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EP0214768A2 Expired / Lapsed EP ⏱️ 0.0 years remaining

Absorption-emission optrode

Assignee: University of California
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Filing: 1986-08-08
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Granted: —
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Expires: 2006-08-08
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Abstract

Abstract A method and apparatus for monitoring the physical and chemical properties of a sample fluid by measuring an optical signal generated by a fluorescent substance and modulated by an absorber substance. The emission band of the fluorescent substance overlaps the absorption band of the absorber substance, and the degree of overlap is dependent on the physical and chemical properties of the sample fluid. The fluorescent substance and absorber substance are immobilized on a substrate so that an effective number of molecules thereof are sufficiently close for resonant energy transfer to occur, thereby providing highly efficient modulation of the fluorescent emissions of the fluorescent substance by the absorber substance.

Inventors

  • 👤 Tomas B. Hirschfeld

Bibliographic Details

Application Number —
Jurisdiction EP
Data Source google_patents
Last Synchronized 2026-10-27 09:38
CPC Classifications
G; G01; G01N; G01N21/00; G01N21/62; G01N21/63; G01N21/64; G01N21/6428; G01N21/643; G01N21/6408; G01N2021/6434; G01N21/75; G01N21/77; G01N21/78; G01N21/783; Y; Y10; Y10T; Y10T436/00; Y10T436/17; Y10T436/177692; Y10T436/18; Y10T436/182; Y10T436/184

Claims Analysis

Total Claims: 16
Claim 1
Independent Claim 189 words
A method for monitoring physical and chemical parameters of an associated sample substance and for generating an optical signal related to said physical and chemical parameters, which comprises: immobilizing with respect to a substrate, a fluorescent substance having an emission band and an absorption band; immobilizing with respect to the same substrate, an absorber substance having an absorption band overlapping the emission band of the fluorescent substance, the degree of overlap being responsive to the physical and chemical parameters of the associated sample substance, and the absorber substance being immobilized such that an effective number of molecules of the absorber substance are closely adjacent e.g. within about 10-100 Angstroms to an effective number of molecules of the fluorescent substance so that resonant energy transfer is capable of occuring therebetween; illuminating the fluorescent substance with an illumination beam having a frequency within the absorption band of the fluorescent substance, so that excited fluorescent states are generated in the fluorescent substance; detecting an optical signal resulting from the decay of the excited fluorescent states; and extracting information concerning the physical and chemical parameters of the associated sample substance from the signal.
Claim 2
Independent Claim 189 words
A method for monitoring physical and chemical parameters of an associated sample substance and for generating an optical signal related to said physical and chemical parameters, which comprises: immobilizing with respect to a substrate, a fluorescent substance having an emission band and an absorption band; immobilizing with respect to the same substrate, an absorber substance having an absorption band overlapping the emission band of the fluorescent substance, the degree of overlap being responsive to the physical and chemical parameters of the associated sample substance, and the absorber substance being immobilized such that an effective number of molecules of the absorber substance are closely adjacent e.g. within about 10-100 Angstroms to an effective number of molecules of the fluorescent substance so that resonant energy transfer is capable of occuring therebetween; illuminating the fluorescent substance with an illumination beam having a frequency within the absorption band of the fluorescent substance, so that excited fluorescent states are generated in the fluorescent substance; detecting an optical signal resulting from the decay of the excited fluorescent states; and extracting information concerning the physical and chemical parameters of the associated sample substance from the signal.
Claim 3
Dependent Claim 111 words
A method as claimed in claim 1 further comprising the steps of: providing a fiber optic through which said illumination beam is transmitted from a first end of the fiber optic to a second end of the fiber optic; attaching said substrate to the second end of the fiber optic such that light from said illumination beam emanating from the second end illuminates said fluorescent substance and such that said resulting optical signal is collected by the second end of the fiber optic and transmitted to the first end of the fiber optic; and separating at the first end of the fiber optic said illumination beam from said resulting optical signal.
Claim 4
Dependent Claim 16 words
A method as claimed in claim 2 wherein said substrate is porous glass or sintered glass.
Claim 5
Independent Claim 166 words
An apparatus for monitoring physical and chemical parameters of an associated sample substance and for generating an optical signal related to said physical and chemical parameters, the apparatus comprising: a fluorescent substance having an absorption band and an emission band; an absorber substance having an absorption band overlapping the emission band of the fluorescent substance, the degree of overlap being responsive to the physical and chemical parameters of the associated sample substance; a substrate on which the fluorescent substance and the absorber substance are immobilized such that an effective number of molecules of the absorber substance are closely adjacent e.g. within about 10-100 Angstroms to an effective number of molecules of the fluorescent substance so that resonant energy transfer is capable of occurring therebetween; means for illuminating the fluorescent substance with light having a wavelength within the absorption band of the fluorescent substance so that excited fluorescent states are generated; and means for detecting an optical signal resulting from the decay of the excited fluorescent states.
Claim 6
Independent Claim 166 words
An apparatus for monitoring physical and chemical parameters of an associated sample substance and for generating an optical signal related to said physical and chemical parameters, the apparatus comprising: a fluorescent substance having an absorption band and an emission band; an absorber substance having an absorption band overlapping the emission band of the fluorescent substance, the degree of overlap being responsive to the physical and chemical parameters of the associated sample substance; a substrate on which the fluorescent substance and the absorber substance are immobilized such that an effective number of molecules of the absorber substance are closely adjacent e.g. within about 10-100 Angstroms to an effective number of molecules of the fluorescent substance so that resonant energy transfer is capable of occurring therebetween; means for illuminating the fluorescent substance with light having a wavelength within the absorption band of the fluorescent substance so that excited fluorescent states are generated; and means for detecting an optical signal resulting from the decay of the excited fluorescent states.
Claim 7
Dependent Claim 131 words
An apparatus as claimed in claim 4 wherein said means for illuminating includes a fiber optic through which an illumination beam from an associated light source is transmitted from a first end to a second end, the fiber optic having a core, and wherein said substrate is attached to the second end of the fiber optic such that light from the illumination beam emanating from the second end of the fiber optic illuminates said fluorescent substance, and such that said resulting optical signal is collected by the second end of the fiber optic and transmitted to the first end of the fiber optic, and wherein said means for illuminating includes separation means adjacent to the first end of the fiber optic for separating the illumination beam from said resulting optical signal.
Claim 8
Dependent Claim 70 words
An apparatus as claimed in claim 4 or claim 5 wherein the substrate is a carrier particle made of, for example, porous glass or sintered glass, said porous glass or sintered glass optionally being doped with ions of fluorescent lanthanides or fluorescent actinides, e.g. by ion implantation so that the implanted ions of said fluorescent lanthanides or fluorescent actinides are between about 10-100 Angstroms of the surface of the glass.
Claim 9
Independent Claim 805 words
A method for detecting: (a) nitrogen oxide in an associated sample substance, the method comprising the steps of: providing a fiber optic through which an illumination beam from an associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic, and a carrier particle attached to the second end of the fiber optic such that light from the illumination beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particles; immobilizing on the carrier particle Saltzman's reagent, the Saltzman's reagent being capable of reacting with nitrogen oxides in the associated sample substance to produce an absorber substance, the absorber substance having an absorption band; immobilizing on the carrier particle a fluorescent substance having an emission band overlapping the absorption band of the absorber substance, and the fluorescent substance being immobilized such that an effective number of molecules of the fluorescent substance are closely adjacent to an effective number of the absorber molecules whenever the Saltzman's reagent reacts with nitrogen oxides in the associated sample fluid; contacting a carrier particle with the associated sample fluid;. illuminating the fluorescent substance with the illumination beam so that excited fluorescent states are generated in the fluorescent substance; collecting at the second end of the fiber optic fluorescent emissions of the fluorescent substance; separating at the first end of the fiber optic the collected fluorescent emissions from the illumination beam; and relating the intensity of the collected and separated fluorescent emissions to the concentration of nitrogen oxides in the associated sample substance; (b) hydrogen sulfide in an associated sample substance, the method comprising the steps of: providing a fiber optic through which an illumination beam from as associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic, and a carrier particle attached to the second end of the fiber optic such that light from the illumination beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particle; immobilizing on the carrier particle lead acetate, the lead acetate being capable of reacting with hydrogen sulfide in the associated sample substance to produce lead sulfide, and the lead sulfide having an absorption band; immobilizing on the carrier particle a fluorescent substance having an emission band overlapping the absorption band of the lead sulfide e.g. fluorescein or acridine orange and the fluorescent substance being immobilized such that an effective number of molecules of the fluorescent substance are closely adjacent to an effective number of lead sulfide molecules whenever lead acetate reacts with hydrogen sulfide; contacting the carrier particle with the associated sample fluid; illuminating the fluorescent substance with the illumination beam so that excited fluorescent states are generated in the fluorescent substance; collecting at the second end of the fiber optic fluorescent emissions of the fluorescent substance; separating at the first end of the fiber optic the collected fluorescent emissions from the illuminating beam; and relating the intensity of collected and separated fluorescent emissions to the concentration of hydrogen sulfide in the associated sample substances; or (c) alkali metal ions e.g. potassium and/or sodium, in an associated sample substance, the method comprising the steps of: providing a fiber optic through which an illumination beam from an associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic; providing a carrier particle attached to the second end of the fiber optic such that light from the illumination beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particle; immobilizing on the carrier particle a chromogenic crown ether, the chromogenic crown ether being capable of interacting with the alkali metal ions in the associated sample substance to produce a crown ether-alkali metal ion complex, e.g. crown-7, crown-6, crown-5 or crown-4 ethers the crown ether-­alkali metal ion complex having an absorption band; immobilizing on the carrier particle a fluorescent substance having an emission band overlapping the absorption band of the crown ether-alkali metal ion complex e.g. fluorescein, the fluorescent substance being immobilized such that an effective number of molecules of the fluorescent substance are closely adjacent to an effective number of crown ether-alkali metal ion complexes whenever said complexes are formed; contacting the carrier particle with the associated sample fluid; illuminating the fluorescent substance with the illumination beam so that excited fluorescent states are generated in the fluorescent substance; collecting at the second end of the fiber optic fluorescent emissions of the fluorescent substance; separating at the first end of the fiber optic the collected fluorescent emissions from the illumination beam; and relating the intensity of the collected and separated fluorescent emissions to the concentration of alkali metal ions in the associated sample substance.
Claim 10
Independent Claim 805 words
A method for detecting: (a) nitrogen oxide in an associated sample substance, the method comprising the steps of: providing a fiber optic through which an illumination beam from an associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic, and a carrier particle attached to the second end of the fiber optic such that light from the illumination beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particles; immobilizing on the carrier particle Saltzman's reagent, the Saltzman's reagent being capable of reacting with nitrogen oxides in the associated sample substance to produce an absorber substance, the absorber substance having an absorption band; immobilizing on the carrier particle a fluorescent substance having an emission band overlapping the absorption band of the absorber substance, and the fluorescent substance being immobilized such that an effective number of molecules of the fluorescent substance are closely adjacent to an effective number of the absorber molecules whenever the Saltzman's reagent reacts with nitrogen oxides in the associated sample fluid; contacting a carrier particle with the associated sample fluid;. illuminating the fluorescent substance with the illumination beam so that excited fluorescent states are generated in the fluorescent substance; collecting at the second end of the fiber optic fluorescent emissions of the fluorescent substance; separating at the first end of the fiber optic the collected fluorescent emissions from the illumination beam; and relating the intensity of the collected and separated fluorescent emissions to the concentration of nitrogen oxides in the associated sample substance; (b) hydrogen sulfide in an associated sample substance, the method comprising the steps of: providing a fiber optic through which an illumination beam from as associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic, and a carrier particle attached to the second end of the fiber optic such that light from the illumination beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particle; immobilizing on the carrier particle lead acetate, the lead acetate being capable of reacting with hydrogen sulfide in the associated sample substance to produce lead sulfide, and the lead sulfide having an absorption band; immobilizing on the carrier particle a fluorescent substance having an emission band overlapping the absorption band of the lead sulfide e.g. fluorescein or acridine orange and the fluorescent substance being immobilized such that an effective number of molecules of the fluorescent substance are closely adjacent to an effective number of lead sulfide molecules whenever lead acetate reacts with hydrogen sulfide; contacting the carrier particle with the associated sample fluid; illuminating the fluorescent substance with the illumination beam so that excited fluorescent states are generated in the fluorescent substance; collecting at the second end of the fiber optic fluorescent emissions of the fluorescent substance; separating at the first end of the fiber optic the collected fluorescent emissions from the illuminating beam; and relating the intensity of collected and separated fluorescent emissions to the concentration of hydrogen sulfide in the associated sample substances; or (c) alkali metal ions e.g. potassium and/or sodium, in an associated sample substance, the method comprising the steps of: providing a fiber optic through which an illumination beam from an associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic; providing a carrier particle attached to the second end of the fiber optic such that light from the illumination beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particle; immobilizing on the carrier particle a chromogenic crown ether, the chromogenic crown ether being capable of interacting with the alkali metal ions in the associated sample substance to produce a crown ether-alkali metal ion complex, e.g. crown-7, crown-6, crown-5 or crown-4 ethers the crown ether-­alkali metal ion complex having an absorption band; immobilizing on the carrier particle a fluorescent substance having an emission band overlapping the absorption band of the crown ether-alkali metal ion complex e.g. fluorescein, the fluorescent substance being immobilized such that an effective number of molecules of the fluorescent substance are closely adjacent to an effective number of crown ether-alkali metal ion complexes whenever said complexes are formed; contacting the carrier particle with the associated sample fluid; illuminating the fluorescent substance with the illumination beam so that excited fluorescent states are generated in the fluorescent substance; collecting at the second end of the fiber optic fluorescent emissions of the fluorescent substance; separating at the first end of the fiber optic the collected fluorescent emissions from the illumination beam; and relating the intensity of the collected and separated fluorescent emissions to the concentration of alkali metal ions in the associated sample substance.
Claim 11
Independent Claim 185 words
An apparatus for monitoring alkali metal ions in an associated sample substance, the apparatus comprising; a fiber optic through which an illumination beam from an associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic; a carrier particle e.g. porous glass attached to the second end of the fiber optic such that light from the illuminator beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particle; an effective number of molecules of a fluorescent substance e.g. fluorescein immobilized on the carrier particle, the fluorescent substance having an emission band; and an effective number of molecules of a chromogenic crown ether immobilized on the carrier particle, the chromogenic crown ether having a first absorption band, and the chromogenic crown ether being capable of forming a crown ether-alkali metal ion complex e.g. 18-crown-6 or 15-crown-5 ether, the crown ether-alkali metal ion complex having a second absorption band, and the first absorption band and the second absorption band overlapping the emission band of the fluorescent substance to different degrees.
Claim 12
Independent Claim 185 words
An apparatus for monitoring alkali metal ions in an associated sample substance, the apparatus comprising; a fiber optic through which an illumination beam from an associated light source is transmitted from a first end of the fiber optic to a second end of the fiber optic; a carrier particle e.g. porous glass attached to the second end of the fiber optic such that light from the illuminator beam emanating from the second end of the fiber optic illuminates a substantial portion of the carrier particle; an effective number of molecules of a fluorescent substance e.g. fluorescein immobilized on the carrier particle, the fluorescent substance having an emission band; and an effective number of molecules of a chromogenic crown ether immobilized on the carrier particle, the chromogenic crown ether having a first absorption band, and the chromogenic crown ether being capable of forming a crown ether-alkali metal ion complex e.g. 18-crown-6 or 15-crown-5 ether, the crown ether-alkali metal ion complex having a second absorption band, and the first absorption band and the second absorption band overlapping the emission band of the fluorescent substance to different degrees.
Claim 13
Independent Claim 109 words
A method of constructing an optrode for sensing alkali metal ions, the method comprising the steps of: providing a fiber optic having a first end and a second end; attaching a carrier particle to the second end of the fiber optic, the carrier particle comprising amino-derivatized controlled pore glass; immersing the carrier particle in a solution of cumene, the solution containing fluorescein isothiocyanate at a concentration of between about 50-150 ppm, and a chromogenic crown ether selected from 4'-picrylaminobenzo-18-crown-6 and 4'-picrylaminobenzo-15-crown-5, the chromogenic crown ether being present at a concentration of between about 50-150 ppm; washing the carrier particle in a solution of cumene; and drying the carrier particle.
Claim 14
Independent Claim 109 words
A method of constructing an optrode for sensing alkali metal ions, the method comprising the steps of: providing a fiber optic having a first end and a second end; attaching a carrier particle to the second end of the fiber optic, the carrier particle comprising amino-derivatized controlled pore glass; immersing the carrier particle in a solution of cumene, the solution containing fluorescein isothiocyanate at a concentration of between about 50-150 ppm, and a chromogenic crown ether selected from 4'-picrylaminobenzo-18-crown-6 and 4'-picrylaminobenzo-15-crown-5, the chromogenic crown ether being present at a concentration of between about 50-150 ppm; washing the carrier particle in a solution of cumene; and drying the carrier particle.
Claim 15
Independent Claim 108 words
A method of constructing an optrode for sensing alkali metal ions, the method comprising the steps of: providing a fiber optic having a first end and a second end; attaching a carrier particle to the second end of the fiber optic, the carrier particle comprising controlled pore glass having a hydrophobic coating; immersing the carrier particle in an organic solvent containing hexadecanoyl fluorescein at a concentration of between about 50-150 ppm, and a chromogenic crown ether selected from the group consisting of 4'-picrylaminobenzo-18-crown-6 and 4'-picrylaminobenzo-15-crown-5, the chromogenic crown ether being present at a concentration of between about 50-150 ppm; and removing the carrier particles from the organic solvent.
Claim 16
Independent Claim 108 words
A method of constructing an optrode for sensing alkali metal ions, the method comprising the steps of: providing a fiber optic having a first end and a second end; attaching a carrier particle to the second end of the fiber optic, the carrier particle comprising controlled pore glass having a hydrophobic coating; immersing the carrier particle in an organic solvent containing hexadecanoyl fluorescein at a concentration of between about 50-150 ppm, and a chromogenic crown ether selected from the group consisting of 4'-picrylaminobenzo-18-crown-6 and 4'-picrylaminobenzo-15-crown-5, the chromogenic crown ether being present at a concentration of between about 50-150 ppm; and removing the carrier particles from the organic solvent.

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