CA2318950A1 - Oxygen sensing membranes and methods of making same - Google Patents

Oxygen sensing membranes and methods of making same Download PDF

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Publication number
CA2318950A1
CA2318950A1 CA002318950A CA2318950A CA2318950A1 CA 2318950 A1 CA2318950 A1 CA 2318950A1 CA 002318950 A CA002318950 A CA 002318950A CA 2318950 A CA2318950 A CA 2318950A CA 2318950 A1 CA2318950 A1 CA 2318950A1
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poly
perm
monomeric units
value
homopolymer
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CA002318950A
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CA2318950C (en
Inventor
Joseph Berger
Thomas C. Collins
Rudolf E. Slovacek
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Siemens Healthcare Diagnostics Inc
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/223Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols
    • G01N31/225Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating presence of specific gases or aerosols for oxygen, e.g. including dissolved oxygen

Abstract

Optical sensor formulations comprising polymeric sensing formulations and methods of predictably making optical sensor formulations, for, e.g., measuring O2 levels in patient blood samples. These formulations may be, e.g., deposited as a membrane on light-transmissive substrates. In an embodiment, O2sensing formulations may be made by a process including selecting a first homopolymer comprised of first monomeric units, the first homopolymer having a first PermO2 value; selecting a second homopolymer comprised of second monomeric units, the second homopolymer having a second PermO2 value that is different from the first PermO2 value; and copolymerizing the first and second monomeric units to obtain a copolymer having an intermediate PermO2 value, i.e., between the two PermO2 values, the intermediate PermO2 providing the desired PermO2 for the desired oxygen sensing formulation. By adjusting the relative amounts of the first and second monomeric units, a series of polymers having a desired range of intermediate permeability values (and hence SternVolmer characteristic kSV values) may be obtained.

Claims (30)

1. A method of preparing a polymeric sensing composition containing a luminescent dye and a light-transmissive, oxygen-permeable matrix material, comprising the steps of:
a. selecting a luminescent dye for incorporation in said polymeric sensing composition;
b. determining a desired oxygen permeability (Perm~2) range for said matrix material which will provide a Stern-Volmer constant in a desired range for said polymeric sensing composition;
c. preparing said light-transmissive, oxygen-permeable matrix material by i. selecting a first homopolymer comprised of first monomeric units, said first homopolymer having a first Perm~2 value;
ii. selecting a second homopolymer comprised of second monomeric units, said second homopolymer having a second Perm~2 value that is different than said first Perm~2 value;
iii. copolymerizing said first and second monomeric units to obtain a copolymer having an intermediate Perm~2 value between said first and second Permo2 values, said intermediate Perm~2 sufficient to provide a Stern-Volmer constant within said desired range of Stern-Volmer constants; and iv. incorporating said luminescent dye in said copolymer.
2. The method of claim 1, wherein said step of incorporating a luminescent dye further comprises incorporating a luminescent dye selected from the group consisting of pyrenes, pyrelenes, ligand metal complexes of ruthenium, Pt chlorin derivatives and Pt-porphyrin derivatives.
3. The method of claim 1, wherein said step of incorporating a luminescent dye further comprises incorporating octaethyl-Pt porphyrin or meso-tetraphenyl-tetrabenzo-Pt-porphyrin.
4. The method of claim 1, wherein said preparing said light-transmissive, oxygen-permeable matrix material step further comprises selecting said homopolymers from the group consisting of poly(amides), poly(acrylamides), poly(styrenes), poly(acrylates), poly(alkylacrylates), poly(nitriles), polyvinyl chlorides), polyvinyl alcohols), poly(dienes), poly(esters), poly(carbonates), poly(siloxanes), poly(urethanes), poly(olefins), poly(imides), and cellulosics.
5. The method of claim 1, wherein said preparing said light-transmissive, oxygen-permeable matrix material step further comprises selecting said monomeric units from the group consisting of ethylhexylmethacrylate and methylmethacrylate.
6. The method of claim 1, wherein said preparing said light-transmissive, oxygen-permeable matrix material step further comprises selecting said monomeric units from the group consisting of styrene and acrylonitrile.
7. The method of claim 1, wherein said preparing said light-transmissive, oxygen-permeable matrix material step further comprises incorporating a scattering filler material in said copolymer.
8. The method of claim 7, wherein said scattering filler material is selected from the group consisting of TiO2, zinc oxide, antimony trioxide, barium sulfate, magnesium oxide, blush polymers, and mixtures thereof.
9. The method of claim 8, wherein said scattering filler material is TiO2 or a blush polymer.
10. The method of claim 1 wherein said copolymerization of said first and second amounts of monomeric units results in a light-transmissive, oxygen-permeable matrix having a Perm~2 value providing a k sw of at least 10x10 -3 at 37°C.
11. A method of preparing a light-transmissive, oxygen-permeable matrix material for use in a polymeric sensing composition, comprising the steps of:
a. determining a desired oxygen permeability (Perm~2) range for said matrix material which will provide a desired range of Stern-Volmer constants for said polymeric sensing composition;
b. selecting a first homopolymer comprised of first monomeric units, said first homopolymer having a first Perm~2 value;

c. selecting a second homopolymer comprised of second monomeric units, said second homopolymer having a second Perm O2 value that is different than said first Perm O2 value; and d. preparing a copolymer having an intermediate Perm O2 value between said first and second Perm O2 values by copolymerizing said first and second monomeric units in a ratio to obtain said copolymer, said intermediate Perm O2 value providing a Stern-Volmer constant in said desired range of Stern-Volmer constants for said polymeric sensing composition.
12. The method of claim 11, wherein a plurality of copolymers each having a separate intermediate Perm O2 value between said first and second Perm O2 values are prepared by copolymerizing said first and second monomeric units in a plurality of ratios to obtain said plurality of copolymers, said intermediate Perm O2 values providing a plurality of Stern-Volmer constants within said desired range for said polymeric sensing compositions.
13. The method of claim 12, further comprising the step of selecting a light-transmissive, oxygen-permeable matrix material having a desired Perm O2 value from said plurality of copolymers.
14. An oxygen sensor formulation comprising:
a. a luminescent dye; and b. a light-transmissive, oxygen-permeable matrix material having a desired oxygen permeability (Perm O2) which provides a Stern-Volmer constant in a desired range for said polymeric sensing composition, made by the process of:
i. selecting a first homopolymer comprised of first monomeric units, said first homopolymer having a first Perm O2 value;
ii. selecting a second homopolymer comprised of second monomeric units, said second homopolymer having a second Perm O2 value that is different than said first Perm O2 value; and iii. copolymerizing said first and second monomeric units to obtain a copolymer having an intermediate Perm O2 value between said first and second Perm O2 values, said intermediate Perm O2 providing said desired Stern-Volmer constant in said range.
15. The sensor formulation of claim 14 wherein said luminescent dye is selected from the group consisting of pyrenes, pyrelenes, ligand metal complexes of ruthenium, Pt-chlorin derivatives and Pt-porphyrin derivatives.
16. The sensor formulation of claim 15, wherein said luminescent dye is octaethyl-Pt porphyrin or meso-tetraphenyl-tetrabenzo-Pt-porphyrin.
17. The sensor formulation of claim 14 wherein said homopolymers are selected from the group consisting of poly(amides), poly(acrylamides), poly(styrenes), poly(acrylates), poly(alkylacrylates), poly(nitriles), polyvinyl chlorides), polyvinyl alcohols), poly(dienes), poly(esters), poly(carbonates), poly(siloxanes), poly(urethanes), poly(olefins), poly(imides), and cellulosics.
18. The sensor formulation of claim 17, wherein said monomeric units are selected from the group consisting of ethylhexylmethacrylate and methylmethacrylate.
19. The sensor formulation of claim 17, wherein said monomeric units are selected from the group consisting of styrene and acrylonitrile.
20. The sensor formulation of claim 14 further comprising a scattering filler material.
21. The sensor formulation of claim 20, wherein said scattering filler material is selected from the group consisting of TiO2, zinc oxide, antimony trioxide, barium sulfate, magnesium oxide, and blush polymers, and mixtures thereof.
22. The sensor formulation of claim 21, wherein said scattering filler material is TiO2 or a blush polymer.
23. The sensor formulation of claim 14, wherein said luminescent dye is octaethyl-Pt porphyrin and said monomeric units are ethylhexylmethacrylate in an amount of between about 5 to 15 mole percent of the total polymerizable monomer; and methylmethacrylate.
24. The sensor formulation of claim 23, wherein said amount of ethylhexylmethacrylate is about 10 mole percent of the total polymerizable monomer.
25. The sensor formulation of claim 14, wherein said luminescent dye is meso-tetraphenyl-tetrabenzo-Pt-porphyrin and said monomeric units are ethylhexylmethacrylate, in an amount of between about 10 to 20 mole percent of the total polymerizable monomer; and methylmethacrylate.
26. The sensor formulation of claim 25, wherein said amount of ethylhexylmethacrylate is about 15 mole percent of the total polymerizable monomer.
27. The sensor formulation of claim 14, wherein the luminescent dye is octaethyl-Pt porphyrin and said monomeric units are styrene, in an amount of between about 25 to 65 mole percent of the total composition of the copolymer; and acrylonitrile.
28. The sensor formulation of claim 27, wherein said styrene content is about 55 mole percent.
29. The sensor formulation of claim 14, wherein the luminescent dye is meso-tetraphenyl-tetrabenzo-Pt-porphyrin and said monomeric units are styrene, in an amount of between about 35 to 75 mole percent of the total composition of the copolymer; and acrylonitrile.
30. The sensor of claim 29, wherein said styrene content is 58 mole percent.
CA2318950A 1998-01-21 1999-01-18 Oxygen sensing membranes and methods of making same Expired - Fee Related CA2318950C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/010,161 1998-01-21
US09/010,161 US6190612B1 (en) 1998-01-21 1998-01-21 Oxygen sensing membranes and methods of making same
PCT/IB1999/000049 WO1999037998A1 (en) 1998-01-21 1999-01-18 Oxygen sensing membranes and methods of making same

Publications (2)

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CA2318950A1 true CA2318950A1 (en) 1999-07-29
CA2318950C CA2318950C (en) 2010-10-26

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US (1) US6190612B1 (en)
EP (1) EP1049924A1 (en)
JP (1) JP4460767B2 (en)
AU (1) AU1778199A (en)
CA (1) CA2318950C (en)
WO (1) WO1999037998A1 (en)

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US6190612B1 (en) 2001-02-20
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CA2318950C (en) 2010-10-26
WO1999037998A1 (en) 1999-07-29

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