JP2652890B2 - How to measure hydrogen peroxide concentration - Google Patents
How to measure hydrogen peroxide concentrationInfo
- Publication number
- JP2652890B2 JP2652890B2 JP1250746A JP25074689A JP2652890B2 JP 2652890 B2 JP2652890 B2 JP 2652890B2 JP 1250746 A JP1250746 A JP 1250746A JP 25074689 A JP25074689 A JP 25074689A JP 2652890 B2 JP2652890 B2 JP 2652890B2
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- concentration
- electrode
- measured
- carbon fiber
- 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.)
- Expired - Lifetime
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims description 42
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 11
- 239000004917 carbon fiber Substances 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001994 activation Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 150000003943 catecholamines Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 過酸化水素濃度の定量的測定は、生化学，臨床化学，
食品化学の分野で重要であり、広く実施されているが、
本発明は、この過酸化水素濃度の測定方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] Quantitative measurement of hydrogen peroxide concentration is performed by biochemistry, clinical chemistry,
Important and widely implemented in the field of food chemistry,
The present invention relates to a method for measuring the concentration of hydrogen peroxide.
上記のように従来から各分野で過酸化水素の濃度が測
定されており、その測定方法は目的，用途等に応じて種
々の方法がなされている。As described above, the concentration of hydrogen peroxide has been conventionally measured in various fields, and various methods for measuring the concentration are used depending on the purpose, application, and the like.
しかしながら、このような従来の過酸化水素濃度の測
定方法では、測定値の検出感度が低く、また、測定時間
も１分以上を要して迅速性に欠けるという問題がある。However, such a conventional method for measuring the concentration of hydrogen peroxide has a problem in that the detection sensitivity of the measured value is low, and the measurement time is one minute or more, and thus the method is lacking in speed.
また、臨床化学等の分野では、生体内に検出用電極を
埋め込むために炭素繊維電極を微小電極として用いる
が、従来においてはこの炭素繊維電極では定量的な濃度
測定は殆ど不可能であつた。In the field of clinical chemistry and the like, a carbon fiber electrode is used as a microelectrode in order to embed a detection electrode in a living body, but it has been almost impossible to quantitatively measure the concentration with the carbon fiber electrode in the past.
本発明は、過酸化水素を含む溶液中に浸した炭素繊維
電極に三角波電圧を加えて活性化工程を行なつた後、こ
の電極に第１のパルス電圧を印加し第１の電流値を測定
し、第２のパルス電圧を印加して第２の電流値を測定
し、両電流値の差から過酸化水素の濃度を測定する。According to the present invention, a triangular wave voltage is applied to a carbon fiber electrode immersed in a solution containing hydrogen peroxide to perform an activation step, and then a first pulse voltage is applied to this electrode to measure a first current value. Then, a second current value is measured by applying a second pulse voltage, and the concentration of hydrogen peroxide is measured from the difference between the two current values.
測定前に電極に所定電圧の三角波信号を印加して電気
化学的に活性化を行ない、２回のパルスにより検出した
電流値の差により、予め作成された対照表等から過酸化
水素濃度を測定する。Before the measurement, a triangular wave signal of a predetermined voltage is applied to the electrode to electrochemically activate the electrode, and the concentration of hydrogen peroxide is measured from a comparison table or the like prepared in advance based on the difference between the current values detected by two pulses. I do.
以下、本発明の実施例を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
第１図は本発明に係る過酸化水素濃度の測定を行なう
マイクロコンピユータ制御構成のブロツク図である。１
は炭素繊維電極からなる作用電極2,参照電極3,補助電極
４を有する電解槽、５は電解槽１の各電極を電気的に制
御し電圧を加えたり電流を検出したりするマイクロ・ポ
テンシヨスタツト、６はアナログ信号をデイジタル信号
に変換するA/D変換器、７はデイジタル信号をアナログ
信号に変換するD/A変換器、８は測定の制御プログラム
を実行するマイクロ・コンピユータ、９は各データや情
報を表示するCRT,プロツタ，プリンタ等の表示装置であ
る。FIG. 1 is a block diagram of a microcomputer control system for measuring the concentration of hydrogen peroxide according to the present invention. 1
Is an electrolytic cell having a working electrode 2, a reference electrode 3, and an auxiliary electrode 4 composed of carbon fiber electrodes. 6, an A / D converter 6 for converting an analog signal into a digital signal, a D / A converter 7 for converting a digital signal into an analog signal, a micro computer 8 for executing a control program for measurement, and a reference numeral 9 for each. It is a display device such as a CRT, plotter, or printer that displays data and information.
第２図は電解槽１の構造図である。10は100mlのリン
酸緩衝水溶液、11は過酸化水素を供給するためのサンプ
ル導入口、12は空気吸入口である。第３図は作用電極２
の構造図である。13はガラスピペツト、14の直径が７ミ
クロン程の炭素繊維、14aはそのガラスピペツト14から
0.5mm程度突出した電極部、15はリード線、16は炭素繊
維14とリード線15を電気的に接続する導電ペースト、17
は炭素繊維14をガラスピペツト13内に保持するエポキシ
樹脂である。FIG. 2 is a structural view of the electrolytic cell 1. Reference numeral 10 denotes a 100 ml aqueous phosphate buffer solution, 11 denotes a sample inlet for supplying hydrogen peroxide, and 12 denotes an air inlet. FIG. 3 shows the working electrode 2
FIG. 13 is a glass pipet, 14 is a carbon fiber having a diameter of about 7 microns, and 14a is a glass pipet from the glass pipet 14.
Electrode part protruding about 0.5 mm, 15 is a lead wire, 16 is a conductive paste for electrically connecting the carbon fiber 14 and the lead wire 15, 17
Is an epoxy resin that holds the carbon fiber 14 in the glass pipette 13.
このような測定装置の構成において、マイクロ・コン
ピユータ８の指令で測定が開始される。In such a configuration of the measuring device, the measurement is started by a command from the micro computer 8.
先ず、作用電極２に三角波電圧のパルスを１つ印加す
る。このパルスの波形は勾配が上昇，下降共に10V/秒の
交流であり、ピーク電圧値は約±2Vである。このピーク
電圧値は1.3〜2.7Vの範囲で適当な値が選択される。こ
れにより電極が活性化される。すなわち、電極の表面の
洗浄がなされ、さらに、電極反応の可能な場所の密度が
高くなり、反応速度も増大させることができる。First, one triangular wave voltage pulse is applied to the working electrode 2. The waveform of this pulse is an alternating current of 10 V / sec in both the rising and falling gradients, and the peak voltage value is about ± 2 V. An appropriate value is selected for this peak voltage value in the range of 1.3 to 2.7V. This activates the electrodes. That is, the surface of the electrode is cleaned, and the density of the place where the electrode reaction is possible is increased, and the reaction speed can be increased.
次に、第４図に示すように、750mVの第１のパルス電
圧を１秒間印加し、その後のT1の期間で電極２に流れる
第１の電流値I1を測定する。Next, as shown in FIG. 4, a first pulse voltage of 750 mV is applied for one second, and a first current value I1 flowing through the electrode 2 during a period T1 is measured.
引きつづき、1100mVの第２のパルス電圧を１秒間印加
し、その後のT2の期間で電極２に流れる第２の電流値I2
を測定する。Subsequently, a second pulse voltage of 1100 mV is applied for one second, and a second current value I2 flowing through the electrode 2 during a period T2 thereafter
Is measured.
このパルス電圧の値は±200mVの変動が許容され、ま
た、印加時間も0.5秒以上なら効果は十分得られる。The value of this pulse voltage is allowed to fluctuate ± 200 mV, and the effect is sufficiently obtained if the application time is 0.5 seconds or more.
次に、マイクロ・コンピユータ８で第１と第２の電流
値I1とI2の差が演算される。この差電流値と過酸化水素
濃度との間には、10-7〜10-3M（M:mol/）の範囲でほ
ぼ直線関係が得られるので、予め既知の過酸化水素濃度
と差電流値との関係をとつてその特性表を記憶させてお
けば、検出した差電流値からこの記憶データに基づき過
酸化水素濃度を瞬時に算出することができる。Next, the difference between the first and second current values I1 and I2 is calculated by the micro computer 8. Since a substantially linear relationship is obtained between the difference current value and the hydrogen peroxide concentration in the range of 10 −7 to 10 −3 M (M: mol /), the hydrogen peroxide concentration and the difference If the characteristic table is stored in relation to the value, the hydrogen peroxide concentration can be calculated instantaneously from the detected difference current value based on the stored data.
第５図および第６図はこの過酸化水素濃度と差電流値
との関係を示すグラフである。第５図は濃度が10-7〜10
-6Mの範囲、第６図は濃度が10-5〜10-4Mの範囲の特性を
示す。5 and 6 are graphs showing the relationship between the hydrogen peroxide concentration and the difference current value. FIG. 5 shows that the concentration is 10 -7 to 10
FIG. 6 shows the characteristics in the range of -6 M and the concentration in the range of 10 -5 to 10 -4 M.
以上の実施例によると、従来１分以上を要していた測
定時間が５秒程度に短縮されると共に、検出感度が従来
10μＭであつたものが0.1μＭに改良され、また、測定
した過酸化水素濃度の値はカテコールアミン，アスコル
ビン酸，アルブミン等の生体内物質の共存に何ら影響を
受けなかつた。また、炭素繊維を使用した作用電極２
は、十分に１年以上の寿命を持つことが確認された。According to the above embodiment, the measurement time, which conventionally required 1 minute or more, is reduced to about 5 seconds, and the detection sensitivity is reduced.
The concentration of 10 μM was improved to 0.1 μM, and the measured value of the hydrogen peroxide concentration was not affected by the coexistence of biological substances such as catecholamine, ascorbic acid and albumin. Also, a working electrode 2 using carbon fiber
Was confirmed to have a lifetime of at least one year.
以上説明したように、本発明に係る過酸化水素濃度の
測定方法によると、過酸化水素濃度を短時間で高検出感
度で測定することができるという優れた効果がある。ま
た、炭素繊維電極を使用しているので、長期に安定性の
よい測定が可能となる。As described above, the method for measuring the concentration of hydrogen peroxide according to the present invention has an excellent effect that the concentration of hydrogen peroxide can be measured in a short time with high detection sensitivity. Further, since a carbon fiber electrode is used, stable measurement can be performed for a long period of time.
第１図は本発明に係る過酸化水素濃度の測定方法を実施
する装置のブロツク図、第２図は電解槽の構造図、第３
図は作用電極の構造図、第４図は電極に印加する電圧波
形図、第５図，第６図は検出した差電流値と過酸化水素
濃度との関係を示すグラフである。 １……電解槽、２……作用電極、８……マイクロ・コン
ピユータ、14……炭素繊維。FIG. 1 is a block diagram of an apparatus for implementing the method for measuring the concentration of hydrogen peroxide according to the present invention, FIG. 2 is a structural diagram of an electrolytic cell, and FIG.
FIG. 4 is a structural diagram of a working electrode, FIG. 4 is a diagram of a voltage waveform applied to the electrode, and FIGS. 5 and 6 are graphs showing the relationship between the detected difference current value and the concentration of hydrogen peroxide. 1 ... electrolyzer, 2 ... working electrode, 8 ... microcomputer, 14 ... carbon fiber.
Claims (1)
電極に三角波電圧を加えて活性化工程を行なつた後、上
記電極に第１のパルス電圧を印加して第１の電流値を測
定し、第２のパルス電圧を印加して第２の電流値を測定
し、両電流値の差から過酸化水素の濃度を測定する過酸
化水素濃度の測定方法。An activation process is performed by applying a triangular wave voltage to a carbon fiber electrode immersed in a solution containing hydrogen peroxide, and then applying a first pulse voltage to the electrode to obtain a first current value. , A second pulse voltage is applied, a second current value is measured, and the hydrogen peroxide concentration is measured from the difference between the two current values.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1250746A JP2652890B2 (en) | 1989-09-28 | 1989-09-28 | How to measure hydrogen peroxide concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1250746A JP2652890B2 (en) | 1989-09-28 | 1989-09-28 | How to measure hydrogen peroxide concentration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03113360A JPH03113360A (en) | 1991-05-14 |
| JP2652890B2 true JP2652890B2 (en) | 1997-09-10 |
Family
ID=17212422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1250746A Expired - Lifetime JP2652890B2 (en) | 1989-09-28 | 1989-09-28 | How to measure hydrogen peroxide concentration |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2652890B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07103939A (en) * | 1993-10-06 | 1995-04-21 | Nec Corp | Measuring method for biosensor |
| US6129831A (en) * | 1995-01-26 | 2000-10-10 | Universiteit Gent - Vakgroep Textielkunde | Hydrogen peroxide sensor |
| BE1009053A5 (en) * | 1995-01-26 | 1996-11-05 | Universiteit Gent Vakgroep Tex | MEASURING PROBE SUITABLE FOR CONTINUED TO MEASURE HYDROGEN CONCENTRATION IN A bleaching bath. |
| JP2006105615A (en) * | 2004-09-30 | 2006-04-20 | Toto Ltd | Electrochemical measuring method and measuring apparatus using it |
| DE102006043718B4 (en) | 2006-09-18 | 2014-12-31 | Alexander Adlassnig | Determination of hydrogen peroxide concentrations |
| JP2010243452A (en) * | 2009-04-10 | 2010-10-28 | Apurikusu:Kk | Method and instrument for continuously measuring concentration of peracetic acid |
| EP2504466B1 (en) * | 2009-11-23 | 2019-11-20 | Proxim Diagnostics Corporation | Controlled electrochemical activation of carbon-based electrodes |
-
1989
- 1989-09-28 JP JP1250746A patent/JP2652890B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03113360A (en) | 1991-05-14 |
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