GB2228082A - Gas or liquid chemical sensor - Google Patents

Gas or liquid chemical sensor Download PDF

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Publication number
GB2228082A
GB2228082A GB8900752A GB8900752A GB2228082A GB 2228082 A GB2228082 A GB 2228082A GB 8900752 A GB8900752 A GB 8900752A GB 8900752 A GB8900752 A GB 8900752A GB 2228082 A GB2228082 A GB 2228082A
Authority
GB
United Kingdom
Prior art keywords
detected
detector
waveguide
sensor according
sensor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB8900752A
Other versions
GB8900752D0 (en
Inventor
Michael Roy Worboys
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BAE Systems Electronics Ltd
Original Assignee
GEC Marconi Ltd
Marconi Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GEC Marconi Ltd, Marconi Co Ltd filed Critical GEC Marconi Ltd
Priority to GB8900752A priority Critical patent/GB2228082A/en
Publication of GB8900752D0 publication Critical patent/GB8900752D0/en
Publication of GB2228082A publication Critical patent/GB2228082A/en
Withdrawn legal-status Critical Current

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Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/645Specially adapted constructive features of fluorimeters
    • G01N21/648Specially adapted constructive features of fluorimeters using evanescent coupling or surface plasmon coupling for the excitation of fluorescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J9/00Measuring optical phase difference; Determining degree of coherence; Measuring optical wavelength
    • G01J9/02Measuring optical phase difference; Determining degree of coherence; Measuring optical wavelength by interferometric methods
    • G01J2009/028Types
    • G01J2009/0288Machzehnder
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432Quenching
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769Measurement method of reaction-produced change in sensor
    • G01N2021/7779Measurement method of reaction-produced change in sensor interferometric
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769Measurement method of reaction-produced change in sensor
    • G01N2021/7786Fluorescence
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G01N21/783Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour for analysing gases

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  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Optics & Photonics (AREA)
  • Molecular Biology (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)

Abstract

A sensor for detecting chemical substances comprises an optical waveguide C, a portion of which has provided thereon a layer A of a detector material whose optical characteristics are changed by contact with a chemical substance to be detected. A light source E is provided at one end of the waveguide, and detector means detect a change in the light emerging from the other end of the waveguide as a result of a change in the optical characteristics of the detector material, thereby indicating the presence of the chemical substance to be detected. The sensor may be in the form of a Mach-Zehnder interferometer or the detector material may be rendered fluorescent, or have its fluorescence reduced, by reaction with the substance to be detected. <IMAGE>

Description

GAS AND LIQUID SENSOR This invention relates to a sensor for detecting gaseous or liquid chemica] substances.
According to the invention, a sensor for detecting chemica] substances comprises an optical waveguide, a portion of which has provided thereon a layer of a detector material whose optical character5 st3 Cs are changed by contact with a. chemical substance to be detected, a Wight. source at. one end of the waveguide, and detector means for detecting a change in the light emerging from the other end of the waveguide as a result of the change in the optica]. characteristics of the detector material.
Preferably the said portion of the optical waveguide forms one branch of a Mach Zehnder Interferometer. The detector material may be, for example, an enzyme, the substrate for which is the chemical substance to be detected. An example of such an enzyme is cholinesterase, for detecting materials such as insecticides harmful to the human nervous system. Alternatively, substances such as porphyrins could be used for the detection of hydrogen cyanide.
Another class of detector material usab3e in the sensor of the invention is antibodies specific to the chemical substance to be detected, in particular monoclonal antibodies.
In one aspect of the invention, the detector material is such as to be rendered fluorescent by reaction with the chemical substance. to be detected.
The light source is arranged to emit light of a.
wavelength which will excite fluorescence in the reacted detector material, and the detector means is arranged to detect light due to the fluorescence. Alternatively, the detector material may he a fluorescent material, the fluorescence of which is reduced by reaction with the chemical substance to be detected.
The detecting material may be directly bonded onto the surface of the waveguide and surrounding support, or it may be included in a polymer, preferably porolls, which is coated onto the surface.
Ry suitable choice. of detector material the sensor -could be made sensitive to different substances. It would be possible, using integrated optics techniques, to design an array of sensors, each coated with a different material so that the sensor would have a broad band response. Pattern recognition techniques could be used to decode the array output and determine which substance had been detected.
The sensor could be used for continuous or intermittent monitoring of various substances. The waveguide portions of the sensors could be mounted on a tape which is used to load a fresh portion into the optical system after it has been triggered by a contact with the material to be detected.
Reference js made to the drawings, in which: Figures 1, 2 and :3 are respectively perspective view, plan view and side elevatidn of a sensor according to one embodiment of the invention, omitting the light source and detector; and Figure 9 is a plan view of a sensor according to an alternative embodiment of the invention.
Referring first to Figures ] to 3, the sensor comprises an optical base D formed of a material such as a glass or a polymer, in which is formed an optical waveguide C, for example by etching recesses in the optical base and filling the recesses with a polymer, or by metal ion exchange in a glass to define the guiding region. The waveguide is in th form of a Mach Zehnder Interferometer, light bering introduced at E and exiting at F. A layer of active detector material, for example an enzyme, is formed over the two branches of the Mach Zehnder Interferometer and one half B of the layer, overlying one of the branches of the interferometer, is deactivated or removed, leaving a panel of active detector material A over the other branch of the interferometer.
When the substance to be detected, for example the substrate of the enzyme, comes into contact with the active layer A either the refractive index of the layer or its the light scattering properties are changed such that the light in the branch of the interferometer underlying the active material undergoes a phase change, and interference occurs at the junction J where the two branches rejoin so that there is a change. in the light output at F-. This change can be detect and can be used eo give a warning of the presence of the substance to be detected.
Over a certain concentration range, the change in light output may be proportional to the concentration and this may permit, at least approximately, an estimate of the concentration of the substance to be detected.
In the alternative embodiment shown in Figure 4, instead of the recombination of the optical waveguide into a single waveguide at junction J, the two waveguides are run alongside each other such that a degree of coupling occurs. The waveguides then separate. By selection of suitable operating conditions, the outputs from each waveguide can be made to be complimentary, such that when a substance is detected, the output from one waveguide will increase while that from the other will decrease. sing this technique enables greater. sensitivity to be achieved, as in the untriggered state both outputs are equivalent.
Measurement of a change in output between the two waveguides is inherently less sensitive to noise fluctuations than determining the absolute output level from a single waveguide.
In another alternative embodiment, not shown, the optical base- in -which the waveguides are defined is formed of an electro--optic material, for example lithium niohate. Electrodes are placed on either side of the waveguide, below the lay of detector material.
Applying a field across the electrodes permits the waveguide to be tuned to its optimum operating conditions for use as a sensor.

Claims (11)

1. A sensor for detecting chemical substances, comprising an optical waveguide a portion of which has provided thereon a layer of a detector material whose optical characteristics are changed hy contact with a chemical substance to be detected, a light source at one end of the waveguide, and detector means for detecting a change in the light emerging from the other end of the waveguide as a result of a change in the optical characteristics of the detector material.
2. A sensor according to Claim 1, wherein the said portion of the optical waveguide forms one branch of a Mach Zehnder interferometer.
3. A sensor according to Claim 1 or 2, wherein the detector material is an enzyme, the substrate for which is the chemical substance to be detected.
4. A sensor according to Claim 3, wherein the enzyme is cholinesterase.
5. A sensor according to Claim 1 or 2, wherein the detector material comprises antibodies specific to- chemical substance to be detected.
6. A sensor according to Claim 1, wherein the detector material is such as to be rendered fluorescent by reaction with the chemical substance to be detected, the light source emits light of a wavelength which will excite fluorescence in the reacted detector material, and the detector means is arranged to detect light due to said fluorescence.
7. A sensor according to Claim 1, wherein the detector material is a fluorescent material, the fluorescence of which is reduced by reaction with the chemical substance to be detected, the light source emits light of a wavelength which will excite fluorescence in the material, and the detector means is arranged to detect a change in the quantity of light due to said fluorescence.
8. A sensor according to Claim 2, wherein the first and second branches of the Mach Zehnder interferometer are coupled together and reseparated, and the detector means comprise a light-sensitive element at the end of each branch to detected the presence or absence of light emerging from each.
9. A sensor according to any preceding claim, wherein the detector material is supported in a porous matrix.
10. A sensor according to any preceding claim, wherein the waveguide is formed in a body of electro-optic material, and means are provided for selectively applying a field across the waveguide, whereby the sensor response may be varied.
11. A sensor for detecting chemical substances, substantially as described with reference to the drawings.
GB8900752A 1989-01-13 1989-01-13 Gas or liquid chemical sensor Withdrawn GB2228082A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8900752A GB2228082A (en) 1989-01-13 1989-01-13 Gas or liquid chemical sensor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8900752A GB2228082A (en) 1989-01-13 1989-01-13 Gas or liquid chemical sensor

Publications (2)

Publication Number Publication Date
GB8900752D0 GB8900752D0 (en) 1990-04-25
GB2228082A true GB2228082A (en) 1990-08-15

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Family Applications (1)

Application Number Title Priority Date Filing Date
GB8900752A Withdrawn GB2228082A (en) 1989-01-13 1989-01-13 Gas or liquid chemical sensor

Country Status (1)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992005429A1 (en) * 1990-09-20 1992-04-02 Battelle Memorial Institute Optical immunoassay
EP0481440A2 (en) * 1990-10-19 1992-04-22 Iot Entwicklungsgesellschaft Für Integrierte Optik-Technologie Mbh Sensor for the detection of a substance
EP0487992A2 (en) * 1990-11-24 1992-06-03 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Optical sensor
WO1993020430A1 (en) * 1992-04-02 1993-10-14 Battelle Memorial Institute Integrated optical compensating refractometer apparatus
FR2694630A1 (en) * 1992-08-10 1994-02-11 Commissariat Energie Atomique Sensor in integrated optics, especially for chemical substances.
EP0731909A1 (en) * 1993-02-05 1996-09-18 The State Of Oregon Acting By And Through The Oregon Stateboard Of Higher Education On Behalf Of Oregon State University Sensors employing interference of electromagnetic waves passing through waveguides having functionalized surfaces
GB2307741A (en) * 1995-11-30 1997-06-04 Fraunhofer Ges Forschung Polymer-based integrated optical sensors
WO1999006819A1 (en) * 1997-07-29 1999-02-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Optical detector device
GB2340231A (en) * 1998-07-28 2000-02-16 Merck Patent Gmbh Optical transducers based on liquid crystalline phases
WO2002008736A1 (en) * 2000-07-25 2002-01-31 Farfield Sensors Limited Sensor device
GB2385915A (en) * 2001-10-19 2003-09-03 Optomed As Fibre optic sensing of measurands within the body
US7440110B2 (en) 2001-10-19 2008-10-21 Invivosense Asa Optical sensing of measurands
CN102042971A (en) * 2010-10-19 2011-05-04 天津天狮生物发展有限公司 Integrated optical ozone production volume detection device, calibration method and measuring method
WO2011157767A1 (en) * 2010-06-17 2011-12-22 Optisense B.V. Integrated optical waveguide evanescent field sensor
EP2400289A1 (en) * 2010-06-17 2011-12-28 Optisense B.V. Integrated optical waveguide evanescent field sensor

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4050895A (en) * 1975-09-26 1977-09-27 Monsanto Research Corporation Optical analytical device, waveguide and method
US4321057A (en) * 1979-09-20 1982-03-23 Buckles Richard G Method for quantitative analysis using optical fibers
US4513087A (en) * 1983-01-31 1985-04-23 The United States Of America As Represented By The Secretary Of The Navy Reversible optical waveguide vapor sensor
GB2174802A (en) * 1985-04-12 1986-11-12 Plessey Co Plc Optic-waveguide biosensor
GB2176626A (en) * 1985-05-29 1986-12-31 Gen Electric Plc Fibre optic coupler
GB2179146A (en) * 1985-07-31 1987-02-25 Sharp Kk Optical sensor
GB2185308A (en) * 1986-01-10 1987-07-15 Stc Plc Optical waveguide material sensor
GB2208711A (en) * 1988-08-16 1989-04-12 Plessey Co Plc Fibre optic sensor
GB2210685A (en) * 1987-10-05 1989-06-14 Atomic Energy Authority Uk Sensor

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4050895A (en) * 1975-09-26 1977-09-27 Monsanto Research Corporation Optical analytical device, waveguide and method
US4321057A (en) * 1979-09-20 1982-03-23 Buckles Richard G Method for quantitative analysis using optical fibers
US4513087A (en) * 1983-01-31 1985-04-23 The United States Of America As Represented By The Secretary Of The Navy Reversible optical waveguide vapor sensor
GB2174802A (en) * 1985-04-12 1986-11-12 Plessey Co Plc Optic-waveguide biosensor
GB2176626A (en) * 1985-05-29 1986-12-31 Gen Electric Plc Fibre optic coupler
GB2179146A (en) * 1985-07-31 1987-02-25 Sharp Kk Optical sensor
GB2185308A (en) * 1986-01-10 1987-07-15 Stc Plc Optical waveguide material sensor
GB2210685A (en) * 1987-10-05 1989-06-14 Atomic Energy Authority Uk Sensor
GB2208711A (en) * 1988-08-16 1989-04-12 Plessey Co Plc Fibre optic sensor

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5377008A (en) * 1990-09-20 1994-12-27 Battelle Memorial Institute Integrated optical compensating refractometer apparatus
WO1992005429A1 (en) * 1990-09-20 1992-04-02 Battelle Memorial Institute Optical immunoassay
EP0481440A3 (en) * 1990-10-19 1992-11-19 Iot Entwicklungsgesellschaft Fuer Integrierte Optik-Technologie Mbh Sensor for the detection of a substance
US5262842A (en) * 1990-10-19 1993-11-16 IOT Entwicklungsgesellschaft fur integrierte Optiktechnologie mbH Optical sensor having a wave guide substrate with interferometer integrated therein
EP0481440A2 (en) * 1990-10-19 1992-04-22 Iot Entwicklungsgesellschaft Für Integrierte Optik-Technologie Mbh Sensor for the detection of a substance
EP0487992A3 (en) * 1990-11-24 1992-11-19 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Optical sensor
EP0487992A2 (en) * 1990-11-24 1992-06-03 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Optical sensor
WO1993020430A1 (en) * 1992-04-02 1993-10-14 Battelle Memorial Institute Integrated optical compensating refractometer apparatus
FR2694630A1 (en) * 1992-08-10 1994-02-11 Commissariat Energie Atomique Sensor in integrated optics, especially for chemical substances.
EP0584005A1 (en) * 1992-08-10 1994-02-23 Commissariat A L'energie Atomique Integrated optical sensor, especially for chemical substances
US5394239A (en) * 1992-08-10 1995-02-28 Commissariat A L'energie Atomique Spinal sensor with integrated optics to detect chemical substances
EP0731909A4 (en) * 1993-02-05 1997-09-03 Oregon State Sensors employing interference of electromagnetic waves passing through waveguides having functionalized surfaces
EP0731909A1 (en) * 1993-02-05 1996-09-18 The State Of Oregon Acting By And Through The Oregon Stateboard Of Higher Education On Behalf Of Oregon State University Sensors employing interference of electromagnetic waves passing through waveguides having functionalized surfaces
GB2307741A (en) * 1995-11-30 1997-06-04 Fraunhofer Ges Forschung Polymer-based integrated optical sensors
FR2741963A1 (en) * 1995-11-30 1997-06-06 Fraunhofer Ges Forschung OPTICAL SENSOR PRODUCED ACCORDING TO THE TECHNIQUE OF INTEGRATED OPTICS AND POLYMER-BASED FORM
GB2307741B (en) * 1995-11-30 2000-03-15 Fraunhofer Ges Forschung Polymer-based integrated optical sensors
WO1999006819A1 (en) * 1997-07-29 1999-02-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Optical detector device
US6239876B1 (en) 1997-07-29 2001-05-29 Fräunhofer-Gesellschaft zur Förderung der Angewandten Forschung e.V. Optical detector device
GB2340231A (en) * 1998-07-28 2000-02-16 Merck Patent Gmbh Optical transducers based on liquid crystalline phases
WO2002008736A1 (en) * 2000-07-25 2002-01-31 Farfield Sensors Limited Sensor device
GB2385915A (en) * 2001-10-19 2003-09-03 Optomed As Fibre optic sensing of measurands within the body
GB2385915B (en) * 2001-10-19 2005-09-28 Optomed As Optical sensing of measurands
US7440110B2 (en) 2001-10-19 2008-10-21 Invivosense Asa Optical sensing of measurands
WO2011157767A1 (en) * 2010-06-17 2011-12-22 Optisense B.V. Integrated optical waveguide evanescent field sensor
EP2400289A1 (en) * 2010-06-17 2011-12-28 Optisense B.V. Integrated optical waveguide evanescent field sensor
CN102042971A (en) * 2010-10-19 2011-05-04 天津天狮生物发展有限公司 Integrated optical ozone production volume detection device, calibration method and measuring method
CN102042971B (en) * 2010-10-19 2012-07-18 天津天狮生物发展有限公司 Integrated optical ozone production volume detection device, calibration method and measuring method

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