Potentiometric electrochemical device for qualitative and quantitative analysis

• US 5,376,254 A
• Filed: 05/14/1993
• Issued: 12/27/1994
• Est. Priority Date: 05/14/1993
• Status: Expired due to Fees

• Current Assignee: Arkady V. Fisher
• Original Assignee: Arkady V. Fisher
• Inventors: Fisher, Arkady V.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Bell, Bruce F.
• Application Number:
  US08/062,962
• Time in Patent Office: 592 Days
• Field of Search: 204/416, 204/403, 204/435, 435/817, 422/82.03
• US Class Current: 204/403.01
• 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: Y10S 435/817 Enzyme or microbe electrode

Abstract

An ion sensitive electrode device which consists of one or more ion-pairs distributed in at least one of two or more immiscible phases consisting of an aqueous phase, an organic phase, a polymer phase or a solid electrolyte phase. A reference solution includes an aqueous solution of the ion-pair and a high concentration of a micelle former such as an anionic or cationic detergent or a ligand. The device can be used to measure organic and inorganic compounds or can be readily modified by the addition of a biological material to the reference solution for the bioassay for bioorganic compounds.

Claims

1. An improved ion selective electrode device for the potentiometric determination inorganic, organic and biological compounds in a liquid, said electrode comprising:

a. a reference electrode portion comprising a hollow electrode body in which is disposed an electrode in electrical communication with means for indicating potential and an electrolyte surrounding said electrode, said electrode portion including an electrically conductive bridge;

b. an ion selective portion comprising a hollow body defining an interior, said interior including at least two immiscible phases selected from the group consisting of an reference solution phase comprising an aqueous solution of a micelle forming agent and an ion pair, an organic phase and a polymer composite phase, at least one of said organic and polymer composite phases containing an ion-pair; and

c. said ion selective portion being affixed to said reference electrode portion for electrical communication between one of said phases and said reference electrode portion through said bridge.

2. The ion selective electrode of claim 1 wherein said micelle forming agent is selected from the group consisting of ligands, anionic detergents, cationic detergents and combinations thereof.

3. The ion selective electrode of claim 2 wherein said reference solution comprises an aqueous detergent solution.

4. The ion selective electrode of claim 1 wherein said ion-pair is present in said organic phase.

5. The ion selective electrode of claim 1 wherein said ion-pair comprises molecules having an association constant on the order of 1×

10⁶ to about 1×

10¹⁷.

6. The ion selective electrode device of claim 1 wherein said ion-pair consists of lauryl sulfate and crystal violet.

7. The ion selective electrode device of claim 6 wherein said ion pair is present in said reference solution phase in the ratio of 4 mols of lauryl sulfate to 3 mols of crystal violet.

8. The ion selective electrode of claim 1 wherein said organic phase is a solid.

9. The ion selective electrode device of claim 8 wherein said ion pair is present in said organic phase in the ratio of 4 mols of lauryl sulfate to 3 mols of crystal violet.

10. The ion selective electrode of claim 8 wherein said micelle forming agent is a detergent having an association constant on the order of 1×

10⁶ to about 1×

10¹⁷ and an alkyl chain of between 7 and 13 carbon atoms.

11. The ion selective electrode of claim 10 wherein said detergent is lauryl sulfate.

12. The ion selective electrode of claim 1 wherein said organic phase is a liquid.

13. The ion selective electrode device of claim 1 wherein said device is adapted for use as a biosensor for the determination of a biological substance by the incorporation in said reference solution phase of a substance which is responsive to said biological substance being determined.

14. The ion selective electrode of claim 1 wherein said aqueous reference solution phase comprises said ion-pair in an aqueous detergent solution, said detergent having a concentration of between about 1×

10^-2 and 5×

10^-3 mols/l.

15. The ion selective electrode device of claim 14 wherein said biological substance being determined is E. coli and said reference solution contains E. coli antibody.

16. The ion selective electrode device of claim 13 wherein said reference solution contains about 1.38×

10^-8 of E. coli antibody and said electrode detects E. coli bacteria in the range of between about 1×

10⁴ and about 1×

10¹⁰ of said bacteria.

17. The ion selective electrode of claim 1 wherein said polymer composite phase comprises at least one of:

b. a liquid organic component consisting of an organic solvent distributed throughout the polymer matrix;

c. a liquid crystal component consisting of a liquid crystal compound distributed throughout the polymer matrix; and

d. a solid electrolyte component consisting of an electrolyte distributed throughout the polymer matrix.

18. The ion selective electrode of claim 17 wherein said polymer is selected from the group consisting of polyethylene, polypropylene and the halogen substituted products thereof.

19. The ion selective electrode device of claim 17 wherein said polymer composite phase incorporates a liquid crystal compound selected from the group consisting of nematic and cholesteric compound.

20. The ion selective electrode device of claim 17 wherein said liquid crystal compound comprises said ion-pair.

21. The ion selective electrode device of claim 17 wherein said polymer composite phase further includes a liquid polymer component comprising a matrix of polyfluoroethylene in which nitrobenzene is dispersed.

22. The ion selective electrode device of claim 17 wherein said polymer composite phase further includes a solid electrolyte component consisting of liquid organic phase dispersed throughout said polymer matrix.

23. The ion selective electrode of claim 17 wherein said polymer composite phase consists of a fluoropolymer having air pockets dispersed therethrough.

24. The ion selective electrode of claim 23 wherein said fluoropolymer is fluoroethylene.

25. The ion selective electrode of claim 23 wherein said air pockets are filled with an electrolyte solution thereby to lower the electrical resistance of said polymer composite phase.

26. The ion selective electrode device of claim 1 wherein said body of said electrode includes means for the ingress and egress of said reference solution phase whereby said reference solution phase is added and withdrawn from said electrode body.

27. The ion selective electrode of claim 1 wherein said electrode body further includes a separate reservoir in communication with said liquid organic phase and means for causing the transport of liquid organic phase between said reservoir and said electrode body.

28. The ion selective electrode device of claim 1 wherein said liquid organic phase comprises nitrobenzene in which said ion-pair is dissolved.

29. The ion selective electrode of claim 1 wherein said electrode body comprises two electrode portions, a first portion comprising said reference solution phase said first portion being connected at one end to said reference electrode and closed at the opposite end by said polymer composite phase and a second removable portion comprising a second hollow body comprising at least said polymer composite phase, said second portion being adapted for removable connection to said first portion, said polymer composite phase closing said first electrode portion providing electrical communication between said first and said second electrode portions.

30. The ion selective electrode of claim 1 wherein a portion of said body of said electrode is U-shaped thereby to reduce leakage of said ion-pair from one phase to another phase.

31. A reference solution for an ion sensitive electrode comprising an aqueous solution of an ion-pair and a micelle forming agent selected from the group consisting of ligands, anionic detergents, cationic detergents and combinations thereof.

32. The reference solution of claim 31 wherein the concentration of micelle former in the reference solution is between about 1×

10^-2 and 5×

10^-3 mols/l.

33. The reference solution of claim 31 wherein said micelle former is a detergent selected from the group consisting of anionic and cationic detergent compositions having an alkyl chain of between 7 and 13 carbon atoms.

34. The reference solution of claim 33 wherein said detergent composition is selected from the group of detergent compositions consisting of sulfonates, sulfoethers and phosphoric ethers having an alkyl chain of between 10 and 12 carbon atoms.

35. The reference solution of claim 31 further including a substance interactive with a material to be determined whereby said reference solution is responsive to the presence of said material to be determined.

36. The reference solution of claim 35 wherein said substance is E. coli bacterium.