Techniques to improve the performance of electrochemical sensors

• US 5,411,647 A
• Filed: 01/25/1994
• Issued: 05/02/1995
• Est. Priority Date: 11/23/1992
• Status: Expired due to Term

• Current Assignee: Disetronic Licensing Ag
• Original Assignee: Eli Lilly and Company
• Inventors: Mastrototaro, John J., Johnson, Kirk W.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Bell, Bruce F.
• Application Number:
  US08/187,121
• Time in Patent Office: 462 Days
• Field of Search: 204/153.12, 204/402, 204/153.1, 204/412, 204/403, 204/400
• US Class Current: 205/777.5
• CPC Class Codes: C12Q 1/006 for glucose
• CPC Class Codes: G01N 27/3271 Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood amperometry per se G01N27/49; aspects concerning the enzyme reagent C12Q1/001
• CPC Class Codes: G01N 27/38 Cleaning of electrodes

Abstract

A method of improving the utility of electrochemical glucose sensors by decreasing either or both their settling time and their sensitivity to interfering compounds. In particular, the settling time of an electrochemical glucose sensor is improved by pretreating the operating electrode with a negative electric current at a constant current density. The sensor'"'"'s sensitivity to intefering compounds is reduced by operating the sensor at a reduced voltage while the glucose concentration measurement is being made.

Claims

1. A method of reducing the settling time of an electrochemical sensor having one or more electrodes, comprising:

pretreating the electrochemical sensor after placement in a medium by applying a controlled electric current to one or more of the electrodes of the sensor before using the sensor to measure the presence or concentration of a substance of interest;

wherein the controlled current is applied at a density and for a time to reduce the settling time of the electrode to less than about 25 minutes.

2. The method of claim 1 in which the pretreating comprises applying a constant electric current.

3. The method of claim 1 in which the electric current is applied to reduce the settling time of the electrode to less than about 15 minutes.

4. The method of claim 1 wherein the current density is a constant current density between about 0.1 mA/cm² and about 1.0 mA/cm² during said pretreatment.

5. The method of claim 4 wherein the constant current density is approximately 0.5 mA/cm² during said pretreatment.

6. The method of claim 1 wherein the current is applied at a constant density for between about one minute and about ten minutes during said pretreatment.

7. The method of claim 6 wherein the current is applied at a constant density for approximately two minutes during said pretreatment.

8. The method of claim 1 wherein the current is a negative current.

9. A method of measuring the concentration of glucose in a liquid medium, comprising the steps of:

contacting a glucose-containing medium with an electrochemical sensor having an electrode;

pretreating the electrode by applying a controlled electric current to the electrode at a current density and for a time to reduce the settling time of the electrode to less than about 25 minutes; and

subsequently

operating the sensor by applying a constant electric potential to the electrode;

measuring the rate of current change as H₂ O₂ is produced from glucose, oxygen and water at the electrode; and

translating the rate of current change to a value of glucose concentration.

10. The method of claim 9 in which the pretreating comprises applying a constant electric current.

11. The method of claim 9 in which tile electric current is applied to reduce the settling time of the electrode to less than about 15 minutes.

12. The method of claim 11 wherein the current density is a constant density between about 0.1 mA/cm² and about 1.0 mA/cm² during said pretreatment.

13. The method of claim 12 wherein tile constant density is approximately 0.5 mA/cm² during said pretreatment.

14. The method of claim 11 wherein the current is applied at a constant density for between about one minute and about ten minutes during said pretreatment.

15. The method of claim 14 wherein the current is applied at a constant density for approximately two minutes during said pretreatment.

16. The method of claim 11 wherein the current is a negative current.

17. The method of claim 11 wherein said contacting step comprises contacting a glucose-containing medium with an electrochemical sensor having a platinum black working electrode, a platinum black counter electrode, and an Ag/AgCl reference electrode.

18. A method of measuring the concentration of glucose in a liquid medium, comprising the steps of:

contacting a glucose-containing medium with an electrochemical sensor, said sensor having a working electrode, a counter electrode and a reference electrode;

applying an electric potential greater than about 0.10 V and less than about 0.40 V to the working electrode;

measuring the rate of current change as H₂ O₂ is produced from glucose, oxygen and water at the working electrode of the sensor; and

translating the rate of current change to a value of glucose concentration.

19. The method of claim 18 wherein the applied electric potential is approximately +0.35 V.

20. The method of claim 18 wherein the glucose-containing medium also contains interfering compounds.

21. The method of claim 20 wherein the glucose-containing medium also contains acetaminophen as an interfering compound.

22. The method of claim 18 wherein the working electrode is the anode, and the counter electrode is the cathode.

23. The method of claim 18 wherein said contacting step comprises contacting a glucose-containing medium with an electrochemical sensor having a platinum black working electrode, a platinum black counter electrode, and an Ag/AgCl reference electrode.

24. A method of measuring the concentration of glucose in a liquid medium, comprising the steps of:

contacting a glucose-containing medium with an electrochemical sensor having an electrode;

pretreating the electrode by applying a controlled electric current to the electrode at a density and for a time to reduce the settling time of the electrode to less than about 25 minutes; and

subsequently

operating the sensor by applying a constant electric potential greater than about 0.1 V and less than about 0.40 V to the working electrode of the sensor;

measuring the rate of current change as H₂ O₂ is produced from glucose, oxygen and water at the working electrode of the sensor; and

translating the rate of current change to a value of glucose concentration.

25. The method of claim 24 in which the pretreating comprises applying a constant electric current.

26. The method of claim 24 in which the electric current is applied to reduce the settling time of the electrode to less than about 15 minutes.

27. The method of claim 24 wherein the current density is a constant current density between about 0.1 mA/cm² and about 1.0 mA/cm² during said pretreatment.

28. The method of claim 27 wherein the constant current density is approximately 0.5 mA/cm² during said pretreatment.

29. The method of claim 24 wherein the current is applied at a constant density for between about one minute and about ten minutes during said pretreatment.

30. The method of claim 24 wherein the applied electric potential is approximately +0.35 V.

31. The method of claim 24 wherein said contacting step comprises contacting a glucose-containing medium with an electrochemical sensor having a working electrode with glucose oxidase deposited thereon.