Apparatus and method for measuring the concentration or partial pressure of oxygen

• US 5,173,432 A
• Filed: 10/13/1988
• Issued: 12/22/1992
• Est. Priority Date: 12/14/1987
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Paquette, Michael S., Webb, Steven P., Lefkowitz, Steven M.
• Primary Examiner(s): Warden, Robert J.
• Assistant Examiner(s): McMahon, Timothy M.
• Application Number:
  US07/257,362
• Time in Patent Office: 1,531 Days
• Field of Search: 422/91, 422/52, 250/458.1, 250/459.1, 350/96.34, 356/41, 436/127, 436/136, 436/172, 436/138, 436/800, 128/633, 128/634, 128/635, 128/664, 128/665, 128/666
• US Class Current: 436/138
• CPC Class Codes: G01N 2021/6434 Optrodes
• CPC Class Codes: G01N 2021/772 Tip coated light guide
• CPC Class Codes: G01N 2021/773 Porous polymer jacket; Polymer matrix with indicator
• CPC Class Codes: G01N 2021/7786 Fluorescence
• CPC Class Codes: G01N 21/6428 Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" in vivo A61B5/00; immunoassay G01N33/53
• 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 436/207497 Molecular oxygen
• CPC Class Codes: Y10T 436/209163 Dissolved or trace oxygen or oxygen content of a sealed environment

Abstract

A sensor and a method for using the sensor to determine the concentration or partial pressure of oxygen in a fluid media is provided. The sensor includes a light modifying medium containing a luminescent dye which is accessible to oxygen. The luminescent dye contains a hexanuclear core of molybdenum, tungsten or mixtures thereof having 14 coordination sites, wherein each site is occupied by a ligand. The sensor also includes an apparatus capable of transmitting and collecting light to and from the light modifying medium.

Claims

1. A sensor useful for determining the concentration or partial pressure of oxygen in a fluid media, the sensor comprising:

(a) means for transmitting and collecting light to and from a light modifying medium; and

(b) a light modifying medium containing a luminescent dye accessible to oxygen, wherein said luminescent dye contains a hexanuclear core of molybdenum, tungsten or mixtures thereof having 14 coordination sites, wherein each site is occupied by a ligand.

2. The sensor of claim 1 wherein the means for transmitting and collecting light is an optical waveguide.

3. The sensor of claim 2 wherein the optical waveguide is an optical fiber.

4. The sensor of claim 1 wherein the net electronic charge of the luminescent dye is greater than zero or positive.

5. The sensor of claim 4 wherein the positively charged luminescent dye is balanced by a counterion.

6. The sensor as claimed in claim 1 wherein the net electronic charge of the luminescent dye is less than zero or negative and is balanced by a counterion.

7. The sensor of claim 6 wherein the counterion is tetrabutyl ammonium.

8. The sensor of claim 6 wherein the luminescent dye is Mo₆ Br₁₄.sup.⊖

⊖ and

the counterion is tetrabutyl ammonium.

9. The sensor of claim 1 wherein the luminescent dye contains a hexanuclear core of molybdenum.

10. The sensor of claim 1 wherein the luminescent dye contains a hexanuclear core of tungsten.

11. The sensor of claim 1 wherein the ligand is halide.

12. The sensor of claim 1 wherein the ligand is bromo.

13. The sensor of claim 1 wherein the ligand is iodo.

14. The sensor of claim 1 wherein the luminescent dye is Mo₆ Br₁₄.sup.⊖

⊖

.

15. The sensor of claim 1 wherein the net electronic charge of luminescent dye is zero or neutral.

16. The sensor of claim 1 wherein the luminescent dye is dispersed in a matrix.

17. The sensor of claim 16 wherein the matrix is a polymeric material.

18. The sensor of claim 16 wherein the matrix is an organic polymeric material.

19. The sensor of claim 16 wherein the matrix is polymethylmethacrylate (PMMA).

20. The sensor of claim 16 wherein the matrix is an organic polymer admixed with a plasticizer.

21. The sensor of claim 16 wherein the matrix polymethylmethacrylate admixed with 2-ethylhexyl diphenyl phosphate (EDPP).

22. A method for determining the concentration or partial pressure of oxygen in a media, comprising:

contacting the media with a light modifying medium comprising a luminescent dye which is accessible to oxygen, wherein said luminescent dye contains a hexanuclear core of molybdenum, tungsten or mixtures thereof each said core having 14 coordination sites, wherein each coordination site is occupied by a ligand;

(B) transmitting and collecting light to and from said light modifying medium;

(C) measuring the intensity of luminescence collected from the light modifying medium and using the measured intensity to determine the concentration or partial pressure of oxygen present in the media.

23. The method of claim 22 wherein the luminescent dye contains a hexanuclear core of molybdenum.

24. The method of claim 22 wherein the luminescent dye contains a hexanuclear core of tungsten.

25. The method of claim 22 wherein the ligand is halide.

26. The method of claim 22 wherein the ligand is bromo.

27. The method of claim 22 wherein the ligand is iodo.

28. The method of claim 22 wherein the luminescent dye is Mo₆ Br₁₄.sup.⊖

⊖

.

29. The method of claim 22 wherein the net electronic charge of luminescent dye is zero or neutral.

30. The method of claim 22 wherein the luminescent dye is dispersed in a matrix.

31. The method of claim 30 wherein the matrix is a polymeric material.

32. The method of claim 30 wherein the matrix is an organic polymeric material.

33. The method of claim 30 wherein the matrix is polymethylmethacrylate (PMMA).

34. The method of claim 30 wherein the matrix is an organic polymer admixed with a plasticizer.

35. The method of claim 30 wherein the matrix is polymethylmethacrylate admixed with 2-ethylhexyl diphenyl phosphate (EDPP).

36. The method of claim 27 wherein the net electronic charge of the luminescent dye is greater than zero or positive.

37. The method of claim 36 wherein the positively charged luminescent dye is balanced by a counterion.

38. The method of claim 22 wherein the net electronic charge of the luminescent dye is less than zero or negative.

39. The method of claim 38 wherein the negatively charged luminescent dye is balanced by a counterion.

40. The method of claim 39 wherein the counterion is tetrabutyl ammonium.

41. The method of claim 39 wherein the luminescent dye is Mo₆ Br₁₄.sup.⊖

⊖ and

the counterion is tetrabutyl ammonium.

42. The method of claim 22 wherein the media comprises a fluid containing oxygen having a partial pressure from about 0 torr to about 270 torr.

43. The method of claim 42 wherein the fluid comprises an animal body fluid.

44. The method of claim 42 wherein the fluid comprises animal blood.

45. The method of claim 44 wherein the animal blood contains an anesthetic in an amount to induce an unconscious state.

46. The method of claim 45 wherein the anesthetic is 1-bromo-1-chloro-2,2,2-trifluoroethane.

47. The method of claim 42 wherein the fluid comprises cell culture fluid.

48. The method of claim 42 wherein the fluid comprises a gas in a fermentation vessel.