JPS6329216B2 - - Google Patents

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Publication number
JPS6329216B2
JPS6329216B2 JP56039349A JP3934981A JPS6329216B2 JP S6329216 B2 JPS6329216 B2 JP S6329216B2 JP 56039349 A JP56039349 A JP 56039349A JP 3934981 A JP3934981 A JP 3934981A JP S6329216 B2 JPS6329216 B2 JP S6329216B2
Authority
JP
Japan
Prior art keywords
electrode
carbon dioxide
membrane
sensitive
buffer solution
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
JP56039349A
Other languages
Japanese (ja)
Other versions
JPS57154048A (en
Inventor
Hiroyuki Myagi
Yasuhisa Shibata
Yoshitada Takada
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.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
Agency of Industrial Science and Technology
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 Agency of Industrial Science and Technology filed Critical Agency of Industrial Science and Technology
Priority to JP56039349A priority Critical patent/JPS57154048A/en
Publication of JPS57154048A publication Critical patent/JPS57154048A/en
Publication of JPS6329216B2 publication Critical patent/JPS6329216B2/ja
Granted legal-status Critical Current

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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
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333Ion-selective electrodes or membranes

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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 Analysing Biological Materials (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)

Description

【発明の詳細な説明】 本発明は液体中の二酸化炭素ガスを測定するに
好適な二酸化炭素測定電極に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carbon dioxide measuring electrode suitable for measuring carbon dioxide gas in a liquid.

近年、血液中のPHや酸素分圧(Po2)と共に二
酸化炭素分圧(Pco2)を測定することが、病態
の診断上から必要性が高まつてきている。しかも
血液の分析では試料量を極力微量にしなければな
らないという制限から、測定用電極を小形化する
ことが望まれている。
In recent years, it has become increasingly necessary to measure blood pH and oxygen partial pressure (Po 2 ) as well as carbon dioxide partial pressure (Pco 2 ) from the standpoint of diagnosing pathological conditions. Moreover, in blood analysis, there is a restriction that the amount of sample must be as small as possible, so it is desired that the measuring electrode be made smaller.

溶液中の二酸化炭素分圧を測定する電極として
は、内部指示電極としてPH測定用ガラス電極を用
いるものが知られている。この種の電極ではガラ
ス電極の感応部の外側に二酸化炭素ガス透過性膜
を覆せ、ガス透過膜と感応部の間に二酸化炭素分
圧に応答してPHが変化する電解液が保持されてい
る。電解液としては塩化ナトリウムと重炭酸ナト
リウムの溶液が用いられている。
As an electrode for measuring the partial pressure of carbon dioxide in a solution, one using a glass electrode for PH measurement as an internal indicator electrode is known. In this type of electrode, a carbon dioxide gas permeable membrane is placed on the outside of the sensitive part of the glass electrode, and an electrolytic solution whose pH changes in response to the partial pressure of carbon dioxide is held between the gas permeable membrane and the sensitive part. . A solution of sodium chloride and sodium bicarbonate is used as the electrolyte.

この種の電極では、内部電解液にナトリウムイ
オンが含まれる結果、長時間使用した際に内部指
示電極であるガラス電極の安定性が問題となる。
また、ガラス電極の加工上の制限から、微小な二
酸化炭素電極を構成することが困難である。
In this type of electrode, as a result of the internal electrolyte containing sodium ions, the stability of the glass electrode, which is the internal indicator electrode, becomes a problem when used for a long time.
Furthermore, it is difficult to construct a minute carbon dioxide electrode due to limitations in the processing of glass electrodes.

本発明はこのような点に鑑みてなされたもので
あり、その目的は、長時間使用しても測定結果の
信頼性が高く、小形化も容易な二酸化炭素測定電
極を提供することにある。
The present invention has been made in view of these points, and its purpose is to provide a carbon dioxide measuring electrode that provides highly reliable measurement results even when used for a long period of time, and that can be easily miniaturized.

本発明は内部指示電極として重炭酸イオン
(HCO- 3)電極を用い、ガス透過膜と内部指示電
極との間に保持された内部緩衝溶液の重炭酸イオ
ン濃度の変化を直接測定可能にする。さらに詳細
には、参照溶液が収容された筒体の端部に、感応
物質として第4級アンモニウム塩が分散された高
分子膜で形成した重炭酸イオン感応膜を設け、こ
の感応膜を二酸化炭素ガス透過性膜で被い、感応
膜とガス透過性膜の間に弱アルカリ性の内部緩衝
溶液を保持せしめ、参照溶液と内部緩衝溶液とに
それぞれ電極線を接触させたことを特徴とする。
The present invention uses a bicarbonate ion (HCO - 3 ) electrode as the internal indicator electrode, making it possible to directly measure changes in the bicarbonate ion concentration of the internal buffer solution held between the gas permeable membrane and the internal indicator electrode. More specifically, a bicarbonate ion sensitive membrane formed of a polymer membrane in which quaternary ammonium salt is dispersed as a sensitive substance is provided at the end of the cylinder housing the reference solution, and this sensitive membrane is connected to carbon dioxide. It is characterized in that it is covered with a gas-permeable membrane, a weakly alkaline internal buffer solution is held between the sensitive membrane and the gas-permeable membrane, and electrode wires are brought into contact with the reference solution and the internal buffer solution, respectively.

第1図は本発明に基づく一実施例を説明するた
めの図である。
FIG. 1 is a diagram for explaining an embodiment based on the present invention.

重炭酸イオンに応答する感応膜4が電極筒1の
下部に接着されており、電極筒1の内にはイオン
電極内部参照溶液3が注入されている。このイオ
ン電極内部参照溶液3に接触するように内部参照
電極線2が挿入されている。筒体、感応膜、参照
溶液を有する重炭酸イオン電極の先端には、二酸
化炭素ガス透過性膜5がO−リング7によつて固
定され、感応膜4とガス透過性膜5の間には内部
緩衝溶液6が満たされている。また、参照電極線
8が内部緩衝溶液6の中に挿入されている。筒体
1の上部はキヤツプ9で被われる。
A sensitive membrane 4 responsive to bicarbonate ions is adhered to the lower part of the electrode tube 1, and an ion electrode internal reference solution 3 is injected into the electrode tube 1. An internal reference electrode wire 2 is inserted so as to be in contact with this ion electrode internal reference solution 3. A carbon dioxide gas permeable membrane 5 is fixed by an O-ring 7 to the tip of the bicarbonate ion electrode having a cylindrical body, a sensitive membrane, and a reference solution. It is filled with an internal buffer solution 6. Also, a reference electrode wire 8 is inserted into the internal buffer solution 6. The upper part of the cylindrical body 1 is covered with a cap 9.

参照電極線2および8は図示しない信号処理系
に接続されており、被検液体中の二酸化炭素濃度
に対応する数値が表示部に表示される。
The reference electrode lines 2 and 8 are connected to a signal processing system (not shown), and a numerical value corresponding to the carbon dioxide concentration in the test liquid is displayed on the display section.

上記した構造の二酸化炭素測定電極の測定原理
は次の通りである。この電極が試料中に挿入され
ると、試料中の二酸化炭素はガス透過膜5を透過
して、内部緩衝溶液6中に拡散する。この内部緩
衝溶液6は重炭酸イオンの生成に適するPH範囲
(7.5〜9.0)になるように調製されているので、
拡散した二酸化炭素は緩衝溶液に溶解し、解離し
て重炭酸イオンを生成する。
The measurement principle of the carbon dioxide measuring electrode having the above structure is as follows. When this electrode is inserted into a sample, carbon dioxide in the sample passes through the gas permeable membrane 5 and diffuses into the internal buffer solution 6. This internal buffer solution 6 is prepared to have a pH range (7.5 to 9.0) suitable for the production of bicarbonate ions, so
The diffused carbon dioxide dissolves in the buffer solution and dissociates to produce bicarbonate ions.

重炭酸イオン電極の出力電位Eは次に示すニコ
ルスキイ(Nicolsky)の式で表わされる。
The output potential E of the bicarbonate ion electrode is expressed by the Nicolsky equation shown below.

E=Eo−2.303RT/ZiFlog{aHCO - 3+〓kHCO - 3,jaj} ……(1) ここで、用いた記号は電気化学に関する教科書
に記載されているものと同じ意味である。第1図
の二酸化炭素測定電極の内部緩衝溶液6内に重炭
酸イオン以外には妨害となるイオンが存在しない
とすれば、(1)式は次のように簡略化される。
E=Eo−2.303RT/ZiFlog {a HCO - 3 +〓k HCO - 3 , ja j } ...(1) Here, the symbols used have the same meaning as those described in textbooks on electrochemistry. . Assuming that there are no interfering ions other than bicarbonate ions in the internal buffer solution 6 of the carbon dioxide measurement electrode shown in FIG. 1, equation (1) can be simplified as follows.

E=Eo−SlogaHcp - 3 ……(2) ただし、Sは濃度を10倍変化させた際の電極出
力である。
E=Eo−Sloga Hcp - 3 ...(2) However, S is the electrode output when the concentration is changed by 10 times.

ところで、重炭酸イオン濃度は二酸化炭素分圧
Pco2、と解離定数Kを用いて次のように表され
る。
By the way, the bicarbonate ion concentration is determined by the carbon dioxide partial pressure.
It is expressed as follows using Pco 2 and dissociation constant K.

〔HCO- 3〕=K/〔H+〕・αPco2 ……(3) (2)、(3)式より、電極出力は E=Eo−S{PH+logK+logα・Pco2} ……(4) と表わされるので、緩衝溶液を用いてPHを一定と
すれば、 E=Eo′−SlogPco2 ……(5) と示され、イオン電極の出力は二酸化炭素分圧と
直接関係することとなる。
[HCO - 3 ]=K/[H + ]・αPco 2 ……(3) From equations (2) and (3), the electrode output is E=Eo−S{PH+logK+logα・Pco 2 } ……(4) Therefore, if the pH is kept constant using a buffer solution, E=Eo′−SlogPco 2 (5), and the output of the ion electrode is directly related to the partial pressure of carbon dioxide.

第1図の実施例では、内部支持電極である重炭
酸イオン電極が、ポリ塩化ビニル(以下PVCと
略す)を母材とした高分子感応膜を用いている。
第4級アンモニウム塩である塩化メチルトリオク
チルアンモニウムからなる感応物質と、フエニー
ルペンタノールあるいはニトロフエニールオクチ
ルエーテルなどからなる可塑剤とをPVC母材中
に分散させた感応膜をPVC製の電極筒体の先端
に接着して用いた。内部参照溶液3としては0.1
モル重炭酸ナトリウム水溶液を用いた。
In the embodiment shown in FIG. 1, the bicarbonate ion electrode serving as the internally supported electrode uses a polymer sensitive membrane made of polyvinyl chloride (hereinafter abbreviated as PVC) as a base material.
A PVC electrode is made of a sensitive film in which a sensitive substance made of methyltrioctylammonium chloride, which is a quaternary ammonium salt, and a plasticizer made of phenyl pentanol or nitrophenyl octyl ether are dispersed in a PVC base material. It was used by gluing it to the tip of the cylinder. 0.1 as internal reference solution 3
A molar aqueous sodium bicarbonate solution was used.

重炭酸イオン電極をガス透過膜5および緩衝溶
液6を備えずに単独で用いた場合の重炭酸イオン
濃度と電極出力の関係を第2図に示す。重炭酸イ
オンが10-4モル以上の濃度であるときに良好な直
線性が得られた。この種の電極はガス透過膜を有
しない場合硝酸イオン及び塩素イオンの妨害が大
きいが、二酸化炭素電極の内部指示電極として用
いる場合には、これらのイオンがガス透過膜を透
過しないので測定の妨害とはならない。
FIG. 2 shows the relationship between the bicarbonate ion concentration and the electrode output when the bicarbonate ion electrode is used alone without the gas permeable membrane 5 and the buffer solution 6. Good linearity was obtained when the concentration of bicarbonate ion was 10 -4 molar or higher. If this type of electrode does not have a gas-permeable membrane, nitrate and chloride ions will interfere with the measurement, but when used as an internal indicator electrode for a carbon dioxide electrode, these ions will not pass through the gas-permeable membrane and will interfere with measurement. It is not.

上記した内部指示電極の先端に二酸化炭素ガス
透過性のポリプロピレン薄膜(厚さ25μm)を装
着し、内部緩衝溶液としてトリスヒドロキシメチ
ルアミノメタン−ホウ酸緩衝溶液(PH8.0)を用
いて二酸化炭素電極とした。また、参照電極線8
は銀/塩化銀線を重炭酸イオン電極の外側に巻き
つけた。第1図の実施例の電極の出力Eと二酸化
炭素分圧Pco2の間には第3図に示す直線関係が
得られた。この電極の応答速度は温度及びガス透
過膜の厚さ並びに内部緩衝溶液の液膜厚さに依存
する。この電極はPVC製電極筒体を外径3mmと
しても十分に実用的に動作し、極めて小形の二酸
化炭素電極を構成することができた。
A polypropylene thin film (thickness 25 μm) permeable to carbon dioxide gas was attached to the tip of the internal indicator electrode described above, and a trishydroxymethylaminomethane-borate buffer solution (PH8.0) was used as the internal buffer solution to connect the carbon dioxide electrode. And so. In addition, the reference electrode wire 8
wrapped a silver/silver chloride wire around the outside of a bicarbonate ion electrode. A linear relationship as shown in FIG. 3 was obtained between the output E of the electrode of the embodiment shown in FIG. 1 and the carbon dioxide partial pressure Pco 2 . The response speed of this electrode depends on the temperature and the thickness of the gas permeable membrane and the liquid membrane thickness of the internal buffer solution. This electrode operated satisfactorily practically even with a PVC electrode cylinder having an outer diameter of 3 mm, making it possible to construct an extremely small carbon dioxide electrode.

二酸化炭素測定電極の内部指示電極の感応膜と
してはPVC支持感応膜のほか、シリコンゴムな
どの高分子膜母材に感応物質を分散させたものも
用いることができる。また、感応物質である第4
級アンモニウム塩としては塩化メチルトリデシル
アンモニウムあるいは塩化メチルトリドデシルア
ンモニウムを用いることができる。さらに第4級
アンモニウム塩以外の感応物質を用いることもで
きる。
As the sensitive membrane of the internal indicator electrode of the carbon dioxide measurement electrode, in addition to a PVC-supported sensitive membrane, a polymeric membrane base material such as silicone rubber in which a sensitive substance is dispersed can also be used. In addition, the fourth is a sensitive substance.
As the class ammonium salt, methyltridecylammonium chloride or methyltridecylammonium chloride can be used. Furthermore, sensitive substances other than quaternary ammonium salts can also be used.

内部緩衝溶液はPH7.5〜9.0の弱アルカリ性で重
炭酸イオンを生成するが、PHが8.5以上では二酸
化炭素の高分圧側から低分圧側へ切替えた際の応
答が遅くなる傾向がある。最も好ましく用いられ
るPHは8.0付近である。
The internal buffer solution is weakly alkaline with a pH of 7.5 to 9.0 and generates bicarbonate ions, but at a pH of 8.5 or higher, the response tends to be slow when switching from the high partial pressure side to the low partial pressure side of carbon dioxide. The most preferably used pH is around 8.0.

第4図は本発明の他の実施例の説明図である。
この例では、二酸化炭素測定電極が血液試料が流
通されるフローセルの流路に面して装着されてい
る。フローセルブロツク12には試料入口18か
ら試料出口19へ連通された流路20が形成され
ており、この流路20に面して二酸化炭素ガス透
過膜16が露出されている。ブロツク12の孔2
1には筒体11が挿入されており、筒体11の先
端の凹部とガス透過膜16の間の間隙には内部緩
衝溶液17が充填されている。筒体11の先端付
近には高分子母材からなる重炭酸イオン感応膜1
5が取り付けられている。筒体11の上部には金
属製リングからなる電極コネクタ13がキヤツプ
23に取付けられ、このコネクタ13に内部緩衝
溶液と接触している参照電極線14が接続され
る。使用時にはコネクタ13が信号処理系に通ず
る導体に挿し込まれ、また参照電極線22も信号
処理系に接続される。流路20の径は0.8mmであ
り、筒体11の外径は3mmである。
FIG. 4 is an explanatory diagram of another embodiment of the present invention.
In this example, the carbon dioxide measuring electrode is mounted facing the flow channel of the flow cell through which the blood sample flows. A flow path 20 communicating from the sample inlet 18 to the sample outlet 19 is formed in the flow cell block 12, and the carbon dioxide gas permeable membrane 16 is exposed facing the flow path 20. Hole 2 of block 12
A cylinder 11 is inserted into the cylinder 1 , and an internal buffer solution 17 is filled in the gap between the recess at the tip of the cylinder 11 and the gas permeable membrane 16 . Near the tip of the cylindrical body 11 is a bicarbonate ion sensitive membrane 1 made of a polymer base material.
5 is attached. An electrode connector 13 made of a metal ring is attached to a cap 23 at the top of the cylinder 11, and a reference electrode wire 14 in contact with the internal buffer solution is connected to this connector 13. In use, the connector 13 is inserted into a conductor leading to a signal processing system, and the reference electrode wire 22 is also connected to the signal processing system. The diameter of the flow path 20 is 0.8 mm, and the outer diameter of the cylinder 11 is 3 mm.

以上説明したように本発明によれば、ガラス電
極を用いずに済むので長時間使用しても測定結果
の信頼性が高く、また感応部に高分子膜を用いる
など加工性もよくなるので小形化も容易となるか
ら、実用上の効果は大きい。
As explained above, according to the present invention, there is no need to use glass electrodes, so the reliability of the measurement results is high even when used for a long time, and the processability is improved by using a polymer membrane for the sensitive part, so the size can be reduced. The practical effect is great because it also makes it easier.

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

第1図は本発明の一実施例を説明するための
図、第2図は第1図の実施例の内の内部指示電極
における応答特性を示す図、第3図は第1図の実
施例の二酸化炭素に対応する応答特性を示す図、
第4図は本発明の他の実施例を説明するための図
である。 1,11……筒体、4,15……感応膜、5,
16……ガス透過膜、6,17……内部緩衝溶
液、20……流路。
FIG. 1 is a diagram for explaining one embodiment of the present invention, FIG. 2 is a diagram showing the response characteristics of the internal indicator electrode in the embodiment of FIG. 1, and FIG. 3 is an example of the embodiment of FIG. 1. A diagram showing the response characteristics corresponding to carbon dioxide,
FIG. 4 is a diagram for explaining another embodiment of the present invention. 1, 11... Cylindrical body, 4, 15... Sensitive membrane, 5,
16... Gas permeable membrane, 6, 17... Internal buffer solution, 20... Channel.

Claims (1)

【特許請求の範囲】[Claims] 1 参照溶液が収容された筒体の端部に、感応物
質として第4級アンモニウム塩が分散された高分
子膜で形成した重炭酸イオン感応膜を設け、この
重炭酸イオン感応膜を二酸化炭素ガス透過性膜で
被い、上記重炭酸イオン感応膜と上記二酸化炭素
ガス透過性膜の間に弱アルカリ性の内部緩衝溶液
を保持せしめ、上記参照溶液と上記内部緩衝溶液
とにそれぞれ電極線を接触させてなる二酸化炭素
測定電極。
1 A bicarbonate ion-sensitive membrane made of a polymer membrane in which quaternary ammonium salt is dispersed as a sensitive substance is provided at the end of the cylinder housing the reference solution, and this bicarbonate ion-sensitive membrane is exposed to carbon dioxide gas. covered with a permeable membrane, a weakly alkaline internal buffer solution is held between the bicarbonate ion sensitive membrane and the carbon dioxide gas permeable membrane, and electrode wires are brought into contact with the reference solution and the internal buffer solution, respectively. Carbon dioxide measuring electrode.
JP56039349A 1981-03-20 1981-03-20 Electrode for measuring carbon dioxide Granted JPS57154048A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP56039349A JPS57154048A (en) 1981-03-20 1981-03-20 Electrode for measuring carbon dioxide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP56039349A JPS57154048A (en) 1981-03-20 1981-03-20 Electrode for measuring carbon dioxide

Publications (2)

Publication Number Publication Date
JPS57154048A JPS57154048A (en) 1982-09-22
JPS6329216B2 true JPS6329216B2 (en) 1988-06-13

Family

ID=12550597

Family Applications (1)

Application Number Title Priority Date Filing Date
JP56039349A Granted JPS57154048A (en) 1981-03-20 1981-03-20 Electrode for measuring carbon dioxide

Country Status (1)

Country Link
JP (1) JPS57154048A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100454012C (en) * 2006-08-21 2009-01-21 浙江大学 Pressure adaptive dissolving carbon dioxide exploring electrode and preparation method

Also Published As

Publication number Publication date
JPS57154048A (en) 1982-09-22

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