JPS61155949A - Ph sensor - Google Patents

Ph sensor

Info

Publication number
JPS61155949A
JPS61155949A JP59281076A JP28107684A JPS61155949A JP S61155949 A JPS61155949 A JP S61155949A JP 59281076 A JP59281076 A JP 59281076A JP 28107684 A JP28107684 A JP 28107684A JP S61155949 A JPS61155949 A JP S61155949A
Authority
JP
Japan
Prior art keywords
film
sensor
carrier
hydrogen ion
redox
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.)
Granted
Application number
JP59281076A
Other languages
Japanese (ja)
Other versions
JPH042902B2 (en
Inventor
Hideichiro Yamaguchi
秀一郎 山口
Norihiko Ushizawa
牛沢　典彦
Takeshi Shimomura
猛 下村
Noboru Koyama
昇 小山
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.)
Terumo Corp
Original Assignee
Terumo Corp
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 Terumo Corp filed Critical Terumo Corp
Priority to JP59281076A priority Critical patent/JPS61155949A/en
Priority to EP85116605A priority patent/EP0186210B1/en
Priority to DE8585116605T priority patent/DE3585915T2/en
Publication of JPS61155949A publication Critical patent/JPS61155949A/en
Priority to US07/577,050 priority patent/US5133856A/en
Publication of JPH042902B2 publication Critical patent/JPH042902B2/ja
Granted legal-status Critical Current

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Classifications

    • 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
    • G01N27/333—Ion-selective electrodes or membranes
    • G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component

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  • 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)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)

Abstract

PURPOSE:To measure the pH of an aqueous solution on the basis of potential response, by forming a film having reversible redox function to the surface of a conductive substrate and further forming a polymer film containing a hydrogen gas carrier to said film. CONSTITUTION:A hydrogen ion carrier membrane 14 is formed so as to cover a redox film 13. This carrier film 14 comprises a composition obtained by containing amine or electrolyte salt as a hydrogen carrier and, if necessary, a polymer plasticizer in a polymer film being a carrier such as polyvinyl chloride film. The hydrogen ion in an aqueous solution is rapidly transported to the film 13 through the carrier film 14 and the film 13 brings about redox reaction to generate electromotive force corresponding to the concn. of the hydrogen ion.

Description

【発明の詳細な説明】 １０発明の背景 〔技術分野〕 この発明は、水溶液中の水素イオン濃度を電位応答で測
定するための一センサーに係り、特には、血液、尿など
生体液中で使用することを目的としたーセンサーに関す
る。Detailed Description of the Invention 10 Background of the Invention [Technical Field] The present invention relates to a sensor for measuring the hydrogen ion concentration in an aqueous solution using potential response, and particularly for use in biological fluids such as blood and urine. - related to sensors.

〔先行技術および問題点〕[Prior art and problems]

従来、水素イオン濃度を測定するためのセンサーとして
、ガラス電極が広く用いられている。Conventionally, glass electrodes have been widely used as sensors for measuring hydrogen ion concentration.

しかしながら、ガラス膜が破損しあるいは汚染しやすい
、アルカリ溶液中での使用に限界があるなどの問題があ
る。また、粘度の高い溶液や吸着性物質を含む溶液中で
は測定精度が短時間で低下する。加えて、ガラス電極は
、内部基準液を保有するため微小化が困難である。However, there are problems such as the glass membrane is easily damaged or contaminated, and there are limits to its use in alkaline solutions. Furthermore, measurement accuracy decreases in a short time in a highly viscous solution or a solution containing an adsorbent substance. In addition, glass electrodes contain an internal reference solution, making it difficult to miniaturize them.

これらの理由から、機能性高分子膜を被覆した電極の開
発がおこなわれるようになってきている。その−例とし
て、特開昭５７−１１８１５３号および同５８−６５７
７５号に、白金基体に、アミン芳香族化合物またはヒド
ロキシ芳香族化合物の電解酸化重合膜を水素イオン選択
透過膜として被着したーセンサーが開示されている。For these reasons, electrodes coated with functional polymer membranes have been developed. Examples include JP-A-57-118153 and JP-A-58-657.
No. 75 discloses a sensor in which an electrolytically oxidized polymer membrane of an amine aromatic compound or a hydroxy aromatic compound is adhered to a platinum substrate as a hydrogen ion selectively permeable membrane.

この−センサーは、基体として白金線を用いており、内
部基準液を必要としないので微小化が容易でちり、また
応答速度もプラス電極に比べて速く、生体内および生体
外での使用が可能である。しかしながら、この−センサ
ーは、測定°水溶液中に、微量の活性イオン糧、蛋白質
、糖が存在していると、それらによって平衡電位値が影
＊１−受けやすい欠点がある。また、酸素ガスを含む測
定溶液系や、人工肺のように大量のガスを封入した測定
系においては、基体の平衡電位値がこれらガスの影響に
より変動することが判明した。This sensor uses a platinum wire as a base and does not require an internal standard solution, making it easy to miniaturize and generate dust.The response speed is also faster than that of a positive electrode, allowing it to be used in vivo and in vitro. It is. However, this sensor has the disadvantage that if trace amounts of active ion food, protein, or sugar are present in the aqueous solution being measured, the equilibrium potential value is likely to be affected by these. It has also been found that in measurement solution systems containing oxygen gas or measurement systems in which a large amount of gas is sealed, such as in an oxygenator, the equilibrium potential value of the substrate fluctuates due to the influence of these gases.

また、がラス電極の原理を利用し、ガラス膜の代りにあ
る種の液膜や高分子膜を用いたーセンサーも報告されて
いる。その内、高分子膜としである種の水素イオンキャ
リアー膜を用いたーセンサーが、Ｗ、　Ｓ１ｍｏｎ他に
よってＡｎａｌｙｔｉｃａＣｈｉｍｉｃａ　Ａｃｔａ’
、　１３１．　ｌ１ｌ（１９８１）に記載されている。Sensors have also been reported that utilize the principle of a glass electrode and use some kind of liquid or polymer film instead of a glass film. Among them, a sensor using a certain kind of hydrogen ion carrier membrane as a polymer membrane was developed by W. S1mon et al. in AnalyticaChimica Acta'
, 131. 111 (1981).

この−センサーは、電解質の種類（標準緩衝液、血清、
血漿等）あるいは血液など体液成分によって電極電位が
変化することがなく、シかも応答速度が速い。しかしな
がら、この−センサーは、上にも述べたように、ガラス
電極の原理を利用しているため内部基準液室を必要とし
、小型化が困難であるとともに内部基準液が流出する恐
れがあるなどの問題がある。This sensor detects the type of electrolyte (standard buffer, serum,
The electrode potential does not change due to body fluid components such as plasma, etc.) or blood, and the response speed is fast. However, as mentioned above, this sensor requires an internal reference liquid chamber because it uses the principle of a glass electrode, which makes it difficult to downsize and there is a risk that the internal reference liquid may leak out. There is a problem.

■０発明の目的 したがって、この発明の目的は、上記従来のめセンサー
の問題点を解決し、生体液成分および酸素の影響を受け
ず、迅速に水溶液中のＰＨｔ−電位応答で測定できるー
センサーを提供することにある。0 Purpose of the Invention Therefore, the purpose of the present invention is to solve the problems of the conventional aqueous sensors described above, and to provide a sensor that can quickly measure PHt-potential response in an aqueous solution without being affected by biological fluid components and oxygen. It is about providing.

この発明の一センサーは、水溶液中の水素イオン濃度を
電位応答で測定する念めの一センサーであって、 （＆）導電性基体と、 伽）該導電性基体の表面に形成された可逆的酸化還元機
能を有する膜であってその酸化還元反応が水素イオンの
付加番離脱を伴なう第１の膜と、 （、）　　該＠１の膜の表面に形成され念高分子膜であ
って該水溶液中の水素イオンを該第１の膜へ輸送するた
めの水素イオンキャリアーを含有する第２の膜とを具備
することを特徴とする・■０発明の詳細な説明 以下、この発明を図面を参照して詳しく説明する。One sensor of the present invention is a sensor for measuring hydrogen ion concentration in an aqueous solution based on potential response, and includes (&) a conductive substrate; a first film having a redox function, the redox reaction of which involves the addition and desorption of hydrogen ions; and a second membrane containing a hydrogen ion carrier for transporting hydrogen ions in the aqueous solution to the first membrane. Please refer to the following for a detailed explanation.

第１図に示すように、この発明の一センサー１０は、導
電性基体１１ｔ−具備している・基体ＩＩの形状に特に
制限はないが、細線形状とすることが微小化の点で好ま
しい。基体１１Ｆｉ、白金、金、銀等の貴金属、導電性
炭素などで形成することができる。また、以後述べる酸
化還元機能を有する膜が形成される基体１１表面に酸化
インジウム、酸化スズ等の半導体材料が被着されていて
もよい。As shown in FIG. 1, one sensor 10 of the present invention includes a conductive substrate 11t. Although there is no particular restriction on the shape of the substrate II, it is preferable to have a thin wire shape from the viewpoint of miniaturization. The base 11Fi can be formed of noble metals such as platinum, gold, and silver, conductive carbon, and the like. Further, a semiconductor material such as indium oxide or tin oxide may be deposited on the surface of the base 11 on which a film having an oxidation-reduction function, which will be described later, is formed.

基体２２０周囲は、先端面を除き、テフロン等の絶縁材
料１２で覆われて゛いる。The periphery of the base body 220, except for the tip end surface, is covered with an insulating material 12 such as Teflon.

基体ＩＩの露出先端面には、可逆的酸化還元機能を有す
る膜１３が被着されている。この酸化還元膜Ｉ３は、測
定水溶液中の水素イオンの酸化還元反応に関与し、した
がってそれ自体の酸化還元反応において水素の付加・離
脱を伴うものである。A film 13 having a reversible redox function is adhered to the exposed end surface of the base body II. This oxidation-reduction film I3 participates in the oxidation-reduction reaction of hydrogen ions in the aqueous solution to be measured, and therefore accompanies addition and desorption of hydrogen in its own oxidation-reduction reaction.

このような酸化還元膜１３として、アミン−キノイド型
酸化還元反応をおこなうものと、キノン−ヒドロキノン
型酸化還元反応をおこなうものがある。As such a redox film 13, there are those that perform an amine-quinoid type redox reaction and those that perform a quinone-hydroquinone type redox reaction.

アミン−キノイド型酸化還元反応をおこなう化合物の例
を挙げると、ｌ−アミノピレン、１．６−ジアミノピレ
ン、ｌ、８−ジアミノピレン、ｌ−アミノクリセン、ｌ
Ｉ４−ジアミノクリセン、ｌ−７ミノ７エナントレン、
９−アミノ７エナントレン、９．ｉｏ−ジアミノフェナ
ントレン、ｌ−アミノアントラセン、ｐ−フェノキシア
ニリン、０−フェニレンジアミン、ｐ−クロロアニリン
、３．５−ジクロロアニリン、２．４．６−ドリクロロ
アニリン、Ｎ−メ、チルアニリン、Ｎ−７・ユニルーｐ
−フェニレンジアミン等である。これら、アミン類は、
一般式 ％式％（１） で示すことができる。この式において、Ａｒは芳香核例
えば、ベンゼン核、ナフタレン核、アントラセン核、ピ
レン核、クリセン核、ペリレン核、コロネン核等である
。これら芳香核は、アルキル基、フェニル基等で置換し
ていてもよい。Examples of compounds that perform amine-quinoid redox reactions include l-aminopyrene, 1,6-diaminopyrene, l,8-diaminopyrene, l-aminochrysene, l-aminopyrene,
I4-diaminochrysene, l-7mino7enanthrene,
9-amino 7-enanthrene, 9. io-diaminophenanthrene, l-aminoanthracene, p-phenoxyaniline, 0-phenylenediamine, p-chloroaniline, 3.5-dichloroaniline, 2.4.6-drichloroaniline, N-me, thylaniline, N- 7.Uniloop
-phenylenediamine, etc. These amines are
It can be represented by the general formula % formula % (1). In this formula, Ar is an aromatic nucleus such as a benzene nucleus, a naphthalene nucleus, an anthracene nucleus, a pyrene nucleus, a chrysene nucleus, a perylene nucleus, a coronene nucleus, etc. These aromatic nuclei may be substituted with an alkyl group, a phenyl group, or the like.

キノン−ヒドロキノン型酸化還元をおこなう化合物の例
を挙げると、１．６−ピレン、１．２．５゜８−テトラ
ヒドロキシキナリザリン、フェナントレンキノン、１−
アミノアントラキノン、プルプリン、１−アミノ−４−
ヒドロキシアントラキノン、アントラルフィン、テトラ
ヒドロキシアトラセン、アシッドブラック等である。こ
れら化合物は、一般式 ％式％（） で示すことができる。ここで、Ａｒは式Ｉに関して述べ
たものと同様の芳香核である。Examples of compounds that perform quinone-hydroquinone type redox include 1.6-pyrene, 1.2.5°8-tetrahydroxyquinalizarin, phenanthrenequinone, 1-
Aminoanthraquinone, purpurin, 1-amino-4-
These include hydroxyanthraquinone, anthralphine, tetrahydroxyatracene, and acid black. These compounds can be represented by the general formula %. Here, Ar is an aromatic nucleus similar to that mentioned with respect to formula I.

さて、式Ｉまたは式■で示される化合物は、これを電解
酸化重合または電解析出法によって基体１１の露出表面
に直接被着させるか、あるいは電子線照射、光、熱など
の適用によって重合させこれを溶媒に溶解して基体ｚｒ
の露出表面に塗布することによって基体ＩＩの露出表面
上に膜として形成する。電解酸化重合による膜形成方法
が最も好ましい。Now, the compound represented by formula I or formula (II) can be directly deposited on the exposed surface of the substrate 11 by electrolytic oxidative polymerization or electrolytic deposition, or can be polymerized by applying electron beam irradiation, light, heat, etc. Dissolve this in a solvent to form a base zr
is formed as a film on the exposed surface of substrate II by coating the exposed surface of substrate II. Most preferred is a film forming method using electrolytic oxidative polymerization.

以上述べた酸化還元膜１３は、緻密であり、また測定水
溶液中の酸素分子の透過を阻止する。The oxidation-reduction film 13 described above is dense and blocks the permeation of oxygen molecules in the measurement aqueous solution.

しかしながら、測定溶液中に電解質（例えば、尿、血液
、血清、高浸透圧液、その他の生体電解質）が存在する
と、電極電位値がその影響により変動する。また、この
酸化還元膜Ｉ３だけでは、応答速度が５分以上かかるな
どの問題がある。However, if an electrolyte (for example, urine, blood, serum, hyperosmotic fluid, or other biological electrolyte) is present in the measurement solution, the electrode potential value will fluctuate due to its influence. Further, there is a problem that the response speed takes more than 5 minutes if only this oxidation-reduction film I3 is used.

そこで、この発明では、この酸化還元膜Ｚ３を覆って、
測定水溶液中の水素イオン？：酸化還元膜Ｉ３へ輸送す
るための水素イオンキャリアー膜１４ｆ形成している。Therefore, in this invention, by covering this redox film Z3,
Hydrogen ions in the measured aqueous solution? : A hydrogen ion carrier film 14f for transporting to the redox film I3 is formed.

この水素イオンキャリアーＩ４は、ポリ塩化ビニル等の
高分子膜を担体とし、これに水素イオンキャリアーとし
てアミン、電解質塩および必要により高分子用可塑剤を
含有させたものである。This hydrogen ion carrier I4 uses a polymer membrane such as polyvinyl chloride as a carrier, and contains an amine as a hydrogen ion carrier, an electrolyte salt, and, if necessary, a polymer plasticizer.

水素イオンキャリアーを形成するアミンは式（ここで、
Ｒ１、Ｒ２およびＲ３のそれぞれは、アルキル基であり
、その内の少なくとも２つは炭素数８ないし１８のアル
キル基好ましくは炭素数１０ないし１６のアルキル基）
、または式（ここで、Ｒは炭素数８ないし１８のアルキ
ル基、好ましくは炭素数１０ないし１６のアルキル基）
で示されるものである。The amine that forms the hydrogen ion carrier has the formula (where,
Each of R1, R2 and R3 is an alkyl group, at least two of which are alkyl groups having 8 to 18 carbon atoms, preferably alkyl groups having 10 to 16 carbon atoms)
, or the formula (where R is an alkyl group having 8 to 18 carbon atoms, preferably an alkyl group having 10 to 16 carbon atoms)
This is shown in .

また、上記水素イオンキャリアー膜Ｉ４を組成する電解
質塩としては、ナトリウムテトラキス（ｐ−クロロフェ
ニル〕ボレート、ナトリウムテトラキス（ｐ−クロロフ
ェニル）リン酸、カリウムテトラキス（ｐ−クロロフェ
ニル）す酸、ＬＩＢＦ４ＬｉＰＦ６などの他、式％式％ （各式において、Ｒはアルキル基、好ましくは炭素数２
ないし６のアルキル基）で示される化合物がある。In addition, the electrolyte salts that compose the hydrogen ion carrier membrane I4 include sodium tetrakis(p-chlorophenyl)borate, sodium tetrakis(p-chlorophenyl)phosphoric acid, potassium tetrakis(p-chlorophenyl)phosphoric acid, LIBF4LiPF6, etc. Formula % Formula % (In each formula, R is an alkyl group, preferably carbon number 2
to 6 alkyl groups).

また、テトラキス−ｐ−クロロフェニルホウ酸カリウム
をイオンキャリアーの導電性を高めるために添加しても
、よい。Further, potassium tetrakis-p-chlorophenylborate may be added to improve the conductivity of the ion carrier.

さらに、上記水素イオンキャリアー膜に必要に応じて配
合される可塑剤としては、高分子膜がポリ塩化ビニルの
場合、塩化ビニル樹脂の可塑剤として用いられている各
徨可塑剤特に、溶出しにくいもの例えばセバシン酸ビス
（２−エチルヘキシル）エステルが挙げられる。担体と
なる高分子はポリ塩化ビニルに限らず、可塑剤を必要と
しないポリエチレン等も使用できるが、ポリ塩化ビニル
は水素イオンキャリアー膜の形成が容易なので好適であ
る・ 水素イオンキャリアー膜１４は、上記担体としての高分
子を溶媒に溶解し、その溶液に上記アミン、電解質塩ま
たは必要により可塑剤を加え、これｔ−酸化還元膜Ｚ３
に塗布乾燥することによって形成できる。Furthermore, when the polymer membrane is made of polyvinyl chloride, the plasticizers that may be added to the hydrogen ion carrier membrane as needed include various free plasticizers that are used as plasticizers for vinyl chloride resins, especially those that are difficult to dissolve. Examples include sebacic acid bis(2-ethylhexyl) ester. The polymer serving as the carrier is not limited to polyvinyl chloride, but polyethylene, etc. that do not require a plasticizer can also be used, but polyvinyl chloride is suitable because it allows easy formation of a hydrogen ion carrier film. The hydrogen ion carrier film 14 is The above polymer as a carrier is dissolved in a solvent, the above amine, electrolyte salt, or a plasticizer is added to the solution, and the t-oxidation-reduction membrane Z3 is
It can be formed by coating and drying.

■０発明の具体的作用 以上述べたこの発明の一センサーを用いて水溶液中の水
素イオン濃度（ｐＨ）を測定するためには、第２図に示
すように、この発明の一センサー１０を飽和カロメル電
極のような基準電極２３とともに、容器２Ｉに収容され
た測定水溶液２２に浸漬する。−センサーＩＯと基準電
糧２３とは、電位差計２４に接続する。水溶液中の水素
イオンは、水素イオンキャリアー膜１４を介して迅速に
酸化還元膜１３に輸送され、酸化還元膜１３は酸化還元
反応を生起し、水素イオン濃度に応じた起電力を発生す
る。この起電力を基準電極２３との差として電位差計２
４で測定する。この発明のめセンサーによる起電力は、
−値と直線関係を満足するので、これによシ測定水溶液
のｐｉｅ知ることができる。■Specific operation of the invention In order to measure the hydrogen ion concentration (pH) in an aqueous solution using the sensor 10 of the invention described above, the sensor 10 of the invention must be saturated as shown in FIG. It is immersed together with a reference electrode 23 such as a calomel electrode in a measurement aqueous solution 22 contained in a container 2I. - the sensor IO and the reference voltage 23 are connected to a potentiometer 24; Hydrogen ions in the aqueous solution are rapidly transported to the redox membrane 13 via the hydrogen ion carrier membrane 14, and the redox membrane 13 causes a redox reaction to generate an electromotive force according to the hydrogen ion concentration. The potentiometer 2 uses this electromotive force as the difference with the reference electrode 23.
Measure at 4. The electromotive force generated by the sensor of this invention is
Since it satisfies a linear relationship with - value, it is possible to know the pie of the measured aqueous solution from this.

以下、この発明の実施４を記載する・ 実施例１ ベーサルプレーングラフティト（ＢＰＧ　）　！　リな
るディスク（直径５関、高さ５　ｙｘ＊　）の表面を鋭
利な刃物で剥離して新しい面ｔ−露出させた。Embodiment 4 of this invention will be described below.Example 1 Basal plane graft (BPG)! The surface of the new disk (diameter 5 mm, height 5 yx*) was peeled off with a sharp knife to expose a new surface.

このディスク基板の外周を熱収縮性チー−プで覆って絶
縁し、チ為−プ内に水銀を入れ、基板とリード線との接
続を計った。これを作用極とし、基準電極として飽和塩
化ナトリウムカロメル電極（ＳＳＣＥ）、対極として白
金網を用い、三極式電解セル内で以下に示す条件で電解
酸化重合をおこなって基板の露出表面に電解酸化重合膜
を被着した。The outer periphery of this disk substrate was covered with a heat-shrinkable chip for insulation, mercury was placed inside the chip, and the connection between the board and the lead wires was established. Using this as a working electrode, a saturated sodium chloride calomel electrode (SSCE) as a reference electrode, and a platinum mesh as a counter electrode, electrolytic oxidative polymerization was performed in a three-electrode electrolytic cell under the conditions shown below to electrolytically oxidize the exposed surface of the substrate. A polymer film was applied.

すなわち、支持電解質として過塩素酸す）　ＩＪウム’
ｉ　０．１モル／リットルの割合で含むアセトニトリル
溶媒に１−アミノピレン（ＡＰ　）ｔ−１θミリモル／
リットルおよびピリジン全１０ミ９ 液とし、作用極の電位を０ボルトから＋１．０ボルト（
対８８ＣＥ）までの間で、５０ミリポルＶ秒の掃引速度
で３回掃引した後、＋１．Ｏポル・ト°（対５ｓｃＥ）
で１０分間定電位電解をおこなっ念。こうしてｌ−アミ
ノピレンの電解酸化重合膜（酸化還元膜）ｔ−基板表面
に被着した。これを充分に水洗し、ｐＨ６．８６のリン
酸緩衝液中に１日間保存して酸化還元膜の酸化還元電位
を安定化させた。これを乾燥後、以下の方法により水素
イオンキャリアー膜を被着した。i.e. perchloric acid as supporting electrolyte)
i 1-aminopyrene (AP) t-1θ mmol/l in acetonitrile solvent at a ratio of 0.1 mol/liter
The potential of the working electrode was changed from 0 volts to +1.0 volts (
+1. O port ° (vs. 5scE)
Perform constant potential electrolysis for 10 minutes. In this way, an electrolytically oxidized polymer film (oxidation-reduction film) of l-aminopyrene was deposited on the surface of the t-substrate. This was thoroughly washed with water and stored in a phosphate buffer solution of pH 6.86 for one day to stabilize the redox potential of the redox membrane. After drying this, a hydrogen ion carrier membrane was applied by the following method.

すなわち、トリーｎ−ドデシルアミン２．５．６ミリグ
ラム、テトラキス−ｐ−クロロフェニルホウ酸カリウム
５、７ミリグラム、セパシン酸ジオクチル７３２ミリグ
ラム、ポリ塩化ビニル（平均重合度１０５０）３６７ミ
リグラムをテトラヒドロ７ラン１０ミリリツトルに溶解
し、この溶液に上記酸化還元膜を被着した基板を浸漬し
、溶媒を除去乾燥して水素イオンキャリアー膜を酸化還
元膜上に被着した。こうしてこの発明の声センサーを作
製した。That is, 2.5.6 milligrams of tri-n-dodecylamine, 5.7 milligrams of potassium tetrakis-p-chlorophenylborate, 732 milligrams of dioctyl sepacate, and 367 milligrams of polyvinyl chloride (average degree of polymerization 1050) were added to 10 milliliters of tetrahydro7ran. The substrate covered with the redox film was immersed in this solution, and the solvent was removed and dried to deposit a hydrogen ion carrier film on the redox film. In this way, the voice sensor of this invention was produced.

実験例１〜６ 実施例１で得たーセンサーを用い、基準電極として８８
ＣＥｔ用いて各電溶液中でのセンサーの平衡電位値と−
との関係を測定した。すなわち、用いた溶液は、牛血（
実験例１）、標準血清（　Ｖ＠ｒｇ＋ａｔｏｌ　Ａ％　
Ｇ＠ｎｅｒａｌ　Ｇｉａｇｏｔｌａｍ　ｄｅｒＷ＠　ｒ
ｎ＊　ｒ　−Ｌａｍｂｓ　ｒ　を社製）（実験例２）、
乳酸リングル液（成分：塩化ナトリウム０．　６チ（ｖ
／ｖ）　。Experimental Examples 1 to 6 Using the sensor obtained in Example 1, 88 cm was used as the reference electrode.
Using CEt, the equilibrium potential value of the sensor in each electrolytic solution and -
We measured the relationship between That is, the solution used was bovine blood (
Experimental Example 1), standard serum (V@rg+atol A%
G@neral Giagotlam derW@r
n* r -Lambs r ) (Experimental Example 2),
Lactate ringle solution (ingredients: sodium chloride 0.6t (v)
/v).

塩化カリウム０．０３％（　ｗ／マ）ｌ乳酸０．３１％
（　ｖ／ｖ　）であり、電解質成分はＮａ　１　３　１
　ｍ９／ｌ　。Potassium chloride 0.03% (w/ma)l Lactic acid 0.31%
(v/v), and the electrolyte component is Na 1 3 1
m9/l.

Ｋ　４　ｕ，　Ｃａ　３　ｍｅ／ｌ　、　ＣＬ　１１０
１９／／　、乳Ｍｌ　根２　８〜／ＩＩ　）　（実験例
３）、０．１Ｍ／ノ生理食塩水にディカリツク液、成分
ニブドウ糖、酢酸カリウム、グルコン酸カルシウム、硫
酸マグネシウム、ＫＨ２ＰＯ４、ｚｎＳＯ４７Ｈ２０、
電解質イオンＫ”（　２　５ｒｎ９）、Ｍｇ”（８．　
５　ｍ９　）、Ｃｍ”（　１　５　０　ｍ？　）、ｓｏ
ニーｃ　１　０μモル））（実験例５）、および人工尿
（　ＵＲ８ｕｒ＠Ｃｈ＠ｍ１ｓｔｒｙ社製Ｕｒｉｎ＠Ｃ
ｏｎｔｒｏｌ−　１　）　（実験例６）である。結果を
それぞれ第３図、（実験例１）第４図（実験例２．５（
一致））、第５図（実験例３．４（一致））に示す＠ 実験例７ 実施例１で作製したーセンサーを用い、リン識緩衝液中
で１１＋Ｈを５．３４から４．６７．７．４６から５．
３４．４．６７から６．２７．６．２７から８．１６．
８．１６から９．１８．９．１８から１０．０２．１０
．０２から１１．０，１２．０から１３．０．１１．０
から１２．０へ変化させたときの応答時間（平衡電位値
に達するまでの時間）を測定した（温度２５Ｃ）。結果
は、第６図中線ａないしｌで示すように、２０秒ないし
２分と著しく速かった。また電極電位も８日間経過後も
変化せず安定であった。K 4 u, Ca 3 me/l, CL 110
19//, Milk Ml Root 28~/II) (Experimental Example 3), 0.1M/N physiological saline, Dicalik's solution, ingredients niglucose, potassium acetate, calcium gluconate, magnesium sulfate, KH2PO4, znSO47H20,
Electrolyte ions K" (2 5rn9), Mg" (8.
5 m9), Cm” (150 m?), so
(experimental example 5), and artificial urine (Urin@C manufactured by UR8ur@Ch@m1stry)
ontrol-1) (Experimental Example 6). The results are shown in Figure 3, (Experiment Example 1) and Figure 4 (Experiment Example 2.5), respectively.
(Concordance)), shown in Figure 5 (Experimental Example 3.4 (Concordance)) @ Experimental Example 7 Using the sensor prepared in Example 1, 11+H was increased from 5.34 to 4.67.7 in a phosphorus buffer. .46 to 5.
34.4.67 to 6.27.6.27 to 8.16.
8.16 to 9.18.9.18 to 10.02.10
．． 02 to 11.0, 12.0 to 13.0.11.0
The response time (time taken to reach the equilibrium potential value) when changing from 12.0 to 12.0 was measured (temperature 25C). The results were extremely fast, ranging from 20 seconds to 2 minutes, as shown by lines a to l in FIG. Further, the electrode potential remained stable without changing even after 8 days.

実験例８ 実施例１で作製したー電極のＩＰＨ当りの起電力変化値
すなわちネルンスト式の直線関係の勾配（ｍＶ／ｐＨ）
を溶液の温度を変えて測定し念。比較のために、ガラス
電極と水素イオン輸送膜を形成しない−センサー（比較
例ｊとにおける勾配の測定もおこなった。結果を表１に
示す。この結果から、この発明の一センサーとガラス電
極との勾配はほぼ同じであり、ガラスｔｔ極で用いられ
ている測定系にこの発明の一センサーを用いることがで
きることがわかった。Experimental Example 8 Change in electromotive force per IPH of the electrode prepared in Example 1, that is, the slope of the Nernst equation linear relationship (mV/pH)
Be sure to measure by changing the temperature of the solution. For comparison, we also measured the slope between a glass electrode and a sensor without a hydrogen ion transport membrane (Comparative Example J). It was found that the slopes of the two electrodes were almost the same, indicating that one sensor of the present invention can be used in the measurement system used in the glass tt electrode.

表　　　１ 実験例９ 実施例１で作製したーセンサーを用い、−６，８６の標
準リン酸緩衝液中で酸素分圧を４７１１）（ｇからｆｉ
３０鵡Ｈｇの範囲で変化させ、平衡電位値に対する酸素
分圧の影響を測定した。測定温度は３７’±Ｏ，ＩＣで
あった。結果を第７図に示す。この結果から、この発明
の一センサーは、酸素の影響を全く受けないことがわか
る。　“実施例２ 酸化還元膜を作成する際、支持電解質として過塩素酸ナ
トリウムの代りにテトラブチルアンモニウムＢＦ４’ｉ
用いた以外は実施例１と同様にして−センサーを作製し
た。Table 1 Experimental Example 9 Using the sensor prepared in Example 1, the oxygen partial pressure was adjusted from 4711) (g to fi
The influence of the oxygen partial pressure on the equilibrium potential value was measured by changing the oxygen pressure within a range of 30 muHg. The measurement temperature was 37'±O, IC. The results are shown in FIG. This result shows that one sensor of the present invention is not affected by oxygen at all. “Example 2 When creating a redox membrane, tetrabutylammonium BF4'i was used instead of sodium perchlorate as a supporting electrolyte.
A sensor was produced in the same manner as in Example 1 except that the following was used.

実験例１０ 実施例２で作製したーセンサーの起電力と−との関係を
測定（３７Ｃ）したところ直線関係を満足した。この直
線の勾配は５８　ｍＶ／ｐＨであった。なお、ｐＨ７，
４のときの起電力値は約４０ｍＶであった０ 実権例３〜４ ベーサルプレーングラフティトの代りに、カーボンファ
イバー（東邦レーヨン社製ＨＴＡ−７Ｗ−１００、非抵
抗的１．５ｘｌＯΩ・α、断面積３、８　Ｘ　ｌ　Ｏ−
’ｃｍ２　）を用イタ以外は実ｍ例１と同様にして−セ
ンサーを作製した（実施例３）。Experimental Example 10 When the relationship between the electromotive force of the sensor produced in Example 2 and - was measured (37C), a linear relationship was satisfied. The slope of this straight line was 58 mV/pH. In addition, pH 7,
4, the electromotive force value was about 40 mV.0 Actual Examples 3-4 Instead of basal plain graftite, carbon fiber (HTA-7W-100 manufactured by Toho Rayon Co., Ltd., non-resistive 1.5xlOΩ・α, disconnected) was used. Area 3,8 X l O-
A sensor was produced in the same manner as in Example 1, except that 1 cm2) was used (Example 3).

・　また、ＢＰＧの径を０．５　ｍｘとしたものを用い
て同様に−センサーを作製した（実施例４）。- In addition, a -sensor was similarly produced using BPG with a diameter of 0.5 mx (Example 4).

実験例１１ 実施例３および４で作製したーセンサーについて、平衡
電位値とめ値との関係を測定したところ、それぞれ直線
関係を満足し、その直線の勾配は、それぞれ６２　ｍＶ
／ｐＨおよび６０　ｍＶ／ｐＨであった。実験例１ない
し６で用いた他の溶液中でも一測定をおこなうことがで
きた。Experimental Example 11 When the relationship between the equilibrium potential value and the reference value was measured for the sensors fabricated in Examples 3 and 4, each satisfied a linear relationship, and the slope of each straight line was 62 mV.
/pH and 60 mV/pH. One measurement was also possible in the other solutions used in Experimental Examples 1 to 6.

実施例５ １−アミノピレンの代りに、ｌ−アミノアントラセンを
用いた以外は実施例１と同様にして一センサーを作製し
た。Example 5 A sensor was produced in the same manner as in Example 1 except that 1-aminoanthracene was used instead of 1-aminopyrene.

実験例１２ 実施例５で作製したーセンサーの平衡電位値と−との関
係を測定し九ところ直線関係を満足した。この直線の勾
配はｐＨ５，１５ないし８．２０の範囲において５６　
ｍＶ／ｐＨであり念。Experimental Example 12 The relationship between the equilibrium potential value of the -sensor prepared in Example 5 and - was measured, and a linear relationship was satisfied in nine cases. The slope of this straight line is 56 in the pH range of 5.15 to 8.20.
Please note that it is mV/pH.

実施例６〜７ 水素イオン輸送膜の被着に際し、トリｎ−ドデシルアミ
ンの代りにトリオクチルアミン（実施例６〕またはトリ
デシルアミン（実施例７）を用いた以外は、実施例１と
同様にして−セン−サーを作製し′た。Examples 6-7 Same as Example 1 except that trioctylamine (Example 6) or tridecylamine (Example 7) was used instead of tri-n-dodecylamine when depositing the hydrogen ion transport membrane. A sensor was fabricated using this method.

実験例１３ 実施例６および７で作製したーセンサーの平衡電位値と
−（値との関係を測定し友ところ直線関係を満足した。Experimental Example 13 The relationship between the equilibrium potential values of the -sensors prepared in Examples 6 and 7 and the -(values) was measured, and a linear relationship was satisfied.

直線の勾配は共に５６　ｍＶ／１侶であった。なお、測
定溶液としてリン酸緩衝液の代りに人工尿を用いた場合
も同様に直線関係を満足し念。The slopes of both lines were 56 mV/1. Note that the same linear relationship is satisfied when artificial urine is used instead of phosphate buffer as the measurement solution.

実施例８〜１１ 基板としてＢＰＧＯ代シに、白金（実施例８）、パラジ
ウム（実施例９）、酸化インジウム（実施例１０）、銀
（実施例１１）を用い、電解酸化重合を表２に示す条件
でおこなりた以外は実施例１と同様にして−センサーを
作製した・１１ｊｌ験例１４ 実施例８〜１１で作製したーセンサーの平衡電位値と一
値との関係を測定（２５Ｃ）Ｌ、たとこるそれぞれ直線
関係を満足した。直線の勾配その他の結果を表３に示す
。Examples 8 to 11 Platinum (Example 8), palladium (Example 9), indium oxide (Example 10), and silver (Example 11) were used as substrates for BPGO, and electrolytic oxidation polymerization was performed as shown in Table 2. EXPERIMENTAL EXAMPLE 14 Measurement of the relationship between the equilibrium potential value and the single value of the sensors produced in Examples 8 to 11 (25C) L , each satisfied the linear relationship. Table 3 shows the slope of the straight line and other results.

表　　　３ 実施例１２ 電解醇化重合に際し、電解液としてｐ−フェノキシアニ
リ７１０　ｍＭ含む０．５　Ｍ濃度の硫酸ナトリウムま
念は硫酸を用いた以外は実施例１と同様にして−センサ
ーを作製した。Table 3 Example 12 A sensor was produced in the same manner as in Example 1, except that sulfuric acid was used as the electrolytic solution, including 710 mM of p-phenoxyaniline and 0.5 M sodium sulfate as the electrolytic solution.

実験例１５ 実施例１２で作製したーセンサーの平衡電位値と一値と
の関係を測定したところ直線関係を満足し、その直線の
勾配は５４　ｍＶ／ｐＨであった曇なお、ｐＨ６，８６
のときの平衡電位値は約６２　ｍＶであシ・応答速度は
約１分であった。Experimental Example 15 When the relationship between the equilibrium potential value and one value of the sensor produced in Example 12 was measured, a linear relationship was satisfied, and the slope of the straight line was 54 mV/pH.
The equilibrium potential value at this time was approximately 62 mV, and the response speed was approximately 1 minute.

実施例１３〜３２ 表４に示す条件でＡＰの電解重合をおこなった以外は、
実施例１と同様に一電＠ｌを作製した。Examples 13 to 32 Except that the electrolytic polymerization of AP was performed under the conditions shown in Table 4,
Ippen@l was produced in the same manner as in Example 1.

表　　　４ 実験例１６〜３５ 実施例１３〜３２で作製したーセンサーを用い、酸素分
圧（ＰＯ□）、標準血清（Ｖｅｒｓａｔｏｌ）の平衡電
位値への影響を検討した。またー＝７．０付近における
応答速度も測定した。結果を表５に示す。この結果を基
に作成した、ＡＰの電解酸化重合におけるピリジン添加
量とΔＥ（飽和酸素分圧下のＥ値マイナス大気下での溶
存酸素分圧下のＥ値）との関係を第８図および第９図に
示す。第８図中白丸印は実験例１６〜２０に相当し、黒
丸印は実験例２１〜２５に相当する。Table 4 Experimental Examples 16 to 35 Using the sensors prepared in Examples 13 to 32, the influence of oxygen partial pressure (PO□) and standard serum (Versatol) on the equilibrium potential value was investigated. The response speed near -=7.0 was also measured. The results are shown in Table 5. Based on this result, the relationship between the amount of pyridine added and ΔE (E value under saturated oxygen partial pressure minus E value under dissolved oxygen partial pressure in the atmosphere) in the electrolytic oxidative polymerization of AP is shown in Figures 8 and 9. As shown in the figure. The white circles in FIG. 8 correspond to Experimental Examples 16 to 20, and the black circles correspond to Experimental Examples 21 to 25.

第９図中線ａは実験例２６〜３０に相当し、線すは実験
例３１〜３５に相当する。この結果、ＴＢＡＢＦ４−Ｔ
ＨＦ系）　ＴＢＡＢＦ４−ＣＨ３ＣＮ系）　ＮｍＣ１−
０４−ＴＨＦ系）　ＮａＣ２Ｏ４−ＣＨ５Ｃ縣の順にΔ
Ｅが小さく酸素分圧に対してこの順に安定であることが
、わかった。Line a in FIG. 9 corresponds to Experimental Examples 26 to 30, and line a corresponds to Experimental Examples 31 to 35. As a result, TBABF4-T
HF type) TBABF4-CH3CN type) NmC1-
04-THF system) Δ in the order of NaC2O4-CH5C
It was found that E is small and stable in this order with respect to oxygen partial pressure.

また、標準血清中でのＥ値と標準液（リン酸緩衝液）中
でのＥ値との差とピリジン添加量との関係を第１０図お
よび第１１図に示す。第１０図中、線ａは実験例１６〜
２０に相当し、線すは実験例２１〜２５に相当する。第
１１図中ＭＡ息は実験例２６〜３Ｇに相当し、線すは実
験例３１〜３５に相当する。この結果から、上記差は、
ＴＢＡＢＦ４−ＣＨ，ＣＮ系）　ＴＢＡＢＦ４−ＴＨＦ
系）Ｎａ　ＣｌＯ４”ＴＨＦ系）　ＮａＣ１Ｏ４−ＣＨ
，ＣＮ系の順に小さく平衡電位が安定であることがわか
る。なお、応答速度は、ＮＡＣｌｏ　４−ＴＨＦ系）　
ＮａＣ２Ｏ４−ＣＨ３ＣＮ系〉ＴＢＡＢＦ４−ＣＨ３Ｃ
Ｎ系）　ＴＢＡＢＦ４−ＴＨＦ系の拳である。Furthermore, the relationship between the difference between the E value in the standard serum and the E value in the standard solution (phosphate buffer) and the amount of pyridine added is shown in FIGS. 10 and 11. In FIG. 10, line a is from Experimental Example 16 to
20, and the lines correspond to Experimental Examples 21 to 25. In FIG. 11, MA breath corresponds to Experimental Examples 26 to 3G, and lines correspond to Experimental Examples 31 to 35. From this result, the above difference is
TBABF4-CH, CN series) TBABF4-THF
system) Na ClO4”THF system) NaC1O4-CH
It can be seen that the equilibrium potential is smaller and more stable in the order of , CN system. Note that the response speed is based on NAClo 4-THF system)
NaC2O4-CH3CN system〉TBABF4-CH3C
N series) TBABF4-THF series fist.

表　　　５ １０発明の具体的効果 以上述べたように、この発明の一センサーは固体型￥１
１極であるので微小化が容易であり、応答速度が速く、
ｆス成分特に酸素ガスの影響を受けず、生体成分例えば
血清、全血、尿等の試料の種類によりて平衡電位値が変
化を受けないため精度がよい。Table 5: 10 Specific Effects of the Invention As stated above, one sensor of the present invention is a solid-state type sensor of ¥1
Since it has one pole, it is easy to miniaturize, and the response speed is fast.
The accuracy is high because the equilibrium potential value is not affected by f gas components, especially oxygen gas, and the equilibrium potential value is not affected by the type of sample such as biological components such as serum, whole blood, and urine.

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

第１図はこの発明の一センサーの断面図、第２図はこの
発明の一センサーの作用を説明するための図、第３図な
いし第１°１図はこの発明の一センサーの特性を示すグ
ラフ図。 ＩＺ・・・導電性基板、Ｚ２・・・酸化還元膜、１３・
・・水素イオンキャリアー膜。 出願人代理人　　弁理士　鈴　江　武　彦第１図 第２図Fig. 1 is a sectional view of one sensor of the present invention, Fig. 2 is a diagram for explaining the action of one sensor of the invention, and Figs. 3 to 1°1 show the characteristics of one sensor of the invention. Graph diagram. IZ...conductive substrate, Z2...oxidation-reduction film, 13.
...Hydrogen ion carrier membrane. Applicant's representative Patent attorney Takehiko Suzue Figure 1 Figure 2

Claims (1)

【特許請求の範囲】[Claims] （１）水溶液中の水素イオン濃度を電位応答で測定する
ためのｐＨセンサーであって、 （ａ）導電性基体と、 （ｂ）該導電性基体の表面に形成された可逆的酸化還元
機能を有する膜であってその酸化還元反応が水素イオン
の付加・離脱を伴なう第１の膜と、 （ｃ）該第１の膜の表面に形成された高分子膜であって
該水溶液中の水素イオンを該第１の膜へ輸送するための
水素イオンキャリアーを含有する第２の膜とを具備する
ことを特徴とするｐＨセンサー。(1) A pH sensor for measuring the hydrogen ion concentration in an aqueous solution by potential response, comprising (a) a conductive substrate, and (b) a reversible redox function formed on the surface of the conductive substrate. (c) a polymer film formed on the surface of the first film in which the redox reaction involves the addition and desorption of hydrogen ions; and a second membrane containing a hydrogen ion carrier for transporting hydrogen ions to the first membrane.
JP59281076A 1984-12-28 1984-12-28 Ph sensor Granted JPS61155949A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP59281076A JPS61155949A (en) 1984-12-28 1984-12-28 Ph sensor
EP85116605A EP0186210B1 (en) 1984-12-28 1985-12-27 Ion sensor
DE8585116605T DE3585915T2 (en) 1984-12-28 1985-12-27 ION SENSOR.
US07/577,050 US5133856A (en) 1984-12-28 1990-09-04 Ion sensor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP59281076A JPS61155949A (en) 1984-12-28 1984-12-28 Ph sensor

Publications (2)

Publication Number Publication Date
JPS61155949A true JPS61155949A (en) 1986-07-15
JPH042902B2 JPH042902B2 (en) 1992-01-21

Family

ID=17633985

Family Applications (1)

Application Number Title Priority Date Filing Date
JP59281076A Granted JPS61155949A (en) 1984-12-28 1984-12-28 Ph sensor

Country Status (1)

Country Link
JP (1) JPS61155949A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61194343A (en) * 1985-02-25 1986-08-28 Terumo Corp Ph sensor
JPS61213662A (en) * 1985-03-19 1986-09-22 Terumo Corp Ph sensor
JPS61213660A (en) * 1985-03-19 1986-09-22 Terumo Corp Ph sensor
JPS61251764A (en) * 1985-04-30 1986-11-08 Terumo Corp Ph sensor
JPS62169043A (en) * 1986-01-21 1987-07-25 Terumo Corp Ph sensor
JPS63131056A (en) * 1986-11-20 1988-06-03 Terumo Corp Fet electrode
WO1988004425A1 (en) * 1986-12-10 1988-06-16 Terumo Kabushiki Kaisha Ion carrier membrane and ion sensor provided with same
WO1988004424A1 (en) * 1986-12-08 1988-06-16 Terumo Kabushiki Kaisha Ion-selective fet sensor
JPS63265153A (en) * 1986-12-10 1988-11-01 Terumo Corp Ion carrier film and ion sensor provided with said ion carrier film
WO1989010554A1 (en) * 1988-04-25 1989-11-02 Terumo Kabushiki Kaisha Ion-sensitive film, a process for producing the same, and ion sensor
GB2501769A (en) * 2012-05-04 2013-11-06 Schlumberger Holdings Electrochemical sensor for pH measurement
US9244034B2 (en) 2010-11-04 2016-01-26 Schlumberger Technology Corporation Electrochemical pH measurement

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59142451A (en) * 1983-02-03 1984-08-15 Terumo Corp Ion sensor

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59142451A (en) * 1983-02-03 1984-08-15 Terumo Corp Ion sensor

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61194343A (en) * 1985-02-25 1986-08-28 Terumo Corp Ph sensor
JPH049471B2 (en) * 1985-03-19 1992-02-20
JPS61213662A (en) * 1985-03-19 1986-09-22 Terumo Corp Ph sensor
JPS61213660A (en) * 1985-03-19 1986-09-22 Terumo Corp Ph sensor
JPH0410985B2 (en) * 1985-03-19 1992-02-27
JPS61251764A (en) * 1985-04-30 1986-11-08 Terumo Corp Ph sensor
JPH0414746B2 (en) * 1986-01-21 1992-03-13 Terumo Corp
JPS62169043A (en) * 1986-01-21 1987-07-25 Terumo Corp Ph sensor
JPS63131056A (en) * 1986-11-20 1988-06-03 Terumo Corp Fet electrode
WO1988004424A1 (en) * 1986-12-08 1988-06-16 Terumo Kabushiki Kaisha Ion-selective fet sensor
JPS63265153A (en) * 1986-12-10 1988-11-01 Terumo Corp Ion carrier film and ion sensor provided with said ion carrier film
WO1988004425A1 (en) * 1986-12-10 1988-06-16 Terumo Kabushiki Kaisha Ion carrier membrane and ion sensor provided with same
WO1989010554A1 (en) * 1988-04-25 1989-11-02 Terumo Kabushiki Kaisha Ion-sensitive film, a process for producing the same, and ion sensor
US5190636A (en) * 1988-04-25 1993-03-02 Terumo Kabushiki Kaisha Ion-sensitive film, method of producing the same and ion sensor
US9244034B2 (en) 2010-11-04 2016-01-26 Schlumberger Technology Corporation Electrochemical pH measurement
GB2501769A (en) * 2012-05-04 2013-11-06 Schlumberger Holdings Electrochemical sensor for pH measurement

Also Published As

Publication number Publication date
JPH042902B2 (en) 1992-01-21

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