Amperometric electrochemical ion sensors and method for determining ion concentration

• US 4,929,313 A
• Filed: 01/04/1988
• Issued: 05/29/1990
• Est. Priority Date: 11/23/1984
• Status: Expired due to Fees

• Current Assignee: Massachusetts Institute of Technology
• Original Assignee: Massachusetts Institute of Technology
• Inventors: Wrighton, Mark S.
• Primary Examiner(s): Nguyen, Nam X.
• Application Number:
  US07/140,621
• Time in Patent Office: 876 Days
• Field of Search: 204/403, 204/412, 204/415, 204/416, 204/418, 204/433, 204/1 T
• US Class Current: 205/778.5
• CPC Class Codes: B82Y 10/00 Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• CPC Class Codes: G01N 27/414 Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
• CPC Class Codes: G02F 1/1533 structural features not otherwise provided for
• CPC Class Codes: H01G 7/00 Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
• CPC Class Codes: H10K 10/701 Organic molecular electronic devices
• CPC Class Codes: H10K 71/125 using electrolytic deposition e.g. in-situ electropolymerisation
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/30 Coordination compounds

Abstract

Electrochemical devices constructed according to the present invention can be used to convert an ion flux into an electric current for determination of ion concentration. The devices are operated without the need for a reference electrode and are specific based on known ion transfer agents. Operation of the devices involves the use of pairs of electrodes modified with electroactive redox materials overlaid with ion selective coatings. An applied potential between a pair of appropriately modified electrodes results in the flow of an electric current between the electrodes which is dependent on the concentration of the ion to be sensed.

Devices constructed by combining electrodes overlaid with electroactive polymers and different ion selective films allow simultaneous determination of diverse ions. For example, these devices are useful for measuring the concentration of total cations, total anions, H⁺, Li⁺, K⁺, Ca²⁺, Na⁺, HCO₃^-, Cl^-, other cations and anions, and combinations thereof. The devices are small and stable enough to be used in vivo, for example, as blood monitoring means, or in large scale water quality monitoring or purification/separations techniques.

Claims

1. An amperometric electrochemical sensor comprising:

a pair of electrically conductive electrodes each overlaid with electroactive polymeric material, at least one electrode having an ion-selective coating thereon, wherein said electrodes are electrically connected and said coating actively and selectively transports ions into the electroactive polymeric material effecting a change in the measured current correlated with the concentration of a substance to be measured.

2. The amperometric ion sensor of claim 1 further comprising means for applying a potential between said electrically conductive electrodes and means for measuring current between said electrodes.

3. The amperometric electrochemical ion sensor of claim 1 wherein said electroactive polymeric material is a polymer formed from electrochemically polymerizable redox active polymers.

4. The ion sensor of claim 3 wherein said polymer is selected from the group consisting of polypyrrole, poly-N-methylpyrrole, polythiophene, polyvinylferrocene, and viologens.

5. The ion sensor of claim 1 wherein said ion-selective coating is selective for cations or anions.

6. The ion sensor of claim 5 wherein the coating transmits an ion selected from the group consisting of H⁺, Li⁺, K⁺, Ca²⁺, Na⁺, HCO₃^- and Cl^-.

7. The ion sensor of claim 5 wherein the ion-selective coating is selected from the group consisting of valinomycin, Nafion™

, ionophores, and polyvinylpyridine.

8. The ion sensor of claim 1 further comprising an electrolyte.

9. The ion sensor of claim 1 further comprising additional pairs of electrodes overlaid with a different combination of electroactive polymeric materials and ion-selective coatings.

10. The sensor of claim 1 wherein the ions are the substance to be measured.

11. The sensor of claim 1 wherein the ions are indicative of the substance to be measured.

12. A method for determining ion concentration comprising providing a pair of electrically conductive electrodes each overlaid with electroactive polymeric material, at least one electrode having an ion-selective coating thereon, wherein said electrodes are electrically connected and said coating actively and selectively transports ions into the electroactive polymeric material effecting a change in the measured current correlated with the concentration of a substance to be measured.

13. The method of claim 12 further comprising providing means for applying a potential to said electrically conductive electrodes and measuring the current between said electrodes.

14. The method of claim 13 further comprising applying a potential to the electrically conductive electrodes and calculating the ion concentration from changes in current as a function of the presence of ions in the electroactive polymeric material underlying the ion-selective coating.

15. The method of claim 13 further comprising placing the electrically connected electrodes in an electrolyte and measuring pH.

16. The method of claim 13 further comprising placing the electrically conductive electrodes in a body fluid selected from the group consisting of blood, lymph, tissue extract, and dialysates thereof and measuring the change in current between said electrodes.

17. The method of claim 12 further comprising selecting the ion-selective coating to transmit cations, anions, or a specific ion.

18. The method of claim 17 wherein the coating is selected to transmit an ion selected from the group consisting of H⁺, Li⁺, K⁺, Ca²⁺, Na⁺, HCO₃^- and Cl^-.

19. The method of claim 12 further comprising providing additional pairs of electrodes overlaid with a different combination of electroactive polymeric materials and ion-selective coatings.

20. The method of claim 19 further comprising selecting the electroactive polymeric materials and ion-selective coatings to enable determination of the concentration of total cations, total anions, H⁺, Li⁺, K⁺, Ca² +, Na⁺, HCO₃^-, Cl^- and combinations thereof.

21. The method of claim 20 further comprising applying a potential to the electrically conductive electrodes and calculating ion concentrations from changes in current as a function of the presence of ions in the electroactive polymeric material underlying the ion-selective coatings.

22. The method of claim 12 wherein the ions are the substance to be measured.

23. The method of claim 12 wherein the ions are indicative of the substance to be measured.