Ion sensor

• US 5,133,856 A
• Filed: 09/04/1990
• Issued: 07/28/1992
• Est. Priority Date: 12/28/1984
• Status: Expired due to Fees

• Current Assignee: Terumo Kabushiki Kaisha
• Original Assignee: Terumo Kabushiki Kaisha
• Inventors: Oyama, Noboru, Yamaguchi, Shuichiro, Shimomura, Takeshi, Ushizawa, Norihiko
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Bell, Bruce F.
• Application Number:
  US07/577,050
• Time in Patent Office: 693 Days
• Field of Search: 204/290 R, 204/98, 204/402, 204/409, 204/290 F, 204/415, 204/418, 204/416
• US Class Current: 204/416
• CPC Class Codes: G01N 27/3335 the membrane containing at least one organic component G01N27/3271 takes precedence; aspects concerning the enzyme reagent in enzyme electrodes C12Q1/001

Abstract

An ion sensor of the type wherein a specific type of ion in an aqueous solution is measured by potential response. The sensor includes a conductor base, and a reversible redox polymer film formed directly on a surface of said conductor base. An ion carrier film is formed directly on a surface of said redox polymer film. The carrier film contains an ion carrier substance for allowing the specific type of ions to permeate from the aqueous solution to said polymer film.

Claims

1. An ion sensor wherein a specific type of ion in an aqueous solution is measured by potential response, comprising:

a conductor base;

a reversible redox polymer film formed directly on a surface of said conductor base; and

an ion carrier film formed directly on a surface of said redox polymer film and containing an ion carrier substance for allowing the specific type of ions to permeate from the aqueous solution to said polymer film;

wherein said conductor base is made of a conductive carbon compound; and

wherein said redox polymer film is capable of performing a reversible oxidation/reduction reaction of quinone-hydroquinone, and is formed by electrooxidation polymerization of at least one first compound selected from the group consisting of phenol, 3,5-, 2,6- and 3,4-xylenols, 2-hydroxy pyridine, o- and m-benzyl alcohols, o-, m- and p-hydroxybenzaldehydes, o-, m- and p-hydroxyacetophenones, o-, m- and p-hydroxypropiophenones, o-, o-, m- and p-benzophenols, o-, m- and p-hydroxybenzophenones, o-, m- and p-carboxyphenols, diphenylphenol, 2-methyl-8-hydroxyquinoline, 5-hydroxy-1,4-naphthoquinone, 4-(p-hydroxyphenyl)-2-butanone, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, bisphenol A, salicylanilide, 5- and 8-hydroxyquinolines, 1,8-dihydroxyanthraquinones, 1,2,5,8-tetrahydroxyquinalizarin, 1-amino-4-hydroxyanthraquinone, 1-aminoanthraquinone, purpurin, and anthrarufin.

2. An ion sensor according to claim 1, wherein said redox polymer film contains at least one electrolyte selected from the group consisting of, dipotassiumhydrogenphosphate, sodium perchlorate, sulfuric acid, sulfates, tetrafluoroborate, tetraphenylborate, phosphates and phosphoric acid.

3. An ion sensor according to claim 1, wherein said ion carrier substance is a hydrogen ion carrier substance.

4. An ion sensor according to claim 3, wherein said hydrogen ion carrier substance is at least one member selected from the group consisting of amines represented by:

##STR12## (wherein each of R¹, R² and R³ is an alkyl group, at least two of which are alkyl groups having 8 to 18 carbon atoms), and pyridine derivatives represented by;

##STR13## (wherein R⁴ is an alkyl group having 8 to 18 carbon atoms).

5. An ion sensor according to claim 1, wherein said ion carrier substance is a potassium ion carrier substance.

6. An ion sensor according to claim 5, wherein said potassium ion carrier substance is at least one member selected from the group consisting of valinomycin, bis(15-crown-5), nonactin, monactin, and crown ether compounds.

7. An ion sensor according to claim 1, wherein said ion carrier substance is a sodium ion carrier substance.

8. An ion sensor according to claim 7, wherein said sodium ion carrier substance is at least one member selected from the group consisting of bis[(12-crown-4)-methyl]dodecylamalonate, N,N,N,N-tetrapropyl-3,6-dioxanate-diamide, 3-methoxy-N,N,N,N-tetrapropyl-1,2-phenylenedioxydiacetoamide, (-)-(R,R)-4,5-dimethyl-N,N,N,N-tetrapropyl-3,6-dioxaoctanediamide, 4-methyl-N,N,N,N-tetrapropyl-3,6-dioxaoctanediamide, N,N,N,N-tetrapropyl-1,2-phenylenedioxydiacetoamide, N,N,N,N-tetrapropyl-2,3-naphtharenedioxydiacetoamide, 4-t-butyl-N,N,N,N-tetrapropyl-1,2-cyclohexanedioxydiaceto amide, 4-t-butyl-N,N'"'"'-di[(11-ethoxycarbonyl)undecyl]-N,N'"'"'-dimethyl-1,2-cyclohexanedioxydiacetoamide, cis-N,N,N,N-tetrapropyl-1,2-cyclohexanedioxydiacetoamide, and trans-N,N,N,N-tetrapropyl-1,2-cyclohexanedioxydiacetoamide.

9. An ion sensor according to claim 1, wherein said ion carrier substance is a calcium ion carrier substance.

10. An ion sensor according to claim 9, wherein said calcium ion carrier substance is at least one member selected from the group consisting of calcium-bis-[di-(n-octylphenyl)phosphate], (-)-(R,R)-N,N'"'"'-bis[(11-ethoxycarbonyl)undecyl]-N,N'"'"'-4,5-tetramethyl-3,6-dioxaoctanediamide, and calcium bis[di(n-decyl) phosphate].

11. An ion sensor according to claim 1, wherein said ion carrier substance is a chlorine ion carrier substance.

12. An ion sensor according to claim 11, wherein said chlorine ion carrier substance is at least one member selected from the group consisting of quaternary ammonium salts represented by the general formula:

##STR14## (wherein each of R⁵, R⁶, R⁷ and R⁸ is independently an alkyl group having 6 to 18 carbon atoms, and at least one of R⁵ to R⁸ can contain a hydrogen atom or a methyl group), and triphenyl tin chloride.

13. An ion sensor according to claim 1, wherein said ion carrier substance contains at least one electrolyte selected from the group consisting of sodium tetrakis(p-chlorophenyl)borate, and potassiumtetrakis (p-chlorophenyl)borate;

and compounds represented by general formulas;

space="preserve" listing-type="equation">(R.sup.15).sub.4 NBF.sub.4

space="preserve" listing-type="equation">and

space="preserve" listing-type="equation">(R.sup.15).sub.4 NPF.sub.4

(wherein each R¹⁵ is independently an alkyl group).

14. An ion sensor according to claim 1, wherein said ion carrier film comprises a polymeric substance selected from the group consisting of polyvinyl chloride, a vinyl chloride-ethylene copolymer, polyester, polyacrylamide, cellulose-based substances, polyurethane, and silicone resin.

15. An ion sensor according to claim 14, wherein said polymeric substance is polyvinyl chloride in a paste form.

16. An ion sensor according to claim 1, wherein said redox polymer film has a thickness of 0.1 μ

m to 0.2 mm.

17. An ion sensor according to claim 1, wherein said ion carrier film has a thickness of 50 μ

m to 10 mm.

18. An ion sensor according to claim 1, wherein said ion carrier substance is selected from the group consisting of a quaternary ammonium salt of the formula:

##STR15## where R⁹ to R¹¹ are independently alkal groups having 8 to 18 carbon atoms and X^- is Cl^-, Br^- or OH^- ;

a tertiary amine of the formula ##STR16## where R¹² is phenyl group, methyl group or hydrogen atom, R¹³ is hydrogen atom or methyl group, and R¹⁴ is hydrogen atom, methyl group or octadecyl group; and

the compounds of formulas;

##STR17##

19. An ion sensor according to claim 1, wherein said ion carrier film has a thickness of 300 μ

m to 1 mm.

33. An ion sensor according to claim 1 or 20 wherein said conductor base is made of basal plane pyrolytic graphite or glassy carbon.

20. An ion sensor wherein a specific type of ion in an aqueous solution is measured by potential response, comprising:

a conductor base;

a reversible redox polymer film formed directly on a surface of said conductor base; and

an ion carrier film formed directly on a surface of said redox polymer film and containing an ion carrier substance for allowing the specific type of ions to permeate from the aqueous solution to said polymer film;

wherein said conductor base is made of a conductive carbon compound; and

wherein said redox polymer film is capable of performing a reversible oxidation/reduction reaction of amine-quinoid, and formed by electrooxidation polymerization of at least one first compound selected from the group consisting of aniline, 1-aminopyrene, 1,2-, 1,6- and 1,8-diaminopyrenes, 1-9, 10-diaminophenanthrenes, 1-aminoanthraquinone, p-phenoxyaniline, o-phenylenediamine, p-chloroaniline, 3,5-dichloroaniline, 2,4,6-trichloroaniline, N-phenyl-p-phenylenediamine, and N-methylaniline.

21. An ion sensor according to claim 20, wherein said redox polymer film further comprises at least one electrolyte selected from the group consisting of, dipotassium-hydrogenphosphate, sodium perchlorate, sulfuric acid, sulfates, tetrafluoroborate, tetraphenylborate, phosphates and phosphoric acid.

22. An ion sensor according to claim 20, wherein said ion carrier substance is a hydrogen ion carrier substance.

23. An ion sensor according to claim 20, wherein said ion carrier substance is a potassium ion carrier substance.

24. An ion sensor according to claim 20, wherein said ion carrier substance is a sodium ion carrier substance.

25. An ion sensor according to claim 20, wherein said ion carrier substance is a calcium ion carrier substance.

26. An ion sensor according to claim 20, wherein said ion carrier substance is a chlorine ion carrier substance.

27. An ion sensor according to claim 20, wherein said ion carrier substance contains at least one electrolyte selected from the group consisting of sodium tetrakis(p-chlorophenyl) borate, and potassiumtetrakis (p-chlorophenyl)borate;

and compounds represented by general formulas;

space="preserve" listing-type="equation">(R.sup.15).sub.4 NBF.sub.4

space="preserve" listing-type="equation">and

space="preserve" listing-type="equation">(R.sup.15).sub.4 NPF.sub.4

(wherein each R¹⁵ is independently an alkyl group).

28. An ion sensor according to claim 20, wherein said ion carrier film comprises a polymeric substance selected from the group consisting of polyvinyl chloride, a vinyl chloride-ethylene copolymer, polyester, polyacrylamide, cellulose-based substances, polyurethane, and silicone resin.

29. An ion sensor according to claim 20, wherein said redox polymer film has a thickness of 0.1 μ

m to 0.2 mm.

30. An ion sensor according to claim 20, wherein said ion carrier film has a thickness of 50 μ

m to 10 mm.

31. An ion sensor according to claim 20, wherein said ion carrier substance is selected from the group consisting of a quaternary ammonium salt of the formula:

##STR18## where R⁹ to R¹¹ are independently alkyl groups having 8 to 18 carbon atoms and X^- is Cl^-, Br^- or OH^- ;

a tertiary amine of the formula ##STR19## where R¹² is phenyl group, methyl group or hydrogen atom, R¹³ is hydrogen atom or methyl group, and R¹⁴ is hydrogen atom, methyl group or octadecyl group; and

the compounds of formulas;

##STR20##

32. An ion sensor according to claim 20, wherein said ion carrier film has a thickness of 300 μ

m to 1 mm.