WO2001098766A1 - Procede pour determiner la concentration d'un compose de type xanthine et detecteur utilise a cette fin - Google Patents

Procede pour determiner la concentration d'un compose de type xanthine et detecteur utilise a cette fin Download PDF

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Publication number
WO2001098766A1
WO2001098766A1 PCT/JP2001/005317 JP0105317W WO0198766A1 WO 2001098766 A1 WO2001098766 A1 WO 2001098766A1 JP 0105317 W JP0105317 W JP 0105317W WO 0198766 A1 WO0198766 A1 WO 0198766A1
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diamond
electrode
formula
concentration
test sample
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PCT/JP2001/005317
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English (en)
Japanese (ja)
Inventor
Akira Fujishima
Donald Alexander Tryk
Nicolae Spataru
Bulusu Venkata Sarada
Tata Narasinga Rao
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Center For Advanced Science And Technology Incubation, Ltd.
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Priority to AU2001274581A priority Critical patent/AU2001274581A1/en
Priority to JP2002504478A priority patent/JPWO2001098766A1/ja
Publication of WO2001098766A1 publication Critical patent/WO2001098766A1/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
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

Definitions

  • the present invention relates to a method for measuring the concentration of xanthine-based compounds such as cuff-in, theophylline, theopromine, and xanthine, which are clinically or foodally important, using a diamond electrode, a sensor used therefor, and an apparatus therefor.
  • xanthine-based compounds such as cuff-in, theophylline, theopromine, and xanthine, which are clinically or foodally important
  • Diamond is inherently the resistivity is an insulating material of about 1 0 1 3 ⁇ cm, obtaining conductivity by doping with trace impurities thereof.
  • This conductive diamond is expected to have various uses. One of them is utilization as an electrode for electrochemical use. When conductive diamond is viewed as an electrode for electrochemical use, it has the excellent features of having a wide potential window and extremely low background current. In addition, it is physically and chemically stable and has excellent durability. Electrodes having a conductive diamond (preferably a thin film thereof) have been commonly referred to as diamond electrodes.
  • xanthine (3,7-dihydro-1H-purine-1,2,6-dione) belongs to purines and plays an important role as an intermediate in the degradation of adenine and guanine into uric acid. Is considered extremely important.
  • xanthine is poorly soluble in water and xanthine, although very rare, can precipitate as aggregates due to metabolic abnormalities.
  • Theophylline (3,7-dihydro-1,3, dimethyl-1H-purine-1,2,6-dione), Theopromine (3,7-dihydro-3,7-dimethyl-1H-purine-12,6-dione) And N-methyl derivatives of xanthine such as caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-1,2,6-dione) are widely distributed in plant products and beverages.
  • Alkaloids are known to have many physiological effects such as gastric acid secretion, diuresis, and central nervous system stimulation.
  • theophylline is useful as a bronchodilator and as a therapeutic agent for bronchial asthma.
  • the present inventors have now found that a diamond electrode is specifically sensitive to a xanthine-based compound, and that the abundance can be quantified from the current value at the oxidation potential.
  • the present invention is based on this finding. is there.
  • an object of the present invention is to provide a method capable of easily and specifically measuring the concentration of a xanthine compound in a short time.
  • Another object of the present invention is to provide a sensor used in the above method and a device therefor.
  • a method for measuring the concentration of a compound represented by the following formula (I) in a test sample comprising:
  • RR 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • a diamond electrode having conductive diamond and a counter electrode are prepared, and the diamond electrode and the counter electrode are brought into contact with a test sample,
  • a sensor for use in the above-mentioned measuring method, wherein the sensor comprises a diamond electrode having conductive diamond.
  • an apparatus for performing the above-mentioned measuring method comprising:
  • R 2 and R 3 independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • FIG. 1 is a view showing the structure of a diamond electrode.
  • FIG. 1 (a) is a cross-sectional view of a diamond electrode 1. This electrode comprises a conductive diamond thin film 3 formed on a substrate 2.
  • (B) is a perspective view of the diamond electrode 1, comprising a conductive diamond thin film 3 formed on a substrate 2.
  • FIG. 2 is a diagram showing a basic structure of a flow cell used in the measurement method according to the present invention.o
  • FIG. 3 is a diagram showing a basic configuration of a measuring device according to the present invention.
  • FIG. 4 is a diagram showing the results of anodic voltammograms for a 5 OM theophylline solution at a sweep rate of 2 O mV s 1 under the conditions of ⁇ 1, 2, 3, 4, and 5.
  • FIG. 5 is a calibration curve of caffeine concentration and peak current value.
  • FIG. 6 is a calibration curve of theophylline concentration and the value of the peak current.
  • the concentration of the compound of the formula (I) in the sample solution can be selectively known.
  • the present inventors have, as described above, that the compound of the formula (I) is specifically oxidized electrochemically on the conductive diamond electrode, and further, the conductive diamond is used as a working electrode, It was also confirmed that the current value generated between the electrode and the counter electrode was directly proportional to the concentration of the compound of the formula (I) in the system. As a result, it has become possible to quantitatively detect the compound of the formula (I) in the test sample.
  • the test sample may be a biological blood, a body fluid or the like which is thought to contain the compound of the formula (I), or a food or a diluted solution or suspension of the food.
  • the alkyl group having 1 to 6 carbon atoms represented by II 1 , R 2 and R 3 may be linear or branched, and may have a substituent. Is also good.
  • the compounds of the formula (I) which are considered particularly biochemically important are as follows.
  • Theopromin H methyl methyl caffeine methyl methyl methyl xanthine is excreted in large quantities in the urine, for example in patients with xanthineuria. Precipitation of xanthine crystals can lead to so-called bladder stones. Therefore, the measuring method according to the present invention, which enables the urinary concentration of xanthine to be measured in a short time and simply, is useful for its diagnosis and treatment.
  • theophylline is used clinically as a bronchodilator, a cardiotonic diuretic and the like, and it is useful to know its blood concentration and the like.
  • theopromin has a cardiotonic effect and a utilization effect similar to theophylline, and it is significant that its blood concentration and the like can be known. Furthermore, caffeine is included in many foods besides pharmaceutical use, In terms of nutrition, it is significant to be able to easily know the concentration.
  • Diamond is inherently a good insulator. However, by adding Group 3 or Group 5 impurities, it becomes semiconductor-like or metal-like conductive.
  • diamond having a semiconductor-metal-like conductive property is used as an electrode.
  • the substance added to impart such a conductive property include elements of Groups 3 and 5 as described above, more preferably, boron, nitrogen, and phosphorus, and most preferably, boron or nitrogen. There. Amount of substance to be added to impart the conductivity may be appropriately determined within the range that can impart conductivity to the diamond, but give example 1 X 10_ 2 ⁇ 10- 6 ⁇ cm approximately conductive It is preferable to add in an amount.
  • the amount of the substance added to impart the conductivity is controlled by the amount added in the process of producing the conductive diamond.
  • the diamond electrode according to the present invention uses the conductive diamond as an electrode.
  • This diamond electrode is extremely interesting because when the electrochemical reaction is carried out in water, oxygen is not generated by the electrolysis of water as an oxidation reaction, and specifically causes the oxidation reaction of the compound of the above formula (I). Had properties. This property is considered to be exhibited regardless of the surface condition of the conductive diamond.
  • the surface of an unprocessed (as grown) diamond thin film manufactured using hydrogen gas as a carrier by the chemical vapor deposition method described later has a hydrogen atom as a terminal carbon atom. Is usually in a bonded state, but the conductive diamond in which the terminating hydrogen atom is replaced with another atom can also specifically cause the oxidation reaction of the compound of the above formula (I). Is considered to be possible.
  • a conductive diamond thin film is formed on the base material, It is preferable to connect a conductive wire to form an electrode.
  • S i e.g., single crystal silicon
  • Mo, W ⁇ Nb, T is Fe, Au, Ni, Co, Ah0 3, S iC ;, S i 3 N4 Zr0 2, MgO, graphite, single Crystal diamond, cBNs quartz glass, etc., especially single crystal silicon, Mo, W, Nb, T i S The use of iC single crystal diamond is preferred.
  • FIG. 1 (a) is a cross-sectional view of a diamond electrode 1, which comprises a conductive diamond thin film 3 formed on a base material 2, and furthermore, a conductive wire 5 Are connected, for example, via gold coating 4.
  • FIG. 1 (b) is a perspective view of the diamond electrode 1, which is composed of a conductive diamond thin film 3 formed on a base material 2, and further has a metal core for using the conductive diamond thin film 3 as an electrode. Conductor 5 is connected via one ting 4.
  • the thickness of the conductive diamond thin film is not particularly limited, but is preferably about 1 to 10 ⁇ 6 ⁇ , more preferably about 5 to 50 m.
  • the diamond electrode according to the present invention can take the form of a micro-hole electrode.
  • the concept of the microphone opening electrode is already known, and in the present invention, the microelectrode-shaped diamond electrode is obtained by cutting the end of a fine wire such as Pt sharply, further sharpening the end by electrolytic polishing, and then polishing the end surface.
  • a fine wire such as Pt sharply, further sharpening the end by electrolytic polishing, and then polishing the end surface.
  • the conductive diamond thin film is preferably produced by a chemical vapor deposition method.
  • Chemical vapor deposition is a method in which a gaseous raw material is chemically reacted in a gas phase to synthesize a substance, and is generally called a CVD (Chemical Vapor Deposition) method. This method is widely used in the semiconductor manufacturing process, and can be used for the production of the conductive diamond thin film of the present invention with appropriate modification.
  • Chemical vapor synthesis of diamond is performed by using a mixture of hydrogen and a carbon-containing gas such as methane as a raw material gas, exciting it with an excitation source, supplying it to a substrate, and depositing it.
  • a carbon-containing gas such as methane
  • Excitation sources include hot filament, microwave, high frequency, DC glow discharge, DC arc discharge, and combustion flame. It is also possible to adjust the nucleation density by combining a plurality of them, and to increase the area and uniformity.
  • C As a raw material, many types that contain a carbon, decomposition by the excitation source is excited, C, activated carbon, such as C 2, and CH, such as CH 2, CH 3, C 2 H 2 Charcoal Compounds that generate hydride radicals are available.
  • Preferred examples include CH 4 , C 2 H 2 C 2 H 4 , CioH 16 s CO, CF 4 as a gas, CH 3 OH, C 2 H 5 OH, (CH 3 ) 2 CO as a liquid, graphite, fullerene, etc. Are mentioned.
  • the addition of a substance that imparts conductivity to diamond can be performed, for example, by placing a disk of the added substance in the system, exciting it in the same manner as the carbon source material, and introducing the added substance into the carbon gas phase,
  • the method can be carried out by, for example, adding an additional substance to the carbon source in advance, introducing the additional substance into the system together with the carbon source, exciting with the excitation source, and introducing the additional substance into the carbon gas phase.
  • the latter method is preferred.
  • the amount is generally about 10 to 12,000 ppm, and preferably about 1,000 to 10,000 ppm.
  • the production of the conductive diamond thin film is preferably performed by a plasma chemical vapor deposition method.
  • This plasma-enhanced chemical vapor synthesis has the advantage that the activation energy for causing a chemical reaction is large and the reaction is fast. Furthermore, according to this method, it is possible to generate a chemical species that does not exist at a high temperature thermodynamically, and to perform a reaction at a low temperature.
  • Several reports have already been made on the production of conductive diamond thin films by the plasma chemical vapor deposition method, including some of the present inventors (for example, Yano et al., J. Electrochem. Soc, 145 (1998)). 1870), preferably according to the method described in these reports.
  • the conductive diamond oxidizes the compound of the above formula (I) electrochemically and specifically, the conductive diamond is used as a working electrode, and the current value generated between the conductive diamond and the counter electrode in the system is Utilizing the property of being directly proportional to the concentration of the compound of the formula (I), the compound of the formula (I) in the test sample is quantitatively detected. Since the measurement is carried out by knowing the current value, the measuring time is short and simple, and the method according to the present invention is extremely advantageous in that the concentration of the compound of the formula (I) can be easily known in a short time. It is advantageous. Also, diamond electrodes have the potential to oxidize compounds other than the compound of formula (I), but are very specifically sensitive to compounds of formula (I).
  • the assay according to the invention makes it possible to specifically measure only compounds of the formula (I).
  • the compound of the formula (1) is preferably distinguished from other substances having a responsiveness to the diamond electrode and subjected to the measuring method according to the present invention.
  • the oxidized voltage is different for each compound, that is, the peak voltage described later is different, it is possible to distinguish a plurality of compounds of the formula (I) by controlling the applied voltage.
  • the compound of the formula (I) can be measured in a wide concentration range from about 1 / mo 1 to a saturated concentration.
  • the electrochemical system for quantifying the compound of the formula (I) is a general electrochemical system except that a conductive diamond is used as a working electrode. System.
  • a conductive diamond is used as a working electrode, brought into contact with a test sample together with a counter electrode, and placed between the two electrodes on a diamond electrode. Apply the voltage at which the oxidation reaction occurs, and measure the current value under this voltage. Then, the concentration of the compound represented by the formula (I) in the test sample is calculated from the obtained current value. As described above, the current value generated between the conductive diamond and the counter electrode by the oxidation of the compound of the formula (I) is directly proportional to the concentration of the compound of the formula (I) in the system.
  • the concentration of the compound represented by the formula (I) is By preparing a calibration curve with the current value in advance, and comparing this calibration curve with the obtained current value, the concentration of the compound of the formula (I) can be known.
  • the voltage applied between the working electrode, the diamond electrode, and the counter electrode is not limited as long as an oxidation reaction of the compound of the formula (I) occurs on the diamond electrode.
  • the applied voltage is preferably a voltage that gives a peak current of oxidation of the compound of the formula (I).
  • the peak current can be determined as a voltage giving a maximum current value by, for example, cyclic voltage measurement.
  • the voltage giving the maximum current value can be determined by a rotating electrode method or a microelectrode method.
  • the rotating electrode method or the microelectrode method is advantageous in that the possibility of measurement error due to measurement conditions and the like can be further eliminated.
  • the reference electrode is brought into contact with the test sample, and the absolute value of a voltage at which an oxidation reaction occurs on the diamond electrode is controlled between the diamond electrode and the counter electrode. It is preferable from the viewpoint of measurement accuracy.
  • a known electrode can be used, and a standard hydrogen electrode, a silver / silver chloride electrode, a mercury / mercury chloride electrode, a hydrogen palladium electrode and the like can be used.
  • the electrochemical system can be a general electrochemical system except that conductive diamond is used as a working electrode.
  • a flow injection method using a flow cell is preferable, in which a predetermined solution is caused to flow through the system as a carrier at a constant flow rate, and a test sample is injected into the carrier solution for measurement.
  • the outline of the flow injection method using a flow cell is as shown in Fig. 2 (a).
  • the carrier solution is injected into the flow cell 21 from the carrier solution reservoir 6 by the pump 7.
  • a test sample inlet 8 is provided between the pump 7 and the flow cell 21 so that the test sample can be injected into the carrier solution.
  • the carrier solution that has passed through the flow cell 21 is collected in the waste liquid reservoir 9.
  • Flow cell Reference numeral 21 denotes a structure in which the diamond electrode 1, the counter electrode 22 and the reference electrode 23 are exposed in the flow channel 24 through which the carrier solution and the test sample flow, and can be brought into contact with the test sample.
  • the diamond electrode 21 basically has the structure shown in FIG. 1.
  • the diamond thin film 3 in FIG. 1 is exposed in the flow channel 24 and comes into contact with the carrier solution and the test sample.
  • the carrier solution enters from the inlet 25 of the flow channel 24, flows as indicated by the arrow in the figure, and reaches the outlet 26.
  • a voltage for causing the compound of the formula (I) to oxidize on the diamond electrode 1 preferably a voltage for generating a peak current, is applied.
  • the measurement is performed as follows. First, only the carrier solution into which the test sample is not injected flows, so that the so-called background current is minimized and stabilized. Diamond electrodes are characterized by a low background current. Next, the test sample is injected from the test sample inlet 8. This injection may be performed continuously, or an amount that can measure the beak current may be injected at a time. When the compound of the formula (I) is contained in the test sample, the compound of the formula (I) is oxidized on the diamond electrode 1, and the current value accompanying the oxidation reaction can be measured. From this current value, the concentration of the compound of formula (I) is known.
  • the pH of the test sample is fixed to an arbitrary specific value before the measurement.
  • the pH that gives the peak current does not have a large pH dependence, but the ranges of the pH of the test object and the preferred test sample are as follows.
  • the diamond electrode 1 in the flow cell 21 is in the form of a microelectrode.
  • the diamond electrode 1 may be a rotating electrode.
  • a sensor for measuring the concentration of the compound of formula (I) comprising a diamond electrode having conductive diamond.
  • an apparatus for measuring the concentration of a compound of the formula (I) in a test sample is as shown in FIG. In the apparatus shown in FIG. 3, the power supply ⁇ ammeter 31 is connected to the conductor A connected to the diamond electrode 1, the conductor B connected to the counter electrode 22, and the reference electrode 23 from the flow cell shown in FIG. Conductor C is connected.
  • the power supply ammeter 31 serves as a means for applying a voltage at which an oxidation reaction occurs on the diamond electrode between the diamond electrode and the counter electrode, and a means for measuring a current value under the applied voltage. is there. That is, a voltage that causes the compound of formula (I) to oxidize the compound of formula (I) on the diamond electrode 1, preferably a voltage that causes a peak current, is applied between the diamond electrode 1 and the counter electrode 22 by the power source and the ammeter 31. Further, the current value accompanying the oxidation reaction of the compound of the formula (I) on the diamond electrode 1 is measured. This current value is sent to the utility pole value comparison / concentration calculation device 32. The calibration curve data 33 is sent to this device 32.
  • the current value sent from the power supply ammeter 31 is compared with the calibration curve data, and the compound of the formula (I) is compared. Calculate the concentration. That is, a means for calculating the concentration of the compound represented by the formula (I) in the test sample from the obtained current value is provided. The obtained concentration of the compound of the formula (I) is displayed on the display device.
  • Diamond thin films were prepared by a micro-mouth-wave plasma-assisted CVD method using a microwave CVD film forming apparatus manufactured by ASTeX. Specifically,
  • the surface of a silicon substrate (S i (100)) was polished with 0.5 ⁇ m diamond powder, and then set on a substrate holder of a CVD film forming apparatus.
  • a mixture of acetone and methanol (mixing ratio 9: 1 (volume ratio)) was used as a carbon source.
  • Boron in a mixture of oxide (B 2 0 3), and the amount dissolve the 10 4 ppm boron / carbon ratio.
  • Pure hydrogen gas was passed through the mixture of carbon sources to replace dissolved gases.
  • pure hydrogen gas was flowed through the chamber at a flow rate of 532 cc / min, and the pressure was set to 115 xtorr (115 x 133.322 Pa).
  • a 2.45 GHz microphone mouth wave was injected into the chamber and discharged, and the output was adjusted to 5 KW.
  • pure hydrogen gas as a carrier gas was flowed through the carbon source mixture at a flow rate of 15 cc / min, and introduced into the chamber to form a film.
  • the deposition rate was 1 to 4 zm / hour. Film formation was performed until a thickness of about 3 was obtained. Although the substrate was not heated, it was observed that the temperature was about 850-950 ° C in the steady state.
  • volumetric measurements were performed in a glass cell at room temperature using a Hokuto Denko HA-502 potentiometer, a Hokuto Denko HB-U function generator, and a Riken Denshi xy recorder.
  • a diamond electrode having a diamond thin film obtained as described above was used as a working electrode (exposed area: 0.07 cm 2 ), and a platinum foil was used as a counter electrode.
  • a saturated calomel electrode (SCE) was used as a reference electrode.
  • aqueous solution was prepared in a concentration range of / 1. Incidentally, using air saturated Brrtton-Robinson buffer containing 0. lMNaC10 4 a (0. 04M) as the electrolyte, pH was measured using a conventional glass electrode.
  • Xanthine 1-1 00 00 04 6 0.9 9 9 9 9 7 Theophylline 1- 400 0.04 43 0.9 9 98 0 Theopromine 1-4 00 00 04 5 0 9 9 8 9
  • concentration exceeded about 150 ⁇ mo1 / 1
  • the peak current value lost its concentration dependence. This may be due to poor solubility of xanthine in the buffer.
  • Example 3 (a) In the same manner as in Example 3 (a), a calibration curve was created for theophylline by obtaining the relationship between the peak current value and the caffeine concentration. The obtained calibration curve was as shown in FIG.
  • the 0. I MHC 10 4 31 Commercial theophylline 100111 tablets as a solvent, is first dissolved in the 5 OML, and further dissolve the solution 0. 04Ml in the solvent 2 OML.
  • the peak current value was determined in the same manner as in Example 3 (b) except that the applied voltage was set to 1.4 V for this solution.
  • the peak current value was 170 OnA, and the theophylline concentration in the solution to be measured was calculated to be 19.96 mmol / l from the above calibration curve. From this concentration, the amount of theophylline in the theophylline 10 Omg tablet was calculated to be 99.8 mg.

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Abstract

La présente invention concerne un procédé pour déterminer la concentration d'un composé de type xanthine, représenté par la formule (I), dans laquelle R?1, R2 et R3¿ représentent indépendamment un atome d'hydrogène ou un groupe alkyle ayant de 1 à 6 atomes de carbone. Ce procédé consiste à disposer d'une électrode en diamant, qui comprend un diamant électroconducteur, et d'une contre-électrode, à mettre en contact l'électrode en diamant et la contre-électrode avec un échantillon à analyser, à appliquer entre l'électrode en diamant et la contre-électrode une tension suffisante pour engendrer une réaction d'oxydation sur l'électrode en diamant, à mesurer une valeur de courant sous tension, puis à calculer la concentration du composé représenté par la formule (I) dans l'échantillon à analyser, à partir de la valeur de courant résultante, par utilisation d'une courbe d'étalonnage établie à l'avance. Ce procédé exploite le fait qu'un composé de type xanthine, représenté par la formule (I), présente la propriété d'être spécifiquement oxydé par voie électrochimique sur une électrode en diamant. Ce procédé peut servir à déterminer rapidement et facilement la concentration d'un composé de type xanthine, tel que la caféine, la théophylline, la théobromine et la xanthine.
PCT/JP2001/005317 2000-06-21 2001-06-21 Procede pour determiner la concentration d'un compose de type xanthine et detecteur utilise a cette fin WO2001098766A1 (fr)

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AU2001274581A AU2001274581A1 (en) 2000-06-21 2001-06-21 Method for determining concentration of xanthin type compound and sensor for usetherein
JP2002504478A JPWO2001098766A1 (ja) 2000-06-21 2001-06-21 キサンチン系化合物の濃度を測定する方法およびそれに用いられるセンサ

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CN100429508C (zh) * 2006-11-22 2008-10-29 哈尔滨工业大学 掺磷非晶金刚石薄膜电极及其制备方法
JP2008292388A (ja) * 2007-05-28 2008-12-04 National Institute Of Advanced Industrial & Technology Ｄｎａ及びｒｎａ中の核酸塩基の電気化学的検出方法
CN104101632A (zh) * 2014-07-29 2014-10-15 无锡百灵传感技术有限公司 用于咖啡因检测的电化学传感器的制备方法
JPWO2018230660A1 (ja) * 2017-06-16 2020-03-26 学校法人慶應義塾 残留塩素測定方法及び残留塩素測定装置
WO2020207978A1 (fr) 2019-04-09 2020-10-15 Element Six Technologies Limited Électrodes en diamant synthétique dopé au bore et matériaux
JP2023060355A (ja) * 2019-07-19 2023-04-27 住友化学株式会社 電気化学センサ用電極

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JPH02266253A (ja) * 1989-04-07 1990-10-31 Idemitsu Petrochem Co Ltd 分析・試験・計測用等電極およびこれを使用した酵素センサー
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EP1055926A2 (fr) * 1999-05-28 2000-11-29 Kabushiki Kaisha Meidensha Analyse électrochimique utilisant une électrode à revêtement de diamant, et système d'analyse électrochimique basé sur celle-ci

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JPS58160860A (ja) * 1982-03-18 1983-09-24 Rikagaku Kenkyusho 電気化学的試験・分析用電極
JPH02266253A (ja) * 1989-04-07 1990-10-31 Idemitsu Petrochem Co Ltd 分析・試験・計測用等電極およびこれを使用した酵素センサー
JPH1183799A (ja) * 1997-07-14 1999-03-26 Imura Japan Kk ダイヤモンド電極を用いた複数被測定物質の濃度測定方法および濃度センサ
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Publication number Priority date Publication date Assignee Title
CN100429508C (zh) * 2006-11-22 2008-10-29 哈尔滨工业大学 掺磷非晶金刚石薄膜电极及其制备方法
JP2008292388A (ja) * 2007-05-28 2008-12-04 National Institute Of Advanced Industrial & Technology Ｄｎａ及びｒｎａ中の核酸塩基の電気化学的検出方法
CN104101632A (zh) * 2014-07-29 2014-10-15 无锡百灵传感技术有限公司 用于咖啡因检测的电化学传感器的制备方法
JPWO2018230660A1 (ja) * 2017-06-16 2020-03-26 学校法人慶應義塾 残留塩素測定方法及び残留塩素測定装置
WO2020207978A1 (fr) 2019-04-09 2020-10-15 Element Six Technologies Limited Électrodes en diamant synthétique dopé au bore et matériaux
JP2023060355A (ja) * 2019-07-19 2023-04-27 住友化学株式会社 電気化学センサ用電極
JP7302111B2 (ja) 2019-07-19 2023-07-03 住友化学株式会社 電気化学センサ用電極

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