Electrochemical sensors

• US 5,494,562 A
• Filed: 06/27/1994
• Issued: 02/27/1996
• Est. Priority Date: 06/27/1994
• Status: Expired due to Term

• Current Assignee: Siemens Healthcare Diagnostics Incorporated (Siemens AG)
• Original Assignee: CIBA Vision Corporation (Bayer AG)
• Inventors: Edelman, Peter G., Flaherty, James E., Mason, Richard W., D'Orazio, Paul A., McCaffrey, Robert R., Dalzell, Bonnie C., Maley, Thomas C.
• Primary Examiner(s): Bell, Bruce F.
• Application Number:
  US08/266,824
• Time in Patent Office: 610 Days
• Field of Search: 204/403, 204/402, 204/415, 204/418, 204/412, 435/817, 435/288, 435/291, 128/635, 427/123, 427/122, 427/124, 427/125
• US Class Current: 257/414
• CPC Class Codes: C12Q 1/001 Enzyme electrodes
• CPC Class Codes: C12Q 1/006 for glucose
• CPC Class Codes: Y10S 435/817 Enzyme or microbe electrode
• CPC Class Codes: Y10T 29/49117 Conductor or circuit manufacturing
• CPC Class Codes: Y10T 29/49204 Contact or terminal manufacturing
• CPC Class Codes: Y10T 29/53261 Means to align and advance work part
• CPC Class Codes: Y10T 29/53265 with work-holder for assembly

Abstract

A solid state, multi-use electrochemical sensor having an electrically nonconductive substrate, a working electrode, and a semi-permeable membrane covering the working electrode. The working electrode includes an electrically conductive material adhered to a portion of the substrate. A first portion of the conductive material is covered with an electrically insulating dielectric coating, and a second portion of the conductive material is covered with an active layer. The active layer includes a catalytically active quantity of an enzyme carried by platinized carbon powder particles, which are distributed throughout the active layer. A sensor package for incorporating a sensor is provided.

Claims

1. A solid state, multi-use electrochemical sensor comprising:

an electrically nonconductive substrate;

a working electrode, including an electrically conductive material adhered to a portion of said substrate, a first portion of said conductive material being covered with an electrically insulating dielectric coating, a second portion of said conductive material being covered with an active layer comprising a catalytically active quantity of an enzyme carried by platinized carbon powder particles, said particles being distributed throughout said active layer;

a counter electrode, including a second electrically conductive material adhered to a second portion of said substrate, a portion of said second conductive material being covered with an electrically insulating dielectric coating, and at least one portion of said second conductive material remaining uncovered by said electrically insulating dielectric coating;

a reference electrode, including a third electrically conductive material adhered to a third portion of said substrate, a portion of said third conductive material being covered with an electrically insulating dielectric coating, and at least one portion of said third conductive material remaining uncovered by said electrically insulating dielectric coating; and

a semi-permeable membrane covering said working electrode, said membrane comprising a mixture of silicone and silica.

2. The sensor of claim 1, wherein said substrate is planar and comprises a material selected from the group consisting of ceramics, glasses, refractories, and combinations thereof.

3. The sensor of claim 1, wherein said substrate comprises an alumina composite admixed with a glass binder.

4. The sensor of claim 1, wherein said conductive material comprises a thick-film paste comprising a metal selected from the group consisting of silver, gold, and platinum.

5. The sensor of claim 4, wherein said electrically conductive material comprises a high-purity, thick-film platinum paste.

6. The sensor of claim 1, wherein said second electrically conductive material is a thick-film paste comprising a metal selected from a group consisting of silver, gold and platinum.

7. The sensor of claim 1, wherein said dielectric coating comprises a material selected from the group consisting of ceramics, glasses, polymers, and combinations thereof.

8. The sensor of claim 1, wherein said semi-permeable membrane is an anionically-stabilized, water-based hydroxyl endblocked polydimethysiloxane elastomer comprising about 10.0 percent silica, by weight.

9. The sensor of claim 1, wherein said semi-permeable membrane is an anionically-stabilized, water-based hydroxyl endblocked polydimethysiloxane elastomer comprising about 14.0 percent silica, by weight.

10. The sensor of claim 1, wherein said third electrically conductive material has deposited over it a layer of silver/silver chloride.

11. The sensor of claim 10, wherein said third electrically conductive material has deposited over it cellulose acetate.

12. The sensor of claim 1, wherein said sensor further comprises an interference correcting electrode, including an electrically conductive material adhered to a portion of said substrate, a first portion of said conductive material being covered with said electrically insulating dielectric coating, and a second portion of said conductive material being covered with an inactive layer comprising an inactive protein immobilized onto platinized carbon powder particles, wherein said particles are distributed substantially uniformly throughout said inactive layer.

13. The sensor of claim 1, wherein said electrochemical sensor is a glucose sensor, and said enzyme is glucose oxidase.

14. The sensor of claim 1, wherein said electrochemical sensor is a lactate sensor, and said enzyme is lactate oxidase.

15. A solid state, multi-use glucose sensor, comprising:

an electrically nonconductive substrate;

a working electrode, including an electrically conductive material adhered to a portion of said substrate, a first portion of said conductive material being covered with an electrically insulating dielectric coating, and a second portion of said conductive material being covered with an active layer comprising a catalytically active quantity of glucose oxidase immobilized onto platinized carbon powder particles, said particles being distributed substantially uniformly throughout said active layer;

a counter electrode, including a second electrically conductive material adhered to a second portion of said substrate, a portion of said second conductive material being covered with an electrically insulating dielectric coating, and at least one portion of said second conductive material remaining uncovered by said electrically insulating dielectric coating;

a reference electrode, including a third electrically conductive material adhered to a third portion of said substrate, a portion of said third conductive material being covered with an electrically insulating dielectric coating, and at least one portion of said third conductive material remaining uncovered by said electrically insulating dielectric coating;

an interference correcting electrode, including an electrically conductive material adhered to a portion of said substrate, a first portion of said conductive material being covered with said electrically insulating dielectric coating, and a second portion of said conductive material being covered with an inactive layer comprising an inactive protein immobilized onto platinized carbon powder particles said particles being distributed substantially uniformly throughout said inactive layer; and

a glucose and oxygen-permeable membrane covering said electrodes.

16. The sensor of claim 15, wherein said glucose and oxygen-permeable membrane is an anionically-stabilized, water-based hydroxyl end blocked polydimethysiloxane elastomer comprising about 14.0 percent silica, by weight.

17. A method for forming a solid state, multi-use electrochemical sensor, comprising:

selecting an electrically nonconductive substrate;

depositing an electrically conductive material onto a portion of said substrate;

depositing an active layer over a portion of said conductive material to form a working electrode, wherein said active layer comprises a catalytically active quantity of an enzyme immobilized onto platinized carbon powder particles, which are distributed substantially uniformly throughout said active layer; and

depositing a second electrically conductive material onto a second portion of said substrate to form a counter electrode;

depositing a third electrically conductive material onto a portion of said substrate to form a reference electrode; and

depositing a semi-permeable membrane over said electrodes said membrane comprising a mixture of silicone and silica.

18. The sensor of claim 17, wherein said electrically conductive materials are deposited according to a thick-film silk-screening technique.

19. The sensor as made by the process of claim 17, wherein said sensor is adapted to perform measurements for the lesser of one thousand (1,000) uses or thirty (30) days.

20. The sensor as made by the process of claim 17, wherein said sensor is adapted to perform measurements for the lesser of two thousand (2,000) uses or sixty (60) days.

21. The sensor of claim 20, wherein said third electrically conductive material comprises a silver/silver chloride thick-film paste.

22. The method of claim 17, wherein said semi-permeable membrane is an anionically-stabilized water-based hydroxyl endblocked polydimethylsiloxane elastomer comprising about 14.0 percent silica, by weight.

23. The method of claim 17 further comprising the step of depositing a fourth electrically conductive material onto a portion of said substrate;

depositing said electrically insulating dielectric material over a portion of said fourth conductive material; and

depositing an inactive layer over a second portion of said fourth conductive material to form an interference correcting electrode, wherein said inactive layer comprises an inactive protein immobilized onto platinized carbon powder particles, which are distributed substantially uniformly throughout said inactive layer.

24. In planar electrodes for use in glucose or lactate determinations in vitro, said electrodes each having an insulating base layer, a conductive layer, an overlying active layer and an outer protective membrane permeable to oxygen and glucose or lactate, the improvement comprising:

said active layer comprising an enzyme reactive with one of glucose or lactate, and platinized carbon powder particles, whereby said active layer causes formation of H₂ O₂ in amounts proportional to the amount of said one glucose or lactate when said one of glucose or lactate is exposed to said active layer; and

and said outer protective membrane comprising a silicone compound having an additive incorporated therein for transporting of said oxygen and one glucose or lactate therethrough whereby said electrode enables rapid and accurate determination of said one glucose or lactate concentration.

25. The electrode of claim 24, wherein said silicone compound comprises a hydroxyl endblocked polydimethylsiloxane elastomer.

26. The electrode of claim 24, wherein said membrane has a plurality of thin layers.

27. The electrode of claim 26, wherein said membrane has four layers and a total thickness of less than about 65.0 microns.

28. The electrode of claim 24, wherein said membrane additive includes at least about 10.0 percent silica, by weight.

29. The electrode of claim 24, wherein said membrane comprises an anionically stabilized, water-based hydroxyl endblocked polydimethylsiloxane elastomer comprising about 14.0 percent silica, by weight.

30. The electrode of claim 24, wherein said membrane is post-treated with an anti-drying material to prolong the storage life or wet-up of said electrode.

31. The electrode of claim 30, wherein said anti-drying material is a high boiling point, water soluble, hydrophilic polymer liquid anti-drying agent.

32. The electrode of claim 30, wherein said anti-drying material is polyethylene glycol having a molecular weight of between about 200 and about 600.

33. A solid state, multi-use electrochemical sensor comprising:

an electrically nonconductive substrate;

an electrode, including an electrically conductive material adhered to a portion of said substrate, a first portion of said conductive material being covered with an electrically insulating dielectric coating, a second portion of said conductive material being covered with an active layer comprising a catalytically active quantity of an enzyme carried by platinized carbon powder particles, said particles being distributed throughout said active layer;

an electrode, including a second electrically conductive material adhered to a second portion of said substrate, a portion of said second conductive material being covered with an electrically insulating dielectric coating, and at least one portion of said second conductive material remaining uncovered by said electrically insulating dielectric coating;

an electrode, including a third electrically conductive material adhered to a portion of said substrate, a first portion of said conductive material being covered with an electrically insulating dielectric coating, and a second portion of said conductive material being covered with an inactive layer comprising an inactive protein immobilized onto platinized carbon powder particles, said particles being distributed throughout said inactive layer; and

a semi-permeable membrane covering said working electrode, said membrane comprising a mixture of silicone and silica.