Chemical sensors

• US 5,308,771 A
• Filed: 04/13/1992
• Issued: 05/03/1994
• Est. Priority Date: 04/13/1992
• Status: Expired due to Term

• Current Assignee: Science Applications International Corporation
• Original Assignee: Geo Corporation
• Inventors: Zhou, Quan, Tabacco, Mary E., Nelson, Bruce N.
• Primary Examiner(s): Johnston, Jill A.
• Application Number:
  US07/868,028
• Time in Patent Office: 750 Days
• Field of Search: 422/82.06-82.08, 422/82.11, 436/111-113, 436/41, 436/39, 436/134, 436/172, 436/166, 436/527, 436/533, 436/534, 436/142, 427/2
• US Class Current: 436/39
• CPC Class Codes: G01N 2021/7783 Transmission, loss
• CPC Class Codes: G01N 21/75 Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated systems in which material is burnt in a flame or plasma G01N21/72, G01N21/73
• CPC Class Codes: G01N 21/7703 using reagent-clad optical fibres or optical waveguides using measurement of total internal reflection or attenuated total reflection G01N21/552; optical fibres or waveguides per se G02B
• CPC Class Codes: Y10T 436/173845 Amine and quaternary ammonium
• CPC Class Codes: Y10T 436/175383 Ammonia
• CPC Class Codes: Y10T 436/205831 Carbon monoxide only
• CPC Class Codes: Y10T 436/216 Unsaturated [e.g., ethylene, diene, etc.]

Abstract

A device for detecting the presence or concentration of an analyte, a method of making the device, and a method of detecting the presence or concentration of an analyte. The invention features one or more supports, such as beads, which carry a thin film of polymer substrate. The polymer substrate has a sensing reagent and a porous matrix. The sensing reagent alters the optical properties of the polymer substrate in the presence of analyte.

Claims

1. A device for detecting the presence or concentration of an analyte comprising:

a sensing element comprising at least one bead having an outer film layer of a polymer substrate, said polymer substrate being capable of receiving and discharging light, and said polymer substrate having a porous matrix and sensing reagent;

said sensing reagent being entrapped within and chemically bound to the polymer substrate and having a first absorption spectra in the presence of analyte and a second absorption spectra in the absence of analyte;

said porous matrix expanding the effective surface area of said polymer substrate for receiving analyte, said polymer substrate allowing said sensing reagent to alter the spectra of light passing through said polymer substrate in the presence of analyte; and

said bead comprising a material for providing mechanical strength to the polymer substrate.

2. The device of claim 1 further comprising light inputting and discharging means in communication with said polymer substrate, said light inputting and discharging means being capable of directing light from a light source into said polymer substrate and receiving light from said polymer substrate.

3. The device of claim 2 wherein said light receiving and discharging means comprise a housing which housing retains said polymer substrate in communication with one or more optical fibers.

4. The device of claim 3 wherein said housing has wall means and two ends defining an interior chamber and an exterior surface, one of said ends having an optical fiber for directing light into said interior chamber, and one of said ends having an optical fiber for receiving light rom said interior chamber, said interior chamber being in communication with said exterior surface by one or more openings in said wall means, and said sensing element being substantially enclosed within said interior chamber.

5. The device of claim 1 wherein said bead is made of glass.

6. The device of claim 1 wherein said sensing element includes a plurality of said beads.

7. The device of claim 6 wherein said bead is approximately 100 to 1000 microns in diameter.

8. The device of claim 6 wherein said polymer substrate film has a thickness of up to about 200 microns.

9. The device of claim 8 wherein said polymer substrate has a pore size of about 50 angstrom to 200 angstroms.

10. The device of claim 1 wherein said sensing reagent has a first absorption spectra and a second absorption spectra in the presence or absence of one or more of the analytes selected from the group consisting of hydrogen ion, hydrazine, ethylene, ammonia, carbon monoxide and water.

11. The device of claim 1 wherein said sensing reagent is selected from the groups of sensing reagents consisting of bromophenol red, bromocresol purple, vanillin, cobalt chloride and palladious chloride.

12. The device of claim 1 wherein said sensing reagent is substantially dispersed in said polymer substrate.

13. The device of claim 1 wherein said polymer substrate is hydrophilic.

14. The device of claim 13 wherein said polymer substrate is 2-hydroxyethyl methacrylate and polyacrylamide.

15. The device of claim 1 wherein said polymer substrate is hydrophobic.

16. The device of claim 15 wherein said polymer substrate is methyl methacrylate and triethylene glycol dimethacrylate.

17. The device of claim 1 wherein said polymer substrate is expanded by the presence of a solvent during a polymerization reaction, which solvent is removed after the polymerization reaction is completed.

18. The device of claim 17 wherein said solvent is an organic solvent.

19. The device of claim 17 wherein said solvent is an inorganic solvent.

20. A method of detecting the presence or concentration of an analyte comprising the following steps:

a) contacting a sample potentially containing analyte with a sensing element comprising at least one bead having an outer film layer of a polymer substrate, said polymer substrate being capable of receiving and discharging light, and said polymer substrate having a porous matrix and sensing reagent;

said sensing reagent being chemically bound to the polymer substrate and having a first absorption spectra in the presence of analyte and a second absorption spectra in the absence of analyte;

said porous matrix expanding the effective surface area of said polymer substrate, said sensing reagent altering the spectra of light passing through said polymeric substrate in the presence of analyte; and

said bead comprising a material which is capable of providing mechanical strength to the polymer substrate; and

b) inputting light into said polymer substrate, said light having a spectra capable of being altered by said sensing reagent; and

c) monitoring light leaving said polymer substrate for alteration indicative of the presence or absence or concentration of analyte.

21. The method of claim 20 wherein said support means and polymer substrate are held in light inputting and discharging means in communication with said polymer substrate, said light inputting and discharging means being capable of directing light from a light source into said polymer substrate and receiving light leaving said polymer substrate.

22. The method of claim 21 wherein said light receiving and discharging means comprise a housing which housing retains said polymer substrate in communication with said one or more optical fibers.

23. The method of claim 22 wherein said housing has wall means and two ends defining an interior chamber and an exterior surface, one of said ends having an optical fiber for directing light into said interior chamber, and one of said ends having an optical fiber for receiving light from said interior chamber, said interior chamber in communication with said exterior surface by at least one opening in said wall means, sensing element being substantially enclosed within said interior chamber.

24. The method of claim 20 wherein said bead is made of glass.

25. The method of claim 20 wherein said sensing element includes a plurality of said beads.

26. The method of claim 25 wherein said bead is approximately 100 to 1000 microns in diameter.

27. The method of claim 25 wherein said polymer substrate film has a thickness of up to about 200 microns.

28. The method of claim 25 wherein said polymer substrate has a pore size of about 50 angstroms to 200 angstroms.

29. The method of claim 20 wherein said sensing reagent has a first absorption spectra and a second absorption spectra in the presence or absence of one or more of the analytes selected from the group consisting of hydrogen ion, ethylene, ammonia, carbon monoxide and water.

30. The method of claim 20 wherein said sensing reagent is selected from the group of sensing reagents consisting of bromophenol red, bromocresol purple, vanillin, cobalt chloride and palladious chloride.

31. The method of claim 20 wherein said polymer substrate is hydrophilic.

32. The method of claim 31 wherein said polymer substrate is 2-hydroxyethyl methacrylate and polyacrylamide.

33. The method of claim 31 wherein said solvent is inorganic.

34. The method of claim 20 wherein said polymer substrate is hydrophobic.

35. The method of claim 34 wherein said polymer substrate is methyl methacrylate and triethylene glycol dimethacrylate.

36. The method of claim 20 wherein said polymer substrate is expanded by the presence of a solvent during a polymeric reaction, which solvent is removed after the polymerization reaction is completed

37. The method of claim 36 wherein said solvent is organic.

38. A method of making a device for detecting the presence or concentration of analyte comprising the following steps:

a) providing a mixture of at least one monomer, sensing reagent and solvent;

b) polymerizing the mixture in the presence of beads to form an outer film layer of a polymer substrate on each of the beads, the polymer substrate including a porous matrix formed by elimination of the solvent and the sensing reagent being chemically bound to the matrix;

wherein said polymer substrate is capable of receiving and discharging light, said sensing reagent having a first absorption spectra in the presence of analyte and a second absorption spectra in the absence of analyte;

said porous matrix expanding the effective surface area of said polymer substrate for receiving analyte, said polymer substrate allowing said sensor reagent to alter the spectra of light passing through said polymer substrate in the presence of analyte; and

said bead comprising the material for providing mechanical support to the polymer substrate.

39. The method of claim 38 wherein said bead is made of glass.

40. The method of claim 39 wherein said film has a thickness of up to about 200 microns.

41. The method of claim 39 wherein said bead is approximately 100 to 1000 microns in diameter.

42. The method of claim 38 wherein said sensing reagent has a first absorption spectra and a second absorption spectra in the presence or absence of one or more of the analytes selected from the group consisting of hydrogen ion, ethylene, ammonia, carbon monoxide and water.

43. The method of claim 38 wherein said sensing reagent is selected from the group of sensing reagents consisting of bromophenol red, bromocresol purple, vanillin, cobalt chloride and palladious chloride.

44. The method of claim 38 wherein said polymer substrate has a pore size of about 50 angstroms to 200 angstroms.

45. The method of claim 38 wherein said polymer substrate is hydrophilic.

46. The method of claim 45 wherein said polymer substrate is 2 hydroxyethyl methacrylate and polyacrylamide.

47. The method of claim 38 wherein said polymer substrate is hydrophobic.

48. The method of claim 47 wherein said polymer substrate is methyl methacrylate and triethylene glycol dimethacrylate.

49. The method of claim 48 wherein said solvent is organic.

50. The method of claim 48 wherein said solvent is inorganic.

51. The method of claim 38 wherein said polymer substrate is expanded by the presence of a solvent during a polymeric reaction, which solvent is removed by washing after the polymerization reaction is completed.