Electrodes with multilayer membranes and methods of making the electrodes

• US 6,746,582 B2
• Filed: 05/11/2001
• Issued: 06/08/2004
• Est. Priority Date: 05/12/2000
• Status: Active Grant

• Current Assignee: Abbott Diabetes Care Incorporated (Abbott Laboratories Incorporated)
• Original Assignee: Therasense Incorporated (Abbott Laboratories Incorporated)
• Inventors: Friedman, Keith A., Chen, Ting, Heller, Adam
• Primary Examiner(s): NOGUEROLA, ALEXANDER STEPHAN
• Application Number:
  US09/854,310
• Publication Number:
  US 20010054319A1
• Time in Patent Office: 1,124 Days
• Field of Search: 204/403.04, 204/403.05, 204/418, 204/403.06, 422/52, 422/56, 422/57, 422/82.05, 422/82.06, 427/2.13, 205/778, 205/793
• US Class Current: 204/403.06
• 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

Abstract

A sensor including a sensing layer is disposed over an electrode or an optode and a layer-by-layer assembled mass transport limiting membrane disposed over the sensing layer. The membrane includes at least one layer of a polyanionic or polycationic material. The assembled layers of the membrane are typically disposed in an alternating manner. The sensor also optionally includes a biocompatible membrane.

Claims

1. A sensor, comprising:

a sensing layer comprising an osmium redox polymer disposed on a substrate;

a multilayer flux-limiting membrane comprising a first layer, any subsequent layers, and a polyanionic last layer disposed over the sensing layer, the first layer disposed on and binding to the sensing layer, at least one of the first layer and any subsequent layer being polycationic and comprising pyridine, each layer disposed on and bound to the immediately preceding layer of the membrane.

2. The sensor of claim 1, wherein the sensor has an active area of 0.1 cm² or less.

3. The sensor of claim 1, wherein the active area is in a range of 10⁻

2 cm² to 10<sup>−

8</sup> cm².

4. The sensor of claim 1, wherein the active area is in a range of 10⁻

3 cm² to 10<sup>−

6</sup> cm².

5. The sensor of claim 1, wherein the sensing layer comprises an enzyme.

6. The sensor of claim 1, wherein the substrate comprises an electrode upon which the sensing layer is disposed.

7. The sensor of claim 1, wherein the substrate comprises an optical fiber upon which the sensing layer is disposed.

8. The sensor of claim 7, wherein the sensing layer is disposed on a tip of the optical fiber.

10. The sensor of claim 1, wherein the multilayer membrane comprises the polycationic layer adjacent the polyanionic last layers.

11. The sensor of claim 1, wherein the sensor is adapted for implantation of at least a portion of the sensor in an animal.

12. The sensor of claim 1, wherein the sensor is adapted for subcutaneous implantation of at least a portion of the sensor in an animal.

13. The sensor of claim 1, further comprising a biocompatible layer disposed over the multilayer membrane.

14. The sensor of claim 1, wherein at least one of the layers of the multilayer membrane comprises functional groups that can capture transition metal ions.

15. The sensor of claim 1, wherein the membrane is configured and arranged to reduce flux of an analyte to the sensing layer.

16. The sensor of claim 1, wherein the membrane is configured and arranged to reduce flux of at least one interferent to the sensing layer.

17. The sensor of claim 1, wherein the multilayer membrane comprises the first layer, the last layer, and one subsequent layer.

18. The sensor of claim 1, wherein the multilayer membrane comprises the first layer, the last layer, and at least four subsequent layers.

9. The sensor of clam 1, wherein the osmium redox polymer comprises a non-leachable redox compound.

19. A method of making a sensor, the method comprising steps of:

disposing a sensing layer on a surface; and

forming a membrane over the sensing layer by chemisorbing, in an alternating and binding manner, at least three layers alternating between polyanionic layers and polycationic layers comprising pyridine, with a last layer being a polyanionic layer.

20. The method of claim 19, further comprising disposing a biocompatible layer over the membrane.

21. A method of making a sensor, the method comprising steps of:

disposing a sensing layer on a substrate;

disposing and binding a first membrane layer on the sensing layer;

optionally disposing one or more subsequent membrane layers on the first membrane layer; and

disposing a polyanionic last membrane layer,

wherein at least one of the first membrane layer and any optional subsequent membrane layer is polycationic and comprises pyridine.

22. The method of claim 21, wherein the membrane layers are bound to the sensing layer or any protecting membrane layer by chemisorption or reactive adsorption.

23. The method of claim 22, further comprising rinsing after disposing at least one of the first membrane layer or any subsequent membrane layers.