Luminescent dye comprising metallocomplex of a oxoporphyrin

• US 5,718,842 A
• Filed: 01/29/1997
• Issued: 02/17/1998
• Est. Priority Date: 10/07/1994
• Status: Expired due to Fees

• Current Assignee: JOANNEUM RESEARCH Forschungsgesellschaft mbH (Province of Styria)
• Original Assignee: JOANNEUM RESEARCH Forschungsgesellschaft mbH (Province of Styria)
• Inventors: Papkovsky, Dmitri Boris, Ponomarev, Gelii Vasilii
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US08/790,489
• Time in Patent Office: 384 Days
• Field of Search: 250/459.1, 436/138, 436/136, 436/172, 436/178, 252/301.16, 252/301.3
• US Class Current: 252/301.16
• CPC Class Codes: C09K 11/06 containing organic luminescent materials
• CPC Class Codes: Y10T 436/207497 Molecular oxygen
• CPC Class Codes: Y10T 436/21 Hydrocarbon
• CPC Class Codes: Y10T 436/255 including use of a solid sorbent, semipermeable membrane, or liquid extraction

Abstract

New luminescent dye including a metallocomplex of an oxoporphyrin having the general formula: ##STR1## wherein R1 to R8 are radicals belonging to the group: H, lower alkyl with number of C≦6 or CH₂ --CH₂ --COO--R₉, with R₉ =H or alkyl with number of C≦18 and M=Pt²⁺ or Pd²⁺.

Claims

1. Luminescent dye comprising a metallocomplex of an oxoporphyrin having a general formula:

##STR4## wherein R1 to R8 are radicals belonging to the group consisting of;

H, lower alkyl (number of C≦

6) or CH₂ --CH₂ --COO--R₉, with R₉ =H or alkyl (number of C≦

18) and M=Pt²⁺ or Pd²⁺.

2. The dye according to claim 1, wherein R1 to R8=ethyl.

3. The dye according to claim 1, wherein R₁ =R₃ =R₅ =R₇ =methyl and R₂ =R₄ =R₆ =R₈ =CH₂ --CH₂ --COO--R₉, with R₉ =H or alkyl (number of C≦

18).

4. The dye according to claim 1, wherein R₁ =R₃ =R₅ =R₇ =methyl and R₂ =R₄ =R₆ =R₈ =CH₂ --CH₃.

5. The dye according to claim 1, wherein R₁ =R₃ =R₅ =R₈ =methyl and R₂ =R₄ =R₆ =R₇ =CH₂ --CH₂ --COO--R₉, with R₉ =H or alkyl (number of C≦

18).

6. Active element for optical determination of oxygen in liquid and gaseous media comprising a composition prepared from at least one oxygen-permeable polymer and at least one luminescent dye distributed in said oxygen-permeable polymer, said polymer having a mass, wherein said luminescent dye is a metallocomplex of the oxoporphyrins having the general formula:

##STR5## wherein R1 to R8 are radicals belonging to a group consisting of;

H, lower alkyl (number of C≦

6) or CH₂ --CH₂ --COO--R₉, with R₉ =H or alkyl (number of C≦

18) and M=Pt²⁺ or Pd²⁺ or Zn²⁺.

7. The active element according to claim 6, wherein said dye is platinum octaethyloxoporphyrin having a concentration of 1-10% of said polymer mass.

8. The active element according to claim 6, wherein said dye is palladium octaethyloxoporphyrin.

9. The active element according to claim 6, wherein said dye is zinc octaethyloxoporphyrin.

10. The active element according to claim 6, wherein said active element is prepared in the form of a film having 1-20 μ

m thickness.

11. The active element according to claim 10, wherein said film is applied onto a suitable solid support or optical element.

12. The active element according to claim 6, wherein said active element is additionally covered with a layer of a certain oxygen-dependent enzyme.

13. The active element according to claim 6, wherein said oxygen-permeable polymer is polystyrene.

19. The active element according to claim 6, wherein said oxygen-permeable polymer is polyvinylchloride.

20. The active element according to claim 6, wherein said oxygen-permeable polymer is plasticized polyvinylchloride.

14. Method for measuring oxygen concentration, including the following steps:

using a sensitive element comprising an oxygen-permeable polymer with a distributed luminescent dye having the general formula;

##STR6## wherein R1 to R8 are radicals belonging to a group consisting of;

H, lower alkyl (number of C≦

6) or CH₂ --CH₂ --COO--R₉, with R₉ =H or alkyl (number of C≦

18) and M=Pt²⁺ or Pd²⁺ or Zn²⁺ ;

bringing said element into contact with a sample to be analyzed;

exciting said sensitive element with an exciting wavelength optimum between 570 and 650 nm;

measuring an emission wavelength optimum between 700 and 850 nm;

calculating the lifetime value of the luminescent decay of said luminescent dye, and

deriving the oxygen concentration from said lifetime value.

15. The method according to claim 14, wherein said sensitive element is linked to a luminescent detector, having its optimum between 700 and 850 nm, by means of fibre optics and wherein excitation is performed with a LED having emission optimum between 570 and 650 mm.

16. The method according to claim 14, wherein said luminescent measurement is performed in pulsed mode with time resolution.

17. The method for measuring oxygen concentration, including the following steps:

using a sensitive element comprising an oxygen-permeable polymer with a distributed luminescent dye having the general formula;

##STR7## wherein R1 to R8 are radicals belonging to a group consisting of;

H, lower alkyl (number of C≦

6) or CH₂ -CH₂ --COO--R₉, with R₉ =H or alkyl (number of C≦

18) and M=Pt²⁺ or Pd²⁺ or Zn²⁺ ;

bringing said element into contact with a sample to be analyzed;

exciting said sensitive element with an exciting wavelength optimum between 570 and 650 nm;

measuring an emission wavelength optimum between 700 and 850 nm;

calculating the intensity value of said luminescence dye, and

deriving the oxygen concentration from said intensity value.

18. The method according to claim 17, wherein said sensitive element is linked to a luminescent detector, having its optimum between 700 and 850 nm, by means of fibre optics and wherein excitation is performed with a LED having emission optimum between 570 and 650 nm.