WO2018100621A1 - Ioniseur et spectromètre de masse - Google Patents

Ioniseur et spectromètre de masse Download PDF

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Publication number
WO2018100621A1
WO2018100621A1 PCT/JP2016/085353 JP2016085353W WO2018100621A1 WO 2018100621 A1 WO2018100621 A1 WO 2018100621A1 JP 2016085353 W JP2016085353 W JP 2016085353W WO 2018100621 A1 WO2018100621 A1 WO 2018100621A1
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WO
WIPO (PCT)
Prior art keywords
sample
gas
ionization
flow path
gas flow
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PCT/JP2016/085353
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English (en)
Japanese (ja)
Inventor
学 上田
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株式会社島津製作所
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Priority to PCT/JP2016/085353 priority Critical patent/WO2018100621A1/fr
Publication of WO2018100621A1 publication Critical patent/WO2018100621A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/622—Ion mobility spectrometry
    • G01N27/623—Ion mobility spectrometry combined with mass spectrometry
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/10—Ion sources; Ion guns

Definitions

  • the present invention relates to an ionizer that ionizes components in a sample and a mass spectrometer equipped with the ionizer, and more specifically, an ionizer suitable for an ion source such as a mass spectrometer and an ion mobility meter, and the ionizer.
  • the present invention relates to a mass spectrometer provided.
  • LC-MS liquid chromatograph mass spectrometer
  • a mass spectrometer as a detector of a liquid chromatograph (LC)
  • electrospray ionization is used to ionize a liquid sample containing components separated by an LC column.
  • An atmospheric pressure ion source using an (ESI) method, an atmospheric pressure chemical ionization (APCI) method, an atmospheric pressure photoionization (APPI) method or the like is used.
  • ESI atmospheric pressure chemical ionization
  • APPI atmospheric pressure photoionization
  • a pressurized liquid feeding method described in Patent Document 1 As a method for introducing a standard sample into an atmospheric pressure ion source of a mass spectrometer, a pressurized liquid feeding method described in Patent Document 1 is conventionally known.
  • an inert gas for example, nitrogen gas
  • the other end of the liquid feeding tube having one end inserted below the liquid surface of the standard sample solution is connected to an ionization probe of the mass spectrometer.
  • the pressurized gas introduced into the internal space of the sealed container pushes down the liquid level of the standard sample solution, whereby the standard sample solution is fed to the ionization probe through the liquid feeding tube.
  • the standard sample solution is fed in a state where the pressurized inert gas is sealed in a sealed container. For this reason, as the gas pressure in the container decreases as the liquid level decreases, the amount of liquid fed gradually decreases, and the standard sample solution cannot be fed to the ionization probe at a constant flow rate.
  • the liquid feeding is continued for a certain long time, for example, every time the liquid level is lowered by a predetermined height, the operator needs to introduce an inert gas into the container. there were.
  • the standard sample solution when the standard sample solution is fed, the standard sample solution does not reach the ionization probe until the flow path in the liquid feeding tube is filled with the standard sample solution. Therefore, even if the standard sample solution starts to be fed, it is necessary to wait for a certain amount of time (for example, 1 minute) until the standard sample solution is introduced into the ionization probe and the components in the sample are ionized. Inefficient.
  • the present invention has been made in view of the above problems, and the main purpose thereof is a component in a standard sample introduced at a stable flow rate over a long period of time without performing complicated work such as additional introduction of gas.
  • An ionization apparatus which has been made to solve the above problems, a) a sample container containing a liquid sample or gas sample; b) a gas flow path through which gas flows, a sample flow path having one end connected in the middle of the gas flow path and the other end connected to the sample container, and a gas supply for feeding gas into the gas flow path A liquid sample or a gas sample in the sample container through the sample channel by the venturi effect by the gas fed from the gas supply unit into the gas channel and mixed with the gas flow A sampling part to perform, c) an ionization unit that introduces at least a part of a gas mixed with a liquid sample or a gas sample in the sample collection unit and ionizes components in the gas; It is characterized by having.
  • the gas sample itself can be stored in the sample container, a solid sample or a liquid sample can be put in the sample container, and a component volatilized from these samples can be used as the gas sample.
  • a gas is supplied at a predetermined flow rate from the gas supply unit to the gas flow path in the sample collection unit.
  • This gas is preferably an inert gas such as nitrogen.
  • the gas flows in the gas flow path, but a sample flow path communicating with the sample container is connected in the middle of the gas flow path, and the connection portion is in a decompressed state in accordance with Bernoulli's law of conservation of energy. As a result, a venturi effect occurs, and the liquid sample in the sample container is sucked to the gas channel side through the sample channel and mixed with the gas flowing in the gas channel.
  • the gas mixed with the liquid sample is introduced into the ionization unit, and components in the liquid sample are ionized in the ionization unit.
  • a gas sample is stored in the sample container.
  • the gas mixed with the sample in the sample collection unit may be entirely introduced into the ionization unit, or only part of the gas may be branched and introduced into the ionization unit.
  • the gas flow rate fed from the gas supply unit into the gas flow path is controlled to be substantially constant, whereby a substantially constant amount of sample is introduced into the ionization unit, and the components in the sample are removed. It can be ionized. Moreover, since the sample is mixed with the gas flow and introduced into the ionization section regardless of the liquid or gas, the sample-derived ions can be generated with almost no delay from the start of gas supply.
  • the ionization unit includes a reaction ion generation unit that ionizes a predetermined liquid or gas to generate a reaction ion, and in the gas in which the liquid sample or the gas sample is mixed
  • the component in the gas in which the liquid sample or the gas sample is mixed can be ionized by an ion-molecule reaction between the component and the reaction ion generated in the reaction ion generation unit.
  • the reactive ion generation unit is configured to generate reactive ions by one or more of an electrospray ionization (ESI) method, an atmospheric pressure chemical ionization (APCI) method, or an atmospheric pressure photoionization (APPI) method.
  • ESI electrospray ionization
  • APCI atmospheric pressure chemical ionization
  • APPI atmospheric pressure photoionization
  • a dedicated ionization probe for the ESI method, APCI method, or APPI method conventionally used, or ionization and APCI by the ESI method as disclosed in Non-Patent Document 1 are used.
  • An ionization probe that can simultaneously perform ionization by the method may be used.
  • such an ionization probe ionizes components in an externally supplied liquid sample such as an LC column.
  • an externally supplied liquid sample such as an LC column.
  • the solvent or mobile phase is used.
  • the reaction ion derived from can be produced
  • the gas supply from the gas supply unit in the sample collection unit is stopped and the sample is stored in the sample container. Is stopped and components in the liquid sample supplied to the ionization probe may be ionized.
  • liquid sample introduction path and the standard sample introduction path which are the purpose of analysis into the ionization section, can be separated, and there is no need to reconnect the pipes between them or to switch the flow path using a valve. In addition, contamination of both samples can be avoided.
  • the ionization unit includes a thermoelectron generation unit that generates thermoelectrons, and the thermoelectrons generated by the thermoelectron generation unit are brought into contact with components in the gas in which the liquid sample or gas sample is mixed. May be ionized by an electron ionization (EI) method.
  • EI electron ionization
  • thermoelectrons ionization by ion-molecule reaction using ions generated by the above ESI method, APCI method or the like is possible in an atmospheric pressure atmosphere, but ionization by the EI method using thermoelectrons is performed in a vacuum atmosphere. There is a need. Therefore, a vacuum that is communicated with the chamber through a small-diameter opening or channel and not evacuated by a vacuum pump, rather than in a chamber at approximately atmospheric pressure to which a gas mixed with a sample is supplied through the gas channel. A thermoelectron generator may be provided indoors. In this configuration, since ionization is performed by the EI method, fragment ions (product ions) are easily generated instead of molecular ions.
  • the mass-to-charge ratio derived from the component is different. Multiple types of fragment ions can be obtained. Thereby, when tuning a mass spectrometer etc. using the ion derived from a standard sample, it is possible to perform tuning at a plurality of different mass-to-charge ratio values.
  • the ionization apparatus may further include an ion dissociation unit that dissociates ions derived from the sample components ionized by the ionization unit.
  • CID collision induced dissociation
  • ETD electron transfer dissociation
  • ECD electron capture dissociation
  • the gas supplied into the gas flow channel at the outlet end of the gas flow channel for introducing the gas mixed with the liquid sample or the gas sample into the ionization unit.
  • a valve body may be provided that is pushed by the flow to open the outlet end and closes the outlet end in a state where the gas flow is stopped.
  • the gas flow path and the ionization unit can be blocked by the valve body. Therefore, when components in the liquid sample to be analyzed are ionized in the ionization section, it is possible to prevent molecules of the components and ions derived from the components from entering the gas flow path. Thereby, when ionizing the component in the standard sample accommodated in the sample container, the contamination by the component in the liquid sample to be analyzed can be avoided.
  • the mass spectrometer according to the present invention is characterized in that any of the above-described ionizers according to the present invention is provided as an ion source. That is, the mass spectrometer according to the present invention is an atmospheric pressure ionization mass spectrometer that ionizes components in a liquid sample at approximately atmospheric pressure and performs mass analysis. For example, a liquid chromatograph mass spectrometer combined with a liquid chromatograph Can be configured.
  • a stable flow rate can be obtained over a long period of time without performing complicated work such as additional introduction of gas required in the conventional pressurized liquid feeding method.
  • a sample such as a standard sample can be introduced into the ionization section, and components in the sample can be ionized. Regardless of whether the sample is liquid or gas, the sample is mixed with the gas flow and introduced into the ionization unit. Therefore, a standard sample can be quickly introduced into the ionization unit during device tuning. Components in the sample can be ionized and subjected to analysis. Thereby, operations such as device tuning can be performed efficiently.
  • the block diagram of the principal part of the mass spectrometer which is one Example of this invention.
  • the schematic block diagram of the modification of a standard sample supply part The schematic block diagram of the other modification of a standard sample supply part.
  • the block diagram of the principal part of the mass spectrometer which is another Example of this invention.
  • the partial block diagram of the principal part of the mass spectrometer which is another Example of this invention.
  • FIG. 1 is a configuration diagram of a main part of the mass spectrometer of the present embodiment
  • FIG. 2 is a schematic configuration diagram of a standard sample supply unit 21 in the mass spectrometer of the present embodiment.
  • an ionization chamber 11 having a substantially atmospheric pressure atmosphere and an analysis chamber 14 maintained in a high vacuum atmosphere by a high performance vacuum pump (not shown) are provided in the housing 10.
  • middle vacuum chamber 13 which are between these ionization chambers 11 and the analysis chambers 14, and whose vacuum degree is increasing in steps are formed. That is, the mass spectrometer of this embodiment has a multistage differential exhaust system configuration.
  • An ionization probe 20 is provided as an ion source in the ionization chamber 11, and the ionization chamber 11 and the first intermediate vacuum chamber 12 communicate with each other through a small-sized desolvation tube 23.
  • ion guides 24 and 26 are provided for transporting ions to the subsequent stage while converging ions, respectively.
  • the chamber 13 is separated by a skimmer 25 having a small hole at the top.
  • a quadrupole mass filter 27 that separates ions according to the mass-to-charge ratio m / z, and an ion detector 28 that detects ions that have passed through the quadrupole mass filter 27.
  • the configuration of each part can be changed as appropriate, such as replacing the quadrupole mass filter 27 with an orthogonal acceleration time-of-flight mass analyzer.
  • the ionization probe 20 ionizes components contained in a liquid sample supplied from the outside by the ESI method.
  • the eluate that has reached the ionization probe 20 is sprayed into the ionization chamber 11, which is an atmosphere at substantially atmospheric pressure, with the help of the nebulizing gas as charged droplets having a biased charge.
  • the charged droplet ejected from the ionization probe 20 is miniaturized by contacting with the surrounding gas, and the vaporization of the solvent in the droplet is promoted.
  • the sample components contained in the charged droplets are ionized in the process of making the charged droplets finer and removing the solvent.
  • a standard sample is supplied from a standard sample supply unit 21 via a sample introduction tube 22 to a region where charged droplets are sprayed from the ionization probe 20, that is, an ionization region in the ionization chamber 11.
  • a sample introduction tube 22 to a region where charged droplets are sprayed from the ionization probe 20, that is, an ionization region in the ionization chamber 11.
  • the generated ions derived from the sample components are sucked into the desolvation tube 23 by the air flow generated mainly by the pressure difference between the ionization chamber 11 and the first intermediate vacuum chamber 12, and then flowed into the first intermediate vacuum chamber 12. Sent.
  • the desolvation tube 23 is heated by a heater (not shown), and the desolvation of the charged droplets is promoted inside the desolvation tube 23 to generate ions derived from the sample components.
  • the ions are converged by the ion guide 24, sent to the second intermediate vacuum chamber 13 through a small hole at the top of the skimmer 25, and further converged by the ion guide 26 and sent to the analysis chamber 14.
  • a predetermined voltage is applied to the four rod electrodes constituting the quadrupole mass filter 27 from a power source (not shown), and only ions having a mass-to-charge ratio corresponding to the voltage pass through the quadrupole mass filter 27 and are ionized.
  • the light enters the detector 28.
  • the ion detector 28 outputs a detection signal corresponding to the amount of incident ions. Therefore, for example, when the voltage applied to the rod electrode constituting the quadrupole mass filter 27 is scanned within a predetermined range, the mass-to-charge ratio of ions that can pass through the quadrupole mass filter 27 is scanned within the predetermined mass-charge ratio range. Is done.
  • a data processor (not shown) can obtain a mass spectrum indicating the signal intensity of ions over a predetermined mass-to-charge ratio range based on the detection signals sequentially obtained at this time.
  • the standard sample supply unit 21 includes a sample container 213 in which a standard sample solution is stored, a gas flow channel 212, one end immersed in the standard sample solution in the sample container 213, and the other end gas.
  • a sample channel 214 connected in the middle of the channel 212 and a gas feeding unit 211 that feeds gas at a predetermined flow rate into the gas channel 212 are included.
  • the end (the right end in FIG. 2) of the gas flow path 212 opposite to where the gas is introduced is connected to the sample introduction tube 22 opened in the ionization chamber 11.
  • the standard sample supply unit 21 sucks and feeds the standard sample solution in the sample container 213 using the venturi effect caused by the gas flowing in the gas flow path 212.
  • the commonly known Bernoulli equation expresses the law of conservation of energy per unit mass of fluid, and is expressed by the following equation (1).
  • (1/2) v 2 + (P / ⁇ ) constant (1)
  • v is the velocity of the fluid
  • P is the pressure of the fluid
  • ⁇ the density of the fluid. From this equation, it can be seen that the pressure decreases as the fluid velocity increases.
  • an inert gas such as nitrogen is allowed to flow from the gas supply unit 211 into the gas flow path 212.
  • P1 the pressure at the connection portion of the sample channel 214 to the gas channel 212
  • P1 the pressure in the upper space in the sample container 213
  • P1 the pressure in the upper space in the sample container 213
  • the standard sample solution is mixed with the gas flowing in the gas channel 212 and introduced into the ionization chamber 11.
  • the gas supplied from the gas supply unit 211 is preferably a high-temperature dry gas. When the sucked standard sample solution is mixed with such dry gas, the solvent in the solution is easily vaporized, and the gas molecules of the standard sample can be introduced into the ionization chamber 11.
  • the ionization probe 20 is supplied with only a liquid sample containing no substantial sample component, for example, a mobile phase used in LC.
  • This sample is electrostatically sprayed from the ionization probe 20 to generate a large amount of solvent molecular ions. That is, many solvent molecular ions exist as reaction ions in the region where the standard sample components are introduced into the ionization chamber 11 together with the gas through the sample introduction tube 22. Therefore, the component molecules derived from the standard sample come into efficient contact with the solvent molecular ions and are ionized by the ion-molecule reaction.
  • the ions derived from the standard sample thus generated are sucked into the desolvation tube 23 on the air flow generated mainly by the pressure difference between the ionization chamber 11 and the first intermediate vacuum chamber 12, and sent to the subsequent stage for mass analysis. To be served.
  • the components in the standard sample are ionized and massed in the ionization chamber 11 instead of the eluate from the LC column. Can be used for analysis.
  • a substantially constant amount of the standard sample can be introduced into the ionization chamber 11.
  • the time taken for the gas delivered from the gas delivery unit 211 to pass through the gas flow path 212 and reach the ionization chamber 11 is short, it will enter the ionization chamber 11 without much time delay from the start of gas delivery.
  • the introduction of standard samples can be started.
  • the standard sample introduction path to the ionization chamber 11 is completely different from the path through which the eluate is sent from the LC column outlet to the ionization probe. There is no need to switch roads. In addition, contamination caused by the sample remaining in the channel can be avoided.
  • the ionization probe 20 performs ionization by the ESI method.
  • the ionization probe 20 may perform ionization by the APCI method or the APPI method.
  • ionization by a plurality of mechanisms may be performed simultaneously.
  • any solvent molecular ion that can be used for the ion-molecule reaction may be supplied to the ionization chamber 11.
  • the standard sample solution was accommodated in the sample container 213.
  • PEG polyethylene glycol
  • PFTBA perfluorotributylamine
  • a volatile solid sample may be accommodated in the sample container 213, and a sample component that volatilizes from the solid sample, that is, a gas sample may be mixed into a gas flow and introduced into the ionization chamber 11.
  • a sample component that volatilizes from a volatile liquid sample stored in the sample container 213 may be introduced into the ionization chamber 11 in a gas flow.
  • the amount of evaporation from the solid sample or liquid sample and the gas flow in the gas channel 212 based on the vapor pressure and pressure difference (P2-P1) of the solid sample.
  • the amount of sample mixed in can be adjusted.
  • the sample mixing amount can also be adjusted by changing to a solid sample having a different vapor pressure, changing the inner diameter of the gas flow path 212, changing the gas flow rate, or the like.
  • FIG. 3 is a schematic configuration diagram of a modified example of the standard sample supply unit 21.
  • the inner diameter of the gas channel 212 is made smaller in the vicinity of the connecting portion of the sample channel 214 than on both sides thereof. Thereby, the flow velocity of the gas passing through the vicinity of the connection portion is increased, and the pressure is decreased, so that the sample is easily sucked up.
  • FIG. 4 is a schematic configuration diagram of another modification of the standard sample supply unit 21.
  • the gas flow channel 212 is divided into a first gas flow channel 212A and a second gas flow channel 212B, and the opposing ends of the two flow channels 212A and 212B are both tapered nozzles. It is formed in a shape.
  • the sample channel 214 is connected to a sealed connection chamber 212c provided so as to surround the facing portions of the two channels 212A and 212B. As a result, the flow rate of the gas passing through the two flow paths 212A and 212B is increased, and the pressure in the connection chamber 212c is reduced, so that the sample is easily sucked up.
  • the component derived from the sample is basically ionized in the ionization chamber 11 which is an atmospheric pressure atmosphere.
  • the gaseous sample component generated by desolvation in the ionization chamber 11 is used. It may be introduced into the first intermediate vacuum chamber 12 and ionized in the first intermediate vacuum chamber. In this case, an ionization method different from the atmospheric pressure ionization method can be used.
  • FIG. 5 is a configuration diagram of a main part of a mass spectrometer which is another embodiment of the present invention.
  • a thermoelectron generator 30 including a filament that generates thermoelectrons by supplying a heating current from the outside into the first intermediate vacuum chamber 12, and thermoelectrons emitted from the thermoelectron generator 30.
  • the trap electrode 31 for receiving is disposed in pairs.
  • sample components are ionized in the ionization chamber 11 and then dissociated in the first intermediate vacuum chamber 12 to generate product ions having various mass-to-charge ratios.
  • in-source CID is generated in the first intermediate vacuum chamber 12
  • a collision cell is disposed in the first intermediate vacuum chamber 12
  • CID is generated in the collision cell
  • ETD or ECD is generated.
  • the sample component ions may be dissociated by utilizing the above.
  • a part of the liquid sample electrostatically sprayed from the ionization probe 20 during normal analysis enters the inside of the sample introduction tube 22 to contaminate the inside of the pipeline and cause contamination. It may be a cause. Therefore, in order to avoid this, as shown in FIG. 6, a valve body 22 a that can be swung by a hinge or the like is provided on the end surface of the sample introduction tube 22 opened in the ionization chamber 11. When the gas is not supplied from the gas supply unit 211 into the gas flow path 212, the valve body 22a closes the end surface of the sample introduction tube 22 as shown in FIG.
  • valve body 22a is opened by the pressure of the gas, and the gas accompanying the sample is ionized. It is introduced into the chamber 11.

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Abstract

L'invention concerne un ioniseur et un spectromètre de masse, une unité d'alimentation en échantillon-type (21), qui est destinée à introduire un échantillon-type dans une chambre d'ionisation dont l'atmosphère a une pression proche de la pression atmosphérique, comprenant : un récipient à échantillon (213) dans lequel un échantillon type est accueilli ; une voie d'écoulement de gaz (212) ; une voie d'écoulement d'échantillon (214) dont une extrémité est reliée à un point intermédiaire de la voie d'écoulement de gaz (212) et l'autre extrémité est reliée au récipient à échantillon (213) ; et une unité d'alimentation en gaz (211) qui introduit un gaz dans la voie d'écoulement de gaz (212). Lorsque du gaz est introduit dans la voie d'écoulement de gaz (212) depuis l'unité d'alimentation en gaz (211), l'échantillon contenu dans le récipient (213) est aspiré en passant par la voie d'écoulement d'échantillon (214) grâce à l'effet Venturi, mélangé au flux de gaz et introduit dans la chambre d'ionisation. Des ions accompagnés de molécules de solvant sont générés dans la chambre d'ionisation par le procédé d'ionisation par électronébulisation ou similaire et les molécules composants l'échantillon sont ionisées par une réaction ion-molécule. Par conséquent, des composants dérivés d'un échantillon-type sont introduits de façon stable dans la chambre d'ionisation par un chemin différent de celui d'une sonde d'ionisation et il est possible d'ioniser les composants.
PCT/JP2016/085353 2016-11-29 2016-11-29 Ioniseur et spectromètre de masse WO2018100621A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021224973A1 (fr) * 2020-05-08 2021-11-11 株式会社島津製作所 Spectromètre de masse-chromatographe en phase gazeuse
CN116358967A (zh) * 2023-05-25 2023-06-30 中国科学院大气物理研究所 一种航天探测用气体检测仪器在轨定标微型标准源装置

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JP2013178194A (ja) * 2012-02-29 2013-09-09 Panasonic Corp 試料気体収集方法
JP2013538430A (ja) * 2010-09-01 2013-10-10 ディーエイチ テクノロジーズ デベロップメント プライベート リミテッド 質量分析計のためのイオン源
JP2015181126A (ja) * 2015-06-04 2015-10-15 株式会社島津製作所 質量分析装置
JP2016157523A (ja) * 2015-02-23 2016-09-01 株式会社島津製作所 イオン化装置
JP6028875B2 (ja) * 2014-01-20 2016-11-24 株式会社島津製作所 タンデム質量分析データ処理装置

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Publication number Priority date Publication date Assignee Title
WO2000008453A1 (fr) * 1998-08-06 2000-02-17 Hitachi, Ltd. Chargeuse d'echantillons, source d'ions et analyseur de masse avec lesquels on utilise la chargeuse
JP2013538430A (ja) * 2010-09-01 2013-10-10 ディーエイチ テクノロジーズ デベロップメント プライベート リミテッド 質量分析計のためのイオン源
JP2013178194A (ja) * 2012-02-29 2013-09-09 Panasonic Corp 試料気体収集方法
JP6028875B2 (ja) * 2014-01-20 2016-11-24 株式会社島津製作所 タンデム質量分析データ処理装置
JP2016157523A (ja) * 2015-02-23 2016-09-01 株式会社島津製作所 イオン化装置
JP2015181126A (ja) * 2015-06-04 2015-10-15 株式会社島津製作所 質量分析装置

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021224973A1 (fr) * 2020-05-08 2021-11-11 株式会社島津製作所 Spectromètre de masse-chromatographe en phase gazeuse
JP7409492B2 (ja) 2020-05-08 2024-01-09 株式会社島津製作所 ガスクロマトグラフ質量分析計
CN116358967A (zh) * 2023-05-25 2023-06-30 中国科学院大气物理研究所 一种航天探测用气体检测仪器在轨定标微型标准源装置
CN116358967B (zh) * 2023-05-25 2023-09-26 中国科学院大气物理研究所 一种航天探测用气体检测仪器在轨定标微型标准源装置

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