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EP0283116A2 Expired / Lapsed EP ⏱️ 0.0 years remaining

Sensor system

Assignee: Shiley Inc
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Filing: 1988-02-04
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Granted: —
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Expires: 2008-02-04
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Abstract

Abstract A sensor system for determining the pH or carbon dioxide concentration of a liquid medium comprising, in combination, a pH-insensitive fluorescent indicator and a pH-sensitive fluorescent indicator which act in concert or a single fluorescence indicator which emits fluorescent signals of different wavelengths in different carriers, which system(s) produce diverging signals, the ratio of which provides an accurate and stable determination of the parameter being measured. A method for determing pH and CO₂ concentration is also disclosed.

Inventors

  • 👤 Matthew James Leader
  • 👤 Tadao Kamiya

Bibliographic Details

Application Number —
Jurisdiction EP
Data Source google_patents
Last Synchronized 2026-11-04 04:16
CPC Classifications
G; G01; G01N; G01N21/00; G01N21/62; G01N21/63; G01N21/64; G01N21/6428; G01N21/643; G01N21/75; G01N21/77; G01N21/7703; G01N21/01; G01N21/03; G01N2021/0385; G01N2021/6417; G01N2021/6421; G01N2021/6434; G01N2021/6439; G01N2021/6441; G01N2021/7706; G01N2021/772; G01N2021/775; G01N2021/7769; G01N2021/7786; G01N21/78; G01N21/80; Y; Y10; Y10T; Y10T436/00; Y10T436/20; Y10T436/204998; Y10T436/25; Y10T436/25375; Y10T436/255

Claims Analysis

Total Claims: 15
Claim 1
Independent Claim 150 words
A sensor system for determining the pH of a liquid medium characterized in that it comprises, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescence emission is highly sensitive to solution pH, which indicator combination is adapted to respond when a source of excitation radiation of wavelength λ o is applied to the system such that said first fluorescent indicator is selectively excited by said excitation radiation to emit pH-insensitive fluorescence emission at wavelength λ ₁, emission overlaps the excitation radiation spectrum of said second fluorescent indicator, and said second indicator being excited by said emission radiation of wavelength λ ₁ and in turn emitting a pH-dependent fluorescence emission of wavelength λ ₂, the ratio of intensities of the radiation of wavelengths λ ₁/ λ ₂ providing a highly accurate, stable determination of the pH of said liquid medium.
Claim 2
Dependent Claim 150 words
A sensor system for determining the pH of a liquid medium characterized in that it comprises, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescence emission is highly sensitive to solution pH, which indicator combination is adapted to respond when a source of excitation radiation of wavelength λ o is applied to the system such that said first fluorescent indicator is selectively excited by said excitation radiation to emit pH-insensitive fluorescence emission at wavelength λ ₁, emission overlaps the excitation radiation spectrum of said second fluorescent indicator, and said second indicator being excited by said emission radiation of wavelength λ ₁ and in turn emitting a pH-dependent fluorescence emission of wavelength λ ₂, the ratio of intensities of the radiation of wavelengths λ ₁/ λ ₂ providing a highly accurate, stable determination of the pH of said liquid medium.
Claim 3
Dependent Claim 49 words
A sensor system according to claim 1, characterized in that includes an optical fiber having a distal end and a proximal end and in which said combination of fluorescent indicators is attached to said distal end and said proximal end is adapted to receive excitation radiation from said source.
Claim 4
Dependent Claim 33 words
A sensor system according to claim 1, characterized in that said first fluorescent indicator is 6,7-dimethoxycoumarin or a pH- insensitive coumarin derivative and said second fluorescent indicator is 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid (HPTA).
Claim 5
Independent Claim 173 words
A method for determining the pH of a liquid medium, characterized in that it comprises contacting said medium with a sensor system comprising, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescence emission is highly sensitive to solution pH, subjecting said sensor system to excitation radiation of a predetermined wavelength λ o, thereby selectively exciting said first fluorescent indicator to emit a pH-insensitive fluorescence emission at a wavelength of λ ₁, which emission overlaps the excitation radiation spectrum of said second fluorescent indicator and thus excites said second indicator to emit a pH-dependent fluorescence emission of wavelength λ ₂, and measuring either (i) the ratio of intensities of the emitted radiation of wavelengths λ ₁/λ ₂, or (ii) the ratio derived from the intensity of the emitted radiation of wavelength       ₁ and the intensity at the isobestic point between the emission curves of said first and second indications, thereby obtaining a highly accurate, stable determination of the pH of said liquid medium.
Claim 6
Independent Claim 173 words
A method for determining the pH of a liquid medium, characterized in that it comprises contacting said medium with a sensor system comprising, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescence emission is highly sensitive to solution pH, subjecting said sensor system to excitation radiation of a predetermined wavelength λ o, thereby selectively exciting said first fluorescent indicator to emit a pH-insensitive fluorescence emission at a wavelength of λ ₁, which emission overlaps the excitation radiation spectrum of said second fluorescent indicator and thus excites said second indicator to emit a pH-dependent fluorescence emission of wavelength λ ₂, and measuring either (i) the ratio of intensities of the emitted radiation of wavelengths λ ₁/λ ₂, or (ii) the ratio derived from the intensity of the emitted radiation of wavelength       ₁ and the intensity at the isobestic point between the emission curves of said first and second indications, thereby obtaining a highly accurate, stable determination of the pH of said liquid medium.
Claim 7
Dependent Claim 100 words
A method according to claim 4, characterized in that the sensor system includes an optical fiber having a distal end and a proximal end, said combination of said first and second fluorescent indicators is attached to the distal end of said optical fiber and said proximal end is adapted to receive excitation radiation of wavelength, λ o, 337 nm from a laser, said first fluorescent indicator is 6, 7-dimethoxycoumarin which emits fluorescent radiation of wavelength, λ ₁, 435 nm and said second, pH-sensitive, fluorescent indicator is 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid which emits fluorescent radiation of wavelength, λ ₂, 510 nm.
Claim 8
Dependent Claim 182 words
A sensor system for the determination of the concentration of carbon dioxide in a liquid medium characterized in that it comprises, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescent emission is highly sensitive to solution pH, which indicator combination is associated with a bicarbonate solution bounded by a carbon dioxide-permeable membrane, and is adapted to respond when a source of excitation radiation of wavelength λ o is applied to the system such that said first fluorescent indicator is selectively excited by said excitation radiation to emit a pH-insensitive fluorescence emission at wavelength λ ₁, which emission overlaps the excitation radiation spectrum of said second fluorescent indicator, said second indicator being excited by said emission radiation of wavelength λ ₁, and in turn emitting a pH-dependent fluorescence emission of wavelength λ ₂, the ratio of intensities of the radiation of wavelengths λ ₁/λ ₂ providing an indication of the solution pH within the membrane and thereby a highly accurate, stable determination of the concentration of carbon dioxide in the liquid medium.
Claim 9
Dependent Claim 182 words
A sensor system for the determination of the concentration of carbon dioxide in a liquid medium characterized in that it comprises, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescent emission is highly sensitive to solution pH, which indicator combination is associated with a bicarbonate solution bounded by a carbon dioxide-permeable membrane, and is adapted to respond when a source of excitation radiation of wavelength λ o is applied to the system such that said first fluorescent indicator is selectively excited by said excitation radiation to emit a pH-insensitive fluorescence emission at wavelength λ ₁, which emission overlaps the excitation radiation spectrum of said second fluorescent indicator, said second indicator being excited by said emission radiation of wavelength λ ₁, and in turn emitting a pH-dependent fluorescence emission of wavelength λ ₂, the ratio of intensities of the radiation of wavelengths λ ₁/λ ₂ providing an indication of the solution pH within the membrane and thereby a highly accurate, stable determination of the concentration of carbon dioxide in the liquid medium.
Claim 10
Dependent Claim 105 words
A sensor system according to claim 6, characterized in that it includes an optical fiber having a distal end and a proximal end and in which said combination of fluorescent indicators, bicarbonate solution and membrane is attached to said distal end and said proximal end is adapted to receive excitation radiation from said source and said first fluorescent indicator is 6, 7-dimethoxycoumarin or a pH-insensitive coumarin derivative which is bonded directly to said optical fiber and said second fluorescent indicator is 8-hydroxy-1, 3, 6-pyrenetrisulfonic acid which is suspended in a gel of carboxymethyl cellulose con­taining said bicarbonate solution and bounded by a silicone rubber membrane.
Claim 11
Independent Claim 204 words
A method for determining the concentration of carbon dioxide in a liquid medium, characterized in that it comprises contacting said medium with a sensor system comprising, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescence emission is highly sensitive to solution pH, which indicators are associated with a bicarbonate solution bounded by a carbon dioxide-permeable membrane, subjecting said sensor system to excitation radiation of a predetermined wavelength λ o, thereby selectively exciting said first fluorescent indicator to emit a pH-insensitive fluorescence emission at a wavelength of λ ₁, which emission overlaps the excitation radiation spectrum of said second fluorescent indicator and thus excites said second indicator to emit a pH-dependent fluorescent emission of wavelength λ ₂, and measuring either (i) the ratio of intensities of the emitted radiation of wavelengths λ ₁/λ ₂, or (ii) the ratio derived from the intensity of the emitted radiation of wavelength       ₁ and the intensity at the isobestic point between the emission curves of said first and second indications, thereby obtaining an indication of the solution pH within the membrane and thus a highly accurate, stable determination of the concentration of carbon dioxide in the liquid medium.
Claim 12
Independent Claim 204 words
A method for determining the concentration of carbon dioxide in a liquid medium, characterized in that it comprises contacting said medium with a sensor system comprising, in combination, a first fluorescent indicator whose fluorescence emission is insensitive to pH and a second fluorescent indicator whose fluorescence emission is highly sensitive to solution pH, which indicators are associated with a bicarbonate solution bounded by a carbon dioxide-permeable membrane, subjecting said sensor system to excitation radiation of a predetermined wavelength λ o, thereby selectively exciting said first fluorescent indicator to emit a pH-insensitive fluorescence emission at a wavelength of λ ₁, which emission overlaps the excitation radiation spectrum of said second fluorescent indicator and thus excites said second indicator to emit a pH-dependent fluorescent emission of wavelength λ ₂, and measuring either (i) the ratio of intensities of the emitted radiation of wavelengths λ ₁/λ ₂, or (ii) the ratio derived from the intensity of the emitted radiation of wavelength       ₁ and the intensity at the isobestic point between the emission curves of said first and second indications, thereby obtaining an indication of the solution pH within the membrane and thus a highly accurate, stable determination of the concentration of carbon dioxide in the liquid medium.
Claim 13
Independent Claim 262 words
A method of measuring the concentration of carbon dioxide in a medium by determining the water content in a pH-independent sensor system comprising an optical fiber having a proximal end and a distal end, said distal end having attached thereto a fluorescence indicator embedded in a carrier matrix with a controlled water content, said carrier matrix containing a miscible mixture of water and non-aqueous solvent in controlled proportions and being separated from said medium by a gas-permeable, water-impermeable diffusion membrane, said indicator, when excited by excitation radiation of a predetermined wavelength λ o, emitting fluorescent emission at a wavelength λ ₂ in the presence of water and at a wavelength λ s in the presence of said non-aqueous solvent, the intensity of each emission being dependent upon the ratio of water to non-aqueous solvent present in the system such that the ratio of the intensities of emitted radiation of wavelengths λ w and λ s is therefore proportional to the amount of water present and diffusion of carbon dioxide through said gas-permeable membrane and subsequent reaction with water to deplete the water content of the system induces a change in the intensities of said emissions, characterized in that it comprises transmitting through said optical fiber, from a source adjacent to its proximal end, excitation radiation of said predetermined wavelength λ o , and measuring the ratio of the intensities of the emitted radiation of wavelengths λ w and λ s , thereby obtaining a determination of the water content and thus a measurement of the carbon dioxide concentration in the surrounding medium.
Claim 14
Independent Claim 262 words
A method of measuring the concentration of carbon dioxide in a medium by determining the water content in a pH-independent sensor system comprising an optical fiber having a proximal end and a distal end, said distal end having attached thereto a fluorescence indicator embedded in a carrier matrix with a controlled water content, said carrier matrix containing a miscible mixture of water and non-aqueous solvent in controlled proportions and being separated from said medium by a gas-permeable, water-impermeable diffusion membrane, said indicator, when excited by excitation radiation of a predetermined wavelength λ o, emitting fluorescent emission at a wavelength λ ₂ in the presence of water and at a wavelength λ s in the presence of said non-aqueous solvent, the intensity of each emission being dependent upon the ratio of water to non-aqueous solvent present in the system such that the ratio of the intensities of emitted radiation of wavelengths λ w and λ s is therefore proportional to the amount of water present and diffusion of carbon dioxide through said gas-permeable membrane and subsequent reaction with water to deplete the water content of the system induces a change in the intensities of said emissions, characterized in that it comprises transmitting through said optical fiber, from a source adjacent to its proximal end, excitation radiation of said predetermined wavelength λ o , and measuring the ratio of the intensities of the emitted radiation of wavelengths λ w and λ s , thereby obtaining a determination of the water content and thus a measurement of the carbon dioxide concentration in the surrounding medium.
Claim 15
Dependent Claim 84 words
A method according to claim 9, characterized in that said fluorescence indicator is 8-hydroxy-1,3,6-pyrenetrisulfonic acid (HPTA) which emits a fluorescent emission at a peak wavelength λ w of 510 nm in the presence of water and a fluorescent emission at a peak wavelength λ s of 440 nm in the presence of non-aqueous solvent when excited with laser radiation of a wavelength λ o of 337 nm, said non-aqueous solvent is ethylene glycol or ethanol, and said gas-permeable membrane is a silicone rubber membrane.

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