WO2021009844A1 - Dispositif de mesure électrochimique et procédé de mesure électrochimique - Google Patents

Dispositif de mesure électrochimique et procédé de mesure électrochimique Download PDF

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Publication number
WO2021009844A1
WO2021009844A1 PCT/JP2019/027918 JP2019027918W WO2021009844A1 WO 2021009844 A1 WO2021009844 A1 WO 2021009844A1 JP 2019027918 W JP2019027918 W JP 2019027918W WO 2021009844 A1 WO2021009844 A1 WO 2021009844A1
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WIPO (PCT)
Prior art keywords
electrode
measurement
electrochemical
electrodes
electrochemical measuring
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PCT/JP2019/027918
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English (en)
Japanese (ja)
Inventor
暁鳴 竇
佳則 山口
子誠 朱
賓 範
Original Assignee
暁鳴 竇
株式会社オプトラン
佳則 山口
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Application filed by 暁鳴 竇, 株式会社オプトラン, 佳則 山口 filed Critical 暁鳴 竇
Priority to PCT/JP2019/027918 priority Critical patent/WO2021009844A1/fr
Publication of WO2021009844A1 publication Critical patent/WO2021009844A1/fr

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    • 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 an electrochemical measuring device and an electrochemical measuring method.
  • the electrochemical measuring device and the electrochemical measuring method include, for example, an environmental test represented by heavy metal measurement applying the principle of electrochemical measurement, a glucose electrode, and an electrochemical measurement such as a food test represented by electrochemical detection of residual pesticides. Used for.
  • Measurements using the principle of electrochemical measurement are used in many situations such as high-sensitivity measurement of heavy metals in solution, glucose measurement using enzyme electrodes, and pH (pH) measurement using ion electrodes ().
  • high-sensitivity measurement of heavy metals in solution glucose measurement using enzyme electrodes
  • pH (pH) measurement using ion electrodes ion electrodes
  • Patent Document 1 the measurement of heavy metals such as cadmium, mercury, arsenic, cobalt, copper, zinc and lead is performed before the amount of those heavy metals contained in water, soil, food, vegetables, rice and drinking water is taken into the body. It is very important to know.
  • the present invention has been made to improve such a situation, and an object of the present invention is to improve reproducibility and detection sensitivity in electrochemical measurement for measuring trace components in a liquid sample.
  • the electrochemical measuring device of the present invention is an electrochemical measuring device that measures trace components in a liquid sample, and includes a plurality of electrode sets having a working electrode, a counter electrode, and a reference electrode that come into contact with the liquid sample, and the plurality of electrodes are provided.
  • the working electrodes of the electrode assembly, the counter electrodes, and the reference electrodes are short-circuited to each other.
  • the electrochemical measuring apparatus of the present invention a plurality of three electrodes of the working electrode, the counter electrode and the reference electrode themselves are arranged, and the working electrodes, the counter electrodes and the reference electrodes are short-circuited (electrically connected) to each electrode assembly.
  • the working electrodes, the counter electrodes and the reference electrodes are short-circuited (electrically connected) to each electrode assembly.
  • the electrode assembly may be provided on a disposable electrode tip.
  • the measurement can be performed without worrying about the accumulation and contamination on the electrode surface by the previous measurement substance.
  • the plurality of electrode sets (working electrode, counter electrode and reference electrode) may be provided on separate electrode tips, or may be provided in separate regions on the same electrode tip.
  • a plurality of the electrode chips having the same configuration may be mounted.
  • the working electrodes, counter electrodes, and reference electrodes of each electrode chip are short-circuited, so that manufacturing variations between the electrode chips can be absorbed. , Reproducibility and detection sensitivity can be improved.
  • the same liquid sample is electrically separated and brought into contact with each electrode set using the electrochemical measurement device of the present invention for measurement.
  • noise can be reduced by electrically separating and contacting the same liquid sample for each electrode set with respect to a plurality of electrode sets connected in parallel. , The detection sensitivity can be improved.
  • the electrochemical measuring device and the electrochemical measuring method of the present invention can improve reproducibility and detection sensitivity.
  • FIG. 1 It is a schematic block diagram which shows one Embodiment of an electrochemical measuring apparatus. It is a top view which shows an example of the electrode chip used in this embodiment. It is a graph which shows the current potential curve obtained in the measurement example 1. FIG. It is a graph which shows the current potential curve obtained in the measurement example 2.
  • FIG. 1 is a schematic configuration diagram showing the embodiment.
  • FIG. 2 is a plan view showing an example of the electrode chip.
  • the electrochemical measuring device 1 includes two electrode tips 2 and 2, a potentiometer 3 connected to the electrode tips 2 and 2, an operation unit 4 connected to the potentiometer 3, and a display unit. 5.
  • the power supply unit 6 and the external output unit 7 are provided.
  • each electrode chip 2 includes a flat plate-shaped substrate 21, and a working electrode 22, a counter electrode 23, and a reference electrode 24 are provided on the substrate 21 so as to be insulated from each other.
  • the substrate 21 has a substantially rectangular shape in a plan view.
  • the electrode assembly 25 of the working electrode 22, the counter electrode 23, and the reference electrode 24 is provided from the vicinity of one end in the longitudinal direction to the vicinity of the other end of the substrate 21.
  • the materials and structures of the working electrode 22, the counter electrode 23 and the reference electrode 24 are the same.
  • each electrode chip 2 a liquid sample 10 containing a substance to be measured is brought into contact with one end side of the working electrode 22, the counter electrode 23, and the reference electrode 24.
  • the working electrode 22, the counter electrode 23, and the other end of the reference electrode 24 of each electrode tip 2 are electrically connected to the potentiostat 3 via a connector 8 and a cable 9 (not shown in FIG. 1).
  • the electrode tip 2 is detachably attached to the connector 8.
  • the working electrode 22, the counter electrode 23, and the reference electrode 24 are made of a carbon thin film formed by, for example, sputtering or print printing.
  • the surface of the carbon thin film may be plated depending on the measurement target.
  • the measurement target is a heavy metal such as arsenic or mercury
  • the surface of the carbon thin film can be plated with gold or the like, whereby the detection sensitivity can be improved.
  • the potentiostat 3 controls the potential of the working electrode 22 to be constant with respect to the reference electrode 24, and can measure the current flowing between the working electrode 22 and the counter electrode 23. Has been done.
  • the potentiostat 3 includes an arithmetic control unit 31, a voltage application unit 32, and a current detection unit 33.
  • the calculation control unit 31 performs a predetermined calculation process using the measured value obtained by the electrochemical measurement, and is required for the voltage application unit 32 based on a command from the user input via the operation unit 4. It is a function of transmitting a signal and displaying information such as a measurement result on the display unit 5.
  • the arithmetic control unit 31 is realized by, for example, a microcomputer executing a predetermined program.
  • the voltage application unit 32 When the voltage application unit 32 receives the measurement start signal from the arithmetic control unit 31, the voltage application unit 32 applies a voltage having a desired waveform between the working electrode 22 and the counter electrode 23 of the electrode chip 2 to and the working electrode 22. It is configured to control the potential between the reference electrode 24 and the reference electrode 24 to be a desired potential.
  • the current detection unit 33 is configured to detect the magnitude of the current flowing between the working electrode 22 of the electrode chip 2 and the counter electrode 23. A signal relating to the magnitude of the current detected by the current detection unit 33 is taken into the arithmetic control unit 31.
  • the arithmetic control unit 31 calculates the concentration of a specific component in the sample solution based on the signal captured from the current detection unit 33, for example, using a calibration curve prepared in advance, and displays the measurement result on the display unit 5. It is configured as follows.
  • two electrode chips 2 and 2 having the same structure are connected to the potentiostat 3.
  • the working electrodes 22, 22 of the two electrode tips 2, 2, the counter electrodes 23, 23, and the reference electrodes 24, 24 are configured to be electrically connected (short-circuited) to each other in the potentiostat 3.
  • the same voltage is simultaneously applied to the two electrode chips 2 and 2 from the voltage application unit 32, and the current flowing between the working electrode 22 and the counter electrode 23 in each of the two electrode chips 2 and 2 is applied. It is detected by the current detection unit 33.
  • the operation unit 4 is an input device for the user to perform operations such as turning on / off the power supply, starting measurement, and changing the information displayed on the display unit 5.
  • the display unit 5 is realized by, for example, a liquid crystal display.
  • the display unit 5 may be composed of a touch panel, and the display unit 5 may have the functions of the operation unit 4.
  • the power supply unit 6 can be realized by, for example, a dry battery or a storage battery. The power supply unit 6 supplies necessary electric power to the potentiometer 3 and the display unit 5.
  • an external output unit 7 is connected to the potentiostat 3 so that information can be output to an external device such as a personal computer by a wired communication means such as a USB (universal serial bus) terminal or a wireless communication means. You may.
  • the arithmetic control unit 31 is configured to output measurement data or the like to an external device via the external output unit 7.
  • the operation unit 4, the display unit 5, the power supply unit 6, and the external output unit 7 may be realized by a mobile computer such as a notebook computer or a tablet, for example.
  • a small potentiometer 3 for example, a small potentiometer "miniSTAT100" (manufactured by Biodevice Technology)
  • the electrochemical measuring device 1 can be configured to be portable. This makes it possible to measure a liquid sample on-site (on-site) using the electrochemical measuring device 1.
  • the electrochemical measurement using the electrochemical measuring device 1 of the present embodiment is performed in a state where the same liquid sample 10 is dropped on each of the two electrode chips 2 and 2.
  • the liquid sample 10 is dropped onto the substrate 21 so as to be in contact with the working electrode 22, the counter electrode 23, and the reference electrode 24.
  • liquid sample 10 on one electrode chip 2 and the liquid sample 10 on the other electrode chip 2 are electrically insulated (separated).
  • Electrochemical measurements were performed by differential pulse voltammetry (DPV). The measurement by DPV was carried out by changing the potential of the working electrode from -1500 mV to 200 mV, increasing the potential at 0.04 V, pulse amplitude of 0.05 V, pulse period of 0.2 seconds, and sweeping speed of 0.01 V / s. About 20 ⁇ L of the above sample was dropped onto the electrode chip 2 for measurement. The obtained current potential curve is shown in FIG. In FIG. 3, the vertical axis represents current and the horizontal axis represents potential.
  • the peak current value can be made larger and the difference in the detected peak current value from the baseline can be made larger than the measurement by the conventional method, and the detection sensitivity can be improved. ..
  • Measurement example 2 A 100 ppm lead standard solution (Cat. No. 24240-1B, manufactured by Kanto Chemical Co., Inc.) diluted to 100 ppb with distilled water was prepared as a sample. The measurement conditions are the same as those in Measurement Example 1. The obtained current potential curve is shown in FIG. In FIG. 4, the vertical axis represents current and the horizontal axis represents potential.
  • the peak current value is larger than that by the conventional method, and the difference between the detected peak current value and the baseline can be increased, so that the detection sensitivity is improved. It was confirmed that it could be done.
  • the electrochemical measuring device 1 of the embodiment includes a plurality of electrode sets 25 having a working electrode 22, a counter electrode 23, and a reference electrode 24 that are in contact with the liquid sample, and the working electrodes 22 and the counter electrodes 23 are located on each other.
  • the reference electrodes 24 are configured to be short-circuited with each other. Then, by measuring in a state where the same liquid sample is in contact with each electrode assembly 25, uneven manufacturing of each electrode 22, 23, 24 (manufacturing variation) and interaction with the sample at the time of detection (contact state). And can be averaged. As a result, the electrochemical measuring device 1 can improve the reproducibility and the detection sensitivity.
  • the electrochemical measuring device 1 since the electrode assembly of the working electrode 22, the counter electrode 23, and the reference electrode 24 is provided on the disposable electrode tip 2, there is concern about accumulation and contamination on the electrode surface due to the previous measurement substance. You can measure without doing anything.
  • the electrochemical measuring device 1 is configured so that a plurality of electrode chips 2 having the same configuration can be mounted, the working electrodes 22 of the respective electrode chips 2 are connected to each other even though the plurality of electrode chips 2 are used. Since the counter electrodes 23 and the reference electrodes 24 are short-circuited, it is possible to absorb manufacturing variations between the electrode chips 2 and improve reproducibility and detection sensitivity.
  • the same liquid sample is electrically separated and brought into contact with each electrode assembly 25 by using the electrochemical measuring device 1, so that noise is measured from two independent detection systems. It can be reduced by adding the above, and the detection sensitivity can be improved.
  • the present invention is not limited to the above-described embodiment, but can be embodied in various aspects.
  • the electrochemical measuring device of the present invention is not limited to a portable configuration, and can be applied to a stationary device.
  • the working electrodes 22 of the two electrode tips 2 and 2, the counter electrodes 23, and the reference electrodes 24 may be electrically connected (short-circuited) to each other outside the potentiostat 3.
  • the two electrode chips 2 and 2 may be short-circuited inside a connector to which they can be attached, or the cables extending from each connector 8 may be short-circuited inside a merged cable.
  • the number of electrode sets 25 provided in the electrochemical measuring device 1 may be three or more. Further, the electrode assembly 25 may further include an electrode in addition to the working electrode 22, the counter electrode 23, and the reference electrode 24.
  • the measuring method using the electrochemical measuring device of the present invention is not limited to differential pulse voltammetry (DPV), but linear sweep voltammetry (LSV), chronoamperemetry (CA), cyclic voltammetry (CV), and short waveform voltammetry. It can also be applied to a method such as (SWV).
  • DDV differential pulse voltammetry
  • LSV linear sweep voltammetry
  • CA chronoamperemetry
  • CV cyclic voltammetry
  • SWV short waveform voltammetry
  • Electrochemical measuring device 2 Electrode chip 3 Potential stat 4 Operation unit 5 Display unit 6 Power supply unit 7 External output unit 8 Connector 9 Cable 10 Liquid sample 21 Substrate 22 Working electrode 23 Counter electrode 24 Reference electrode 25 Electrode assembly 31 Calculation control unit 32 Voltage Applying unit 33 Current detecting unit

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention améliore la reproductibilité et la sensibilité de détection d'un dispositif de mesure électrochimique.　Le dispositif de mesure électrochimique 1 mesure de fines quantités de constituants dans un échantillon liquide. Le dispositif de mesure électrochimique 1 comprend une pluralité de jeux d'électrodes 25, chacun desquels possède une électrode d'utilisation 22 qui est en contact avec l'échantillon liquide, une contre-électrode 23 et une électrode de référence 24. Les électrodes d'utilisation 22, les contre-électrodes 23 et les électrodes de référence 24 dans la pluralité de jeux d'électrodes 25 sont réciproquement court-circuitées.
PCT/JP2019/027918 2019-07-16 2019-07-16 Dispositif de mesure électrochimique et procédé de mesure électrochimique WO2021009844A1 (fr)

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PCT/JP2019/027918 WO2021009844A1 (fr) 2019-07-16 2019-07-16 Dispositif de mesure électrochimique et procédé de mesure électrochimique

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10267887A (ja) * 1997-01-23 1998-10-09 Daikin Ind Ltd センサ装置
JPH10325821A (ja) * 1997-05-26 1998-12-08 Nec Corp 電気化学測定装置
JP2004117342A (ja) * 2002-09-03 2004-04-15 Matsushita Electric Ind Co Ltd バイオセンサ及びそれを用いた測定法
JP2004329919A (ja) * 2003-05-07 2004-11-25 I-Sens Inc 両方向血糖測定器
JP2013238399A (ja) * 2012-05-11 2013-11-28 Funai Electric Advanced Applied Technology Research Institute Inc センサシステム及び当該センサシステムを用いた検出対象物質測定方法
KR20150085147A (ko) * 2014-01-13 2015-07-23 재단법인 다차원 스마트 아이티 융합시스템 연구단 복수의 바이오 센서 스트립들 중 적어도 하나를 선택적으로 스위칭하는 스위칭 회로를 포함하는 바이오 센서 장치
JP2017167104A (ja) * 2016-03-18 2017-09-21 国立大学法人東北大学 電極チップ

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10267887A (ja) * 1997-01-23 1998-10-09 Daikin Ind Ltd センサ装置
JPH10325821A (ja) * 1997-05-26 1998-12-08 Nec Corp 電気化学測定装置
JP2004117342A (ja) * 2002-09-03 2004-04-15 Matsushita Electric Ind Co Ltd バイオセンサ及びそれを用いた測定法
JP2004329919A (ja) * 2003-05-07 2004-11-25 I-Sens Inc 両方向血糖測定器
JP2013238399A (ja) * 2012-05-11 2013-11-28 Funai Electric Advanced Applied Technology Research Institute Inc センサシステム及び当該センサシステムを用いた検出対象物質測定方法
KR20150085147A (ko) * 2014-01-13 2015-07-23 재단법인 다차원 스마트 아이티 융합시스템 연구단 복수의 바이오 센서 스트립들 중 적어도 하나를 선택적으로 스위칭하는 스위칭 회로를 포함하는 바이오 센서 장치
JP2017167104A (ja) * 2016-03-18 2017-09-21 国立大学法人東北大学 電極チップ

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