Optical detection of oxygen

• US 5,043,285 A
• Filed: 07/09/1987
• Issued: 08/27/1991
• Est. Priority Date: 07/09/1987
• Status: Expired due to Fees

• Current Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Original Assignee: Alliedsignal Inc. (Honeywell International Inc.)
• Inventors: Surgi, Marion R.
• Primary Examiner(s): Lacey, David L.
• Assistant Examiner(s): Snay, Jeffrey R.
• Application Number:
  US07/071,445
• Time in Patent Office: 1,510 Days
• Field of Search: 422/68, 422/83, 422/88, 422/91, 422/82.05, 422/82.06, 422/82.07, 422/82.08, 436/68, 436/136, 436/172, 128/634, 128/665, 128/666, 250/458.1, 250/459.1, 356/39-41
• US Class Current: 436/136
• CPC Class Codes: G01N 2021/6432 Quenching
• 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: Y10T 436/207497 Molecular oxygen

Abstract

This invention is a method and apparatus for detecting the presence of gaseous oxygen and measuring the amount present. In the practice of the invention, luminescence from a luminophor compound is quenched by oxygen. The luminiphor is a conjugated aromatic carbonyl. The intensity of the emitted light is related to the concentration of oxygen in the atmosphere surrounding the conjugated aromatic carbonyl compound. The luminophor compound is located on a polar substrate having free hydroxyl groups at its surface and also having at its surface, in locations adjacent to the luminophor compound, a halogenated hydrocarbon compound containing at least one halogen selected from a group consisting of chlorine, bromine, and iodine. In a preferred embodiment, the invention comprises an oxygen sensor utilizing a fiber-optic light guide to conduct excitation light to a substrate comprised of activated silica gel particles having methylene chloride and N-methylacridone co-deposited on them. A fiber-optic light guide is used to conduct emitted light away from the substrate.

Claims

1. Apparatus for detecting the presence of gaseous oxygen and measuring the amount present, comprising:

a) means for producing substantially monochromatic excitation light;

b) a sensing element comprised of;

(1) a polar substrate having free hydroxyl groups at its surface;

(2) a luminophor compound, which is a conjugated aromatic carbonyl compound, deposited on the surface of said substrate wherein said luminophore compound is N-methylacridone; and

,

(3) a halogenated hydrocarbon compound deposited on the surface of said substrate at locations adjacent to said carbonyl compound, wherein the halogenated hydrocarbon compound contains at least one halogen selected from the group consisting of chlorine, bromine, and iodine;

c) means for exposing said sensing element to said excitation light;

d) means for collecting light emitted by said carbonyl compound;

e) means for filtering said collected light to remove scattered excitation light and stray light which is collected along with said emitted light;

f) means for measuring the intensity of said filtered light;

g) means for exposing said sensing element to a sample environment comprising gaseous oxygen;

h) means for exposing said sensing element to calibration environments; and

,

i) means for determining oxygen concentration in said sample environment by comparing light intensity measured while the sensing element is exposed to said sample environment to light intensities measured while the sensing element is exposed to said calibration environments.

2. The apparatus of claim 1 wherein said means for producing substantially monochromatic excitation light is comprised of a light source which produces light of numerous wavelengths and an optical filter which passes only light having wavelengths in a narrow band of wavelengths.

3. The apparatus of claim 1 wherein said means for filtering collected light passes only light having wavelengths centered about 460 nanometers.

4. The apparatus of claim 1 wherein each of said means for exposing said sensing element to said excitation light and said means for collecting light comprises a fiber-optic light guide to conduct excitation light to said sensing element and to conduct emitted light away from said sensing element.

5. A sensor for gaseous oxygen comprised of:

a) a polar substrate having free hydroxyl groups at its surface;

b) a luminophor compound, which is a conjugated aromatic carbonyl compound, deposited on the surface of said substrate wherein said luminophore compound is N-methylacridone;

c) a halogenated hydrocarbon compound deposited on the surface of said substrate at locations adjacent to said carbonyl compound, wherein the halogenated hydrocarbon compound contains at least one halogen selected from the group consisting of chlorine, bromine, and iodine;

d) at least one fiber-optic light guide for conducting excitation light to said substrate; and

,

e) at least one fiber-optic light guide for conducting light emitted by said carbonyl compound away from said substrate.

6. The sensor of claim 5 wherein said substrate is chosen from the group consisting of alpha alumina, etched glass beads, strongly acidic ion-exchange resins, and activated silica gel.

7. The sensor of claim 5 wherein said halogenated hydrocarbon compound is chosen from the group consisting of dichloromethane, diiodonmethane, methyl iodide, 1-bromo-2-chloroethane, 1-bromo-1-chloroethane, iodoform, 1,1-dibromoethane, and methylene chloride.

8. The sensor of claim 5 wherein each molecule of said halogenated hydrocarbon compound contains no more than four carbon atoms.

9. The sensor of claim 5 wherein said halogenated hydrocarbon compound is methylene chloride.

10. The sensor of claim 5 wherein said substrate, with said luminophor and halogenated hydrocarbon compounds located thereon, is enclosed within a selectively permeable membrane which prevents interfering substances from contacting said luminophor.

11. The sensor of claim 5 wherein said substrate is comprised of particles of activated silica gel and said particles are contained within a gas permeable membrane.

12. The sensor of claim 11 wherein said particles range in size from a mean particle diameter of about 10 microns to about 100 microns.

13. A method for detecting the presence of gaseous oxygen and measuring the amount present comprising:

a) exciting a luminophor compound with substantially monochromatic light having wavelengths effective for absorption by said luminophor, wherein the luminophor is located on a polar substrate having free hydroxyl groups, wherein a halogenated hydrocarbon compound containing at least one halogen selected from the group consisting of chlorine, bromine, and iodine is located on the substrate at locations adjacent to the luminophor, and wherein the luminophor is N-methylacridone;

b) collecting light emitted by the luminophor at wavelengths different from those of said excitation light;

c) measuring the intensities of said collected light when said luminophor is located in a calibration environment comprising gaseous oxygen of at least two different concentrations, thus providing at least two intensity measurements;

d) measuring the intensity of said collected light when said luminophor is located in a sample environment comprising gaseous oxygen; and

,

e) determining the oxygen concentration of said sample environment by comparing said sample environment intensity to said calibration environment intensities.

14. The method of claim 13 wherein wavelengths of said substantially monochromatic excitation light are centered about 400 nanometers.

15. The method of claim 13 wherein the wavelengths of said emitted light are centered about 460 nanometers.

16. The method of claim 13 wherein said halogenated hydrocarbon is methylene chloride.

17. The method of claim 15 wherein said substrate is activated silica gel.