Ion sensor

• US 5,472,590 A
• Filed: 12/13/1994
• Issued: 12/05/1995
• Est. Priority Date: 12/15/1993
• Status: Expired due to Fees

• Current Assignee: Hitachi, Ltd.
• Original Assignee: Hitachi, Ltd.
• Inventors: Watanabe, Yoshio, Miyahara, Yuji, Ozawa, Satoshi, Yamashita, Koutarou, Fujii, Toshiko, Taki, Mamoru
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Bell, Bruce F.
• Application Number:
  US08/354,643
• Time in Patent Office: 357 Days
• Field of Search: 204/415, 204/418, 204/419, 204/416, 204/403, 204/409, 422/82.03
• US Class Current: 257/253
• 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
• CPC Class Codes: G01N 27/414 Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS

Abstract

An ion sensor having an ion selectivity, which comprises an internal electrode of metal/metal salt, composed of an electroconductive layer of at least one metal and a layer of an insoluble salt of the metal in contact with the electroconductive layer, an ion selective membrane whose supporting membrane is composed of a hydrophobic polymer, and an intermediate layer capable of keeping water molecules, provided between the internal solid electrode and the ion selective membrane, where the organic compound having a water-keeping property is polymethylene glycol, polyethylene glycol or polypropylene glycol, each having a molecular weight of 200 to 600, and the inorganic compound having a water-keeping property is calcium chloride, gold chloride, magnesium perchlorate, magnesium fluoride or vanadium chloride dioxide, is suitable for analysis of specific ion species in a biological fluid with practically prolonged maintenance of properties of electrode.

Claims

1. An ion sensor having an ion selectivity, which comprises an internal solid electrode of metal/metal salt, comprising of an electroconductive layer of at least one metal and a layer of an insoluble salt of the metal in contact with the electroconductive layer, an ion selective membrane whose supporting membrane comprises a hydrophobic polymer, and an intermediate layer which keeps water molecules, provided between the internal solid electrode and the ion selective membrane, the intermediate layer comprises of dried residues of an aqueous solution comprising an inorganic compound having a water-keeping property or an organic compound having a water-keeping property, a hydrophilic polymer and an inorganic salt.

2. An ion sensor according to claim 1, where the inorganic compound is an inorganic salt having water of crystallization.

3. An ion sensor according to claim 2, wherein the inorganic salt is calcium chloride, gold chloride, magnesium perchlorate, magnesium fluoride or vanadium chloride dioxide.

4. An ion sensor according to claim 1, wherein the organic compound forms a hydrogen bond with water molecules.

5. An ion sensor according to claim 4, wherein the organic compound has a characteristic group of nitroso, sulfonic acid, alcohol or hydrazine.

6. An ion sensor according to claim 5, wherein the organic compound is selected from the group consisting of ethylene glycol, glycerol, N,N-dimethylhydrazine, 2-aminoethanol, 2-cyanopropionic acid and phenol-2,4-disulfonic acid.

7. An ion sensor according to claim 1, wherein the organic compound is a poly(alkyl oxide) having a molecular weight of 200 to 600, represented by the following chemical formula:

space="preserve" listing-type="equation">HO[(CH.sub.2).sub.n O].sub.m H

wherein n and m are each ≧

1.

8. An ion sensor according to claim 7, wherein the poly(alkyl oxide) is selected from the group consisting of polymethylene glycol, polyethylene glycol and polypropylene glycol.

9. An ion sensor according to claim 1, wherein the inorganic salt has a concentration in terms of a ratio to the hydrophilic polymer of 0.1 to 2 by weight and the organic compound having a water-keeping property has a concentration in terms of a ratio to the hydrophilic polymer of 0.1 to 5 by weight.

10. An ion sensor according to claim 1, wherein the inorganic compound having a water-keeping property has a concentration in terms of a ratio to the hydrophilic polymer of 0.1 to 10 by weight.

11. An ion sensor according to claim 1, wherein the hydrophilic polymer is poly(vinyl alcohol) and the organic compound having a water-keeping property is a poly(alkyl oxide) having a molecular weight of 200 to 600.

12. An ion sensor according to claim 11, wherein the hydrophilic polymer is poly(vinyl alcohol) and the organic compound having a water-keeping property is polyethylene glycol having a molecular weight of 600.

27. An ion sensor according to any one of claims 1, 13, 20, 21 and 22, wherein the insoluble salt of the internal solid electrode has an anion selected from the group consisting of halide ion, tetraphenylborate ion, tetraphenylborate derivative ion, tetraalkylborate ion and tetraalkylborate derivative ion.

28. An ion sensor according to any one of claims 1, 13, 20, 21 and 22, wherein the hydrophilic polymer is selected from the group consisting of poly(vinyl alcohol), polyethylene oxide, polypropylene oxide, polyacrylic acid salt, polymethacrylic acid salt, polystyrene sulfonic acid salt, carboxymethyl cellulose and a derivative thereof.

29. An ion sensor according to any one of claims 1, 13, 20, 21 and 22, wherein a plurality of the ion sensors are provided along a path through which a liquid sample is passed, where the ion selective membranes of the respective ion sensors are in contact with the liquid sample.

13. An ion sensor having an ion selectivity, which comprises an internal solid electrode of metal/metal salt, comprising of an electroconductive layer of at least one metal and a layer of an insoluble salt of the metal in contact with the electroconductive layer, an ion selective membrane whose supporting membrane comprises a hydrophobic polymer, and an intermediate layer which keeps water molecules, provided between the internal solid electrode and the ion selective membrane, the intermediate layer comprises dried residues of an aqueous solution comprising a mixture of a hydrophilic polymer, an inorganic salt, an inorganic compound having a water-keeping property and an organic compound having a water-keeping property.

14. An ion sensor according to claim 13, wherein the inorganic salt has a concentration in terms of a ratio to the hydrophilic polymer of 0.1 to 2 by weight and the organic compound having a water-keeping property has a concentration in terms of a ratio to the hydrophilic polymer of 0.1 to 5 by weight.

15. An ion sensor according to claim 13, wherein the inorganic compound having a water-keeping property has a concentration in terms of a ratio to the hydrophilic polymer of 0.1 to 10 by weight.

16. An ion sensor according to claim 13, wherein the hydrophilic polymer is poly(vinyl alcohol) and the organic compound having a water-keeping property is poly(alkyl oxide) having a molecular weight of 200 to 600.

17. An ion sensor according to claim 13, wherein the hydrophilic polymer is poly(vinyl alcohol) and the organic compound having a water-keeping property is polyethylene glycol having a molecular weight of 600.

18. An ion sensor according to claim 13, wherein the inorganic salt is calcium chloride, gold chloride, magnesium perchlorate, magnesium fluoride or vanadium chloride dioxide.

19. An ion sensor according to claim 16, wherein the poly(alkyl oxide) is selected from the group consisting of polyethylene glycol, polyethylene glycol and polypropylene glycol.

20. An ion sensor having an ion selectivity, which comprises an internal solid electrode of metal/metal salt, comprising an electroconductive layer of at least one metal and a layer of an insoluble salt of the metal in contact with the electroconductive layer, an ion selective membrane whose supporting membrane comprises a hydrophobic polymer, and an intermediate layer which keeps water molecules, provided between the internal solid electrode and the ion selective membrane, the intermediate layer comprises dried residues of an aqueous solution comprising an inorganic compound having a water-keeping property or an organic compound having a water-keeping property, a hydrophilic polymer and an inorganic salt, where the organic compound having a water-keeping property is selected from the group consisting of polymethylene glycol, polyethylene glycol and polypropylene glycol and has a molecular weight of 200 to 600, and the inorganic compound having a water-keeping property is selected from the group consisting of calcium chloride, gold chloride, magnesium perchlorate, magnesium fluoride and vanadium chloride dioxide.

21. An ion sensor having an ion selectivity, which comprises an internal solid electrode of metal/metal salt, comprising of an electroconductive layer of at least one metal and a layer of an insoluble salt of the metal in contact with the electroconductive layer, an ion selective membrane whose supporting membrane comprises a hydrophobic polymer, and an intermediate layer which keeps water-molecules, provided between the internal solid electrode and the ion selective membrane, the intermediate layer comprises dried residues of an aqueous solution comprising a hydrophilic polymer, an inorganic salt and a polymer of hydrazine derivative represented by the following chemical formula:

##STR3## where R and R'"'"' are hydrogen atoms, alkyl groups or hydroxyl groups and n>

1.

22. An ion sensor having an ion selectivity, which comprises an internal solid electrode of metal/metal salt, comprising an electroconductive layer of at least one metal and a layer of an insoluble salt of the metal in contact with the electroconductive layer, an ion selective membrane whose supporting membrane comprises a hydrophobic polymer, and an intermediate layer which keeps water molecules, provided between the internal solid electrode and the ion selective membrane, the intermediate layer comprises dried residues of an aqueous solution comprising a chain compound or a cyclic compound having at least one double bond and containing at least one nitrogen atom, and a hydrophilic polymer.

23. An ion sensor according to claim 22, wherein the chain compound or the cyclic compound is pyridine, pyridazine, pyrazine, s-triazine, quinoline, isoquinoline, isoquinoline, quinoxaline, acridine or a derivative thereof.

24. An ion sensor according to claim 22, wherein the intermediate layer further contains an inorganic salt, selected from the group consisting of calcium chloride, gold chloride, magnesium perchlorate, magnesium fluoride and vanadium chloride dioxide.

25. An ion sensor according to claim 24, wherein the chain compound or the cyclic compound and the inorganic salt are each in a ratio to the hydrophilic polymer of 1 to 5% by weight.

26. An ion sensor according to claim 22, wherein the intermediate layer further contains an inorganic salt selected from the group consisting of calcium chloride, gold chloride, magnesium perchlorate, magnesium fluoride and vanadium chloride dioxide, and the chain compound or the cyclic compound is pyridine, pyridazine, pyrazine, s-triazine, quinoline, isoquinoline, isoquinoline, quinoxaline, acridive or a derivative thereof.

30. An ion sensitive field effect transistor, which comprises a substrate, source and drain formed on the substrate, an insulation membrane covering the sources and the drains, and an ion selective membrane whose supporting membrane comprises a hydrophobic polymer, and an intermediate layer provided between the insulation membrane and the ion selective membrane, the intermediate layer comprises dried residues of one of an aqueous solution comprising an inorganic compound having a water-keeping property or an organic compound having a water-keeping property, a hydrophilic polymer and an inorganic salt;

an aqueous solution comprising a mixture of a hydrophilic polymer, an inorganic salt, an inorganic compound having a water-keeping property and an organic compound having a water-keeping property;

an aqueous solution comprising an inorganic compound having a water-keeping property or an organic compound having a water-keeping property, a hydrophilic polymer and an inorganic salt, where the organic compound having a water-keeping property is selected from the group consisting of polymethylene glycol, polyethylene glycol and polypropylene glycol and has a molecular weight of 200 to 600, and the inorganic compound having a water-keeping property is selected from the group consisting of calcium chloride, gold chloride, magnesium perchlorate, magnesium fluoride and vanadium chloride dioxide;

an aqueous solution comprising a hydrophilic polymer, an inorganic salt and a polymer of hydrazine derivative represented by the following chemical formula;

##STR4## where R and R'"'"' are hydrogen atoms, alkyl groups or hydroxyl groups and n≧

1; and

an aqueous solution comprising a chain compound or a cylic compound having at least one double bond and containing at least one nitrogen atom and a hydrophilic polymer.