Chemical and biological sensors having electroactive polymer thin films attached to microfabricated devices and possessing immobilized indicator moieties

• US 5,766,934 A
• Filed: 10/04/1994
• Issued: 06/16/1998
• Est. Priority Date: 03/13/1989
• Status: Expired due to Fees

• Current Assignee: Allage Associates
• Original Assignee: Allage Associates
• Inventors: Guiseppi-Elie, Anthony
• Primary Examiner(s): Redding, David A.
• Application Number:
  US08/318,494
• Time in Patent Office: 1,351 Days
• Field of Search: 435/287.7, 435/287.8, 435/287.9, 435/817, 204/403, 204/414, 204/415, 204/416, 204/418
• US Class Current: 435/287.9
• CPC Class Codes: C12Q 1/005 involving specific analytes or enzymes including groups of enzymes, e.g. oxydases; C12Q1/004 takes precedence
• CPC Class Codes: C12Q 1/006 for glucose
• CPC Class Codes: Y10S 435/817 Enzyme or microbe electrode

Abstract

Chemical and biological sensors are provided that convert the chemical potential energy of an analyte into a proportionate electrical signal through the transducer action of a microfabricated device with an integral electroconductive polymer film. The microsensor devices possess a coplanar arrangement of at least one, and typically three, microfabricated interdigitated microsensor electrode arrays each with line and space dimensions that may range from 2-20 μm and is typically 10 μm, a platinized platinum counter electrode of area at least 10 times the area of the interdigitated microsensor electrode array and a chloridized silver/silver chloride reference electrode. Chemical and biological sensors constructed according to the present invention employ a thin electrically conducting polymer film that is specifically attached via covalent bond formation to the interdigitated microsensor electrode component of the devices. The electrically conducting polymer film is formed in three layers, the first layer possesses high electrical conductivity and is covalently attached to the device surface, the second layer possess an inorganic catalyst and is covalently attached to the first, and the third layer possesses an indicator molecule which may be a bioactive molecule such as an enzyme or member of specific binding pair of biological origin and is itself covalently attached to the second layer. Binding of an analyte or member of the specific binding pair reagent may result in a change in the electrical impedance (resistance and capacitance or both) of the highly electrically conducting layer. The electrical change in the polymer layers is a sensitive measure of the extent of binding of the binding agent and forms an analytical signal for the binding agent.

Claims

1. A sensor comprising:

a microfabricated chip comprising at least one interdigitated microsensor electrode array, a first electrode of platinized platinum, and a second reference electrode, said first electrode and second reference electrode being coplanar on the chip with said array, said chip further comprising,

an interdigit area that is chemically modified and derivatized to promote adhesion over said interdigitated electrode array,

a first layer of electroactive polymer material formed over the interdigit area, and being covalently attached, adhered, and contiguous with the interdigit area of the chip,

a second layer of electroactive polymer material, including an inorganic catalyst, formed over said first electroactive polymer layer, and

a third layer of electroactive polymer material, including an indicator agent, formed over said second electroactive polymer layer.

2. The sensor of claim 1 wherein said sensor comprises a chemical sensor.

3. The sensor of claim 1 wherein said sensor comprises a biological sensor.

4. The sensor of claim 1 wherein said interdigitated microsensor electrode array comprises gold or platinum.

5. The sensor of claim 1 wherein the reference electrode comprises silver/silver chloride.

6. The sensor of claim 1 wherein said interdigit area is chemically modified using a functional silane which is subsequently derivatized with a polymerizable moiety of pyrrole, thiophene or aniline.

7. The sensor of claim 1 wherein said first electroactive polymer comprises polypyrrole, polythiophene or polyaniline.

8. A sensor of claim 1 comprising three interdigitated microsensor electrode arrays, each with line and space dimensions which range from about 2 to 20 μ

m, a platinized platinum counter electrode having an area of at least 10 times the area of the interdigitated microsensor electrode array, and a reference electrode of chloridized silver/silver chloride (Ag°

/AgCl).

9. A sensor of claim 1 wherein the interdigitated microsensor electrode array comprises ten (10) opposing digit pairs, each digit being about 2.999 mm long with 10 μ

m line and space dimensions.

10. The sensor of claim 1 wherein the interdigit areas are chemically modified with 3-aminopropyltrimethoxysilane and the free primary amine derivatized by direct linking of the 1°

amine of the silane to the carboxylic acid group of 3-(1-pyrrolyl)propionic acid.

11. The sensor of claim 1 wherein the inorganic catalyst is drawn form the class containing Mo₇ O₂₄^6- (Mo^VI).

12. The sensor of claim 1 in which the indictor agent is drawn from the class containing enzymes or member of a specific binding pair reagent.

13. A chemical sensor comprising:

a microfabricated chip comprising a plurality of interdigitated microsensor electrode arrays, a first electrode of platinized platinum, and a second reference electrode, said first electrode and second reference electrode being coplanar on the chip with said arrays, said chip further comprising,

an interdigit area that is chemically modified with a functional silane and derivatized to promote adhesion over said interdigitated electrode arrays,

a first layer of electroactive polymer material formed over the interdigit area, and being covalently attached, adhered, and contiguous with the interdigit area of the chip,

a second layer of electroactive polymer material, including an inorganic catalyst, formed over said first electroactive polymer layer, and

a third layer of electroactive polymer material, including an indicator agent, formed over said second electroactive polymer layer.

14. A biological sensor comprising:

a microfabricated chip comprising a plurality of interdigitated microsensor electrode arrays, a first electrode of platinized platinum, and a second reference electrode, said first electrode and second reference electrode being coplanar on the chip with said array, said chip further comprising,

an interdigit area that is chemically modified and derivatized to promote adhesion over said interdigitated electrode array,

a first layer of electroactive polymer material formed over the interdigit area, and being covalently attached, adhered, and contiguous with the interdigit area of the chip,

a second layer of electroactive polymer material, including an inorganic catalyst, formed over said first electroactive polymer layer, and

a third layer of electroactive polymer material, including an indicator agent, formed over said second electroactive polymer layer.