JPS6069545A - Electrode device for measuring ion concentration - Google Patents
Electrode device for measuring ion concentrationInfo
- Publication number
- JPS6069545A JPS6069545A JP58176458A JP17645883A JPS6069545A JP S6069545 A JPS6069545 A JP S6069545A JP 58176458 A JP58176458 A JP 58176458A JP 17645883 A JP17645883 A JP 17645883A JP S6069545 A JPS6069545 A JP S6069545A
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- Prior art keywords
- electrode
- ion
- chamber
- sensitive
- sample chamber
- Prior art date
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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
- G01N27/38—Cleaning of electrodes
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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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は工業用水や化学反応の過程におけるいろいろな
溶液、特に、臨床応用での血液中のイオン濃度を再現性
よく測定するだめのイオン濃度測定電極装置に関する。Detailed Description of the Invention (Field of Industrial Application) The present invention is useful for measuring ion concentrations in industrial water and various solutions used in chemical reaction processes, especially in blood in clinical applications with good reproducibility. This invention relates to a measurement electrode device.
（従来例の構成とその問題点）
溶液中のイオン濃度の測定はいろいろな工業用水の濃度
調整や化学反応槽において行なわれる。(Structure of conventional example and its problems) Measurement of ion concentration in a solution is performed in various industrial water concentration adjustment or chemical reaction tanks.
捷だ、近年臨床医学の分野においては血中イオン濃度の
測定が病態の診断にしばしば利用されている。電極法に
よるイオン濃度の測定はイオン選択註電極と参照電極を
被検液に接触させて、それらの間に発生する起電力の大
きさでその濃度を測定する。このようなイオン選択性電
極は内液式のものが普通に用いられている。これは第１
図に示すように、イオン濃度の変化に感応するガラス感
応膜ｌを管体２の先端を封するように融着し、上記感応
膜１の内部に起電力が取シ出せるように塩酸あるいはシ
ん酸水溶液等の電解液３にリード４付き甘木電極５を浸
漬したものであり、電解液３のもれを防ぐために蓋６を
被せたものである。このような内液式のイオン選択性電
極は電解液が封入されているために、ガラス感応膜を下
に向けて電解液とガラス感応膜がたえず接触している状
態で使用し左ければならず、倒立して使用するときには
やや不便である。In recent years, in the field of clinical medicine, measurement of blood ion concentrations has often been used to diagnose pathological conditions. Measuring ion concentration using the electrode method involves bringing an ion-selective electrode and a reference electrode into contact with the test liquid, and measuring the concentration based on the magnitude of the electromotive force generated between them. As such ion-selective electrodes, internal liquid type electrodes are commonly used. This is the first
As shown in the figure, a glass sensitive membrane 1 that is sensitive to changes in ion concentration is fused to seal the tip of the tube body 2, and hydrochloric acid or hydrochloric acid is added so that an electromotive force can be extracted inside the sensitive membrane 1. Amagi electrodes 5 with leads 4 are immersed in an electrolytic solution 3 such as an aqueous phosphoric acid solution, and a lid 6 is placed over the electrolytic solution 3 to prevent the electrolytic solution 3 from leaking. Since such an internal solution type ion-selective electrode has an electrolyte sealed in it, it must be used with the glass sensitive membrane facing down so that the electrolyte and the glass sensitive membrane are in constant contact. However, it is somewhat inconvenient when used upside down.
参照電極は、銀−塩化銀電極と呼ばれるものが用いられ
る。これは第２図に示すように先端にピンホール７を設
けたガラスシリンダ８に起電力を取シだすために、塩化
カリウム等の水溶液からなる電解液９およびリード線１
０を接続した銀−塩化銀電極１１をそれぞれ入れて蓋１
２で封じたものである。なお、ピンホール７を設ける代
りに、ガラスの磨り合せを用いたスリーブ型やファイ／
（−を用いたファイバー型も同様に使用できる。また、
ガラスシリンダーの代りにフッ素樹脂のような樹脂製の
容器を用いて液絡には多孔質の樹脂やセラミック等を用
いることもできる。The reference electrode used is what is called a silver-silver chloride electrode. As shown in Fig. 2, in order to extract electromotive force from a glass cylinder 8 with a pinhole 7 at its tip, an electrolytic solution 9 made of an aqueous solution such as potassium chloride and a lead wire 1 are used.
Insert the silver-silver chloride electrodes 11 connected to each other and close the lid 1.
It is sealed in 2. In addition, instead of providing the pinhole 7, a sleeve type or fi/
(A fiber type using - can be used as well. Also,
Instead of the glass cylinder, a container made of resin such as fluororesin may be used, and porous resin, ceramic, or the like may be used for the liquid junction.
以上説明したイオン選択性電極と参照電極を試料液に挿
入して血中イオンを測定するような場合、血液は非常に
凝固しやすいために、これらの電極の感応膜面にしだい
に血中成分が沈着し、応答速度を遅くしたり、再現性を
わるくしたシする不都合が生じていた。また、懸濁粒子
を含む被検液の場合においても微粒子の電極面への付着
が生じ電極を被検液からしばしば取り出して洗浄したり
、交換したりしなければならず、このような保守点検の
労力が不可欠であった。When measuring blood ions by inserting the ion-selective electrode and reference electrode described above into a sample solution, blood components gradually form on the sensitive membrane surface of these electrodes, as blood is very prone to coagulation. This causes problems such as slow response speed and poor reproducibility. In addition, even in the case of test liquids containing suspended particles, particles may adhere to the electrode surface, requiring the electrodes to be frequently removed from the test liquid and cleaned or replaced. effort was essential.
（発明の目的）
本発明の目的は上記の従来の欠点をなくするもので、電
極の感応部に凝血防止機能を゛具備せしめることにより
、保守点検なしに、常時、再現よく溶液中のイオン濃度
を測定することのできるイオン濃度測定電極装置を提供
するものである。(Objective of the Invention) The object of the present invention is to eliminate the above-mentioned conventional drawbacks, and by equipping the sensitive part of the electrode with an anti-coagulant function, the ion concentration in the solution can be constantly and reproducibly controlled without maintenance and inspection. An object of the present invention is to provide an ion concentration measuring electrode device that can measure ion concentration.
（発明の構成）
本発明のイオン濃度測定電極装置は、イオン選択性電極
および参照電極のうちいずれかひとつの電極の感応部が
試料室の底部、もうひとつの電極の感応部が上記試料室
の側壁をそれぞれ構成する上記試料室に磁性回転子を挿
入［７、上記磁性回転子の底面と側面で上記電極の２つ
の感応部をそれぞれ擦るように構成したことを特徴とし
、電極表面とこれに接触しながら回転する磁性回転子の
作用によ）、電極の感応部への微粒子や血液の沈着を防
止して、電極を常に清浄な状態に維持することを可能に
したもので、これにより、上記目的は達成される。(Structure of the Invention) In the ion concentration measuring electrode device of the present invention, the sensitive part of one of the ion-selective electrode and the reference electrode is located at the bottom of the sample chamber, and the sensitive part of the other electrode is located at the bottom of the sample chamber. A magnetic rotor is inserted into the sample chamber constituting each side wall. By the action of a magnetic rotor that rotates while making contact with the electrode, it is possible to prevent fine particles and blood from depositing on the sensitive part of the electrode, and to keep the electrode clean at all times. The above objectives are achieved.
（実施例の説明）
以下、第３図、第４図にもとすいて本発明の一実施例を
詳細に説明する。(Description of Embodiment) Hereinafter, an embodiment of the present invention will be described in detail with reference to FIGS. 3 and 4.
第３図は本発明によるイオン濃度測定電極装置の縦断面
図金星す。同図において２１は固体式イオン選択性電極
、２２はそのリード線、２３は参照電極、２４はそのリ
ード線である。２５はグラスチック製の測定セルで、試
料室２６はセル２５の中央部に位置し試料室２６の底部
が上記イオン選択性電極２１の感応膜（感応部） ２１
．１ 、側壁の一部が参照電極２３の感応部２３１で構
成されている。被検液は入口２７から導入され、試料室
２６に至シ濃度が測定され、出口２８から流出される。FIG. 3 is a longitudinal sectional view of the ion concentration measuring electrode device according to the present invention. In the figure, 21 is a solid-state ion-selective electrode, 22 is its lead wire, 23 is a reference electrode, and 24 is its lead wire. 25 is a measurement cell made of glass, a sample chamber 26 is located in the center of the cell 25, and the bottom of the sample chamber 26 is a sensitive membrane (sensing part) of the ion-selective electrode 21.
．． 1. A part of the side wall is constituted by the sensitive part 231 of the reference electrode 23. The test liquid is introduced from the inlet 27, its concentration is measured into the sample chamber 26, and then flows out from the outlet 28.
なお入口２７と出口２８は、被検液の貫流と試料室２６
内での被検液の置換が容易に行なわれるよう配慮して第
３図の如く設けるのが望せしい。２９は上記セル２５の
試料室２６内に封入された磁性回転子で、その表面を樹
脂、あるいはＳｉＣやＡｚ２ｏ３などの研摩剤や研摩布
で被覆したものが用いられる。こうすることにより、回
転子２９の防錆にも役立ち、研摩効果もすぐれたものと
なる。３０は試料室２６の外部に配設された回転磁界発
生用の磁性体で、モータ３１によって回転させて、試料
室２６内の磁性回転子２９を水平方向に回転させる。３
２はモータ３１を収納するだめの容器である。磁性回転
子２９は電極２１の感応膜２１１に接触すると同時に、
試料室２６の側壁に位置する参照電極２３の感応部２３
１にも接触しながら回転する。その結果、電極表面への
血液の沈着が防止され、長期間にわたって使用しても電
極は清浄な状態に維持できる。Note that the inlet 27 and the outlet 28 are connected to the throughflow of the test liquid and the sample chamber 26.
It is desirable to provide the test liquid as shown in FIG. 3, so that the test liquid can be easily replaced within the chamber. A magnetic rotor 29 is enclosed in the sample chamber 26 of the cell 25, and its surface is coated with resin, an abrasive such as SiC or Az2O3, or an abrasive cloth. By doing so, it is useful to prevent rust of the rotor 29, and the polishing effect is also excellent. Reference numeral 30 denotes a magnetic body for generating a rotating magnetic field, which is disposed outside the sample chamber 26, and is rotated by a motor 31 to horizontally rotate the magnetic rotor 29 within the sample chamber 26. 3
2 is a container for storing the motor 31. At the same time as the magnetic rotor 29 contacts the sensitive film 211 of the electrode 21,
Sensing part 23 of the reference electrode 23 located on the side wall of the sample chamber 26
It rotates while also touching 1. As a result, deposition of blood on the electrode surface is prevented, and the electrode can be maintained in a clean state even after long-term use.
本発明の電極装置に適するイオン選択性電極は内液式の
ものよりも固体式のものである。この固体式の電極２１
は第４図に示すように、直径３〜３０ｍｍ、厚さ５０〜
５００ミクロンの薄い円板状に切りだしたガラス感応膜
２１１０片面に１０％フッ化銀水溶液を塗布して約４０
℃で乾燥させる。Ion-selective electrodes suitable for the electrode device of the present invention are solid-state rather than liquid-based. This solid-state electrode 21
As shown in Figure 4, the diameter is 3 to 30 mm and the thickness is 50 to 30 mm.
A 10% silver fluoride aqueous solution was applied to one side of the glass sensitive membrane 2110, which was cut into a 500-micron thin disk shape, and was heated for about 40 minutes.
Dry at °C.
このような処理を赦シ１Ｇ・′ｃ７ｊツたって実施して
、上記ガラス感応膜２１１にフッ化銀層を生成させて一
昼夜放置後１．５係塩化リチウム溶液に浸漬して約２０
時間放置して、フッ化銀層を塩化銀層にかえて、よシ安
定に起電力を取り出せるようにする。This treatment was carried out for 1 G·'c7j to form a silver fluoride layer on the glass sensitive film 211, and after leaving it for a day and night, it was immersed in a 1.5 lithium chloride solution for about 20 min.
After leaving it for some time, the silver fluoride layer is replaced with a silver chloride layer, allowing more stable electromotive force to be extracted.
これを水洗してから：ｉ ｔｌ Ｑ Ｃで２時間にわた
ってアルゴン又は窒素中で熱処理して、上記ガラス感応
膜２１１と塩化銀層２１２との密着性をよくする。その
後、塩化銀層２１２に銀ペイントのような導電性樹脂２
１３を用いてリード線２１４を接続し、その上から樹脂
２１５を流して硬化させて棒状電極とする。このような
固体式電極は内液式の電極と異なり、内部に電解液を含
まないため使用に際しての方向性に制限がない。いろい
ろなイオン選択性電極に使用するガラス組成について（
り、これまでに多くの研究がなされているが、その代表
的なものはＨ＋イオン感応膜としては５３５ｉ０２・２
８ Ｌｉ２Ｏ・２ Ｃｓ０ ・５ Ｂａ０ ・２ Ｌａ
２Ｏ５の如きリチウム系ガラスが用いられ、Ｎａ”ｔオ
ン用としては７１５ｉ０２ ・１８ ＡＡ２０３ ・１
１ Ｎａ２Ｏ、Ｋ＋イオン用としては７０ ＳｉＯ２・
３ ＡＡ２０３ ・２７ Ｎａ２Ｏがよく用いら）′し
る。捷た、ｃｔ−イオン用としては、Ａｇ（８０ｗｔ係
）−Ａｇｓ （２０ｗｔ係）からなる焼結体膜が適当で
ｔｒ’）る。After washing it with water, it is heat-treated in argon or nitrogen for 2 hours at ITlQC to improve the adhesion between the glass sensitive film 211 and the silver chloride layer 212. After that, a conductive resin 2 such as silver paint is applied to the silver chloride layer 212.
13 to connect a lead wire 214, and resin 215 is poured over the lead wire 215 and hardened to form a rod-shaped electrode. Unlike internal liquid type electrodes, such solid-state electrodes do not contain an electrolyte inside, so there are no restrictions on the direction in which they can be used. Regarding glass compositions used in various ion-selective electrodes (
A lot of research has been done so far, but the representative one is 535i02.2 as an H+ ion sensitive membrane.
8 Li2O・2 Cs0 ・5 Ba0 ・2 La
Lithium-based glass such as 2O5 is used, and for Na"t on, 715i02 ・18 AA203 ・1
1 For Na2O and K+ ions, 70 SiO2.
3 AA203 ・27 Na2O is often used)'. A sintered body film made of Ag (80wt)-Ags (20wt) is suitable for the shredded ct-ions.
（発明の効果）
以上説明したように本発明のイオン濃度測定電極装置は
、イオン選択性電極、および参照ｆ！：’、 ４ｒ：’
Ｆ！、のうちいずれかひとつの電極の感応部が試料室の
底部、もうひとつの電極の感応部が上記試料室の側壁を
それぞれ構成する上記試料室に磁性回転子を挿入し、上
記磁性回転子の底面と側面で上記電極の２つの感応部を
それぞれ擦るよう構成したものであり、磁性回転子の回
転によってイオン選択性電極の感応膜および参照電極の
感応部への血液の沈着を防止でき、絶えずこれらの電極
を清浄な状態に維持できるグこめ、測定値の再現性がよ
く、また従来から臨床医学の分野で望捷れていた血中イ
オン濃度の連続測定を容易に実現できるものである。捷
だ、本発明の電極装置は、測定の際に試料室に空気等の
気体が流入しても、試料室の底部と側壁にイオン選択性
電極あるいは参照電極の感応部が位置しているためそれ
ぞれの感応部で、ガスが伺着した１寸滞留することはま
ったくなく測定値の再現性は極めてよい。(Effects of the Invention) As explained above, the ion concentration measuring electrode device of the present invention includes an ion selective electrode and a reference f! :', 4r:'
F! , the magnetic rotor is inserted into the sample chamber in which the sensitive part of one of the electrodes constitutes the bottom of the sample chamber, and the sensitive part of the other electrode constitutes the side wall of the sample chamber, and the magnetic rotor is inserted into the sample chamber. The bottom and side surfaces are configured to rub the two sensitive parts of the electrode, and the rotation of the magnetic rotor prevents blood from depositing on the sensitive membrane of the ion-selective electrode and the sensitive part of the reference electrode. Since these electrodes can be maintained in a clean state, the reproducibility of measured values is good, and continuous measurement of blood ion concentration, which has been desired in the field of clinical medicine, can be easily realized. Unfortunately, with the electrode device of the present invention, even if gas such as air flows into the sample chamber during measurement, the sensitive part of the ion-selective electrode or reference electrode is located at the bottom and side wall of the sample chamber. The reproducibility of the measured values is extremely good, with no gas remaining in each sensitive part for even one inch.
第１図は従来のイオン選択性電極の断面図、第２図は参
照電極の断面図、第３図は本発明の一実施例におけるイ
オン濃度測定電極装置の縦断面図、第４図は本発明に適
したイオン選択性電極の一例を示す断面図である。
２１・・・固体式イオン選択性電極、２１１ ・感応膜
（感応部）、２３・・・参照電極、２３１・感応部、２
５・・・セル、２６・・・試料室、２９ 磁性回転子、
３０・・・磁性体、３１・・・モータ。
特許出願人 松下電器産業株式会社
代 理 人 星 野 恒 司FIG. 1 is a sectional view of a conventional ion-selective electrode, FIG. 2 is a sectional view of a reference electrode, FIG. 3 is a longitudinal sectional view of an ion concentration measuring electrode device according to an embodiment of the present invention, and FIG. FIG. 2 is a cross-sectional view showing an example of an ion-selective electrode suitable for the invention. 21... Solid ion selective electrode, 211 - Sensitive membrane (sensing part), 23... Reference electrode, 231 - Sensing part, 2
5... Cell, 26... Sample chamber, 29 Magnetic rotor,
30...Magnetic material, 31...Motor. Patent applicant: Matsushita Electric Industrial Co., Ltd. Representative: Hisashi Hoshino
Claims (6)
かひとつの電極の感応部が試料室の底部、もうひとつの
電極の感応部が上記試料室の側壁をそれぞれ構成する上
記試料室に磁性回転子を挿入し、上記磁性回転子の底面
と側面で上記電極の２つの感応部をそれぞれ擦るよう構
成したイオン濃度測定電極装置。(1) A magnetic rotor is placed in the sample chamber, where the sensitive part of one of the ion-selective electrodes and the reference electrode constitutes the bottom of the sample chamber, and the sensitive part of the other electrode constitutes the side wall of the sample chamber. An ion concentration measuring electrode device configured to insert a magnetic rotor into the magnetic rotor and rub two sensitive parts of the electrode with the bottom and side surfaces of the magnetic rotor.
照電極の感応部が上記試料室の側壁をそれぞれ構成する
特許請求の範囲第（１）項記載のイオン濃度測定電極装
置。(2) The ion concentration measuring electrode device according to claim (1), wherein the sensitive part of the ion-selective electrode constitutes the bottom of the sample chamber, and the sensitive part of the reference electrode constitutes the side wall of the sample chamber.
・セラミック電極である特許請求の範囲第（１）項記載
のイオン濃度測定電極装置。(3) The ion concentration measuring electrode device according to claim (1), wherein the ion selective electrode is a solid glass electrode or a ceramic electrode.
で被覆されている特許請求の範囲第（１）項記載のイオ
ン濃度測定電極装置。(4) The ion concentration measuring electrode device according to claim (1), wherein the surface of the magnetic rotor is coated with a resin, an abrasive, or an abrasive cloth.
井にそれぞれ設けてなる特許請求の範囲第（１）項記載
のイオン濃度測定電極装置。(5) The ion concentration measuring electrode device according to claim (1), wherein the inlet and outlet of the test liquid are provided on the side wall and ceiling of the sample chamber, respectively.
極がＡｇＣ１およびＡｇＳからなる組成物である特許請
求の範囲第（１）項記載のイオン濃度測定電極装置。(6) The ion concentration measuring electrode device according to claim (1), wherein among the ion-selective electrodes, the chloride ion-selective electrode is a composition consisting of AgCl and AgS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58176458A JPS6069545A (en) | 1983-09-26 | 1983-09-26 | Electrode device for measuring ion concentration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58176458A JPS6069545A (en) | 1983-09-26 | 1983-09-26 | Electrode device for measuring ion concentration |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6069545A true JPS6069545A (en) | 1985-04-20 |
Family
ID=16014046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58176458A Pending JPS6069545A (en) | 1983-09-26 | 1983-09-26 | Electrode device for measuring ion concentration |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6069545A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100778237B1 (en) | 2006-06-26 | 2007-11-22 | 한국바이오시스템(주) | Heavy Metal Online Analysis System |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5129191A (en) * | 1974-09-04 | 1976-03-12 | Matsushita Electric Industrial Co Ltd | Ionkenshutsusochi |
-
1983
- 1983-09-26 JP JP58176458A patent/JPS6069545A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5129191A (en) * | 1974-09-04 | 1976-03-12 | Matsushita Electric Industrial Co Ltd | Ionkenshutsusochi |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100778237B1 (en) | 2006-06-26 | 2007-11-22 | 한국바이오시스템(주) | Heavy Metal Online Analysis System |
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