WO2004083841A1 - 電極およびそれを用いたセンサー - Google Patents
電極およびそれを用いたセンサー Download PDFInfo
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- WO2004083841A1 WO2004083841A1 PCT/JP2004/003467 JP2004003467W WO2004083841A1 WO 2004083841 A1 WO2004083841 A1 WO 2004083841A1 JP 2004003467 W JP2004003467 W JP 2004003467W WO 2004083841 A1 WO2004083841 A1 WO 2004083841A1
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- 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
- C12Q1/001—Enzyme electrodes
- C12Q1/002—Electrode membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- 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
Definitions
- the present invention relates to a sensor for measuring an object to be measured by an electrochemical reaction, and an electrode used for the sensor.
- Various chemical sensors and biosensors are known that measure an object to be measured in a sample using an electrochemical reaction.
- a sensor in which a substance for reacting an object to be measured with an electrode is fixed to the electrode by a self-assembled monolayer.
- the sample measured by the sensor may include an interfering substance that interferes with an electrochemical reaction between the measurement target and the electrode as a foreign substance other than the measurement target. It has been pointed out that this interfering substance affects the measurement results of the measurement target. Ascorrosic acid and uric acid are known as interfering substances that affect the measurement results.
- fructose fructose
- 10-car boxy-1-decanetiol was used as a self-assembled monolayer to prevent electrochemical reactions due to contaminants such as ascorbic acid and uric acid, which are present in biological samples in relatively large amounts.
- Technology is disclosed (Hiroaki Shinohara, “Highly selective sensing of biologically important substances by designing electrode interface molecular integrated film”, Construction and Electrode Reaction See 1998 Report, 1999, p.145-146). Disclosure of the invention
- An object of the present invention is to provide an electrode capable of improving measurement accuracy by using a novel self-assembled monolayer that suppresses the influence of an interfering substance in the measurement of a measurement object, and a sensor using the electrode. Is to do.
- FIG. 1 is a schematic configuration diagram of the sensor according to the present embodiment.
- FIG. 2A is a plan view showing the configuration of the modified electrode according to the present embodiment
- FIG. 2B is a cross-sectional view taken along the line II in FIG. 2A.
- FIG. 3 is a diagram showing a configuration of a fructos sensor.
- FIG. 4 is a cross-sectional view of a modified electrode used in an experiment for confirming the selectivity of a self-assembled monolayer.
- FIG. 5 is a cyclic voltammogram for ascorbic acid obtained in an experiment for confirming the selectivity of the self-assembled monolayer.
- Figure 8 shows that Co (phen) obtained in the experiment confirming the selectivity of the self-assembled monolayer. ) Is a cyclic voltammogram for the 3 2 +.
- FIG. 7 is a diagram showing a configuration of a glucose sensor.
- Co (phen) 3 Ru good 2 + a glucose sensor using as mediator evening is a diagram showing the concentration measurement result of the glucose.
- FIG. 9 is a diagram showing a configuration of a catecholamine sensor.
- FIG. 10 is a diagram showing the measurement results obtained by measuring the reaction between dopamine and ascorbic acid using a catecholamine sensor.
- FIG. 11 is a diagram showing a calibration curve of dopamine using a catecholamine sensor.
- Figure 12 is a diagram showing the relationship between the alkyl chains of lipids that form self-assembled monolayers and dopamine selectivity.
- FIG. 13 is a plan view of a sensor module according to a modification of the embodiment of the present invention.o Best mode for carrying out the invention
- FIG. 1 is a schematic configuration diagram of an embodiment of a sensor according to the present invention.
- the sensor 10 shown in Fig. 1 is composed of a container (vial) 3 containing a sample solution 5 in which the measurement object whose concentration is to be measured is dissolved, a counter electrode 11 made of platinum (Pt) wire, and a modified electrode ( A working electrode) ⁇ 2, a silver-chloride (AgZAgCl) electrode reference electrode 13, a potentiostat (potentio galvano stat) device 7 as potential applying means, and a computer 9 as arithmetic processing means Have.
- the counter electrode 11, the modified electrode 12, and the reference electrode 13 are, for example, fixed to an upper cover (not shown) and immersed in the sample solution 5 in the container 3.
- a silver / silver chloride 0 ⁇ g / AgCl silver / silver chloride 0 ⁇ g / AgCl
- a saturated calomel electrode can also be used in addition to the silver Z silver chloride electrode.
- Potentiation Galvanos sunset device 7 is connected to qualified electrode 12 via wires WO, Wl, W2, connected to counter electrode 11 via wires, and referenced electrode via wire W4 Connected to 13. ,
- the galvanic device 7 functions as a potentiostat that controls the potential of the modified electrode 12 within a certain range, and a galvanos device that detects a current flowing between the modified electrode 12 and the counter electrode 11. It is a device that also has the function of evening, and is generally used for electrochemical measurements. The detected current value is sent to Combination 9.
- the potentiostat and galvanostat device 7 applies a predetermined potential to the modified electrode 12 to cause an electrode reaction at the modified electrode 12.
- an electrode reaction occurs in which electrons are given to the substance in the solution at the modified electrode 12
- the opposite reaction reaction to transfer electrons from the substance in the solution
- the electrochemical reaction is measured based on the principle that a current flows through the circuit.
- the potentiometer / galvano-slit device 7 applies a predetermined voltage to the reference electrode 13 different from the modified electrode 12 and the counter electrode 11. Is applied. Then, a predetermined potential is applied to the modified electrode 12 based on the applied potential to the reference electrode 13.
- the computer 9 derives the measured object from the measured current value of the sample solution 5 in the container 3 based on, for example, a calibration curve stored in advance in a memory, which represents a relationship between the concentration of the measured object and the current. Is determined.
- the computer 9 outputs the calculated concentration of the object to be measured, for example, on its display.
- FIG. 2 is a configuration diagram of one embodiment of the modified electrode ⁇ 2 according to the present embodiment.
- FIG. 2A is a plan view of the modified electrode 12
- FIG. 2B is a cross-sectional view taken along the line II in FIG. 2A.
- the modified electrode 12 includes, for example, a gold electrode (electrode substrate) 16 fixed to a glass or plastic substrate 15, a self-assembled monolayer 18 covering the surface of the gold electrode ⁇ 6, Braided monomolecular film] with enzyme immobilized on 8.
- the gold electrode 18 is connected to a secretion W0 for applying a potential and measuring a current.
- Examples of the measurement target include biological substances and chemical substances such as fructoses, glucose, catecholamines, quinones, serotonin, and hydrophobic amino acids.
- the thiol compound reacts with the gold surface to form a gold-cysteamine (Au-S) bond.
- Au-S gold-cysteamine
- an alkanethiol compound Van der Waals interaction between alkyl chains acts in addition to the Au-S bond, producing a defect-free t-monolayer with high orientation. It is possible.
- Such a monolayer is called a self-assembled monolayer. Modification of the gold electrode ⁇ 6 with the self-assembled monolayer ⁇ 8 is possible only by immersing the gold electrode 16 in a thiol compound solution.
- the self-assembled monolayer 18 repels water-soluble and electrochemically active interfering substances such as ascorbic acid and uric acid by its carboxyl group and repels them. Prevent reaching.
- the enzyme 19 is selected, for example, according to the measurement object. If the object to be measured is fructose, for example, fructose dehydrogenase (FDH) is used as the enzyme 19. If the measurement target is glucose, use glucose oxidase (GOD), which is a glucose oxidase, as the enzyme 9 In the present embodiment, the oxidation reaction of the object to be measured by the enzyme ⁇ 9 is converted into an electric signal at the gold electrode 16 by mediating the reaction using a mediator (arbitration means or electrochemically active species). By detecting this electric signal, the presence of the object to be measured can be detected.
- FDH fructose dehydrogenase
- GOD glucose oxidase
- a hydrophobic material is preferable.
- Such a Medeie Isseki for example, cobalt phenanthroline complex (Fuenanto port Rinkoparuto complex) [Co (phen) 3 2 +] (phenanthrol ine cobalt (II) com lex) and, using a Hue spout complex body .
- Co (phen) s 2 + is easy to adjust, capable of reversible oxidation and reduction, has a relatively low potential for oxidation, and is a metal complex containing funanthroline as a ligand. Has the advantage of being the lowest.
- Co (phen) 3 2 + for example, previously mixed into the sample solution 5 as a solution.
- the best mediator at this time is the copartopentanantroline complex.
- the cobalt phenanthroline complex has an oxidation potential of about 20 OmV, which is lower than the oxidation potential of Huacene. As described above, since the reaction is performed at a low potential, it is hardly affected by substances such as ascorbic acid.
- the self-assembled monolayer 18 having the above chemical structural formula allows only a substance that generates an electrochemical reaction at the gold electrode 16 for measurement of an object to be measured to pass. Ie, Co (phen) 3 2 + etc. Medeie Isseki of passed through, contaminants such as Asukoru bottles acid and uric acid in the sample solution 5 causes dismissed from the gold electrodes 1 6 without passing. Ascorbic acid and uric acid are present in vegetables and fruits, blood and urine containing the measurement target in a relatively large amount, and cause an oxidation reaction at the gold electrode 16. The following equation is an equation showing the oxidation-reduction reaction of ascorbic acid. Monoascorbi Nodehi Dehi D
- Ascorbic acid loses two atoms of hydrogen in the oxidation reaction via monoascorbic acid anion and monodehydroascorbic acid to become dehydroascorbic acid. At that time, an electric current flows in the reaction relating to monodehydroascorbic acid.
- ascorbic acid when ascorbic acid is present in the vicinity of the gold electrode 16, when an electrode reaction potential is applied to the gold electrode 16, ascorbic acid itself is oxidized and a current flows. For this reason, if ascorbic acid is contained in the sample solution 5, it behaves as an interfering substance that interferes with the electrode reaction between the measurement object and the gold electrode 16 and the measurement accuracy of the concentration of the measurement object by the sensor 10 is reduced. Lower.
- uric acid itself oxidizes and behaves as an interfering substance.
- the self-assembled monolayer 18 rejects impurities such as ascorbic acid and uric acid and prevents the monolayer 18 from reaching the gold electrode 16, and is used for measurement of an object to be measured. A substance causing an electrochemical reaction is selectively passed.
- a potentiometer When measuring the concentration of the object to be measured in the sample solution 5 using the sensor 10 having the above-described configuration, a potentiometer is used.
- the Galvanos sunset device 7 accurately applies a predetermined potential to the reference electrode 13 via the electric wire ff4.
- the galvanostat device 7 uses the applied potential to the reference electrode 13 With reference to the above, a predetermined potential is applied to the decoration electrode 12 via the electric wires W 1 and W 2 connected to the modification electrode 12.
- Potential applied to the modified electrode 1 2 is, for example, a potential of Co (phen) 3 below electrode reaction of the 2 + gold electrodes 1 6 occurs.
- the gold electrode 16 of the modified electrode 12 is modified by the self-assembled monolayer 18 and the enzyme 19 is further fixed. I have. In this way, it is possible to prevent the interference substance that generates a reaction other than the electrochemical reaction for measurement from reaching the gold electrode 6. As a result, the selectivity of the modified electrode 12 is improved, and the measurement accuracy of the measurement target by the sensor 10 is improved.
- the self-assembled monolayer 18 can be prepared simply by immersing the gold electrode in the thiol compound solution, the modified electrode 12 and the sensor 10 can be easily manufactured at low cost.
- the apparatus and the measuring method are not complicated as in the oxidation element titration method and the gas chromatography method, and the measuring object can be easily measured. Further, since it does not react to pudose, it does not require labor for removing the influence of pudose, and can easily and accurately measure the concentration of an object to be measured such as fructose. Further, in the present embodiment, three electrodes, the modified electrode 12, the counter electrode ⁇ 1, and the reference electrode 13, are used, and the electrode reaction with the modified electrode 12 is performed based on the potential applied to the reference electrode 13. The measurement is performed by a three-electrode system to which a potential is applied. For this reason, a change in the potential of the modified electrode 2 due to the electrode reaction is suppressed, and highly accurate measurement can be performed.
- fructose sensor that measures the concentration of fructose as an object to be measured will be described.
- FDH as the enzyme 19 is immobilized on the gold electrode 16.
- the self-assembled monolayer 18 is formed by, for example, 7-carboxy-l-heptanthiol (7C). As shown in Fig. 3, 7C has van der Waals interaction between the alkyl chains 20 in addition to the Au-S bond, which makes it possible to produce a defect-free monolayer with high orientation. is there.
- FDH binds to the alkyl plating 20 of the self-assembled monolayer 18 of 7C. As a result, the FDH is fixed to the gold electrode 16.
- FDH is a pyrroloquinoline quinone (PQQ) -dependent oxyreductase with a molecular weight of 140,00 ODa consisting of three supunits. FDH is tightly bound to PQQ. FDH is a D- Fourques toast 5-keto (keto) - oxidized to Fourques toast (fructose), PQQ is Nokomoto to PQQH 2.
- PQQ pyrroloquinoline quinone
- Oxidation of fructose in the sample solution 5 by FDH produces a reduced form of a co-phenanthroline complex.
- An electric signal is generated at the gold electrode 16 by oxidizing the self-assembled copartand penanthroline complex on the surface of the gold electrode 16 through the self-assembled monolayer 18. Further, even if impurities such as ascorbic acid and uric acid were present in the sample solution 5 of the container 3, the impurities were prevented from reaching the gold electrode ⁇ 6 by the self-assembled monolayer 18 and were described above.
- the self-assembled monolayer 18 composed of 7 C repels water-soluble and electrochemically active interfering substances such as ascorbic acid and uric acid due to its carboxyl group and repels them, and the gold electrode ⁇ 6 Prevent reaching.
- FIG. 4 is a cross-sectional view of the modified electrode used in this experiment.
- the modified electrode 30 shown in FIG. 4 is obtained by removing the enzyme 19 from the modified electrode 12 shown in FIG. 2B. For this reason, the same components are denoted by the same reference numerals, and detailed description is omitted.
- the self-assembled monolayer 18 is formed by directly modifying 7 C on the gold electrode 6 by Au—S bond.
- the modified electrode 30 is used in place of the modified electrode 12 to examine the relationship between the applied potential and the electrode reaction.
- modified electrodes were prepared by modifying the gold electrode ⁇ 6 with FDH, Gluta.mate, and CN-5-Amino-l-Carboxypentyl) imino diacetic acid (AB-NTA). The same CV measurement was performed as in the case of using the modified C.
- the FDH-modified electrode was prepared by modifying a gold electrode 16 with 0.5 rag / ml Cystamine-, 5% glutaradehyde, introducing an aldehyde group, and then immobilizing 0.5 mg / iil FDH.
- the Glutamate-modified electrode and the AB-NTA-modified electrode were prepared by immobilizing Glutaraldehyde in the same manner as the above-mentioned FDH modification, and then modifying only Glutamate and AB-NTA, respectively.
- the Glutamate molecule has no alkyl chain but has two carboxyl groups.
- AB-NTA has three carboxyl groups per alkyl chain.
- Figure 5 shows the cyclic voltammograms for each of the above four modified electrodes.
- the horizontal axis is the potential [raV] applied to the modified electrode, and the vertical axis is the current [A] detected by the potentiometer-galvano-sunset device 7.
- the ⁇ marks indicate the results when the AB-NTA-modified electrode was used, and the marks indicate the results when the Glutamate-modified electrodes were used.
- the X mark shows the result when the FDH modified electrode was used, and the ⁇ mark shows the result when the 7C modified electrode was used.
- FIG. 5 shows that as the value of the current is larger, the oxidation reaction of ascorbic acid is occurring at the gold electrode 16.
- the 7C-modified electrode was effective in preventing the oxidation reaction of ascorbic acid.
- the 7 C-modified electrode in order to use it as a fructose sensor, it is necessary for the 7 C-modified electrode to generate an electrode reaction with the medium.
- the input is the l mM of Co (phen) 3 2 + solution in the container 3 as Isseki Medeie was performed CV measurement by the sensor 1 0 with 7 C modified electrode.
- Figure 6 shows the results.
- the horizontal axis and the vertical axis of the cyclic voltammogram shown in FIG. 6 represent the potential [mV] applied to the modified electrode and the current [A] detected by the potentio-galvanostat device 7, respectively, as in FIG. .
- the self-assembled monolayer 18 using 7 C selectively passes Co (phen) s 2 + and has selectivity for measuring fructose in the 7 C-modified electrode.
- the oxidation current increased about 1.23 times compared to when fructose was not added. That is, the oxidation reaction of fructose by FDH was measured as an oxidation current at the gold electrode 16 from Co (phen) s 2+ .
- the sensor having the 7C-modified electrode can be practically used as a fructose sensor.
- the fructose sensor having a 7C-modified electrode can suppress the interference of ascorbic acid, and therefore has high selectivity for fructose and higher measurement accuracy than before.
- FIG. 7 shows the configuration of the Darco ⁇ "sensor. Self-assembled monolayer composed of 7C. Glucose oxidase (GOD), which is an enzyme for oxidizing glucose, is formed as an enzyme 19 on a monolayer 18. ) was immobilized to produce a glucose sensor.
- GOD Glucose oxidase
- the GOD may be immobilized by directly binding to 7 C by a carpoimide method utilizing a carboxyl group, or by providing a layer of GOD alone without binding to 7 C.
- Fig. 8 shows the measurement results when Co (phen) s 2+ was used as a mediator. As shown in FIG. 8, it can be seen that the detected current depends on the glucose concentration and can be used for selective measurement of glucose.
- the fact that the 7C-modified electrode prevents the oxidation reaction of ascorbic acid at the gold electrode 18 is shown in Fig. 5.
- 7 C modified electrode is Co (phen) for 3 2+ consists mediation point generating electrode reaction against evening is verified in FIG.
- the sensor having the 1 C-modified electrode can be practically used as a glucose sensor. Since the glucose sensor having the 7C-modified electrode can suppress the interference of ascorbic acid, it has high selectivity for glucose and higher measurement accuracy than before.
- FIG. 9 is a diagram showing a configuration of a catecholamine sensor.
- the surface of the gold electrode 16 was immersed in 0.15 nig / ml of 7 C for 1 hour to produce a modified electrode as shown in FIG. Then, using the modified electrode, a predetermined potential was applied by a potentio-galvanostat device 7 to cause an electrode reaction.
- FIG. 10 shows the CV measurement results obtained by measuring the reaction between dopamine (DP) and ascorbic acid (A Sc) using the modified electrode.
- the horizontal axis of the cyclic voltammogram shown in FIG. 10 is the voltage [mV] applied to the modified electrode, and the vertical axis is the current [A] detected by the potentio-galvanostat device 7.
- FIG. 11 shows a calibration curve of dopamine using a modified electrode modified with a self-assembled monolayer. As shown in Fig. 11, it can be seen that the current of dopamine depends on the dopamine concentration and can be used for selective measurement of dopamine.
- a sensor having a 7 C-modified electrode can be practically used as a catecholamine sensor containing dopamine.
- Catecholamine sensor with 7C-modified electrode can suppress ascorbic acid interference Therefore, the selectivity for force techolamine is high, and the measurement accuracy is higher than before.
- FIG. 12 is a diagram showing a comparison between the alkyl chain length of lipids forming a self-assembled monolayer and the selectivity of dopamine obtained by the above measurement.
- FIG. 13 is a plan view of a sensor module according to a modification of the embodiment of the present invention.
- the sensor module 100 shown in FIG. 13 has a modified electrode 120 and a counter electrode (CE
- ) 110 is integrally installed facing a substrate 150 made of glass, plastic, or the like.
- the modified electrode 120 like the modified electrode 12 shown in FIG.
- the enzyme is immobilized by forming a woven monolayer.
- the modified electrode 120 is connected to the potentiometer and the galvano-silicon device 7 via the electric wire, and the counter electrode 110 is connected to the galvanic joint device 7 via the electric wire W3.
- a sensor in which the modified electrode ⁇ 2 and the counter electrode ⁇ 1 shown in FIG. 1 are modularized can be obtained.
- a compact and easy-to-handle sensor can be manufactured by modularizing the electrodes.
- the self-assembled monolayer 18 prevents not only ascorbic acid but also other water-soluble and electrochemically active substances such as uric acid from approaching the electrode substrate.
- the center of the present invention is applicable not only to the fructose sensor, glucose sensor, and catecholamine sensor described in the embodiment, but also to various biosensors and chemical sensors.
- the object to be measured is such that the self-assembled monolayer 18 directly passes through it, it is not necessary to use other components such as the enzyme 19 1 mediator.
- the senor may be constituted by a two-electrode system except for the reference electrode 13.
- the size and price of the sensor can be further reduced.
- electrodes such as a platinum mesh and a platinum plate can be used for the counter electrode used in the sensor depending on the application.
- metals other than gold can be used, and various shapes such as a plate shape and a linear shape can be used.
- gold is the best electrode substrate for sensors.
- the use of a self-assembled monolayer suppresses the influence of an interfering substance in the measurement of an object to be measured and improves the measurement accuracy, and the electrode.
- the electrode according to the present invention and the sensor using the same can be applied to various fields such as food engineering, urinary science, engineering, and chemistry, depending on an object to be measured.
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JP2005503686A JPWO2004083841A1 (ja) | 2003-03-18 | 2004-03-16 | 電極およびそれを用いたセンサー |
US10/549,479 US20060254909A1 (en) | 2003-03-18 | 2004-03-16 | Electrode and sensor using same |
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Cited By (3)
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JP2006134764A (ja) * | 2004-11-08 | 2006-05-25 | Toyota Motor Corp | 燃料電池用部材、燃料電池用セパレータ、および燃料電池 |
JP2007309912A (ja) * | 2006-04-17 | 2007-11-29 | Japan Advanced Institute Of Science & Technology Hokuriku | 電気化学検出センサー及びその製造方法 |
JP2019039921A (ja) * | 2017-08-25 | 2019-03-14 | アークレイ株式会社 | 酵素電気化学インピーダンス計測法に基づく新規バイオセンシング技術 |
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US7955483B2 (en) * | 2002-03-18 | 2011-06-07 | Honeywell International Inc. | Carbon nanotube-based glucose sensor |
EP3249050B1 (en) * | 2016-05-23 | 2019-01-23 | ARKRAY, Inc. | Enzyme electrode and biosensor using the same |
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JP2001264284A (ja) * | 2000-03-15 | 2001-09-26 | Matsushita Kotobuki Electronics Industries Ltd | バイオセンサ |
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US6241863B1 (en) * | 1998-04-27 | 2001-06-05 | Harold G. Monbouquette | Amperometric biosensors based on redox enzymes |
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- 2004-03-16 JP JP2005503686A patent/JPWO2004083841A1/ja active Pending
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JP2001264284A (ja) * | 2000-03-15 | 2001-09-26 | Matsushita Kotobuki Electronics Industries Ltd | バイオセンサ |
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SHINOHARA HIROAKI: "Denkyoku kaimen bunshi shuseki maku no sekkei ni yoru seitai juyo busshitsu no kosentaku sensing", MINISTRY OF EDUCATION KAGAKU KENKYUHI HOJOKIN JUTEN RYOIKI KENKYU KOZO KISEI KINO KAIMEN NO KOCHIKU TO DENKYOKU HAN'NO HEISEI 9 NENDO SEIKA HOKOKUSHO, 1988, pages 139 - 140, XP002904075 * |
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ZHANG HAI-GIAN ET AL.: "Selective redox reaction of a hydrophobic mediator on a self-assembled monolayer electrode and its application to a high performance enzyme sensor", ELECTROCHEMISTRY, vol. 67, no. 12, 5 December 1999 (1999-12-05), pages 1206 - 1207, XP008040157 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006134764A (ja) * | 2004-11-08 | 2006-05-25 | Toyota Motor Corp | 燃料電池用部材、燃料電池用セパレータ、および燃料電池 |
JP2007309912A (ja) * | 2006-04-17 | 2007-11-29 | Japan Advanced Institute Of Science & Technology Hokuriku | 電気化学検出センサー及びその製造方法 |
JP2019039921A (ja) * | 2017-08-25 | 2019-03-14 | アークレイ株式会社 | 酵素電気化学インピーダンス計測法に基づく新規バイオセンシング技術 |
JP7164778B2 (ja) | 2017-08-25 | 2022-11-02 | アークレイ株式会社 | 酵素電気化学インピーダンス計測法に基づく新規バイオセンシング技術 |
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US20060254909A1 (en) | 2006-11-16 |
JPWO2004083841A1 (ja) | 2006-06-22 |
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