face.
  • a noble gas preferably argon
  • the sputtering gas for example a noble gas, preferably argon, is used as the sputtering gas. The pressure of the sputtering gas is appropriately set.
  • the power density applied to the target is, for example, 1 W/cm 2 or less, preferably 0.5 W/cm 2 or less, more preferably 0.3 W/cm 2 or less, still more preferably 0.2 W/cm 2 or less, and for example, 0.01 W/cm 2 or more, preferably 0.05 W/cm 2 or more.
  • the ratio of the power density applied to the metal (preferably gold) target to the power density applied to the metal (preferably gold) material of the metal layer 5 is, for example, 0.0001 or more, preferably 0.0001 or more. 001 or more, and for example, 0.1 or less, preferably 0.05 or less.
  • the electrode 1 can be used as various electrodes, preferably an electrode for electrochemical measurements for performing electrochemical measurements, specifically a working electrode (working electrode) for performing cyclic voltammetry (CV), It can be used as a working electrode (working electrode) for performing square wave voltammetry (SWV), anodic-stripping-voltammetry (ASV), and amperometry.
  • an electrode for electrochemical measurements for performing electrochemical measurements specifically a working electrode (working electrode) for performing cyclic voltammetry (CV)
  • CV cyclic voltammetry
  • SWV square wave voltammetry
  • ASV anodic-stripping-voltammetry
  • amperometry amperometry
  • this electrode 1 has a high signal-background ratio when measuring physiologically active substances.
  • Physiologically active substances include, for example, blood sugar. Blood sugar contains glucose.
  • an enzyme-modified electrode 10 is formed by arranging a known enzyme on one side of the electrode 1 in the thickness direction by a known method.
  • the conductive carbon layer 4 includes sp 2- bonded atoms and sp 3- bonded atoms, and the area ratio of the metal layer 5 on one surface 41 of the conductive carbon layer 4 is 95% or less. Therefore, the signal-to-background ratio is high.
  • the metal layer 5 is a gold layer, the signal-background ratio is even higher.
  • the signal-background ratio is even higher.
  • the ratio of the number of sp 3- bonded atoms to the sum of the number of sp 3 -bonded atoms and the number of sp 2- bonded atoms is 0.30 or higher, the signal-to-background ratio is even higher.
  • the signal-background ratio is even higher.
  • the electrode 1 further includes the metal base layer 3, the adhesiveness of the conductive carbon layer 4 is improved, and when the material of the base material 2 is polyester (specifically, PET), the base material 2 There is an effect of suppressing degassing from.
  • polyester specifically, PET
  • the electrode 1 is excellent in handleability if the substrate 2 is a flexible film.
  • the electrode 1 of this modification includes a metal layer 5, a conductive carbon layer 4, a metal base layer 3, a substrate 2, a metal base layer 3, a conductive carbon layer 4, a metal A layer 5 is provided in order toward one side in the thickness direction.
  • the electrode 1 does not include the metal underlayer 3.
  • the conductive carbon layer 4 is arranged on one surface of the base material 2 in the thickness direction.
  • Examples and comparative examples are shown below to describe the present invention more specifically.
  • the present invention is not limited to Examples and Comparative Examples.
  • specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( Content ratio), physical properties, parameters, etc. be able to.
  • Examples 1 to 5 and Comparative Example 1 A base material (flexible film) 2 made of PET was prepared.
  • a metal base layer 3 made of titanium and having a thickness of 7 nm, a conductive carbon layer 4 having a thickness of 10 nm, and a metal layer 5 having a thickness of 0.5 to 10 nm are formed on the substrate 2 using a DC magnetron sputtering apparatus. , in order toward one side in the thickness direction.
  • the sputtering conditions for each of the metal underlayer 3, the conductive carbon layer 4 and the metal layer 5 are shown in Table 1.
  • the area ratio of the metal layer 5 on the one surface 41 of the conductive carbon layer 4 was adjusted by the sputtering time.
  • the ratio of the number of sp 3- bonded atoms (sp 3 /sp 3 +sp 2 ) in each of the conductive carbon layers 4 of Examples 1 to 4 and Comparative Example 1 was 0.30.
  • the ratio of the number of sp 3- bonded atoms (sp 3 /sp 3 +sp 2 ) in the conductive carbon layer 4 of Example 5 was 0.35.
  • the above ratios were measured using X-ray photoelectron spectroscopy (XPS, Shimadzu Corporation).
  • the electrode 1 was manufactured, which includes the substrate 2, the metal underlayer 3, the conductive carbon layer 4, and the metal layer 5 in order toward one side in the thickness direction.
  • Electrode 1 was manufactured in the same manner as in Example 1. However, the electrode 1 was not provided with the metal layer 5 .
  • Comparative example 3 HOPG (highly oriented pyrolytic graphite, manufactured by Momentive, grade ZYA) having an sp 3- bonded atom number ratio (sp 3 /sp 3 +sp 2 ) of 0.00 was used as a substrate, and one side of the substrate was A metal layer 5 (gold layer) having a thickness of 0.5 nm was formed on the substrate by sputtering.
  • Comparative example 4 HOPG (highly oriented pyrolytic graphite, manufactured by Momentive, grade ZYA) having an sp 3- bonded atom number ratio (sp 3 /sp 3 +sp 2 ) of 0.00 was used as a substrate, and one side of the substrate was A metal layer 5 (gold layer) having a thickness of 1 nm was formed on the substrate by sputtering.
  • HOPG highly oriented pyrolytic graphite, manufactured by Momentive, grade ZYA
  • sp 3- bonded atom number ratio (sp 3 /sp 3 +sp 2 ) of 0.00 was used as a substrate, and one side of the substrate was A metal layer 5 (gold layer) having a thickness of 1 nm was formed on the substrate by sputtering.
  • Area ratio of metal layer 5 on one surface 41 of conductive carbon layer 4 Area ratio of metal layer 5 on one surface 41 of conductive carbon layer 4 is measured by Tapping mode with an atomic force microscope (AFM, Bruker). It was calculated from the phase image obtained in . The image range was from the minimum phase difference to the maximum phase difference. In this phase image, the bright portion was the metal layer 5 and the dark portion was the conductive carbon layer 4, and the image was binarized according to the brightness using image analysis software (WinROOF). The brightness distribution of the image was obtained, and the image was binarized by assigning the brightness up to 70% of the maximum frequency of the bright area to the gold area and the darker area to the conductive carbon area. Using software, the area ratio of the metal layer 5 on the one surface 41 of the conductive carbon layer 4 was calculated from the obtained binarized image.
  • AFM atomic force microscope
  • glucose dehydrogenase 0.8 mg, 4 wt% bovine serum albumin aqueous solution 1.5 ⁇ L, 1% glutaraldehyde aqueous solution 1.2 ⁇ L, 0.05 M 0.3 ⁇ L of potassium phosphate buffer (pH 6.5) was mixed to prepare an enzyme solution.
  • an insulating tape with a hole with a diameter of 2 mm was attached to one side of the electrode 1 in the thickness direction to prepare the electrode 1 with a known area.
  • the enzyme solution was added dropwise to the electrode 1 and stored overnight in a refrigerator at 3° C. to prepare an enzyme-modified carbon electrode 10 .
  • the enzyme-modified carbon electrode 10 is used as a working electrode, and this is connected to a potentiostat (manufactured by IVIUM Technologies, pocketSTAT) together with a reference electrode (Ag/AgCl) and a counter electrode (Pt).
  • a measurement system was constructed. Then, 1 mL of each concentration of glucose solution was spread on the enzyme-modified carbon electrode 10 for 1 minute. After that, with respect to the reference electrode of these electrochemical measurement systems, cyclic voltammetry (CV) measurement was performed by setting the scanning speed to 0.1 V/sec within the potential sweep range of ⁇ 0.2 to 0.8 V. bottom. From the results of CV measurement, the value of the current value at 600 mg/dl with respect to the current value at a glucose concentration of 0 mg/dl at 0.3 V was taken as the signal-background ratio.
  • CV cyclic voltammetry
  • the thickness of the metal layer 5 was measured by a fluorescent X-ray analyzer (XRF, Rigaku). The intensity of fluorescent X-rays (Au-L ⁇ rays) of gold was measured, and the thickness of the gold layer was calculated from the intensity using the following formula.
  • Gold layer thickness (gold fluorescent X-ray intensity - 0.0055)/0.1579
  • An electrode for electrochemical measurement which is used for example, is used as a working electrode.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Hematology (AREA)
  • Non-Insulated Conductors (AREA)
  • Laminated Bodies (AREA)
  • Hybrid Cells (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
PCT/JP2022/033886 2021-09-30 2022-09-09 電極 Ceased WO2023053905A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2023550524A JPWO2023053905A1 (https=) 2021-09-30 2022-09-09
CN202280060335.5A CN117957440A (zh) 2021-09-30 2022-09-09 电极
US18/696,709 US20250012753A1 (en) 2021-09-30 2022-09-09 Electrode

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021160995 2021-09-30
JP2021-160995 2021-09-30

Publications (1)

Publication Number Publication Date
WO2023053905A1 true WO2023053905A1 (ja) 2023-04-06

Family

ID=85782387

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/033886 Ceased WO2023053905A1 (ja) 2021-09-30 2022-09-09 電極

Country Status (5)

Country Link
US (1) US20250012753A1 (https=)
JP (1) JPWO2023053905A1 (https=)
CN (1) CN117957440A (https=)
TW (1) TW202321684A (https=)
WO (1) WO2023053905A1 (https=)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20260098830A1 (en) * 2024-10-07 2026-04-09 Saint-Gobain Performance Plastics Corporation Electrode and method for making an electrode

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004156928A (ja) * 2002-11-01 2004-06-03 Tsukuba Materials Information Laboratory Ltd センサ支持体とその製造方法、電気化学センサとその製造方法および基質濃度測定方法
WO2016013478A1 (ja) * 2014-07-22 2016-01-28 東洋紡株式会社 薄膜積層フィルム
WO2019117112A1 (ja) * 2017-12-11 2019-06-20 日東電工株式会社 電極フィルムおよび電気化学測定システム
JP2020144116A (ja) * 2019-02-28 2020-09-10 日東電工株式会社 電極および電気化学測定システム
WO2021193631A1 (ja) * 2020-03-26 2021-09-30 日東電工株式会社 電極
WO2022071101A1 (ja) * 2020-09-30 2022-04-07 日東電工株式会社 電極

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004156928A (ja) * 2002-11-01 2004-06-03 Tsukuba Materials Information Laboratory Ltd センサ支持体とその製造方法、電気化学センサとその製造方法および基質濃度測定方法
WO2016013478A1 (ja) * 2014-07-22 2016-01-28 東洋紡株式会社 薄膜積層フィルム
WO2019117112A1 (ja) * 2017-12-11 2019-06-20 日東電工株式会社 電極フィルムおよび電気化学測定システム
JP2020144116A (ja) * 2019-02-28 2020-09-10 日東電工株式会社 電極および電気化学測定システム
WO2021193631A1 (ja) * 2020-03-26 2021-09-30 日東電工株式会社 電極
WO2022071101A1 (ja) * 2020-09-30 2022-04-07 日東電工株式会社 電極

Also Published As

Publication number Publication date
TW202321684A (zh) 2023-06-01
CN117957440A (zh) 2024-04-30
US20250012753A1 (en) 2025-01-09
JPWO2023053905A1 (https=) 2023-04-06

Similar Documents

Publication Publication Date Title
Rao et al. Electrochemical oxidation of NADH at highly boron-doped diamond electrodes
Solanki et al. Zinc oxide-chitosan nanobiocomposite for urea sensor
Singh et al. Gold nanoparticles-reduced graphene oxide based electrochemical immunosensor for the cardiac biomarker myoglobin
Wang et al. Improved enzyme immobilization for enhanced bioelectrocatalytic activity of glucose sensor
Gamero et al. Nanostructured rough gold electrodes for the development of lactate oxidase-based biosensors
US9506890B2 (en) Physical vapor deposited biosensor components
KR102547061B1 (ko) 물리적 증착에 의해 제조된 바이오센서 전극
US20220349028A1 (en) Electrodes for biosensors
JP2000097898A (ja) 電気化学的センサに使用される導体組成物および作用電極
US11624723B2 (en) Biosensor electrodes prepared by physical vapor deposition
CN107422015A (zh) 金膜电极、电化学生物传感器电极、传感器及其制备方法
Saha et al. Influence of surface defects in ZnO thin films on its biosensing response characteristic
Periasamy et al. Glucose oxidase and horseradish peroxidase like activities of cuprous oxide/polypyrrole composites
CN107422012A (zh) 电化学生物传感器电极、传感器及其制备方法
Mano et al. Detection of glucose at 2 fM concentration
WO2023053905A1 (ja) 電極
Razumiene et al. Modified graphitized carbon black as transducing material for reagentless H2O2 and enzyme sensors
Lee et al. Nonenzymatic glucose sensors based on Nanoporous copper thin films fabricated by laser-induced Photoreduction
Coyle et al. Hydrogen bubble templated growth of honeycomb-like Au-Pt alloy films for non-enzymatic glucose sensing
CN110220953A (zh) 过氧化氢电化学传感器电极、制备方法及传感器
Farzana et al. A sensing platform for direct electron transfer study of horseradish peroxidase
Gougis et al. Tungsten oxide-Au nanosized film composites for glucose oxidation and sensing in neutral medium
Tian et al. Electrochemical determination of glutathione using an annealed nickel ion implanted-modified electrode
Batchelor-McAuley et al. The contrasting behaviour of polycrystalline bulk gold and gold nanoparticle modified electrodes towards the underpotential deposition of thallium
KR102451440B1 (ko) 물리적 증착된 바이오센서 컴포넌트

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22875777

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023550524

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 202280060335.5

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 18696709

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22875777

Country of ref document: EP

Kind code of ref document: A1