Method and apparatus for determining the concentration of oxygen

• US 5,242,835 A
• Filed: 07/21/1992
• Issued: 09/07/1993
• Est. Priority Date: 11/03/1987
• Status: Expired due to Fees

• Current Assignee: Radiometer A/S (Danaher Corporation)
• Original Assignee: Radiometer A/S (Danaher Corporation)
• Inventors: Jensen, Niels-Henrik
• Primary Examiner(s): Housel, James C.
• Assistant Examiner(s): Snay, Jeffrey R.
• Application Number:
  US07/917,905
• Time in Patent Office: 413 Days
• Field of Search: 436/68, 436/136, 436/138, 436/167, 436/169, 436/172, 422/82.05, 422/91, 422/82.06, 356/39-41, 250/458.1, 250/459.1, 128/633, 128/634, 128/654, 128/665
• US Class Current: 436/136
• CPC Class Codes: G01N 2021/6482 Sample cells, cuvettes
• CPC Class Codes: G01N 2035/1062 for testing the liquid while it is in the transfer device
• CPC Class Codes: G01N 21/274 Calibration, base line adjustment, drift correction
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: Y10T 436/207497 Molecular oxygen

Abstract

The concentration of molecular oxygen in a sample is determined by exciting oxygen molecules of the sample from the electronic ground state to the excited ¹ Δ_g state (excited singlet state), measuring a 1270-nm luminescence characteristic of the excited oxygen molecules (singlet oxygen) and correlating the luminescence characteristic measured with the concentration of molecular oxygen in the sample. Normally, the 1270-nm luminescence characteristic is the 1270-nm luminescence intensity. Preferably, the oxygen molecules are excited by being subjected to diffusion contact with a sensitizer such as a porphyrin or a porphyrin-related compound, e.g. a transition metal complex of a porphyrin. The sensitizer is brought into an oxygen-exciting electronic state by absorption of electromagnetic radiation such as light, the oxygen-exciting electronic state optionally being adapted to the measuring system employed by means of a quencher such as a substituted polyene. The sensitizer may be present in an organic solvent or a polymer such as polyvinylchloride. The oxygen-containing sample is preferably a sample of biological origin such as a blood sample.

Claims

1. A method of determining the concentration of ground state molecular oxygen in a test sample, said method comprising:

(a) exciting oxygen molecules of the test sample from the electronic ground state to the excited ¹ Δ

_g state (excited singlet state),

(b) measuring a 1270-nm luminescence characteristic of the excited oxygen molecules in the test sample,

(c) quantitatively correlating the measured 1270-nm luminescence characteristic with standard values determined on the basis of a positive quantitative correlation between (i) 1270-nm luminescence signals of excited oxygen molecules in reference samples having known, pre-selected concentrations of ground state molecular oxygen and (ii) the concentrations of ground state molecular oxygen in the reference samples, and

(d) quantifying the content of ground state molecular oxygen in the test sample on the basis of the quantitative correlation of the measured 1270-nm luminescence characteristic with the standard values.

2. A method according to claim 1 wherein the 1270-nm luminescence characteristic is the 1270-nm luminescence intensity.

3. A method according to claim 1 wherein the excitation of the ground state oxygen molecules is performed by means of a sensitizing agent having an excited electronic state (sensitizing excited state) capable of exciting molecular oxygen from the electronic ground state to the excited singlet state, the sensitizing agent being in diffusion contact with the sample.

4. A method according to claim 3 wherein the energy of the excited state of the sensitizing agent is higher than 0.98 eV.

5. A method according to claim 3 wherein the sensitizing agent comprises a sensitizer having an excited state capable of exciting molecular oxygen from the electronic ground state to the excited singlet state and a quencher capable of deactivating the excited state of the sensitizer so as to reduce the excited state lifetime of the sensitizer, the quencher being in diffusion contact with the sensitizer.

6. A method according to claim 3 wherein the sensitizing excited state of the sensitizing agent is the excited triplet state.

7. A method according to claim 3 wherein the diffusion contact between the sensitizing agent and the sample is established at an interface between the sensitizing agent and the sample.

8. A method according to claim 3 wherein the oxidation potential of the excited state of the sensitizing agent is of a size which essentially renders the sensitizing agent incapable of converting molecular oxygen to the superoxide.

9. A method according to claim 8 wherein the oxidation potential of the excited state of the sensitizing agent is higher than -0.7 V versus saturated Calomel Electrode.

10. A method according to claim 3 wherein the sensitizing agent is selected from the group consisting of porphyrins and porphyrin-related compounds.

11. A method according to claim 10 wherein the sensitizing agent is selected from the group consisting of metal-free porphyrins, metallo-porphyrins, phtalocyanins, metallo-phtalocyanins and derivatives thereof.

12. A method according to claim 3 wherein the sensitizing agent is embedded in a matrix.

13. A method according to claim 12 wherein the matrix comprises an organic solvent.

14. A method according to claim 12 wherein the matrix in which the sensitizing agent is embedded is free of OH-groups so as to maximize the luminescence intensity of excited singlet oxygen.

15. A method according to claim 12 wherein the diffusion contact between the sensitizing agent and the sample is established through a membrane which separates said matrix containing the sensitizing agent and the sample containing the ground state molecular oxygen to be measured.

16. A method according to claim 12 wherein the matrix comprises a polymer.

17. A method according to claim 12 wherein the sensitizing agent and the matrix in which it is present are selected so as to affect the excited state lifetime of the sensitizing agent and the oxygen permeability of the matrix to thereby obtain a luminescence characteristic of a sufficient size variation over the ground state oxygen concentration range to be measured.

18. A method according to claim 17 wherein the sensitizing agent and the matrix in which it is present are adapted to a particular maximum ambient oxygen concentration to be measured so that a matrix oxygen concentration of at the most 50 •

[O₂ ]_1/2 will be obtained on contacting the matrix with a sample of the particular maximum ambient ground state oxygen concentration.

19. A method according to claim 18 wherein a matrix oxygen concentration of at the most 20 •

[O₂ ]_1/2 is obtained.

20. A method according to claim 18 wherein a matrix oxygen concentration of at the most 10 •

[O₂ ]_1/2 is obtained.

21. A method according to claim 3 wherein the excited state of the sensitizing agent is formed from another electronic state of the sensitizing agent by absorption of electromagnetic radiation.

22. A method according to claim 21 wherein the electromagnetic radiation is of a wavelength of less than 1270 nm.

23. A method according to claim 22 wherein the electromagnetic radiation is of a wavelength in the range of 300-1000 nm.

24. A method according to claim 22 wherein the sensitizing agent is selected from transition metal complexes.

25. A method according to claim 24 wherein the sensitizing agent is selected from the group consisting of complexes of Zn(II), Pd(II), Pt(II), Ru(II) and Os(II).

26. A method of determining the concentration of ground state molecular oxygen in a test sample which is a fluid sample of biological origin having a molecular oxygen concentration at a physiological level, said method comprising:

(a) exciting oxygen molecules of the test sample from the electronic ground state to the excited ¹ Δ

_g state (excited singlet state),

(b) measuring a 1270-nm luminescence characteristic of the excited oxygen molecules in the test sample,

(c) quantitatively correlating the measured 1270-nm luminescence characteristic with standard values determined on the basis of a positive quantitative correlation between (i) 1270-nm luminescence signals of excited oxygen molecules in reference samples having known, pre-selected concentrations of ground state molecular oxygen and (ii) the concentrations of ground state molecular oxygen in the reference samples, and

(d) quantifying the content of ground state molecular oxygen in the test sample on the basis of the quantitative correlation of the measured 1270-nm luminescence characteristic with the standard values.

27. A method according to claim 26 wherein the fluid sample of biological origin is blood.

28. A method according to claim 26 wherein the fluid sample is an oxygen-containing gas of biological origin.

29. A system for determining the concentration of ground state molecular oxygen in a test sample, said system comprising:

(a) means for exciting oxygen molecules of the test sample from the electronic ground state to the excited ¹ Δ

_g state (excited singlet state), said means comprising an electromagnetic radiation source and a sensitizing agent, said sensitizing agent being in diffusion contact with the sample,

(b) means for measuring a 1270-nm luminescence characteristic of the excited oxygen molecules in the test sample, and

(c) means for quantifying the content of ground state molecular oxygen in the test sample based on a quantitative correlation of the measured 1270-nm luminescence characteristic with standard values determined on the basis of a positive quantitative correlation between (i) 1270-nm luminescence signals of excited oxygen molecules in reference samples having known, pre-selected concentrations of ground state molecular oxygen and (ii) the concentrations of ground state molecular oxygen in the reference samples.

30. A system according to claim 29 wherein the sensitizing agent is embedded in a matrix, the matrix being an organic solvent.

31. A system according to claim 29 wherein said means for quantifying comprises a signal or data processing means.

32. A system according to claim 29 wherein the sensitizing agent has an excited electronic state capable of exciting molecular oxygen from the electronic ground state to the excited singlet state.

33. A system according to claim 32 wherein the sensitizing agent has an excited electronic state, the energy of which is higher than 0.98 eV.

34. A system according to claim 29 wherein the electromagnetic radiation is of a wavelength of less than 1270 nm.

35. A system according to claim 34 wherein the electromagnetic radiation is of a wave length in the range of 300-1000 nm.

36. A system according to claim 29 wherein the means for measuring a 1270-nm luminescence characteristic of the excited oxygen molecules comprises a detector being capable of measuring said luminescence characteristic at a wavelength of about 1270 nm.

37. A system according to claim 36, wherein said detector is covered by a filter.

38. A system according to claim 36 wherein said detector is connected to an amplifier circuit.

39. A system according to claim 29 wherein the sensitizing agent is embedded in a matrix.

40. A system according to claim 39 wherein the sensitizing agent and the matrix in which it is present are selected so as to affect the excited state lifetime of the sensitizing agent and the oxygen permeability of the matrix to thereby obtain a luminescence characteristic of a sufficient size variation over the ground state oxygen concentration range to be measured.

41. A system according to claim 39 wherein the diffusion contact between the sensitizing agent and the sample is established through a membrane which separates said matrix containing the sensitizing agent and the sample containing the ground state molecular oxygen to be measured.

42. A system according to claim 39 wherein the matrix is a polymer which is free of OH groups.