JPS6329215B2 - - Google Patents
Info
- Publication number
- JPS6329215B2 JPS6329215B2 JP56100562A JP10056281A JPS6329215B2 JP S6329215 B2 JPS6329215 B2 JP S6329215B2 JP 56100562 A JP56100562 A JP 56100562A JP 10056281 A JP10056281 A JP 10056281A JP S6329215 B2 JPS6329215 B2 JP S6329215B2
- Authority
- JP
- Japan
- Prior art keywords
- ion
- selective
- plasticizer
- electrode
- membrane
- 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
Links
- 239000012528 membrane Substances 0.000 claims description 36
- 239000004014 plasticizer Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 6
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 description 62
- 229910001414 potassium ion Inorganic materials 0.000 description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 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 6
- 108010067973 Valinomycin Proteins 0.000 description 5
- 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 5
- 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 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 210000002966 serum Anatomy 0.000 description 4
- -1 Cl - Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 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
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-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
- 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
- RMIXHJPMNBXMBU-QIIXEHPYSA-N Nonactin 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](C)OC(=O)[C@H]1C)C)C(=O)O[C@H](C)C[C@H]2CC[C@@H]1O2 RMIXHJPMNBXMBU-QIIXEHPYSA-N 0.000 description 1
- RMIXHJPMNBXMBU-UHFFFAOYSA-N Nonactin Natural products CC1C(=O)OC(C)CC(O2)CCC2C(C)C(=O)OC(C)CC(O2)CCC2C(C)C(=O)OC(C)CC(O2)CCC2C(C)C(=O)OC(C)CC2CCC1O2 RMIXHJPMNBXMBU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 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
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 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
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 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
- 238000002474 experimental method Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 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
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 description 1
- DFQMKYUSAALDDY-MQEBUAKTSA-N trinactin 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](C)C[C@@H]2CC[C@H]1O2 DFQMKYUSAALDDY-MQEBUAKTSA-N 0.000 description 1
- DFQMKYUSAALDDY-UHFFFAOYSA-N trinactin 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(C)CC2CCC1O2 DFQMKYUSAALDDY-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2410/00—Assays, e.g. immunoassays or enzyme assays, involving peptides of less than 20 animo acids
- G01N2410/10—Valinomycins and derivatives thereof
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)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Description
【発明の詳細な説明】
本発明は長寿命化処理を施したイオン選択性膜
を有するイオン選択性電極に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an ion-selective electrode having an ion-selective membrane treated to extend its life.
従来イオン選択性電極は、被測定液中に浸漬し
たときその測定電位が測定対象イオンの活量の対
数に比例するので被測定液中のイオン濃度を容易
に定量することができるため、工業プリセス制
御、公害水質監視、水質分析などの広い分野で用
いられている。近年各種イオンに対して特異的な
選択性を示すクラウンエーテルのような巨大環状
物質が着目され、これをポリ塩化ビニールのよう
な高分子物質からなる膜中に含有させて調製した
イオン選択性膜で構成された高分子膜形イオン選
択性電極の開発がなされている。とくに、最近で
は医療用、とりわけ血液中に存在するNa+、K+、
Cl-などの各種イオンの濃度分析に用いる試みが
盛んになり実用化されている。 Conventional ion-selective electrodes have a measurement potential proportional to the logarithm of the activity of the ion to be measured when immersed in the liquid to be measured, making it easy to quantify the ion concentration in the liquid to be measured, making it suitable for industrial processes. It is used in a wide range of fields such as control, pollution water quality monitoring, and water quality analysis. In recent years, attention has been drawn to large cyclic substances such as crown ethers that exhibit specific selectivity for various ions, and ion-selective membranes prepared by incorporating these substances into membranes made of polymeric substances such as polyvinyl chloride have been developed. A polymer membrane-type ion-selective electrode composed of is being developed. In particular, recently it has been used for medical purposes, especially Na + , K + , which exists in blood.
Many attempts have been made to use it to analyze the concentration of various ions such as Cl -, and it has been put into practical use.
しかしながら、従来のイオン選択性電極は血液
や血清等の被測定液に浸漬するとイオン選択性膜
中に含まれている可塑剤がバクテリアに浸食され
たり被測定液中に拡散したりしてイオン選択性膜
中の可塑剤含有量が減少する為、イオン選択性電
極の劣化が促進されるという欠点があつた。この
ような欠点のため前記の如き被測定液を測定対象
とする場合には、前記イオン選択性電極や劣化す
るたびにイオン選択性電極の交換や、イオン選択
性電極のイオン選択性膜を貼換える作業を頻繁に
行なわなければならない等の欠点を有していた。 However, when conventional ion-selective electrodes are immersed in a liquid to be measured such as blood or serum, the plasticizer contained in the ion-selective membrane is eroded by bacteria or diffuses into the liquid to be measured, causing ion selection. This method has the disadvantage that the deterioration of the ion-selective electrode is accelerated because the content of plasticizer in the ion-selective electrode is reduced. Due to these drawbacks, when measuring the liquid to be measured as described above, it is necessary to replace the ion-selective electrode each time it deteriorates, or to paste an ion-selective membrane on the ion-selective electrode. This method has drawbacks such as the need for frequent replacement work.
本発明は従来の欠点を解決し、長寿命化したイ
オン選択性膜を有するイオン選択性電極を提供す
ることを目的とするものである。 The present invention aims to solve the conventional drawbacks and provide an ion-selective electrode having an ion-selective membrane with a longer service life.
本発明は、すなわち、内部に導電性物質を収納
した容器と、この容器の先端部に貼着したイオン
選択性膜と、前記容器内に支持された内部基準電
極とこの電極に接続されたリード線とを具備し前
記イオン選択性膜は高分子物質を基材とし、その
基材中にイオン選択性物質と可塑剤を含有する担
体を含み、前記担体の含有する可塑剤濃度は前記
イオン選択性膜自体の可塑剤濃度より高濃度に選
定されることを特徴とするイオン選択性電極に係
るものである。 The present invention consists of a container containing a conductive substance therein, an ion-selective membrane attached to the tip of the container, an internal reference electrode supported in the container, and a lead connected to the electrode. The ion-selective membrane is made of a polymer material as a base material, and includes a carrier containing an ion-selective substance and a plasticizer in the base material, and the concentration of the plasticizer contained in the carrier is set at a concentration of the ion-selective material. The present invention relates to an ion-selective electrode characterized in that the concentration of plasticizer is selected to be higher than that of the plasticizer itself.
本発明のイオン選択性電極は、高分子膜にイオ
ン選択性物質と可塑剤と可塑剤を含有する担体と
からなるイオン選択性膜において、前記イオン選
択性膜中に分散された担体が可塑剤を充分に含有
し、しかも前記イオン選択性膜中の可塑剤が被測
定液に拡散しても前記担体から前記イオン選択性
膜中に可塑剤が浸透補充される。イオン選択性膜
中に含まれる担体の含有する可塑剤の濃度は、前
記イオン選択性膜に含有される可塑剤の濃度より
充分に高く調製するように考慮される。 The ion-selective electrode of the present invention is an ion-selective membrane comprising an ion-selective substance, a plasticizer, and a carrier containing the plasticizer in a polymer membrane, wherein the carrier dispersed in the ion-selective membrane contains a plasticizer. Even if the plasticizer in the ion-selective membrane diffuses into the liquid to be measured, the plasticizer is replenished by permeation from the carrier into the ion-selective membrane. The concentration of the plasticizer contained in the carrier contained in the ion-selective membrane is considered to be sufficiently higher than the concentration of the plasticizer contained in the ion-selective membrane.
すなわち本発明に係る電極のイオン選択性膜
は、例えば、まず、イオン選択性物質含有量5wt
％、可塑剤含有量60wt％、となるようにした高
分子溶液に、前記可塑剤と同じ可塑剤を充分に含
有し微粒子化した担体を加え高分子溶液中に分散
させて、担体の含有する可塑剤濃度の方がより高
濃度としたイオン選択性膜を形成する。 That is, the ion-selective membrane of the electrode according to the present invention, for example, first has an ion-selective substance content of 5 wt.
%, and a plasticizer content of 60 wt%, a finely divided carrier containing a sufficient amount of the same plasticizer as the above plasticizer is added and dispersed in the polymer solution to reduce the content of the carrier. Forms an ion-selective membrane with a higher concentration of plasticizer.
本発明のイオン選択性電極が有効であること
は、例えば高分子物質中に可塑剤としてのアジピ
ン酸ジオクチル、イオン選択性物質であるバリノ
マイシンを含むカリウムイオン選択性膜を有する
カリウムイオン選択性電極を血清中で長時間使用
した場合に劣化し、ネルンスト応答を示さなくな
ると共に応答速度も遅くなるが、前記劣化したイ
オン選択性電極を単に可塑剤であるアジピン酸ジ
オクチルに浸漬する等して可塑剤を前記劣化した
イオン選択性電極のイオン選択性膜に供給すれ
ば、再びネルンスト応答を示し応答速度も速くな
る事を発見した最近の実験結果からも明らかであ
る。例えば、血清中で１ケ月程度使用してネルン
スト応答を示さなくなつたカリウムイオン選択性
電極を約１時間アジピン酸ジオクチル中に浸漬し
可塑剤を供給したところ、再びネルンスト応答を
示すようになつた（37.0℃でネルンスト傾斜60.5
ｍＶ／decade）。この実験事実は前記カリウムイ
オン選択性電極を血清などの被測定液に浸漬する
と、イオン選択性膜中から可塑剤でありしかも親
油性のイオン選択性物質であるバリノマイシンを
高分子物質中で溶解しているところのアジピン酸
ジオクチルが失なわれることを示している。 The effectiveness of the ion-selective electrode of the present invention is demonstrated by, for example, a potassium ion-selective electrode having a potassium ion-selective membrane containing dioctyl adipate as a plasticizer and valinomycin as an ion-selective substance in a polymeric material. When used for a long time in serum, it deteriorates and does not exhibit a Nernst response and the response speed becomes slow. It is clear from recent experimental results that it was discovered that if the ion-selective membrane of the deteriorated ion-selective electrode is supplied, the Nernst response will be exhibited again and the response speed will become faster. For example, when a potassium ion-selective electrode that had stopped showing a Nernstian response after being used in serum for about a month was immersed in dioctyl adipate for about an hour and a plasticizer was supplied, it started showing a Nernstian response again. (Nernst slope 60.5 at 37.0℃
mV/decade). The fact of this experiment is that when the potassium ion-selective electrode is immersed in a liquid to be measured such as serum, valinomycin, which is a plasticizer and a lipophilic ion-selective substance, is dissolved in the polymer substance from the ion-selective membrane. This shows that dioctyl adipate, which is currently in use, is lost.
上記アジピン酸ジオクチルが失なわれるとバリ
ノマイシンがイオン選択性膜中で析出し、カリウ
ムイオンとの錯形成能力が減少し、カリウムイオ
ン選択性電極がネルンスト応答を示さなくなるも
のと考えられる。それ故に本発明の如き、イオン
選択性膜中に可塑剤を充分に含有した担体を混合
している構造のイオン選択性電極は有効である。 It is thought that when the above-mentioned dioctyl adipate is lost, valinomycin precipitates in the ion-selective membrane, the ability to form a complex with potassium ions decreases, and the potassium ion-selective electrode no longer exhibits a Nernst response. Therefore, an ion-selective electrode having a structure in which a carrier sufficiently containing a plasticizer is mixed in an ion-selective membrane as in the present invention is effective.
本発明のイオン選択性膜用に適する高分子物質
としては、例えばポリ塩化ビニール、ポリウレタ
ン、シリコーンゴム、ポリスチレン、ポリメチル
メタアクリレート、などである。本発明において
適するイオン選択性物質としては、例えばバリノ
マイシン、ジベンゾー18−クラウン−６、ジシク
ロヘキシル−18−クラウン−６、ノナクチン、ジ
ナクチン、トリナクチン、テトラナクチン、グラ
ミンジン、モネンシン、ニゲリシン、メチルトリ
ドデシルアンモニウムクロライド、メチルトリカ
プリルアンモニウムクロライド、などがあげられ
る。本発明における可塑剤とは、アジピン酸ジオ
クチル、アジピン酸ジイソデシル、フタル酸ジオ
クチル、フタル酸ジイソデシル、セバシン酸ジオ
クチル、リン酸トリクレジル、オルトニトロフエ
ニルオクチルエーテル、などがあげられる。本発
明における担体とは、けいそう土、活性炭、シリ
カゲル、アルミナ、活性白土、モレキユラシー
ブ、などがあげられる。 Examples of polymeric substances suitable for the ion-selective membrane of the present invention include polyvinyl chloride, polyurethane, silicone rubber, polystyrene, polymethyl methacrylate, and the like. Suitable ion-selective substances in the present invention include, for example, valinomycin, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, nonactin, dinactin, trinactin, tetranactin, gramindin, monensin, nigericin, methyltridodecylammonium chloride, methyl Examples include tricaprylammonium chloride. Examples of the plasticizer in the present invention include dioctyl adipate, diisodecyl adipate, dioctyl phthalate, diisodecyl phthalate, dioctyl sebacate, tricresyl phosphate, orthonitrophenyl octyl ether, and the like. Examples of the carrier in the present invention include diatomaceous earth, activated carbon, silica gel, alumina, activated clay, and molecular sieve.
本発明において用いるイオン選択性膜中に包含
されるイオン選択性物質の量は、該物質の種類に
よつても異なるが、通常0.5〜30重量％である。
又、担体の割合は、通常１〜５重量％、好ましく
は２〜３重量％である。担体中に含浸される可塑
剤の量は、飽和含浸量である。 The amount of the ion-selective substance included in the ion-selective membrane used in the present invention varies depending on the type of the substance, but is usually 0.5 to 30% by weight.
Further, the proportion of the carrier is usually 1 to 5% by weight, preferably 2 to 3% by weight. The amount of plasticizer impregnated into the carrier is the saturation impregnation amount.
本発明を実施例について説明すれば、本発明の
イオン選択性電極は、内部に電解液となる導電性
物質１１を収納した筒状容器１２と、その容器の
先端部に貼着したカリウムイオン選択性膜１３
と、前記容器内に支持された内部基準電極１４
と、この電極に接続されたリード線１５と、この
リード線が貫通し前記容器の上部に設けたキヤツ
プ１６とからなる構造を有し、前記イオン選択性
膜１３は高分子物質であるポリ塩化ビニール0.5
ｇ、イオン選択性物質となるバリノマイシン20
mg、可塑剤のアジピン酸ジオクチル１ｇ及びカリ
ウムテトラフエニルボレート１mgを溶剤のテトラ
ヒドロフラン20mlに充分混合溶解した後、前記と
は別に80〜100メツシユを通過したけいそう土
（セライト545）50mgにアジピン酸ジオクチルを充
分に浸み込ませた可塑剤含有の担体を前記混合溶
液中に加え迅速に高分子溶液中に担体を分散させ
た後に、内径９cmのフラツトシヤーレ内に混合溶
解液の全量を注ぎ込み乾燥して厚さ180μｍのカ
リウムイオン選択性膜を調製する。このようにし
て得られたイオン選択性電極の性能を比較するた
め、可塑剤を含有した担体が膜中に加えられてい
ない従来の膜を上記イオン選択性膜と同じ成分仕
様で作り、比較した。第２図ａ曲線は従来のカリ
ウムイオン選択性膜によるイオン選択性電極、ｂ
曲線は本発明実施例によるイオン選択性電極で、
使用日数に対してカリウム活量の10倍変化に対す
る電位変化を示す出力感度（ΔE）を示すもので、
本発明の実施例は従来例より使用可能日数が長い
ことが判る。 To explain the present invention with reference to an embodiment, the ion-selective electrode of the present invention includes a cylindrical container 12 containing a conductive substance 11 serving as an electrolyte inside, and a potassium ion selective electrode attached to the tip of the container. sexual membrane 13
and an internal reference electrode 14 supported within the container.
It has a structure consisting of a lead wire 15 connected to this electrode, and a cap 16 provided on the upper part of the container through which this lead wire passes. vinyl 0.5
g, valinomycin 20, which is an ion-selective substance
After thoroughly mixing and dissolving 1 g of dioctyl adipate as a plasticizer and 1 mg of potassium tetraphenylborate in 20 ml of tetrahydrofuran as a solvent, add adipic acid to 50 mg of diatomaceous earth (Celite 545) that has passed through an 80 to 100 mesh separately from the above. After adding a plasticizer-containing carrier sufficiently impregnated with dioctyl to the mixed solution and quickly dispersing the carrier in the polymer solution, the entire mixed solution was poured into a flat shear with an inner diameter of 9 cm and dried. Prepare a potassium ion selective membrane with a thickness of 180 μm. In order to compare the performance of the ion-selective electrodes obtained in this way, a conventional membrane without a plasticizer-containing carrier added to the membrane was prepared with the same component specifications as the above-mentioned ion-selective membrane, and compared. . Figure 2 a curve is an ion-selective electrode using a conventional potassium ion-selective membrane, b
The curve is an ion-selective electrode according to an embodiment of the present invention,
This shows the output sensitivity (ΔE), which shows the potential change in response to a 10-fold change in potassium activity over the number of days of use.
It can be seen that the example of the present invention can be used for a longer period of time than the conventional example.
以上、比較例で明らかな如く、本発明のイオン
選択性電極は、イオン選択性膜中に可塑剤を充分
に含有させた微粒子化した担体を分散させておけ
ば、被検液中へ可塑剤が拡散損失しイオン選択性
物質の錯形成能力が低下することの無い様に膜中
の可塑剤濃度を維持できるものであり、しかもイ
オン選択性膜の調製方法は簡易である。さらに、
本発明電極によれば安価に長寿命のイオン選択性
電極が得られ有用である。 As is clear from the comparative examples above, the ion-selective electrode of the present invention is capable of dispersing the plasticizer into the test liquid by dispersing the micronized carrier containing a sufficient amount of plasticizer in the ion-selective membrane. The concentration of plasticizer in the membrane can be maintained so that the complex-forming ability of the ion-selective substance does not decrease due to diffusion loss, and the method for preparing the ion-selective membrane is simple. moreover,
According to the electrode of the present invention, an ion-selective electrode with a long life can be obtained at low cost and is useful.
第１図は本発明に係るイオン選択性電極の断面
図、第２図は本発明電極と従来のイオン選択性電
極との性能を比較する特性曲線図である。
１１……導電性物質、１２……容器、１３……
イオン選択性膜、１４……内部基準電極、１５…
…リード線、１６……キヤツプ。
FIG. 1 is a sectional view of an ion-selective electrode according to the present invention, and FIG. 2 is a characteristic curve diagram comparing the performance of the electrode of the present invention and a conventional ion-selective electrode. 11... Conductive substance, 12... Container, 13...
Ion selective membrane, 14... Internal reference electrode, 15...
...Lead wire, 16...cap.
Claims (1)
器の先端部に貼着したイオン選択性膜と、前記容
器内に支持された内部基準電極と、この電極に接
続されたリード線とを具備し、前記イオン選択性
膜は高分子物質を基材とし、その基材中にイオン
選択性物質と可塑剤及び可塑剤を含有する担体を
含み、前記担体の含有する可塑剤濃度は前記イオ
ン選択性膜自体の可塑剤濃度より高濃度に選定さ
れることを特徴とするイオン選択性電極。1 A container containing a conductive substance inside, an ion-selective membrane attached to the tip of the container, an internal reference electrode supported in the container, and a lead wire connected to the electrode. The ion-selective membrane is made of a polymeric substance as a base material, and includes an ion-selective substance, a plasticizer, and a carrier containing the plasticizer in the base material, and the concentration of the plasticizer contained in the carrier is determined by the ion-selective membrane. An ion-selective electrode characterized in that the concentration of plasticizer is selected to be higher than that of the plasticizer itself.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56100562A JPS582733A (en) | 1981-06-30 | 1981-06-30 | Ion selective electrode |
| US06/391,133 US4409088A (en) | 1981-06-30 | 1982-06-23 | Regeneration method of ion-selective electrode, and ion-selective electrode and ion-concentration analyzer containing means adapted to practice said method |
| DE8282105825T DE3273555D1 (en) | 1981-06-30 | 1982-06-30 | Regeneration method of ion-selective electrode, and ion-selective electrode and ion-concentration analyzer containing means adapted to practise said method |
| EP82105825A EP0068505B1 (en) | 1981-06-30 | 1982-06-30 | Regeneration method of ion-selective electrode, and ion-selective electrode and ion-concentration analyzer containing means adapted to practise said method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56100562A JPS582733A (en) | 1981-06-30 | 1981-06-30 | Ion selective electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS582733A JPS582733A (en) | 1983-01-08 |
| JPS6329215B2 true JPS6329215B2 (en) | 1988-06-13 |
Family
ID=14277356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56100562A Granted JPS582733A (en) | 1981-06-30 | 1981-06-30 | Ion selective electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS582733A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1210674A (en) * | 1983-06-20 | 1986-09-02 | Eastman Kodak Company | Potassium ion-selective compositions and electrodes containing same |
| JPH076942B2 (en) * | 1987-03-18 | 1995-01-30 | 工業技術院長 | Ion-selective electrode |
-
1981
- 1981-06-30 JP JP56100562A patent/JPS582733A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS582733A (en) | 1983-01-08 |
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