JPH0469335B2 - - Google Patents
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- Publication number
- JPH0469335B2 JPH0469335B2 JP58107867A JP10786783A JPH0469335B2 JP H0469335 B2 JPH0469335 B2 JP H0469335B2 JP 58107867 A JP58107867 A JP 58107867A JP 10786783 A JP10786783 A JP 10786783A JP H0469335 B2 JPH0469335 B2 JP H0469335B2
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- JP
- Japan
- Prior art keywords
- selective
- electrode
- anion
- ion
- substance
- 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.)
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- 150000001450 anions Chemical class 0.000 claims description 54
- 239000000126 substance Substances 0.000 claims description 47
- 150000002500 ions Chemical class 0.000 claims description 39
- 239000012528 membrane Substances 0.000 claims description 35
- 150000001768 cations Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 9
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 19
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 10
- 229920000915 polyvinyl chloride Polymers 0.000 description 10
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 229940037179 potassium ion Drugs 0.000 description 10
- 229910001414 potassium ion Inorganic materials 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 108010067973 Valinomycin Proteins 0.000 description 9
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 description 9
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 description 7
- -1 K + and C - Chemical class 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- CTZNINKRTKCWGU-UHFFFAOYSA-N Dinactin Natural products CC1C(=O)OC(C)CC(O2)CCC2C(C)C(=O)OC(CC)CC(O2)CCC2C(C)C(=O)OC(CC)CC(O2)CCC2C(C)C(=O)OC(C)CC2CCC1O2 CTZNINKRTKCWGU-UHFFFAOYSA-N 0.000 description 1
- 108010026389 Gramicidin Proteins 0.000 description 1
- 229930191564 Monensin Natural products 0.000 description 1
- GAOZTHIDHYLHMS-UHFFFAOYSA-N Monensin A Natural products O1C(CC)(C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CCC1C(O1)(C)CCC21CC(O)C(C)C(C(C)C(OC)C(C)C(O)=O)O2 GAOZTHIDHYLHMS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NKNPHSJWQZXWIX-DCVDGXQQSA-N Tetranactin Chemical compound C[C@H]([C@H]1CC[C@H](O1)C[C@@H](OC(=O)[C@@H](C)[C@@H]1CC[C@@H](O1)C[C@@H](CC)OC(=O)[C@H](C)[C@H]1CC[C@H](O1)C[C@H](CC)OC(=O)[C@H]1C)CC)C(=O)O[C@H](CC)C[C@H]2CC[C@@H]1O2 NKNPHSJWQZXWIX-DCVDGXQQSA-N 0.000 description 1
- NKNPHSJWQZXWIX-UHFFFAOYSA-N Tetranactin Natural products CC1C(=O)OC(CC)CC(O2)CCC2C(C)C(=O)OC(CC)CC(O2)CCC2C(C)C(=O)OC(CC)CC(O2)CCC2C(C)C(=O)OC(CC)CC2CCC1O2 NKNPHSJWQZXWIX-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBDGIMZKOJALMU-MVWQHRGOSA-N dinactin Chemical compound C[C@@H]([C@@H]1CC[C@@H](O1)C[C@@H](OC(=O)[C@@H](C)[C@H]1CC[C@H](O1)C[C@@H](C)OC(=O)[C@@H](C)[C@@H]1CC[C@@H](O1)C[C@H](CC)OC(=O)[C@H]1C)CC)C(=O)O[C@H](C)C[C@@H]2CC[C@H]1O2 ZBDGIMZKOJALMU-MVWQHRGOSA-N 0.000 description 1
- DANUORFCFTYTSZ-UHFFFAOYSA-N epinigericin Natural products O1C2(C(CC(C)(O2)C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)C)C(C)C(OC)CC1CC1CCC(C)C(C(C)C(O)=O)O1 DANUORFCFTYTSZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004905 gramicidin Drugs 0.000 description 1
- ZWCXYZRRTRDGQE-SORVKSEFSA-N gramicidina Chemical compound C1=CC=C2C(C[C@H](NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CC=3C4=CC=CC=C4NC=3)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CC=3C4=CC=CC=C4NC=3)NC(=O)[C@@H](CC(C)C)NC(=O)[C@H](CC=3C4=CC=CC=C4NC=3)NC(=O)[C@H](C(C)C)NC(=O)[C@H](C(C)C)NC(=O)[C@@H](C(C)C)NC(=O)[C@H](C)NC(=O)[C@H](NC(=O)[C@H](C)NC(=O)CNC(=O)[C@@H](NC=O)C(C)C)CC(C)C)C(=O)NCCO)=CNC2=C1 ZWCXYZRRTRDGQE-SORVKSEFSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- RYVLCGMJGXFCNZ-UHFFFAOYSA-M methyl-tri(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(CCCCCCCCCCCCCC)CCCCCCCCCCCCCC RYVLCGMJGXFCNZ-UHFFFAOYSA-M 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 229960005358 monensin Drugs 0.000 description 1
- GAOZTHIDHYLHMS-KEOBGNEYSA-N monensin A Chemical compound C([C@@](O1)(C)[C@H]2CC[C@@](O2)(CC)[C@H]2[C@H](C[C@@H](O2)[C@@H]2[C@H](C[C@@H](C)[C@](O)(CO)O2)C)C)C[C@@]21C[C@H](O)[C@@H](C)[C@@H]([C@@H](C)[C@@H](OC)[C@H](C)C(O)=O)O2 GAOZTHIDHYLHMS-KEOBGNEYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- DANUORFCFTYTSZ-BIBFWWMMSA-N nigericin Chemical compound C([C@@H]1C[C@H]([C@H]([C@]2([C@@H](C[C@](C)(O2)C2O[C@@](C)(CC2)C2[C@H](CC(O2)[C@@H]2[C@H](C[C@@H](C)[C@](O)(CO)O2)C)C)C)O1)C)OC)[C@H]1CC[C@H](C)C([C@@H](C)C(O)=O)O1 DANUORFCFTYTSZ-BIBFWWMMSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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
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)
- Inert Electrodes (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Description
【発明の詳細な説明】
〔発明の技術分野〕
本発明は陰イオン選択性電極に関し、更に詳し
くは、多項目型イオン選択性電極において使用さ
れる陰イオン選択性電極に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to anion-selective electrodes, and more particularly to anion-selective electrodes used in multi-item ion-selective electrodes.
イオン選択性電極は従来より液中の特定のイオ
ンの濃度を選択的に定量できるという特色があ
り、これまでも、特定イオンの濃度のモニタ、水
質分析など広い分野において使われてきた。
Ion-selective electrodes have traditionally had the feature of being able to selectively quantify the concentration of specific ions in a liquid, and have been used in a wide range of fields such as monitoring the concentration of specific ions and analyzing water quality.
これは、たとえば陽イオン選択性物質の場合に
は対象とする陽イオンの活量a+と陽イオン選択
性電極が示す電位Ｅとの間には
Ｅ＝E0＋2.303（RT／ZF）log a+ ……(1)
のようなまた、陰イオン選択性電極の場合には対
象とする陰イオンの活量a-と陰イオン選択性電
極が示す電位Ｅとの間には
Ｅ＝E0＋2.303（RT／ZF）log a- ……(2)
のような活量の対数と電位とが比例する関係が成
立し、電位の測定値から目的とするイオンの活量
が簡単に計算できるからである。 For example, in the case of a cation-selective substance, the difference between the activity a + of the target cation and the potential E shown by the cation-selective electrode is E=E 0 +2.303 (RT/ZF) In addition, in the case of an anion -selective electrode, the relationship between the activity a - of the anion of interest and the potential E exhibited by the anion-selective electrode is E=E, such as log a + ...(1) 0 +2.303(RT/ZF)log a - ...(2) A relationship is established in which the logarithm of the activity is proportional to the potential, and the activity of the target ion can be easily determined from the measured value of the potential. This is because it can be calculated.
なお前記(1)式及び(2)式において、Ｒは気体定
数、Ｔは絶対温度、Ｚはイオン価、Ｆはフアラデ
ー定数、E0は系の標準電極電位である。 In the above equations (1) and (2), R is a gas constant, T is an absolute temperature, Z is an ionic valence, F is a Faraday constant, and E 0 is a standard electrode potential of the system.
このようにイオン選択性電極を用いれば、電位
を測定するだけで広い濃度範囲でのイオンの定量
が可能となる。また、イオン選択性電極を用い、
電極部を小型にすることにより、少量のサンプル
での測定が可能となる。このようなイオン選択性
電極の便利さのため、最近ではこれを医療用、と
くに血液中にとけているイオンたとえばNa+、
K+、Ｃ-などのイオンの定量に用いようとする
試みがさかんになり、Na+、K+、Ｃ-のイオン
選択性電極をフローセルに配列して組込んだ形式
の生化学自動分析装置が実用化されるまでになつ
た。 By using an ion-selective electrode in this way, it becomes possible to quantify ions in a wide concentration range simply by measuring the potential. In addition, using an ion-selective electrode,
By making the electrode part smaller, it becomes possible to measure a small amount of sample. Due to the convenience of such ion-selective electrodes, they have recently been used for medical purposes, especially for ions dissolved in blood, such as Na + ,
Many attempts have been made to quantify ions such as K + and C - , and automatic biochemical analyzers have been developed that incorporate ion-selective electrodes for Na + , K + and C - arranged in a flow cell. has reached the point where it has been put into practical use.
しかしながら、イオン選択性電極を長時間使用
すると、該電極の先端に設けられたイオン選択膜
が劣化して、該電極の機能が損われてしまう場合
があつた。特に、イオン選択物質をポリ塩化ビニ
ル等の有機高分子材料及び可塑剤で結着してなる
イオン選択膜が装着されたイオン選択性電極にお
いて、この電極を他のイオン選択性電極と共に一
つのフローセル内に配列して多項目分析を行つた
場合、各イオン選択膜中の可塑剤及びイオン選択
物質がフローセル内の被検液中に溶出して他の電
極の機能に影響を及ぼし、その結果、各電極の寿
命が短縮化されるという問題があつた。この問題
は、塩素イオン選択性電極を陽イオン（Na+、
K+等）選択性電極と共にフローセル内に配列し
た場合に顕著であり、これは塩素イオン選択物質
が陽イオン選択物質に与える影響が大であつたた
めである。 However, when an ion-selective electrode is used for a long time, the ion-selective membrane provided at the tip of the electrode deteriorates, and the function of the electrode is sometimes impaired. In particular, in an ion-selective electrode equipped with an ion-selective membrane formed by binding an ion-selective substance with an organic polymer material such as polyvinyl chloride and a plasticizer, this electrode is combined with other ion-selective electrodes in one flow cell. When performing multi-item analysis by arranging electrodes within the membrane, the plasticizer and ion-selective substance in each ion-selective membrane elutes into the sample liquid in the flow cell and affects the functions of other electrodes. There was a problem that the life of each electrode was shortened. This problem is solved by using a chloride-selective electrode for cations (Na + ,
This was noticeable when the chloride ion selective substance was arranged in a flow cell together with a selective electrode (K +, etc.), and this was because the chloride ion selective substance had a large influence on the cation selective substance.
そこで、従来は、可塑剤及びイオン選択物質の
溶出を抑制するために、イオン選択膜中に三次元
構造を有する網目状の高分子物質を含有させてお
く方法、又はイオン選択物質の保持材として他の
有機高分子物質を配合する等の方法が検討されて
きた。しかしながら、前者の方法では著しい抑制
効果が得られず、また、後者の方法にあつては、
血液等の生化学試料用の支持材はポリ塩化ビニル
が最適であつて、現在のところ他に優れた材料が
見当らないことから、いずれの方法によつても電
極の長寿命化を図ることができなかつた。 Therefore, conventionally, in order to suppress the elution of plasticizers and ion-selective substances, methods have been proposed in which a network-like polymeric substance having a three-dimensional structure is contained in the ion-selective membrane, or as a retaining material for the ion-selective substance. Methods such as blending other organic polymer substances have been investigated. However, the former method does not have a significant suppressive effect, and the latter method
Since polyvinyl chloride is the optimal support material for biochemical samples such as blood, and no other superior material has been found at present, it is not possible to extend the life of the electrode using either method. I couldn't do it.
本発明は、フローセル内に多項目のイオン選択
性電極を配列してイオン濃度測定を行つた場合
に、他の陽イオン選択性電極に対して悪影響を与
えることがなく、長寿命化することが可能な陰イ
オン選択性電極を提供することを目的とする。
According to the present invention, when ion concentration measurement is performed by arranging multiple ion-selective electrodes in a flow cell, there is no adverse effect on other cation-selective electrodes, and the lifespan can be extended. The aim is to provide a possible anion selective electrode.
本発明者らは、上記目的を達成すべく、鋭意研
究を重ねた結果、陰イオン選択膜中に、該陰イオ
ン選択膜を機能させる陰イオン選択物質ととも
に、陽イオン選択物質を分散してなる陰イオン選
択性電極は、長期間に亘つて安定した出力感度を
示し、かつ他の陽イオン選択性電極に悪影響を及
ぼさないことを見出し、本発明を完成するに至つ
た。
In order to achieve the above object, the present inventors have conducted intensive research and found that a cation-selective substance is dispersed in an anion-selective membrane along with an anion-selective substance that makes the anion-selective membrane function. The present invention was completed based on the discovery that the anion-selective electrode exhibits stable output sensitivity over a long period of time and does not adversely affect other cation-selective electrodes.
すなわち、本発明は、陰イオン選択物質として
四級アンモニウム塩と、その支持材とを含む陰イ
オン選択膜を有する陰イオン選択性電極におい
て、該陰イオン選択膜中に、該陰イオン選択物質
に対して５倍モル以下の陽イオン選択物質が分散
されていることを特徴とする。 That is, the present invention provides an anion-selective electrode having an anion-selective membrane containing a quaternary ammonium salt as an anion-selective substance and a supporting material for the anion-selective substance. It is characterized in that the cation selective substance is dispersed in an amount of 5 times the mole or less.
以下、本発明の陰イオン選択性電極を第１図に
示した一電極例に基づき説明する。図示した電極
は、電極筒体１の端部に陰イオン選択膜２を取着
し、内部電解液３が満たされた該電極筒体１内に
内部基準電極４を設けてなるものである。 Hereinafter, the anion selective electrode of the present invention will be explained based on an example of the electrode shown in FIG. The illustrated electrode has an anion selective membrane 2 attached to the end of an electrode cylinder 1, and an internal reference electrode 4 provided inside the electrode cylinder 1 filled with an internal electrolyte 3.
該電極において、陰イオン選択膜の組成以外の
構成は従来と同一であり、例えば、電極筒体の材
質としてはポリ塩化ビニル等、内部電解液として
は塩化カリウム水溶液等、内部基準電極としては
Ag／AgC等が使用される。 In this electrode, the configuration other than the composition of the anion selective membrane is the same as the conventional one, for example, the material of the electrode cylinder is polyvinyl chloride, the internal electrolyte is a potassium chloride aqueous solution, etc., and the internal reference electrode is made of polyvinyl chloride, etc.
Ag/AgC etc. are used.
陰イオン選択膜は、陽イオン選択物質を含有し
ていること以外は、従来のものと同様の構成を有
する。通常、本発明の選択膜は、陰イオン（Ｃ
−）選択物質である四級アンモニウム塩、陽イオ
ン選択物質及びこれらの物質の支持材である有機
高分子物質とからなるが、この他にも可塑剤等の
添加剤を含有していてもよい。ここで、本発明に
おいて使用される四級アンモニウム塩としては、
陰イオン選択物質として知られている全ての化合
物が使用可能であるが、メチルトリオクチルアン
モニウムクロリド、メチルトリテトラデシルアン
モニウムクロリド、メチルトリドデシルアンモニ
ウムクロリド等が好ましい。また、本発明におい
て、陰イオン選択物質の溶出を防止するために陰
イオン選択膜に配合される陽イオン選択物質とし
ては、陽イオン選択性電極において選択物質とし
て用いられるものと同じ範囲から選ばれ、例えば
Na+、K+又はCa2+等の陽イオン選択物質である
モネンシン、ノナクシン、ジナクチン、テトラナ
クチン、グラミシジン、ニゲリシン、バリノマイ
シン等が挙げられる。イオン選択膜の支持材であ
る有機高分子物質としては、例えばポリウレタ
ン、シリコーンゴム、ポリスチレン、ポリメチル
メタクリレート等が挙げられる。更に可塑剤とし
ては、例えばアジピン酸ジオクチル、フタル酸ジ
オクチル、オルトニトロフエニルオクチルエーテ
ル等を用いることが好ましい。以上の陰イオン選
択膜において、陽イオン選択物質は、陰イオン選
択物質に対して、５倍モル以下、好ましくは同モ
ル量以上２倍モル以下の範囲で添加される。な
お、陰イオン選択物質としては四級アンモニウム
塩が、該膜中に、通常0.2〜70重量％、好ましく
は５〜25重量％の範囲で添加される。 The anion selective membrane has the same configuration as a conventional membrane except that it contains a cation selective substance. Typically, the selective membrane of the present invention contains anions (C
- ) Consists of a quaternary ammonium salt as a selective substance, a cation selective substance, and an organic polymeric substance as a support material for these substances, but may also contain additives such as plasticizers. . Here, as the quaternary ammonium salt used in the present invention,
All compounds known as anion selective materials can be used, but methyltrioctylammonium chloride, methyltritetradecylammonium chloride, methyltridedecylammonium chloride and the like are preferred. In addition, in the present invention, the cation-selective substance added to the anion-selective membrane to prevent elution of the anion-selective substance is selected from the same range as that used as the selective substance in the cation-selective electrode. ,for example
Examples include monensin, nonaxin, dinactin, tetranactin, gramicidin, nigericin, and valinomycin, which are cation selective substances such as Na + , K + , or Ca 2+ . Examples of organic polymeric substances that are supporting materials for the ion selective membrane include polyurethane, silicone rubber, polystyrene, and polymethyl methacrylate. Furthermore, as the plasticizer, it is preferable to use, for example, dioctyl adipate, dioctyl phthalate, orthonitrophenyl octyl ether, and the like. In the above anion-selective membrane, the cation-selective substance is added in an amount of not more than 5 times the amount of the anion-selective substance, preferably not less than the same molar amount and not more than 2 times the amount of the anion-selective substance. As an anion selective substance, a quaternary ammonium salt is added to the membrane in an amount usually from 0.2 to 70% by weight, preferably from 5 to 25% by weight.
本発明の陰イオン選択性電極は、格別第１図に
示した構造であることに限定されず、上記組成か
らなる陰イオン選択膜を有する電極であればいか
なるものであつてもよい。 The anion-selective electrode of the present invention is not particularly limited to the structure shown in FIG. 1, but may be any electrode having an anion-selective membrane having the above composition.
本発明電極は、例えば次のようにして製造され
る。まず、陰イオン選択物質並びに陽イオン選択
物質、有機高分子物質及び必要であれば可塑剤等
を溶媒に溶解してイオン選択膜剤を調整し、これ
をガラスシヤーレに流し込んだ後、溶媒を蒸発乾
燥して陰イオン選択膜を製造する。なお、溶媒と
しては、例えばアセトン、ベンゼン、四塩化炭
素、テトラヒドロフラン等が用いられる。次い
で、得られた陰イオン選択膜を電極筒体の端部に
取着し、最後に該筒体内に内部電解液を満たし、
内部基準電極を設けることにより、本発明電極が
得られる。 The electrode of the present invention is manufactured, for example, as follows. First, prepare an ion-selective membrane agent by dissolving an anion-selective substance, a cation-selective substance, an organic polymer substance, and a plasticizer if necessary in a solvent. After pouring this into a glass shear, the solvent is evaporated and dried. to produce an anion selective membrane. In addition, as a solvent, acetone, benzene, carbon tetrachloride, tetrahydrofuran, etc. are used, for example. Next, the obtained anion selective membrane is attached to the end of the electrode cylinder, and finally the cylinder is filled with an internal electrolyte,
By providing an internal reference electrode, the electrode of the present invention can be obtained.
次に、本発明電極の使用例を第２図に基づき説
明する。本発明電極２１は、陽イオン選択性電極
２２及び比較電極２３と共にフローセル２４に装
着され、該フローセル２４内に吸引された被検液
２５中の陰イオンを検知する。測定後は、洗浄用
イオン交換水２６によつてフローセル２４内が洗
浄される。なお、被検液２５及びイオン交換水２
６は、三方コツク２７の切変えとポンプ２８によ
る吸引によつて、連続的にフローセル内に供給さ
れる。イオンを検出した各電極の出力信号は、リ
ード線を介して該電極と接続されたエレクトロメ
ーター２９で読み取られ、イオン濃度値が表示さ
れる。 Next, an example of use of the electrode of the present invention will be explained based on FIG. 2. The electrode 21 of the present invention is attached to the flow cell 24 together with the cation-selective electrode 22 and the comparison electrode 23, and detects anions in the test liquid 25 drawn into the flow cell 24. After the measurement, the inside of the flow cell 24 is cleaned with ion-exchanged water 26 for cleaning. In addition, the test liquid 25 and ion exchange water 2
6 is continuously supplied into the flow cell by switching the three-way tank 27 and suctioning by the pump 28. The output signal of each electrode that detected ions is read by an electrometer 29 connected to the electrode via a lead wire, and the ion concentration value is displayed.
本発明の陰イオン選択性電極によれば、陰イオ
ン選択膜中に陽イオン選択物質が予め分散されて
いるので、陰イオン選択物質と陽イオン選択物質
とは互いに結合しており、その結果、該電極中か
ら被検液中に陰イオン選択物質が単独で溶出する
おそれはない。従つて、被検液を介して隣接する
陽イオン選択性電極中の陽イオン選択物質が溶出
した陰イオン選択物質によつて補捉されることは
ないので、該陽イオン選択性電極は機能が低下す
ることなく、安定した感度を有し、長寿命化が図
られる。一方、本発明の陰イオン選択性電極にあ
つても、陰イオン選択物質はイオン感応部位以外
の箇所で陽イオン選択物質と結合していると考え
られるため、従来と同様に安定な感度を有してい
る。よつて、その工業的価値は極めて大である。
According to the anion-selective electrode of the present invention, since the cation-selective substance is pre-dispersed in the anion-selective membrane, the anion-selective substance and the cation-selective substance are bonded to each other, and as a result, There is no possibility that the anion selective substance will be eluted alone from the electrode into the test liquid. Therefore, the cation-selective substance in the adjacent cation-selective electrode is not captured by the eluted anion-selective substance via the test liquid, so the cation-selective electrode is not functional. It has stable sensitivity without deterioration and has a long service life. On the other hand, even in the anion-selective electrode of the present invention, it is thought that the anion-selective substance is bound to the cation-selective substance at a location other than the ion-sensitive site, so it has stable sensitivity as in the past. are doing. Therefore, its industrial value is extremely large.
実施例
まず、メチルトリドデシルアンモニウムクロリ
ド50mg、バリノマイシン200mg、カリウムテトラ
フエニルボレート２mg、アジピン酸ジオクチル
850mg及びポリ塩化ビニル560mgをテトラヒドロフ
ラン20mlに充分に攪拌混合した後、これをガラス
シヤーレ中に流し込み、溶媒のテトラヒドロフラ
ンを蒸発乾燥させて厚さ300μmの塩素イオン選択
膜を得た。この塩素イオン選択膜を第１図に示し
た電極に装着し、塩素イオン選択性電極とした。
Example First, 50 mg of methyl tridodecylammonium chloride, 200 mg of valinomycin, 2 mg of potassium tetraphenylborate, dioctyl adipate.
After thoroughly stirring and mixing 850 mg of polyvinyl chloride and 560 mg of polyvinyl chloride in 20 ml of tetrahydrofuran, the mixture was poured into a glass shear dish, and the solvent tetrahydrofuran was evaporated to dryness to obtain a chloride ion selective membrane with a thickness of 300 μm. This chloride ion selective membrane was attached to the electrode shown in FIG. 1 to form a chloride ion selective electrode.
次に、バリノマイシン20mg、カリウムテトラフ
エニルボレート２mg、アジピン酸ジオクチル850
mg及びポリ塩化ビニル560mgから成るカリウムイ
オン選択膜を同様の方法で調製し、カリウムイオ
ン選択性電極を得た。 Next, 20 mg of valinomycin, 2 mg of potassium tetraphenylborate, and 850 mg of dioctyl adipate.
A potassium ion-selective membrane consisting of 560 mg of polyvinyl chloride and 560 mg of polyvinyl chloride was prepared in the same manner to obtain a potassium ion-selective electrode.
一方、本発明の電極と性能を比較するために、
メチルトリドデシルアンモニウムクロリド50mg、
カリウムテトラフエニルボレート２mg、アジピン
酸ジオクチル850mg及びポリ塩化ビニル560mgの組
成の塩素イオン選択膜を調製し、従来の塩素イオ
ン選択性電極を得た。 On the other hand, in order to compare the performance with the electrode of the present invention,
Methyl tridodecylammonium chloride 50mg,
A chloride ion selective membrane having a composition of 2 mg of potassium tetraphenylborate, 850 mg of dioctyl adipate, and 560 mg of polyvinyl chloride was prepared to obtain a conventional chloride ion selective electrode.
得られたイオン選択性電極の性能を評価するた
め、第２図に示した装置を製造した。本発明の塩
素イオン選択性電極２１とカリウムイオン選択性
電極２２及び比較電極２３をフローセル２４に装
着し、まず血清２５を30秒間フローセル２４内に
貯留せしめ、次いで三方コツク２７を切変えて洗
浄用イオン交換水２６を30秒間、ポンプ２８を駆
動して50μ／分の流速でフローセル２４内に通
流せしめるという操作を繰返した。イオン濃度に
ついての各々の電極の出力信号をエレクトロメー
ター２９で読取り、得られた結果を第３図に示し
た。その結果、塩素イオン選択性電極（図中、黒
丸で示す）もカリウムイオン選択性電極（図中、
白丸で示す）も、どちらも感度が低下していない
ことが判明した。 In order to evaluate the performance of the obtained ion-selective electrode, an apparatus shown in FIG. 2 was manufactured. The chloride ion selective electrode 21, the potassium ion selective electrode 22, and the reference electrode 23 of the present invention are attached to the flow cell 24, and the serum 25 is first stored in the flow cell 24 for 30 seconds, and then the three-way socket 27 is switched for cleaning. The operation of driving the pump 28 to flow the ion-exchanged water 26 into the flow cell 24 at a flow rate of 50 μ/min for 30 seconds was repeated. The output signal of each electrode regarding ion concentration was read by an electrometer 29, and the obtained results are shown in FIG. As a result, both the chloride ion selective electrode (indicated by a black circle in the figure) and the potassium ion selective electrode (indicated by a black circle in the figure)
It was found that the sensitivity did not decrease in both cases (indicated by white circles).
比較のために、上記と同様な評価系を用いて従
来の塩素イオン選択性電極２１をフローセル２４
に装着して連続測定した結果を第４図に示した。
図から明らかなように、塩素イオン選択性電極
（黒丸）には感度の低下はみられないが、同じフ
ローセル内に装着されたカリウムイオン選択性電
極（白丸）は20日経過後から急速に感度が低下し
ていた。 For comparison, a conventional chloride ion selective electrode 21 was used in the flow cell 24 using the same evaluation system as above.
Figure 4 shows the results of continuous measurements taken with the device attached to the camera.
As is clear from the figure, the sensitivity of the chloride-selective electrode (black circle) does not decrease, but the sensitivity of the potassium-ion-selective electrode (white circle) installed in the same flow cell rapidly decreases after 20 days. It was declining.
以上、述べた第３図と第４図に示した結果を検
討すると、従来の塩素イオン選択性電極は隣接す
るカリウムイオン選択性電極の寿命を短かくして
いることが明らかで、本発明の塩素イオン選択性
電極が性能的に優れていることが判る。 Examining the results shown in Figures 3 and 4 above, it is clear that the conventional chloride ion selective electrode shortens the life of the adjacent potassium ion selective electrode, and the chloride ion selective electrode of the present invention shortens the life of the adjacent potassium ion selective electrode. It can be seen that the selective electrode has superior performance.
試験例
陰イオン選択膜中に各種の濃度で陽イオン選択
物質を添加した場合、陽イオン選択物質が陰イオ
ン選択性電極に与える影響について調べた。実験
にあたつては、第１図に示した電極を用いた。該
電極において用いた陰イオン選択性膜は、ポリ塩
化ビニル、メチルトリドデシルアンモニウムクロ
リド（MTDA−Ｃ）、アジピン酸ジオクチル及
びバリノマイシンからなり、MTDA−Ｃ含有
量を一定（８×10-5モル）にして、バリノマイシ
ン含有量をモル比で0.5倍から３倍まで変化させ
たものである。Test Example When a cation-selective substance was added to an anion-selective membrane at various concentrations, the effect of the cation-selective substance on the anion-selective electrode was investigated. In the experiment, the electrodes shown in FIG. 1 were used. The anion-selective membrane used in the electrode was made of polyvinyl chloride, methyltridodecylammonium chloride (MTDA-C), dioctyl adipate, and valinomycin, and the MTDA-C content was kept constant (8 × 10 -5 mol). The molar ratio of valinomycin content was varied from 0.5 times to 3 times.
第５図はこれらの陰イオン選択膜を取付けたイ
オン選択性電極の塩化カリウム水溶液中の塩素イ
オンに対する感度を示したものである。図から明
らかな如く、カリウムイオン選択物質であるバリ
ノマイシンの含有量がMTDA−Ｃの３倍のモ
ル量まで増しても塩素イオンに対する感度は何ら
変化せず、陰イオンに対する感度が優先的に働い
ていることが判明した。 FIG. 5 shows the sensitivity of the ion-selective electrode equipped with these anion-selective membranes to chlorine ions in an aqueous potassium chloride solution. As is clear from the figure, even when the content of valinomycin, a potassium ion selective substance, increases to three times the molar amount of MTDA-C, the sensitivity to chloride ions does not change at all, and the sensitivity to anions works preferentially. It turned out that there was.
次に、第６図は上記と同様のイオン選択膜を用
い水溶液中の塩素イオン濃度を10倍にした時の95
％応答速度を示したものである。図から明らかな
ように、その応答速度はバリノマイシンの添加に
よつてほとんど影響されないことが判明した。し
たがつてカリウムイオン選択性物質であるバリノ
マイシンを広範囲の濃度でイオン選択膜中に分散
させても、MTDA−Ｃのイオン選択能は正常
に働き、塩素イオン選択性電極として従来の電極
に劣ることなく機能することが判明した。 Next, Figure 6 shows 95% when the chloride ion concentration in the aqueous solution is increased by 10 times using the same ion-selective membrane as above.
% response speed is shown. As is clear from the figure, the response rate was found to be hardly affected by the addition of valinomycin. Therefore, even when valinomycin, a potassium ion-selective substance, is dispersed in an ion-selective membrane in a wide range of concentrations, the ion-selective ability of MTDA-C works normally, and as a chloride-selective electrode it is inferior to conventional electrodes. It turned out to work without any problems.
第１図は本発明の陰イオン選択性電極の縦断面
図、第２図は陰イオン選択性電極及び陽イオン選
択性電極を用いて各種イオンの多項目測定を行う
場合の使用態様を示した図、第３図及び第４図
は、各々、本発明の陰イオン選択性電極及び従来
の陰イオン選択性電極が陽イオン選択性電極に与
える影響を示した図、第５図及び第６図は、
各々、本発明電極の陰イオン選択膜中に添加され
た各種のバリノマイシン量に対する感度及び応答
性の関係を示した図である。
１……電極筒体、２……イオン選択膜、３……
内部電解液、４……内部基準電極、２１……塩素
イオン選択性電極、２２……カリウムイオン選択
性電極、２３……比較基準電極、２４……フロー
セル、２５……血清、２６……イオン交換水、２
７……三方コツク、２８……ポンプ、２９……エ
レクトロメーター。
Fig. 1 is a longitudinal cross-sectional view of the anion-selective electrode of the present invention, and Fig. 2 shows how the anion-selective electrode and the cation-selective electrode are used to perform multi-item measurements of various ions. Figures 3 and 4 are diagrams illustrating the effects of the anion-selective electrode of the present invention and the conventional anion-selective electrode on the cation-selective electrode, Figures 5 and 6, respectively. teeth,
FIG. 3 is a diagram showing the relationship between sensitivity and responsiveness to various amounts of valinomycin added to the anion-selective membrane of the electrode of the present invention. 1... Electrode barrel, 2... Ion selective membrane, 3...
Internal electrolyte, 4... Internal reference electrode, 21... Chloride ion selective electrode, 22... Potassium ion selective electrode, 23... Comparison reference electrode, 24... Flow cell, 25... Serum, 26... Ion Exchange water, 2
7...Mikata Kotsuku, 28...Pump, 29...Electrometer.
Claims (1)
と、その支持材とを含む陰イオン選択膜を有する
陰イオン選択性電極において、 該イオン選択膜中に、該陰イオン選択物質に対
して５倍モル以下の陽イオン選択物質が分散され
ていることを特徴とする陰イオン選択性電極。[Scope of Claims] 1. An anion-selective electrode having an anion-selective membrane containing a quaternary ammonium salt as an anion-selective substance and a supporting material thereof, wherein the anion-selective substance is contained in the ion-selective membrane. An anion-selective electrode characterized in that a cation-selective substance is dispersed in an amount of 5 times the mole or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58107867A JPS601547A (en) | 1983-06-17 | 1983-06-17 | Anion selective electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58107867A JPS601547A (en) | 1983-06-17 | 1983-06-17 | Anion selective electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS601547A JPS601547A (en) | 1985-01-07 |
| JPH0469335B2 true JPH0469335B2 (en) | 1992-11-05 |
Family
ID=14470085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58107867A Granted JPS601547A (en) | 1983-06-17 | 1983-06-17 | Anion selective electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS601547A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2567895B2 (en) * | 1988-02-03 | 1996-12-25 | 株式会社トクヤマ | Ion sensitive membrane |
| US6096275A (en) * | 1998-05-01 | 2000-08-01 | Biological Technologies International, Inc. | Biological fluid testing device |
-
1983
- 1983-06-17 JP JP58107867A patent/JPS601547A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS601547A (en) | 1985-01-07 |
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