Conductive organic sensors, arrays and methods of use

• US 8,394,330 B1
• Filed: 10/01/1999
• Issued: 03/12/2013
• Est. Priority Date: 10/02/1998
• Status: Expired due to Term

• Current Assignee: California Institute of Technology
• Original Assignee: California Institute of Technology
• Inventors: Lewis, Nathan S., Grubbs, Robert, Lewis, Carol, Sotzing, Gregory Allen
• Primary Examiner(s): Soderquist, Arlen
• Application Number:
  US09/409,644
• Time in Patent Office: 4,911 Days
• Field of Search: 422/88, 422/90, 422/98, 204/403, 73/232, 73/233, 73/233.1, 73/233.4, 73/290.1, 73/310.1, 73/310.5, 733/350.5
• US Class Current: 422/98
• CPC Class Codes: G01N 27/126 comprising organic polymers
• CPC Class Codes: G01N 33/0031 comprising two or more sensors, e.g. a sensor array electrochemical electrode arrays G01N27/27
• CPC Class Codes: G01N 33/497 of gaseous biological material, e.g. breath

Abstract

The present invention provides a class of sensors prepared from regions of conducting organic materials and conducting materials that show an increase sensitivity detection limit for amines. The present class of sensors have applications in the detection of spoiled food products and in testing for diseases, such as cholera and lung cancer, which have amines as biomarkers.

Claims

1. A sensor, comprising:

at least two conductive leads;

a sensing area comprising alternating regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black disposed between, and in contact with, the at least two conductive leads, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the sensing area provides an electrical path through the regions of the conductive organic polymer material and the inorganic conductive material or carbon black, and wherein the sensing area is in direct contact with a vapor comprising an analyte to be detected, wherein the inorganic conductive material is selected from the group consisting of an inorganic conductor, and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal, a metal alloy, a metal oxide, a superconductor, or a combination thereof and wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increase; and

an apparatus in electrical communication with the conductive leads for detecting a change in the sensing area between the at least two conductive leads when contacted with an analyte.

2. The sensor according to claim 1, wherein the conductive organic polymer material is selected from the group consisting of a polyaniline, an emeraldine salt of polyaniline, a polypyrrole, a polythiophene, a polyEDOT, and derivatives thereof.

3. The sensor according to claim 1, further comprising an insulator or plasticizer.

4. The sensor of claim 1, wherein the conductive organic polymer material is an emeraldine salt of polyaniline and the sensor comprises carbon black.

5. The sensor of claim 1, wherein the conductive organic polymer material is a doped polyaniline and the sensor comprises carbon black.

6. A sensor, comprising:

at least two conductive leads;

a sensing area comprising alternating interpenetrating regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black disposed between and in contact with the at least two conductive leads, wherein the regions of inorganic conductive organic material or carbon black are separated by about 10-1000 angstroms, wherein the sensing area provides an electrical path through the regions of the conductive organic polymer material and the regions of the inorganic conductive material or carbon black, and wherein the sensing area is in direct contact with a vapor comprising an analyte to be detected, wherein the inorganic conductive material is selected form the group consisting of an inorganic conductor and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal, a metal alloy, a metal oxide, or a superconductor, or a combination thereof and wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases; and

an apparatus in electrical communication with the conductive leads for detecting a change in the sensing area between the at least two conductive leads when contacted with an analyte.

7. A sensor, comprising:

at least two conductive leads;

a sensing area comprising dispersed regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black wherein the dispersed regions provide interpenetrating regions of the conductive organic polymer material and an inorganic conductive material or carbon black, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, the sensing area disposed between and in contact with the at least two conductive leads, wherein the sensing area provides an electrical path through the regions of the conductive organic polymer material and the regions of the inorganic conductive material or carbon black, and wherein the sensing area is in direct contact with a vapor comprising an analyte to be detected, wherein the inorganic conductive material is selected from the group consisting of an organic conductor, an organic complex, an inorganic conductor and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal, a metal alloy, a metal oxide, or a superconductor, or a combination thereof and wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases; and

an apparatus in electrical communication with the conductive leads for detecting a change in the sensing area between the at least two conductive leads when contacted with an analyte.

8. A sensor, comprising:

at least two conductive leads;

a sensing area comprising alternating interpenetrating regions of a doped or undoped polyaniline or an emeraldine salt of polyaniline and an inorganic conductive material disposed between, and in contact with, the at least two conductive leads, wherein the regions of the inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the sensing area provides an electrical path through the alternating interpenetrating regions of polyaniline or emeraldine salt of polyaniline and the inorganic conductive material; and

an apparatus in electrical communication with the conductive leads for detecting a change in the sensing area between the at least two conductive leads when contacted with an analyte.

9. The sensor of claim 8, wherein the inorganic conductive material is selected from the group consisting of an inorganic conductor, and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal, a metal alloy, a metal oxide, an oxidized metal, a superconductor, and any combination thereof.

10. A sensor array comprising:

a plurality of sensors, wherein at least one sensor comprises;

at least two conductive leads;

a sensing area comprising alternating interpenetrating regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black disposed between an in contact with the at least two conductive leads, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the sensing area provides an electrical path through the alternating interpenetrating regions of the conductive organic polymer material and the regions of the inorganic conductive material or carbon black, wherein the sensing area is in direct contact with a vapor comprising an analyte to be detected, wherein the inorganic conductive material is selected from the group consisting of an an inorganic conductor and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal, a metal alloy, a metal oxide, or a superconductor, or a combination thereof and wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases.

11. The sensor array according to claim 10, wherein the sensor array comprises a plurality of sensors each comprising regions of a conductive organic polymer material and regions of an inorganic conductive material or carbon black wherein the conductive organic polymer material of at least one sensor is different from the conductive organic polymer material of at least one other sensor.

12. The sensor array according to claim 10, wherein the conductive organic polymer material is selected from the group consisting of a polyaniline, an emeraldine salt of polyaniline, a polypyrrole, a polythiophene, and a polyEDOT, and the inorganic conductive material is selected from the group consisting of Ag, Au, Cu, Pt, and AuCu.

13. The sensor array according to claim 10 or 12, further comprising a temperature control apparatus in thermal communication with at least one sensor.

14. The sensor array according to claim 10 or 12, further comprising an apparatus for detecting a change selected from the group consisting of resistance, conductance, impedance, and capacitance in the electrical properties of at least one sensor.

15. The sensor array according to claim 14, further comprising a temperature control apparatus in thermal communication with at least one sensor.

16. The sensor array according to claim 10, wherein the inorganic conductive material is selected from the group consisting of Ag, Au, Cu, Pt, and AuCu.

17. The sensor array according to claim 10, wherein the sensor comprises carbon black.

18. The sensor array according to claim 10, wherein the inorganic conductive material is a member selected from the group consisting of a metal, a metal alloy, a metal oxide, an organic complex, a superconductor, and a mixed inorganic/organic conductor.

19. The sensor array according to claim 10, wherein the inorganic conductive material is a particle.

20. The sensor array of claim 10, wherein the plurality of sensors comprise at least two conductive leads and a sensing area comprising alternating interpenetrating regions of a conductive organic polymer material and an inorganic conductive material or carbon black disposed between and in electrical communication with the at least two conductive leads.

21. The sensor array according to claim 20, wherein the conductive organic polymer material of one sensor of the plurality of sensors is compositionally different than at least one other sensor of the plurality of sensors.

34. The sensor array system according to claim 14 or 32, wherein the change in electrical properties is a change in an electrical impedance.

35. The sensor array system according to claim 34, further comprising a temperature control apparatus in thermal communication with at least one sensor.

22. A sensor array comprising:

a plurality of sensors, wherein at least one sensor comprises;

at least two conductive leads;

a sensing area comprising alternating interpenetrating regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black disposed between, and in contact with, the at least two conductive leads, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the sensing area provides an electrical path through the regions of the conductive organic polymer material and the regions of the inorganic conductive material or carbon black, wherein the sensing area is in direct contact with a vapor comprising an analyte to bet detected, wherein the inorganic conductive material is selected form the group consisting of an inorganic conductor, and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal a metal alloy, a metal oxide, a superconductor, or a combination thereof, wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases; and

a measuring apparatus electrically coupled to the at least two conductive leads for detecting a change in the sensing area when contacted with an analyte.

23. A sensor array comprising:

a plurality of sensor wherein at least one sensor comprise alternating interpenetrating regions of a doped or undoped conductive organic polymer material and regions of an inorganic conductive material or carbon black wherein the sensors are in direct contact with a vapor comprising an analyte to be detected, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the inorganic conductive material is selected form the group consisting of an inorganic conductor, and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal a metal alloy, a metal oxide, a superconductor, or a combination thereof, wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases; and

means, electrically coupled to the plurality of sensors, for detecting a change in the plurality of sensors when contacted with an analyte.

24. A sensor array system comprising:

a plurality of sensors, wherein at least one sensor comprises;

at least two conductive leads;

a sensing area comprising alternating interpenetrating regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black disposed between and in contact with the at least two conductive leads, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the sensing area provides an electrical path through the regions of the conductive organic polymer material and the regions of the inorganic conductive material or carbon black, wherein the sensing area is in direct contact with a vapor comprising an analyte to be detected, wherein the inorganic conductive material is selected from the group consisting of an inorganic conductor and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal, a metal alloy, a metal oxide, or a superconductor or a combination thereof and wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases;

a measuring apparatus that detects a change in the electrical properties of the at least one sensor, wherein at least one sensor is in communication with the measuring apparatus; and

a computer comprising a resident algorithm, wherein the computer processes the change in the electrical properties.

25. The sensor array system according to claim 24, wherein the measuring apparatus is an electrical measuring device.

26. The sensor array system according to claim 24, wherein the inorganic conductive material is an inorganic conductor.

27. The sensor array system according to claim 26, wherein the inorganic conductive material is a member selected from the group consisting of Ag, Au, Cu, Pt, and AuCu.

28. The sensor array system according to claim 24, wherein the plurality of sensors each comprise regions of a conductive organic polymer material and regions of an inorganic conductive material or carbon black.

29. The sensor array system according to claim 28, wherein the conductive organic polymer material of at least one sensor is different from the conductive organic polymer material of at least one other sensor.

30. The sensor array system according to claim 28, wherein the conductive organic polymer material of the plurality of sensors are compositionally the same.

31. The sensor array system according to claim 24, wherein the change in electrical properties is selected from the group consisting of impedance, conductance, capacitance, inductance, and resistance in the sensors.

32. The sensor array system according to claim 24, wherein the conductive organic polymer material is selected from the group consisting of a polyaniline, an emeraldine salt of polyaniline, a polypyrrole, a polythiophene, and a polyEDOT, and the inorganic conductive material is selected from the group consisting of Ag, Au, Cu, Pt, and AuCu.

33. The sensor array system according to claim 24 or 32, further comprising a temperature control apparatus in thermal communication with at least one sensor.

36. The sensor array system according to claim 24, wherein the sensor comprises carbon black.

37. The sensor array system according to claim 24, wherein the inorganic conductive material is selected from the group consisting of an organic conductor, an inorganic conductor, and a mixed inorganic/organic conductor.

38. The sensor array system according to claim 24, wherein the inorganic conductive is selected from the group consisting of a metal, a metal alloy, a metal oxide, a superconductor, and a mixed inorganic/organic conductor.

39. The sensor array system according to claim 24, wherein the inorganic conductive material is a particle.

40. The sensor array system according to claim 24, wherein each of the sensors comprises a conductive organic polymer material.

41. The sensor array system according to claim 24, wherein the resident algorithm is a member selected from the group consisting of principal component analysis, Fisher linear analysis, neural networks, genetic algorithms, fuzzy logic, pattern recognition, and combinations thereof.

42. A system for identifying a microorganism, the system comprising:

a measuring apparatus;

a sensor array comprising a plurality of sensors in communication with the measuring apparatus, wherein at least one sensor comprises;

at least two conductive leads;

a sensing area comprising alternating regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black disposed between and in electrical communication with the at least two conductive leads, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the inorganic conductive material is selected form the group consisting of an inorganic conductor, and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal a metal alloy, a metal oxide, a superconductor, or a combination thereof, wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases, wherein the sensing area provides an electrical path through the regions of the conductive organic polymer material and the regions of the inorganic conductive material or carbon black, and wherein the sensing are is in direct contact with a vapor comprising a biomarker to be detected; and

a computer comprising a resident algorithm;

wherein the measuring apparatus is capable of detecting a response from each sensor in the array wherein the response are indicative of the presence of a biomarker of a microorganism and the computer is capable of assembling the responses into a response profile whereby the computer associates the response profile indicative of the biomarker with a microorganism for microorganism identification.

43. The system for identifying a microorganism in accordance with claim 42, wherein the resident algorithm of the computer is a member selected from the group consisting of principal component analysis, Fisher linear analysis, neural networks, genetic algorithms, fuzzy logic, pattern recognition, and combinations thereof.

44. The system for identifying a microorganism in accordance with claim 42, further comprising the steps of:

providing an information storage device coupled to the measuring apparatus; and

storing information in the information storage device.

45. The system for identifying a microorganism in accordance with claim 42, wherein the measuring apparatus includes a digital-analog converter.

46. A system for detecting an analyte in a sample, comprising:

a substrate having a plurality of sensors wherein at least one sensor comprises;

at least two conductive leads;

a sensing area comprising alternating interpenetrating regions of a doped or undoped conductive organic polymer material and an inorganic conductive material or carbon black disposed between, and in contact with, the at least two conductive leads, wherein the regions of inorganic conductive material or carbon black are separated by about 10-1000 angstroms, wherein the sensing area provides an electrical path through the regions of the conductive organic polymer material and the regions of the inorganic conductive material or carbon black such that the at least one sensor provides a response that varies according to the presence of an analyte in contact with it, wherein the sensing area is in direct contact with a vapor comprising an analyte to be detected, wherein the inorganic conductive material is selected form the group consisting of an inorganic conductor and a mixed inorganic/organic conductor, wherein the inorganic conductor is a metal, a metal alloy, a metal oxide, or a superconductor, or a combination thereof and wherein the inorganic conductor has an electrical conductivity that decreases as the temperature increases;

a detector operatively associated with the plurality of sensors, for measuring the response of the plurality of sensor when contacted with the sample;

a sample delivery unit for delivering the sample to be tested to the plurality of sensors; and

an information storage and processing device configured to store an ideal response for a predetermined analyte and to compare the response of the plurality of sensor with the stored ideal response, to detect the presence of the analyte in the sample.

47. The system in accordance with claim 46, wherein the information storage and processing device is configured to store ideal responses for a plurality of predetermined analytes;

and

the information storage and processing device further is configured to compare the response of the plurality of sensors with the plurality of stored ideal responses, to detect the presence of each analyte in the sample.

48. The system in accordance with claim 46, wherein the sample is a liquid and the sample delivery unit comprises:

a flow passage interconnecting the substrate comprising the plurality of sensor with a mixture containing the liquid;

a gas-permeable, liquid-impermeable shield interposed in the flow passage; and

a device for extracting vapor from the liquid and for delivering the extracted vapor along the flow passage to the substrate comprising the plurality of sensors via the flow passage.

49. The system in accordance with claim 46, wherein the sample is gaseous and the sample delivery unit comprises:

a gas flow passage; and

a pump for pumping the gaseous sample to the substrate comprising the plurality of sensors via the gas flow passage.

50. The system in accordance with claim 46, wherein the sample is a vapor extracted from a solid and the sample delivery unit comprises:

a vapor flow passage; and

a pump for pumping the vapor extracted from the solid to the substrate comprising the plurality of sensors via the vapor flow passage.

51. The system in accordance with claim 46, wherein the detector detects a member selected from the group consisting of electromagnetic energy, optical properties, resistance, capacitance, inductance, impedance, and combinations thereof.

52. The system in accordance with claim 46, wherein at least one other sensor I the plurality of sensors comprises a member selected from the group consisting of a surface acoustic wave sensor;

a quartz microbalance sensor;

a conductive composite;

a chemiresistor;

a metal oxide gas sensor;

a conducting polymer sensor;

a dye-impregnated polymer film on fiber optic detector;

a polymer-coated micromirror;

an electrochemical gas detector;

a chemically sensitive field-effect transistor;

a carbon black-polymer composite;

a micro-electro-mechanical system device; and

a micro-opto-electro-mechanical system device.