Extended use planar sensors

• US 6,068,748 A
• Filed: 08/25/1997
• Issued: 05/30/2000
• Est. Priority Date: 04/09/1993
• Status: Expired due to Term

• Current Assignee: Novartis Ag, Siemens Healthcare Diagnostics Incorporated (Siemens AG)
• Original Assignee: Bayer Corporation (Bayer AG), Novartis Ag
• Inventors: Edelman, Peter G., Berger, Joseph
• Primary Examiner(s): Zitomer, Fred
• Application Number:
  US08/918,204
• Time in Patent Office: 1,009 Days
• Field of Search: 521/27, 204/296, 204/415, 204/418, 204/431, 204/424, 204/426, 526/307.7, 526/297, 526/310, 526/342, 526/319
• US Class Current: 204/426
• CPC Class Codes: C08F 220/14 Methyl esters , e.g. methyl (meth)acrylate
• CPC Class Codes: G01N 27/404 Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid , e.g. Clark-type oxygen sensors
• CPC Class Codes: G01N 33/4925 measuring blood gas content, e.g. O2, CO2 , HCO3
• CPC Class Codes: Y10T 29/49117 Conductor or circuit manufacturing
• CPC Class Codes: Y10T 29/5313 Means to assemble electrical device
• CPC Class Codes: Y10T 29/5317 Laminated device
• CPC Class Codes: Y10T 29/532 Conductor
• CPC Class Codes: Y10T 29/53204 Electrode

Abstract

A planar, solid-state electrochemical oxygen sensor having a substrate, conductive strips deposited on the substrate, and a dielectric layer insulating portions of the conductive strips except those portions which define a working electrode and at least one second electrode. The working electrode may be defined by an open printed region of the dielectric, or by a needle-punched or laser-burned hole or opening in the dielectric which exposes a small region of one of the conduct strips. A solid electrolyte contacting the electrodes is covered by a semipermeable membrane which may comprise an acrylonitrile butadiene copolymer or an acrylate-based copolymer. A sample chamber is defined by the membrane, a cover member, and a gasket therebetween, and has a volume of from about 1 to about 2 μl. The gasket is formulated from the highly cross-linked polymerization product of epichlorohydrin. All sensor components are selected such that a sensor operable for at least 2 days under normal conditions is produced.

Claims

1. A membrane suitable for use with a planar oxygen sensor comprising the polymerization product of:

at least one monomer having the formula CH₂ ═

C(R₁)(COOR₂), where R₁ and R₂ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁ and R₂ can be the same or different;

at least one monomer selected from the group consisting of those having the formulas CH₂ ═

C(R₁)(CONR₂ R₃), CH₂ ═

C(R₁)(OCOR₂), where R₁, R₂, and R₃ are each selected from the group consisting of hydrogen, hydrocarbon groups, and alcohol groups and R₁, R₂, and R₃ can be the same or different; and

at least one nitrile-containing monomer,

wherein the composition is constructed and arranged as a membrane, suitable for use with an electrochemical planar oxygen sensor for separating electrodes from a sample, and having impermeability to liquid water, but rapid permeability to water vapor.

2. A membrane as in claim 1 wherein the membrane comprises the polymerization product of:

at least one monomer having the formula CH₂ ═

C(R₁)(COOR₂), where R₁ is selected from the group consisting of hydrogen and lower allyl groups, R₂ is selected from the group consisting of linear, branched and cyclic hydrocarbons and alcohols of from 1 to 20 carbon atoms, R₁ and R₂ being the same or different, said monomer being present in an amount of from about 20% to about 80% by weight based on the weight of the composition;

at least one nitrile-containing monomer, said nitrile-containing monomer being present in an amount of from about 15% to about 80% by weight; and

at least one monomer selected from the group consisting of those having the formula CH₂ ═

C(R₁)(OCOR₂) where R₁ and R₂ are each selected from the group consisting of hydrogen, lower alkyl groups and lower alcohols and R₁ and R₂ can be the same or different, or those having the formula CH₂ ═

C(R₁)(CONR₂ R₃) where R₁, R₂, and R₃ are each selected from the group consisting of hydrogen and lower alkyl groups and R₁, R₂, and R₃ can be the same or different, and a combination of the two.

3. A membrane as in claim 1 wherein the membrane comprises the polymerization product of:

at least one monomer having the formula CH₂ ═

C(R₁)(COOR₂), where R₁ is selected from the group consisting of hydrogen and lower alkyl groups, R₂ is selected from the group consisting of linear, branched and cyclic hydrocarbons and alcohols of from 1 to 20 carbon atoms, R₁ and R₂ being the same or different, said monomer being present in an amount of from about 40% to about 60% by weight based on the weight of the composition;

at least one nitrile-containing monomer, said nitrile-containing monomer being present in an amount of from about 20% to about 30% by weight; and

at least one monomer having the formula CH₂ ═

C(R₁)(OCOR₂), where R₁ and R₂ are each selected from the group consisting of hydrogen, lower alkyl groups and lower alcohols and R₁ and R₂ can be the same or different, said monomer being present in an amount of from about 15% to about 30% by weight.

4. A membrane as in claim 1 in which the polymerization product possesses pendant side groups in the polymer chains selected to render the membrane impermeable to ions, other blood constituents and liquid water while rendering the membrane permeable to water vapor, and in which the polymerization product possesses pendant side groups in the polymer chains that have sufficient polarity to decrease the free volume which decreases oxygen transport.

5. A membrane as in claim 1, formulated to provide limited oxygen permeability.

6. A membrane as in claim 1, having an oxygen permeability of less than 8 Barrers.

7. A membrane as in claim 6, having an oxygen permeability of from about 0.1 to about 5 Barrers.

8. A membrane as in claim 7, having an oxygen permeability of from about 0.2 to about 3 Barrers.

9. A membrane as in claim 1, having a water vapor permeability of no more than 3 Barrers.

10. A membrane as in claim 1, having an impedance across the membrane of at least 12 megaohms.

11. A membrane as in claim 1, having a glass transition temperature of from bout -40°

C. to about 110°

C.

12. A membrane as in claim 11, having a glass transition temperature of from about -15°

C. to about 85°

C.

13. A membrane as in claim 1, having a standard ASTM Shore A hardness of at least about 20.

14. A membrane as in claim 13, having a standard ASTM Shore A hardness of at least about 50.

15. A membrane as in claim 14, having a standard ASTM Shore A hardness of at least about 70.

16. A membrane as in claim 1, possessing a polymer structure to satisfy both oxygen and water vapor permeability requirements, formed from simple solvent based spin-casting processes.