EP1996920A1 - Dispositif d'analyse spectroscopique d'un gaz - Google Patents

Dispositif d'analyse spectroscopique d'un gaz

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Publication number
EP1996920A1
EP1996920A1 EP07723482A EP07723482A EP1996920A1 EP 1996920 A1 EP1996920 A1 EP 1996920A1 EP 07723482 A EP07723482 A EP 07723482A EP 07723482 A EP07723482 A EP 07723482A EP 1996920 A1 EP1996920 A1 EP 1996920A1
Authority
EP
European Patent Office
Prior art keywords
gas
spectroscopic analysis
sample
sample chamber
gas according
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.)
Ceased
Application number
EP07723482A
Other languages
German (de)
English (en)
Inventor
Martin Stockmann
Björn RIECKE
Karsten Heyne
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.)
Charite Universitaetsmedizin Berlin
Freie Universitaet Berlin
Original Assignee
Charite Universitaetsmedizin Berlin
Freie Universitaet Berlin
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 Charite Universitaetsmedizin Berlin, Freie Universitaet Berlin filed Critical Charite Universitaetsmedizin Berlin
Publication of EP1996920A1 publication Critical patent/EP1996920A1/fr
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
    • A61B5/083—Measuring rate of metabolism by using breath test, e.g. measuring rate of oxygen consumption
    • A61B5/0836—Measuring rate of CO2 production
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/08—Detecting, measuring or recording devices for evaluating the respiratory organs
    • A61B5/087—Measuring breath flow
    • A61B5/0873—Measuring breath flow using optical means
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/497—Physical analysis of biological material of gaseous biological material, e.g. breath
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/004—CO or CO2

Definitions

  • the invention relates to a device for spectroscopic analysis of a gas according to the preamble of claim 1, a method for the spectroscopic analysis of a gas according to the preamble of claim 18 and the use of a device according to the invention according to the preamble of claim 28.
  • the analysis of a gas has a variety of applications, especially in medicine.
  • the concentration of 13 CO 2 for example, in the exhaled air of patients who were previously administered 13 C-labeled substances that are metabolized by the body and lead to the production of 13 CO 2 ( 13 C-breath tests) is often examined.
  • Such studies are useful, for example, for the diagnosis of Helicobacter pylori, for measurements of gastric emptying time or for liver function tests.
  • the 13 CO 2 concentration is determined in the prior art by mass spectrometry, Fourier transform infrared spectrometry or by direct inorganic chemical analysis.
  • the use of said techniques usually requires a great deal of expensive equipment or structures that can not be used directly on the patient.
  • NIRS non-dispersive isotope-selective infrared spectroscopy
  • LMA infrared emission and absorption
  • NDIRS The method of NDIRS is sensitive enough to measure, for example, the relative 13 CO 2 concentration changes in the exhaled volume of patients, but shows strongly deviant and therefore difficult to use results for different carrier gas mixtures (eg O 2 ) and allows only a very slow by their slow measurement method limited resolution of 13 C metabolism.
  • the measurement accuracy of the NDIRS is also limited and especially for direct quantitative measurements such as the determination of the quantitative liver function capacity, especially not sufficient, if other measurement influences such as changing carrier gases to occur (Perri, F., RM Zagari, et al. (2003) Inter- and intra-laboratory comparison of breath 13 CO 2 analysis. "Aliment. Pharmacol. Ther. 17 (10): 1291-7).
  • NDIRS devices are not mobile.
  • US 2004/0211905 A1 describes a respiratory analyzer in which parts of exhaled respiratory air are introduced via a gas transfer system into a spectrometer for analysis. In this analyzer, only the relative ratio of two isotopes of a gas to each other can be determined, but not the absolute concentration of a
  • the present invention was based on the problem to provide a device which is suitable for determining the absolute concentration of a gas in a gas mixture; To develop a method by which such a determination is made and to provide a suitable use for a device according to the invention.
  • Such a device for the spectroscopic analysis of a gas has at least one radiation source, at least one detection device, at least one sample chamber and a system of optical elements, which is provided and arranged for this, at least a part of the radiation emitted by the radiation source through the sample chamber to the detection device guide, wherein the sample chamber for receiving a gaseous sample containing the gas to be analyzed, is used.
  • This device is characterized in that it is designed such that the sample can flow through the sample chamber continuously, and that means are provided for determining the pressure and / or the volume and / or the concentration of the sample in the sample chamber.
  • Such means may be, for example, a pressure gauge or a volume meter, optionally in conjunction with a temperature gauge.
  • the system of optical elements consists of lenses, mirrors, filters and beam splitters and comparable elements, the number and sequence of which in the beam path of the device being freely selectable, provided that the desired steering effect is achieved. As a rule, only as many optical elements are used as are necessary for the best possible performance of the device.
  • the device for the spectroscopic analysis of a gas is designed so that essentially only an absorption of a single isotope of the gas is excited by the emitted radiation and / or detected by the detection device.
  • the emitted radiation preferably passes through a filter which is continuous only for radiation in the desired wavelength range.
  • a narrow-band detection device is preferably used which is particularly sensitive in the wavelength range to be analyzed and whose detection power is not significantly influenced by any incident radiation having a different wavelength.
  • the aforementioned functional elements can be used individually or in any combination in a device according to the invention, in order to enable the substantially isotope-selective excitation.
  • the device is preferably designed in such a way that the spectroscopic analysis of the gas takes place in a time-resolved manner.
  • a radiation source is used, which emits pulsed light or a chopper positioned in the beam path, which can convert a continuous radiation by interruptions of the light beam into a radiation with a defined repetition rate.
  • the time resolution is preferably better than 1 second, and more preferably between 0.2 and 0.4 seconds (for example, 0.3 seconds or better). With a preferred embodiment of the invention, therefore, more than 3 measurements per second can be performed, resulting in a fine screening of a time course of the analysis performed.
  • the radiation source preferably emits light having a wavelength from the infrared region, with the middle infrared being particularly preferred.
  • the middle infrared light has a wavelength of about 2.5 to 50 ⁇ m (corresponding to 4000 to 200 cm -1 ).
  • a quantum cascade laser is preferably used.
  • a quantum cascade laser which emits light from a wavenumber range of about 2280 to 2230 cm -1 .
  • the P branch of 13 absorbs CO 2 in the gas phase, while virtually no other interfering absorptions of about 12 CO 2 , H 2 O or O 2 can be observed.
  • a photovoltaic mercury cadmium telluride detector (MCT detector) is preferably used, which does not require cooling by liquid nitrogen.
  • a detection maximum of the detector of approximately 2270 cm -1 is advantageous.
  • Method can also be applied to other substances that have only a low extinction coefficient in each examined area.
  • the mirrors are arranged such that the beam path to be traveled by the light beam within the sample chamber is longer than 1.5 m and up to 2.5 m or longer.
  • the sample chamber itself is only a few centimeters or decimetres tall.
  • the sample to be examined is respiratory air containing the gas to be analyzed.
  • the breathing air is preferably exhaled directly from an individual into the device, so that the breathing air is exhaled air.
  • the gas to be analyzed is 13 CO 2 in a preferred embodiment of the invention.
  • exhaled breath or other sample is preferably by means of a tube which is heated in a preferred embodiment to prevent water from collecting in the tube and to ensure that the gas temperature remains constant.
  • a tube which is heated in a preferred embodiment to prevent water from collecting in the tube and to ensure that the gas temperature remains constant.
  • it is preferably designed such that only specially developed D
  • Hoses can be connected to the device. If necessary, use a first adapter for the connection. If breathing air is to be analyzed as a sample, it is expedient to provide the hose with a second adapter in the form of a mouthpiece in order to allow a simple injection of breathing air into the hose.
  • the sample which has flowed into the sample chamber can also leave the sample chamber again, it is preferably provided with a gas outlet means, which mediates the sample to flow out of the sample chamber.
  • the gas outlet means is designed such that it allows only an outflow of the sample or another substance from the sample chamber, but not an inflow of sample or substance into the sample chamber.
  • the gas outlet means may, for example, be designed so that it opens at a certain pressure in the sample chamber and sample can flow out of the sample chamber. This pressure can be only slightly greater than the normal ambient air pressure.
  • a method for the spectroscopic analysis of a gas comprises the following steps: introduction of a sample containing the gas to be analyzed into a sample chamber in which the sample flows into the sample chamber, the sample chamber allowing a later outflow of the sample from the sample chamber a portion of a radiation emitted by a radiation source through the sample chamber to a detection device by means of a system of optical elements for analyzing the gas and detecting absorption of the radiation by the gas to be analyzed by means of the detection device.
  • a change in the pressure and / or the volume and / or the concentration of the sample in the sample chamber during the spectroscopic analysis is determined by suitable means.
  • the absolute concentration of an isotope of the gas can be determined.
  • the spectroscopic analysis is time-resolved in order to obtain analytical measured values as a function of time.
  • changes in the concentration of the gas to be analyzed can be determined over the course of the analysis.
  • the time resolution is preferably better than about 1 second and more preferably between 0.2 or 0.4 seconds (about 0.3 seconds or better). With such a time resolution, even rapid metabolic processes can still be studied in detail without the fear of significant loss of information due to averaging or non-detection of different states due to excessively long measurement intervals.
  • absorption of the gas to be analyzed is detected in the mid-infrared range, with detection in the wavenumber range of 2230 to 2280 cm -1 being particularly preferred.
  • the sample to be examined is exhaled breathing air, the gas to be analyzed preferably being 13 CO 2 .
  • the breathing air is preferably introduced into the sample chamber with a tube which is heated in order to prevent condensation of gaseous constituents of the sample on the tube inner wall or local deposition of liquid portions of the sample and to ensure temperature control of the sample.
  • the outflow of the sample from the sample chamber is effected by an outlet means, which prevents substances from entering the sample chamber.
  • the outlet means thus allows an exclusive sample transport out of the sample chamber.
  • a device lends itself to the determination of a biological parameter of an individual, in particular of a human being, for which purpose a spectroscopic analysis of a gaseous sample originating from the individual is carried out.
  • a gaseous sample originating from the individual is carried out.
  • exhaled air is considered as a gaseous sample.
  • the sample is analyzed outside the body of the individual.
  • the biological parameter is preferably the function of an organ of the individual, with function and capacity determinations of the liver and pancreas being particularly preferred.
  • the device can also be used to determine the concentration of an enzyme, such as the lactase, by means of analysis of the To determine respiratory air of the individual and thus to be able to draw conclusions on enzyme deficiency states of the individual.
  • an enzyme such as the lactase
  • the device can also be used to determine the concentration of a microbial species such as a particular bacterium, a virus or a fungus in an organ or tissue of the individual. This may preferably be the determination of the Helicobacter pylori concentration in the stomach of the individual.
  • a microbial species such as a particular bacterium, a virus or a fungus in an organ or tissue of the individual. This may preferably be the determination of the Helicobacter pylori concentration in the stomach of the individual.
  • FIG. 2 is a diagram for calculating a difference signal from signals detected by a device according to FIG. 1, and FIG.
  • Fig. 3 is a schematic representation of possible courses of 13 CO 2 concentration in exhaled breath.
  • FIG. 1 shows a schematic representation, not to scale, of an infrared spectrometer as an exemplary embodiment of a device according to the invention for the spectroscopic analysis of a gas.
  • the infrared spectrometer has a radiation source 1 in the form of a laser or a globar and a driver 2 for the radiation source 1, which is electronically connected to the radiation source 1.
  • the radiation source 1 emits radiation in the form of a light beam 3 which has a wavelength in the mid-infrared range. After its exit from the radiation source 1, the light beam 3 initially strikes a cylindrical lens 4, which ensures a parallel propagation of the light beam 3. After a variable distance, it strikes a first lens 5, which is arranged on the same optical axis as the cylindrical lens 4 and focuses the light beam 3 onto a second lens 6, which likewise is arranged on the same optical axis as the cylindrical lens 4 and the first lens 5 is.
  • the second lens 6 ensures a highly concentrated, substantially parallel propagation of the light beam 3.
  • the light beam strikes a filter 7, which is continuous only for the part of the light beam 3 which is to be used for the detection of a sample.
  • the filter 7 is an infrared narrow band filter which passes only light having a wavelength corresponding to a wave number of about 2260 ⁇ 20 cm -1 .
  • a chopper 8 is arranged, which is used in particular when a globar is used as the radiation source 1. While a laser can emit radiation already pulsed, the radiation emitted by a globar is a continuous unpulsed radiation.
  • the chopper 8 which is electronically connected to the driver 2 of the radiation source 1, the radiation emitted by a Globar radiation can be pulsed.
  • the radiation emitted by a preferably used quantum cascade laser has a repetition rate of 10 kHz. If a globar is used instead of the laser, a repetition rate of about 10 kHz is set via the chopper 8.
  • the light beam 3 After the light beam 3 has passed the filter 7, it encounters a beam splitter 9 which divides the light beam 3 into a first partial beam 3a and a second partial beam 3b.
  • the first partial beam 3a is deflected by the beam splitter by 90 °, while the second partial beam 3b passes through the beam splitter in extension of the original propagation direction of the light beam 3.
  • the first partial beam 3a is directed by means of a deflection mirror 10 and a third lens 11 to a first detector 12, which detects the intensity of the first partial beam 3a.
  • the second partial beam 3b is conducted into a sample chamber 13.
  • the sample chamber 13 is filled with a gaseous sample which is supplied to the sample chamber 13 via a gas inlet 14 in the arrow direction and which can leave the sample chamber 13 through a gas outlet 15 in the direction of the arrow.
  • the gas outlet 15 is designed such that no gas can enter the sample chamber 13 through the gas outlet.
  • a gas flow meter 16 By means of a gas flow meter 16, the gas volume supplied to the sample chamber 13 through the gas inlet 14 is measured, so that the amount of gas that is in the sample chamber 13, is always known exactly.
  • the gas flow meter 16 is electronically connected to a computer 17 and can thus transmit the data determined by him to the computer 17.
  • a system of a plurality of mirrors 18 is arranged, which deflect the second part of the beam 3b so within the sample chamber 13 and that the Beam path of the second partial beam 3b is extended in the sample chamber relative to the actual longitudinal extent of the sample chamber 13. Finally, one of the mirrors deflects the second partial beam 3b out of the sample chamber. After passing through a fourth lens 19, the second partial beam 3b strikes a second detector 20, from which the intensity of the second partial beam 3b is detected.
  • the intensity of the first partial beam 3a which experiences no attenuation by an absorbing substance, is always measured parallel to the intensity of the second partial beam 3b, which is attenuated by the absorption of the sample in the sample chamber 13, smaller intensity differences of the radiation source 1 emitted radiation 3 are compensated. In this way measurement errors that might arise due to such smaller intensity differences are avoided.
  • the first detector 12 is electronically connected to a first lock-in amplifier 21 and to a second lock-in amplifier 22.
  • the second detector 20 is connected to the second
  • Lock-in amplifier 22 electronically connected. Both lock-in amplifiers 21 and 22 serve to amplify the relatively weak detected by the two detectors 12 and 20
  • the two lock-in amplifiers are part of an electronic component assembly of the infrared spectrometer, including the driver 2 of the radiation source 1, the chopper 8, the gas flow meter 16, the first
  • Detector 12 the second detector 20 and the computer 17 belong.
  • the chopper 8 is electronically connected directly to the driver 2 of the radiation source 1, the first detector 12, the first lock-in amplifier 21, and the second lock-in amplifier 22. Further, the first lock-in amplifier 21 and the second lock-in amplifier 22 are directly connected to each other and the computer 17. The respective electronic connections are used for data transmission and synchronization of the individual components with each other.
  • the computer 17 serves to display and evaluate the determined data.
  • an infrared narrow-band filter is used as the filter 7, which determines the proportion of infrared light passing through the filter can be limited to those wavelengths in which 13 CO 2 shows characteristic absorption bands. This is preferably the wavelength range which corresponds to wavenumbers of 2280 to 2230 cm -1 . It is also possible to use a filter which passes only light from a wavelength range corresponding to wavenumbers of 2282 to 2250 cm -1 .
  • the first detector 12 and the second detector 20 are each a photovoltaic mercury cadmium telluride detector (MCT detector) having a peak response of 1.6 A / W.
  • MCT detector photovoltaic mercury cadmium telluride detector
  • These MCT detectors unlike conventional MCT detectors, do not need to be cooled with liquid nitrogen. The cooling is done rather by means of a Peltier element.
  • With an average power of a laser as a radiation source 1 of about 0.3 mW distributed to 40 cm '1 results in a Messsig ⁇ al of a few hundred uA.
  • the noise of each of the two lock-in amplifiers 21 and 22 is in the pA range and thus far away from the signal range. The signal can still be - without coming into the noise area - greatly attenuated.
  • FIG. 1 Compared with the prior art, the following advantages and improvements are achieved by a device according to the invention, as described in FIG. 1:
  • the concentration measurement is faster, so that a faster evaluation of the data is possible.
  • Concentration changes can be tracked directly in real time.
  • the flow measurement technology allows a continuous measurement of the gas samples. - The measurement of the 13 CO 2 concentration is independent of the 12 CO 2 concentration.
  • Carrier gases also gases used in anesthesia, can be used.
  • the device can be used directly on a patient.
  • a compact design makes mobile use possible.
  • FIG. 2 shows in conjunction with and with reference to the infrared spectrometer shown in FIG. 1 a scheme for calculating a difference signal S D from two individual signals D 1 and D 2 detected by the first detector 12 and the second detector 20 ,
  • Numerical reference numbers refer to FIG. 1, letters as reference numbers refer to FIG. 2.
  • the difference signal S D is measured with the sub-signals S 3 and S 4 , which respectively comprise the main components of the detector signals D 1 and D 2 .
  • the two signals S 1 and S 0 are connected to the first and second lock-in amplifiers 21 and 22 (or alternatively in a
  • Digital converter in the computer 17 converted into digital signals.
  • ⁇ is the extinction coefficient of 13 CO 2
  • c is the concentration
  • d is the beam path of the second partial beam 3b in the sample chamber 13.
  • the constant parameter ⁇ contains structural characteristics such as the division ratio of the beam splitter 9 and the 13 CO 2 base concentration in the infrared spectrometer.
  • the measurement signal thus provides directly the desired 13 CO 2 concentration c of the sample at known (and constant) quantities ⁇ , d and ⁇ .
  • the absorption data is correlated with the gas flow meter 16, so that an adaptation to the concentration differences of the sample in the sample chamber 13 can be performed.
  • FIG. 3 shows schematically two courses of the 13 CO 2 concentration in exhaled breath air applied over a period of a few seconds. Such courses can be determined by means of a device according to the invention, as shown in FIG.
  • Example 1 Use as Breath Analyzer for Liver Function Determination
  • an application of a device according to the invention is not limited only to respiratory tests but can generally be used for the analysis of any gas mixtures, it is suitable for use in respiratory analysis.
  • the liver function of an individual can be determined quantitatively.
  • Chronic liver disease is widespread in Europe, with hepatitis C alone, 8.9 million people are infected. These patients are usually in permanent medical care as the disease progresses.
  • therapy and management of patients with chronic liver disease a much better therapy control can be achieved by quantification of liver function.
  • the assessment of liver function is decisive for the precipitation of suitable therapeutic decisions.
  • Liver resection is a common procedure in today's surgery. It is performed as segmental resection or hemihepatectomy along the anatomical boundaries.
  • liver transplantation the assessment of liver function is of particular importance because here the organ function is estimated at short notice and a fast therapy decision has to be made.
  • Another application of a device according to the invention is the measurement of gastric emptying time.
  • gastrointestinal diseases is the
  • Gastric emptying time disturbed (gastroparesis). This can be the case for diabetic patients, for example
  • Gastric emptying time is a test meal with a 13 C-labeled test substance (eg
  • Octanoic acid and also measured the abatement of 13 CO 2 .
  • a continuous measurement by means of a device according to the invention also provides a significantly better accuracy in the analysis of the data.

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Abstract

L'invention concerne un dispositif d'analyse spectroscopique d'un gaz comprenant au moins une source (1) de rayonnement, au moins un dispositif (12 ; 20) de détection, au moins une chambre (13) à échantillon et un système d'éléments (4 ; 5 ; 6 ; 7 ; 9 ; 10 ; 11 ; 18 ; 19) optiques qui est prévu et organisé pour dévier au moins une partie (3b) du rayonnement (3) émis par la source (1) de rayonnement à travers la chambre (13) à échantillon sur le dispositif (20) de détection, la chambre (13) à échantillon servant à accueillir un échantillon gazeux qui contient le gaz à analyser et le dispositif étant configuré de telle sorte que l'échantillon peut s'écouler continuellement à travers la chambre (13) à échantillon et que des moyens (16) sont prévus pour déterminer la pression et/ou le volume et/ou la concentration de l'échantillon dans la chambre (13) à échantillon. L'invention concerne de plus un procédé correspondant d'analyse spectroscopique d'un gaz.
EP07723482A 2006-03-17 2007-03-16 Dispositif d'analyse spectroscopique d'un gaz Ceased EP1996920A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102006012740 2006-03-17
DE102006018862A DE102006018862A1 (de) 2006-03-17 2006-04-13 Vorrichtung zur spektroskopischen Analyse eines Gases
PCT/EP2007/002525 WO2007107366A1 (fr) 2006-03-17 2007-03-16 Dispositif d'analyse spectroscopique d'un gaz

Publications (1)

Publication Number Publication Date
EP1996920A1 true EP1996920A1 (fr) 2008-12-03

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EP07723482A Ceased EP1996920A1 (fr) 2006-03-17 2007-03-16 Dispositif d'analyse spectroscopique d'un gaz

Country Status (6)

Country Link
US (1) US20090124918A1 (fr)
EP (1) EP1996920A1 (fr)
AU (1) AU2007228959B2 (fr)
CA (1) CA2645445A1 (fr)
DE (1) DE102006018862A1 (fr)
WO (1) WO2007107366A1 (fr)

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JP7108327B2 (ja) * 2018-09-21 2022-07-28 大塚電子株式会社 測定装置、および測定方法
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DE102006018862A1 (de) 2007-09-20
AU2007228959A1 (en) 2007-09-27

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