Sensor element for determining the oxygen content and a method of preparing the same

• US 4,657,736 A
• Filed: 07/14/1986
• Issued: 04/14/1987
• Est. Priority Date: 11/23/1982
• Status: Expired due to Term

• Current Assignee: AVL AG
• Original Assignee: AVL AG
• Inventors: Wolfbeis, Otto, Kroneis, Herbert, Marsoner, Hermann
• Primary Examiner(s): Swisher, Nancy
• Application Number:
  US06/883,430
• Time in Patent Office: 274 Days
• Field of Search: 428/447, 428/690, 250/462.1, 252/408.1, 422/52, 422/55, 422/56, 422/87, 436/136, 436/138, 436/172
• US Class Current: 422/429
• CPC Class Codes: C09K 11/02 Use of particular materials as binders, particle coatings or suspension media therefor
• CPC Class Codes: C09K 11/025 non-luminescent particle coatings or suspension media
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• 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 21/643 non-biological material
• CPC Class Codes: G01N 21/648 using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
• CPC Class Codes: Y10T 436/207497 Molecular oxygen

Abstract

In an O₂ sensor element which contains a fluorescent indicator substance, a polymerized silicone polymer is used as a carrier material in which the indicator substance is incorporated in solubilized form and in an at least approximately homogeneous distribution. Solubilization of the indicator substance may essentially be performed in analogy to Friedel-Crafts alkylation of aromatics, which will increase solubility of the indicator substance in the polymer carrier without affecting quenching behavior.

Claims

1. A sensor element which, when placed in contact with a sample containing oxygen, is capable of indicating the oxygen content in said sample, said sensor element comprising a cured silicone polymer carrier matrix which is permeable to oxygen molecules and a chemically modified, solubilized, oxygen-sensitive fluorescent indicator substance which is generally homogeneously embedded within said cured silicone polymer carrier matrix, said oxygen-sensitive fluorescent indicator substance, upon excitation, emitting light of a certain wavelength and of varying intensity depending on the amount of oxygen from said sample in contact therewith, said sensor element being produced by a method which comprises the steps of

(a) combining an oxygen-sensitive fluorescent indicator substance with tertiary butyl chloride,

(b) catalytically reacting said oxygen-sensitive fluorescent indicator substance and said tertiary butyl chloride and recovering a solubilized fluorescent indicator substance,

(c) mixing said solubilized fluorescent indicator substance with an uncured silicone polymer to form a homogeneous mixture, and

(d) curing said mixture to form said sensor element.

2. A sensor element according to claim 1, wherein said cured silicone polymer carrier matrix is shaped to include a flat surface which is intended to face the sample containing oxygen, and wherein said sensor element includes a polymer layer having low transparency covering said flat surface of said cured silicone polymer carrier, said polymer layer being permeable to oxygen molecules.

3. A sensor element according to claim 2, wherein said polymer layer comprises a silicone coating having particles of ferrous oxide therein.

4. A sensor element according to claim 1, wherein said cured silicone polymer carrier matrix is shaped to include a flat surface which is intended to face the sample containing oxygen, and wherein said cured silicone polymer carrier matrix includes a thin mesh screen embedded therein adjacent said flat surface thereof.

5. A sensor element according to claim 1, wherein said fluorescent indicator substance is a compound which includes molecules selected from the group consisting of polycyclic aromatic molecules, homocyclic aromatic molecules and heterocyclic aromatic molecules.

6. A sensor element according to claim 5, wherein said fluorescent indicator substance comprises a polycyclic aromatic hydrocarbon which displays fluorescence decay times τ

_o greater than 5 ns.

7. A sensor element according to claim 1, wherein said cured silicone polymer carrier matrix includes pigment particles therein.

8. A sensor element according to claim 7, wherein said pigment particles are ferrous oxide particles.

9. A sensor element according to claim 7, wherein said cured silicone polymer carrier matrix is generally plate shaped so as to have a first flat surface which is intended to face the sample containing oxygen and a second flat surface which is intended to face away from the sample containing oxygen, and wherein said pigment particles are contained in said cured silicone polymer carrier matrix in increasing amounts in the direction between said second flat surface and said first flat surface.

10. A sensor element according to claim 1, wherein said fluorescent indicator substance includes hydrocarbon chains containing between 3 and 20 carbons atoms.

11. A method of producing a sensor element which, when placed in contact with a sample containing oxygen, is capable of indicating the oxygen content in said sample, said sensor element comprising a cured silicone polymer carrier matrix which is permeable to oxygen molecules and a chemically modified, solubilized, oxygen-sensitive fluorescent indicator substance which is generally homogeneously embedded within said cured silicone polymer carrier matrix, said oxygen-sensitive fluorescent indicator substance, upon excitation, emitting light of a certain wavelength and of varying intensity depending on the amount of oxygen from said sample in contact therewith, said method comprising the steps of

(a) combining an oxygen-sensitive fluorescent indicator substance with tertiary butyl chloride,

(b) catalytically reacting said oxygen-sensitive fluorescent indicator substance and said tertiary butyl chloride and recovering a solubilized fluorescent indicator substance,

(c) mixing said solubilized fluorescent indicator substance with an uncured silicone polymer to form a homogeneous mixture, and

(d) curing said mixture to form said sensor element.

12. A method according to claim 11, wherein in step (a) said oxygen-sensitive fluorescent indicator substance and said tertiary butyl chloride are dissolved in a solvent.

13. A method according to claim 12, wherein said solvent consists of CS₂.

14. A method according to claim 11, wherein in step (b) said oxygen-sensitive fluorescent indicator substance and said tertiary butyl chloride are reacted in the presence of aluminum chloride.

15. A method according to claim 11, wherein in step (a) said oxygen-sensitive fluorescent indicator substance is dissolved in an excess of tertiary butyl chloride.

16. A method according to claim 11, including between steps (c) and (d) the step (c'"'"') of moulding said mixture.

17. A method according to claim 16, wherein in step (c'"'"') said mixture is moulded into the general form of a flat plate.

18. A method according to claim 16, including between steps (c) and (c'"'"') the step (c") of adding ferrous oxide particles to said mixture, and between steps (c") and (c'"'"') the step (c'"'"'") of applying a force field to said moulded mixture so as to cause said ferrous oxide particles to be graded in amount through said moulded mixture.