JPH0337703B2 - - Google Patents

Info

Publication number
JPH0337703B2
JPH0337703B2 JP7238082A JP7238082A JPH0337703B2 JP H0337703 B2 JPH0337703 B2 JP H0337703B2 JP 7238082 A JP7238082 A JP 7238082A JP 7238082 A JP7238082 A JP 7238082A JP H0337703 B2 JPH0337703 B2 JP H0337703B2
Authority
JP
Japan
Prior art keywords
electrode
hydrogen peroxide
pretreatment
pretreatment method
polishing
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
Application number
JP7238082A
Other languages
Japanese (ja)
Other versions
JPS58189551A (en
Inventor
Masami Kuroda
Kenji Harada
Hisao Oosawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuji Electric Co Ltd
Original Assignee
Fuji Electric Corporate Research and Development Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Electric Corporate Research and Development Ltd filed Critical Fuji Electric Corporate Research and Development Ltd
Priority to JP7238082A priority Critical patent/JPS58189551A/en
Publication of JPS58189551A publication Critical patent/JPS58189551A/en
Publication of JPH0337703B2 publication Critical patent/JPH0337703B2/ja
Granted legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/404Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors
    • G01N27/4045Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors for gases other than oxygen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)

Description

【発明の詳細な説明】 本発明は、固定化酵素膜を用いる酵素電極の一
種である過酸化水素電極(過酸化水素検出用隔膜
被覆電極)の活性が長期使用に伴ない劣化するた
め、これを改善し長期間安定で、かつ応答性の高
い電極を得るための表面処理法に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention is aimed at solving the problem that the activity of a hydrogen peroxide electrode (diaphragm-coated electrode for detecting hydrogen peroxide), which is a type of enzyme electrode using an immobilized enzyme membrane, deteriorates with long-term use. This paper relates to a surface treatment method for improving electrodes that are stable for a long period of time and have high responsiveness.

酵素電極は酵素と電極とを一体化したものであ
り、選択的、迅速、正確等の長所を有するため、
臨床化学分析、環境分析などの分野で広く用いら
れている。酵素電極を構成する電極としての過酸
化水素電極は、酵素の触媒作用により生成した過
酸化水素を白金などを用いたアノードで酸化し、
その酸化電流値から特定成分を定量する目的で使
用されている。この種の電極は一般に高感度およ
び高寿命であることが望まれる。
Enzyme electrodes integrate enzymes and electrodes, and have the advantages of being selective, rapid, and accurate.
Widely used in fields such as clinical chemistry analysis and environmental analysis. The hydrogen peroxide electrode that constitutes the enzyme electrode oxidizes hydrogen peroxide produced by the catalytic action of an enzyme with an anode made of platinum or the like.
It is used for the purpose of quantifying specific components from the oxidation current value. It is generally desired that this type of electrode has high sensitivity and long life.

過酸化水素の濃度の計測法としては、白金をア
ノード、銀をカソードとして使用し、両電極間に
一定電圧を印加しつつ電解電流を測定し、検量線
法あるいは校正法により、過酸化水素を決定する
ものが多い。白金極の電位を銀極に対して0.6V
以上印加することにより、電解電流は過酸化水素
の拡散律速となる。この計測法による過酸化水素
電極は長期間の使用に伴い、電極の活性低下が認
められる場合が多い。活性度の低下は精度の低下
と検出限界能の悪化をもたらす。劣化が著しい場
合は校正法を適用できなくなる。
To measure the concentration of hydrogen peroxide, use platinum as an anode and silver as a cathode, measure the electrolytic current while applying a constant voltage between the two electrodes, and measure the concentration of hydrogen peroxide using the calibration curve method or calibration method. There are many decisions to be made. The potential of the platinum electrode is 0.6V with respect to the silver electrode.
By applying the above amount, the electrolytic current becomes rate-limited by the diffusion of hydrogen peroxide. Hydrogen peroxide electrodes based on this measurement method often show a decrease in electrode activity after long-term use. A decrease in activity leads to a decrease in accuracy and deterioration of detection limit capability. If the deterioration is significant, the calibration method cannot be applied.

本発明は、上述の欠点を除去し、より高感度で
安定な過酸化水素電極とするための電極表面処理
法を提供することを目的とする。
An object of the present invention is to provide an electrode surface treatment method that eliminates the above-mentioned drawbacks and provides a more sensitive and stable hydrogen peroxide electrode.

活性度の劣化は、白金極には常に一定の電位が
印加されているので、長期間の使用に伴い白金ア
ノード表面に白金酸化物が生成したり、反応液中
に溶存している有機物、無機物が吸着したりする
ためと考えられている。この発明者らはこの点に
着目し、過酸化水素電極の活性度の低下を小さく
し、長期安定な電極を提供するための表面処理法
を見い出した。
Deterioration of activity is caused by the formation of platinum oxide on the surface of the platinum anode due to long-term use, as a constant potential is always applied to the platinum electrode, and organic and inorganic substances dissolved in the reaction solution. It is thought that this is due to the adsorption of The inventors focused on this point and discovered a surface treatment method for reducing the decrease in activity of the hydrogen peroxide electrode and providing a long-term stable electrode.

次に本発明の実施例を図面に基づいて詳細に説
明する。
Next, embodiments of the present invention will be described in detail based on the drawings.

対象とする過酸化水素電極は第1図に示されて
いる。第1図において、1はアノードとしての白
金電極、2は電極支持絶縁体、3はカソードとし
ての銀電極である。白金電極1は銀電極3の中心
部に設けられている。4および5はそれぞれ白金
電極1および銀電極3から導出されたリード線で
ある。このように構成された過酸化水素電極は、
第1A図に示すように、固定化酵素膜装着ガイド
6に収容され、固定化酵素膜5が取付けられて、
酵素電極として使用される。なお、7は0−リン
グである。この第1A図に示した酵素電極は図示
していない測定セル部に固定され、白金電極1と
銀電極3との間に0.6〜0.8Vの範囲の一定電圧が
印加される。
The hydrogen peroxide electrode of interest is shown in FIG. In FIG. 1, 1 is a platinum electrode as an anode, 2 is an electrode supporting insulator, and 3 is a silver electrode as a cathode. The platinum electrode 1 is provided at the center of the silver electrode 3. 4 and 5 are lead wires led out from the platinum electrode 1 and the silver electrode 3, respectively. The hydrogen peroxide electrode configured in this way is
As shown in FIG. 1A, the immobilized enzyme membrane 5 is accommodated in the immobilized enzyme membrane mounting guide 6 and attached.
Used as an enzyme electrode. Note that 7 is a 0-ring. The enzyme electrode shown in FIG. 1A is fixed to a measuring cell section (not shown), and a constant voltage in the range of 0.6 to 0.8 V is applied between the platinum electrode 1 and the silver electrode 3.

過酸化水素電極の前処理法のフローチヤートを
第2図に示す。まず、第1図に示すように成型し
た電極の表面を粗いエメリーペーパー(#300〜
400程度)で粗削りし、細かいエメリーペーパー
(#1200〜1500程度)で仕上げを行なう(研磨工
程11)。次の工程の超音波洗浄は表面に付着し
たエメリーペーパーの粒子、ゴミ等を落すための
操作である。(超音波洗浄工程12)。また表面の
有機物等を除去するため重曹により充分脱脂を行
なう(脱脂工程13)。さらに超音波洗浄を行な
い(超音波洗浄工程14)、硝酸に電極表面を浸
し、他金属粉末等を溶解し取り除く(酸処理工程
15)。また長期使用により生成する酸化物等の
影響を低減するため電極を燐酸塩緩衝液(PH8.5)
に浸し、0.6〜0.8Vの一定電圧を印加し、エージ
ングを行なう(エージング工程16)。これによ
り電極感度は長期の使用に渡り安定し、高寿命が
得られる。本発明につき第1図に示した型の過酸
化水素電極を用いた場合の実験結果を示し説明す
る。
A flowchart of the pretreatment method for the hydrogen peroxide electrode is shown in FIG. First, as shown in Figure 1, the surface of the molded electrode was coated with rough emery paper (#300~
400) and finish with fine emery paper (#1200 to 1500) (polishing step 11). The next step, ultrasonic cleaning, is an operation to remove emery paper particles, dirt, etc. that have adhered to the surface. (Ultrasonic cleaning step 12). Further, in order to remove organic substances on the surface, sufficient degreasing is performed using baking soda (degreasing step 13). Further, ultrasonic cleaning is performed (ultrasonic cleaning step 14), and the electrode surface is immersed in nitric acid to dissolve and remove other metal powders (acid treatment step 15). In addition, in order to reduce the effects of oxides etc. generated during long-term use, the electrodes are placed in a phosphate buffer solution (PH8.5).
A constant voltage of 0.6 to 0.8 V is applied to perform aging (aging step 16). As a result, the electrode sensitivity remains stable over long periods of use, resulting in a long service life. The present invention will be explained by showing experimental results using a hydrogen peroxide electrode of the type shown in FIG.

第3図は前処理を行つた過酸化水素電極を透過
性膜(たとえば多孔質の高分子膜)とともに反応
セル部に装着し、ポーラログラフ法により過酸化
水素溶液を測定した実験結果である。第3図に示
すように、前処理を行うことにより、過酸化水素
溶液に対し良好な直線性が得られた。また、電流
−電圧変換器を用いて同様な測定を行つた結果、
第4図に示すように、過酸化水素稀薄溶液につい
ても優れた直線性が得られた。
FIG. 3 shows the results of an experiment in which a pretreated hydrogen peroxide electrode was attached to a reaction cell together with a permeable membrane (for example, a porous polymer membrane), and a hydrogen peroxide solution was measured by the polarographic method. As shown in FIG. 3, by performing the pretreatment, good linearity with respect to the hydrogen peroxide solution was obtained. Also, as a result of similar measurements using a current-voltage converter,
As shown in FIG. 4, excellent linearity was also obtained with the dilute hydrogen peroxide solution.

第5図は、過酸化水素溶液を反応セル部に注入
したときの応答性を示すものである。第5図のよ
うに、前処理を行つた電極は過酸化水素濃度に対
し応答が極めて早く、90%応答時間定常値の90%
値に達する時間)は注入後5秒以内である。また
第6図は電極に固定化酵素(グルコースオキシタ
ーゼ)膜を装着した場合(第1A図の酵素電極)
のグルコース溶液に対する応答性である。固定化
酵素膜を装着した場合でも、いずれのグルコース
濃度(500mg/dl、300mg/dl、100mg/dl)につ
いて応答は非常に早く、90%応答時間は10秒以内
である。これに対し、第7図に前処理(重曹脱
脂)をしない電極のグルコース溶液(500mg/dl、
300mg/dl、100mg/dl)に対する応答性を示す。
第6図と第7図との比較から、重曹脱脂を行うこ
とにより、固定化酵素膜を装着した場合でも、良
好な応答性が得られることがわかる。
FIG. 5 shows the response when a hydrogen peroxide solution was injected into the reaction cell section. As shown in Figure 5, the pretreated electrode responds extremely quickly to the hydrogen peroxide concentration, with a 90% response time of 90% of the steady value.
The time to reach the value is within 5 seconds after injection. Figure 6 shows a case where an immobilized enzyme (glucose oxidase) membrane is attached to the electrode (enzyme electrode in Figure 1A).
This is the responsiveness to a glucose solution. Even when equipped with an immobilized enzyme membrane, the response is very fast for all glucose concentrations (500 mg/dl, 300 mg/dl, 100 mg/dl), with a 90% response time of less than 10 seconds. In contrast, Figure 7 shows the glucose solution (500 mg/dl,
300mg/dl, 100mg/dl).
A comparison between FIG. 6 and FIG. 7 shows that by performing baking soda degreasing, good responsiveness can be obtained even when an immobilized enzyme membrane is attached.

第8図は本発明による前処理を行つた過酸化水
素電極の活性度の安定性を示したものである。固
定化グルコースオキシターゼ膜を装着した状態で
グルコース溶液150mg/dlにて測定を行い、3週
間以上にわたる安定性が得られた。また固定化酵
素膜を交換することにより初期値が再現された。
エージング処理を行わない場合には、初期に劣化
が大きく3日間で初期値の約1/4〜1/2となること
があり、エージングを行うことにより高感度で長
期間安定な過酸化水素電極を得ることができる。
FIG. 8 shows the stability of the activity of a hydrogen peroxide electrode subjected to the pretreatment according to the present invention. Measurement was performed using a glucose solution of 150 mg/dl with the immobilized glucose oxidase membrane attached, and stability for over 3 weeks was obtained. In addition, the initial values were reproduced by replacing the immobilized enzyme membrane.
If no aging treatment is performed, the deterioration will be large in the initial stage and the initial value may drop to about 1/4 to 1/2 within 3 days. can be obtained.

本発明方法を実施することにより、、酵素電極
用過酸化水素電極の活性度が安定化するため、過
酸化水素電極および固定化酵素膜の交換の回数を
減少させることができる。このことは過酸化水素
電極、固定化酵素膜の有効利用ができることを意
味する。更には酸化電流と残余電流の比が過酸化
水素電極の活性度の安定化と共に安定するため、
より正確な基質及び過酸化水素の定量が可能とな
る。
By carrying out the method of the present invention, the activity of the hydrogen peroxide electrode for enzyme electrodes is stabilized, so that the number of exchanges of the hydrogen peroxide electrode and the immobilized enzyme membrane can be reduced. This means that the hydrogen peroxide electrode and the immobilized enzyme membrane can be used effectively. Furthermore, the ratio of oxidation current to residual current stabilizes as the activity of the hydrogen peroxide electrode stabilizes.
More accurate determination of substrate and hydrogen peroxide is possible.

過酸化水素検出用隔膜被覆電極は臨床化学分
析、環境分析には広く利用されているが、今度は
有機化学分析、化学プロセス制御の分野にもその
発展が期待できる。本発明方法は他の物質(例え
ば金、パラジウム)の電極にも適用できる。ま
た、酸化物電極に対しても悪同様である。
Diaphragm-coated electrodes for detecting hydrogen peroxide are widely used in clinical chemistry analysis and environmental analysis, but their development is also expected in the fields of organic chemistry analysis and chemical process control. The method of the invention can also be applied to electrodes of other materials (eg gold, palladium). The same applies to oxide electrodes.

以上に説明したように、本発明による過酸化水
素電極の前処理方法は、過酸化水素電極の電極表
面を研磨する研磨工程と、前記電極表面に付着し
ている汚れを落とす超音波洗浄工程と、前記電極
表面に付着している有機物等を除去して脱脂を行
なう脱脂工程と、前記電極表面に付着している金
属粉末等を除去する酸処理工程と、前記電極の活
性度の安定化を図るエージング工程とを有するこ
とによつて、より高感度で安定な過酸化水素電極
を提供することができる。
As explained above, the pretreatment method for a hydrogen peroxide electrode according to the present invention includes a polishing step for polishing the electrode surface of the hydrogen peroxide electrode, and an ultrasonic cleaning step for removing dirt adhering to the electrode surface. , a degreasing step for removing organic matter etc. adhering to the electrode surface and degreasing; an acid treatment step for removing metal powder etc. adhering to the electrode surface; and stabilization of the activity of the electrode. By including the aging step, it is possible to provide a more sensitive and stable hydrogen peroxide electrode.

なお、第2図のフローチヤートにおいて、脱脂
工程は酸処理行程の後に行なつてもよい。
In addition, in the flowchart of FIG. 2, the degreasing step may be performed after the acid treatment step.

【図面の簡単な説明】[Brief explanation of drawings]

第1図は過酸化水素電極の概略断面図、第1A
図は酵素電極の概略断面図、第2図は本発明によ
る前処理方法のフローチヤート、第3図ないし第
8図は本発明方法の効果を説明するための実験結
果を示す特性図である。 1……白金電極、2……絶縁体、3……銀電
極、5……固定化酵素膜。
Figure 1 is a schematic cross-sectional view of a hydrogen peroxide electrode, 1A
The figure is a schematic sectional view of an enzyme electrode, FIG. 2 is a flowchart of the pretreatment method according to the present invention, and FIGS. 3 to 8 are characteristic diagrams showing experimental results for explaining the effects of the method of the present invention. 1... Platinum electrode, 2... Insulator, 3... Silver electrode, 5... Immobilized enzyme membrane.

Claims (1)

【特許請求の範囲】 1 カソードとしての銀電極と、アノードとして
前記銀電極の中心部に絶縁して設けられた白金電
極とから成る過酸化水素電極の前処理方法におい
て、前記過酸化水素電極の電極表面を研磨する研
磨工程と、前記電極表面に付着している汚れを落
とす超音波洗浄工程と、前記電極表面に付着して
いる有機物等を除去して脱脂を行う脱脂工程と、
前記電極表面に付着している金属粉末等を除去す
る酸処理工程と、前記電極の活性度の安定化を図
るエージング工程とを有することを特徴とする過
酸化水素電極の前処理方法。 2 特許請求の範囲第1項記載の前処理方法にお
いて、研磨工程は、電極表面を粗いエメリーペー
パーで粗削りし、次に細かいエメリーペーパーで
仕上げを行うことより成ることを特徴とする過酸
化水素電極の前処理方法。 3 特許請求の範囲第1項または第2項記載の前
処理方法において、脱脂工程は、重曹を用いて行
われることを特徴とする過酸化水素電極の前処理
方法。 4 特許請求の範囲第1項ないし第3項記載のい
ずれかの項記載の前処理方法において、酸処理工
程は、硝酸に電極表面を浸して行われることを特
徴とする過酸化水素電極の前処理方法。 5 特許請求の範囲第1項ないし第4項記載のい
ずれかの項記載の前処理方法において、エージン
グ工程は、電極を燐酸塩緩衝液に浸し、電極に所
定の電圧を印加して行われることを特徴とする過
酸化水素電極の前処理方法。
[Scope of Claims] 1. A method for pretreatment of a hydrogen peroxide electrode comprising a silver electrode as a cathode and a platinum electrode insulated at the center of the silver electrode as an anode. a polishing step for polishing the electrode surface; an ultrasonic cleaning step for removing dirt adhering to the electrode surface; and a degreasing step for removing organic substances and the like adhering to the electrode surface.
A pretreatment method for a hydrogen peroxide electrode, comprising an acid treatment step for removing metal powder etc. adhering to the electrode surface, and an aging step for stabilizing the activity of the electrode. 2. A hydrogen peroxide electrode in the pretreatment method according to claim 1, characterized in that the polishing step consists of roughly polishing the electrode surface with coarse emery paper, and then finishing with fine emery paper. Pretreatment method. 3. A pretreatment method for a hydrogen peroxide electrode according to claim 1 or 2, wherein the degreasing step is performed using baking soda. 4. In the pretreatment method described in any one of claims 1 to 3, the acid treatment step is performed by immersing the electrode surface in nitric acid. Processing method. 5. In the pretreatment method according to any one of claims 1 to 4, the aging step is performed by immersing the electrode in a phosphate buffer and applying a predetermined voltage to the electrode. A method for pretreatment of a hydrogen peroxide electrode, characterized by:
JP7238082A 1982-04-28 1982-04-28 Pretreatment of hydrogen peroxide electrode Granted JPS58189551A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7238082A JPS58189551A (en) 1982-04-28 1982-04-28 Pretreatment of hydrogen peroxide electrode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7238082A JPS58189551A (en) 1982-04-28 1982-04-28 Pretreatment of hydrogen peroxide electrode

Publications (2)

Publication Number Publication Date
JPS58189551A JPS58189551A (en) 1983-11-05
JPH0337703B2 true JPH0337703B2 (en) 1991-06-06

Family

ID=13487624

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7238082A Granted JPS58189551A (en) 1982-04-28 1982-04-28 Pretreatment of hydrogen peroxide electrode

Country Status (1)

Country Link
JP (1) JPS58189551A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2201248B (en) * 1987-02-24 1991-04-17 Ici Plc Enzyme electrode sensors
JPH0727847B2 (en) * 1987-06-16 1995-03-29 昭和電工株式会社 Method for manufacturing solid electrolytic capacitor

Also Published As

Publication number Publication date
JPS58189551A (en) 1983-11-05

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