WO2022014119A1 - ガスクロマトグラフ質量分析装置 - Google Patents

ガスクロマトグラフ質量分析装置 Download PDF

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Publication number
WO2022014119A1
WO2022014119A1 PCT/JP2021/016773 JP2021016773W WO2022014119A1 WO 2022014119 A1 WO2022014119 A1 WO 2022014119A1 JP 2021016773 W JP2021016773 W JP 2021016773W WO 2022014119 A1 WO2022014119 A1 WO 2022014119A1
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WO
WIPO (PCT)
Prior art keywords
unit
filament
ion source
source box
gas chromatograph
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
PCT/JP2021/016773
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English (en)
French (fr)
Japanese (ja)
Inventor
茂捻 原田
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.)
Shimadzu Corp
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Shimadzu Corp
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 Shimadzu Corp filed Critical Shimadzu Corp
Priority to JP2022536141A priority Critical patent/JP7414146B2/ja
Priority to US18/015,887 priority patent/US20230243787A1/en
Priority to CN202180049657.5A priority patent/CN115836220B/zh
Publication of WO2022014119A1 publication Critical patent/WO2022014119A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
    • 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
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/62—Detectors specially adapted therefor
    • G01N30/72—Mass spectrometers
    • G01N30/7206—Mass spectrometers interfaced to gas chromatograph
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/426—Methods for controlling ions
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
    • G01N2030/025—Gas chromatography

Definitions

  • the present invention relates to a gas chromatograph mass spectrometer.
  • a gas chromatograph unit that separates the components in the sample gas by a separation column and a component separated by the gas chromatograph unit are ionized, and the ratio m / z of the mass m and the charge z of the ionized component is m / z. It is an apparatus provided with a mass spectrometric unit for analysis using the above (see Patent Document 1).
  • the EI (Electron Ionization) method is known as one of the methods for ionizing the components separated by the gas chromatograph unit.
  • the EI method is a method in which thermoelectrons are made to collide with a component from the gas chromatograph unit to ionize it.
  • a metal box called an ion source box is provided in the ionization section that employs the EI method, and filaments and emission electrodes are arranged on the outside of the ion source box with the ion source box interposed therebetween.
  • a voltage is applied to the filament, the thermions are generated in the filament, and the thermions move across the interior of the ion source box toward the emission electrode.
  • thermions collide with the components emitted from the gas chromatograph section into the ion source box, so that the components from the gas chromatograph section are ionized.
  • the sample injected into the gas chromatograph unit contains a solvent, and the solvent component comes out from the gas chromatograph unit before the component to be analyzed. It has been found that if a voltage is applied to the filament while the solvent component from the gas chromatograph section is being released into the ion source box, the filament will be damaged. Therefore, it is common to start applying the voltage to the filament after the release of the solvent component from the gas chromatograph unit into the ion source box is completed.
  • the temperature of the ion source box affects the ionization efficiency in the ion source box. Therefore, a heater and a temperature sensor are attached to the ion source box, and control such as feedback control is performed so that the temperature of the ion source box is maintained at the set temperature.
  • the present invention has been made in view of the above problems, and an object of the present invention is to improve the temperature stability of the ion source box.
  • the gas chromatograph mass spectrometer has a gas chromatograph unit that generates sample gas from an injected sample and separates components in the sample gas by a separation column, and an outlet of the separation column of the gas chromatograph unit. It is provided with an ionization unit for ionizing the components that have come out, a mass spectrometric unit having a detection unit for detecting the components ionized by the ionization unit, and a control unit that controls at least the ionization unit.
  • the ionization unit of the mass spectrometric unit includes an ion source box having a space inside for ionizing the components coming out from the outlet of the separation column, a heater for adjusting the temperature of the ion source box, and the above.
  • a filament which is arranged outside the ion source box and emits electrons for ionizing components toward the space, is provided, and the control unit generates heat of the filament after applying a voltage to the filament.
  • controlling the output of the heater "in relation to the magnitude of heat generation of the filament” is the magnitude of the voltage applied to the filament, the magnitude of the current flowing through the filament, and the emission current. It includes controlling the output of the heater based on any of the magnitudes.
  • the influence of heat generated from the filament is controlled by controlling the output of the heater in relation to the magnitude of heat generation of the filament. Since the temperature of the received ion source box is adjusted to a predetermined temperature, the temperature stability of the ion source box is improved.
  • the gas chromatograph mass spectrometer 1 includes a gas chromatograph unit 2, a mass spectrometer 4, and a control device 6.
  • the mass spectrometry unit 4 includes an ionization unit 14 and a detection unit 16.
  • the gas chromatograph unit 2 and the mass spectrometry unit 4 are housed inside a housing (not shown), and at least the mass spectrometry unit 4 is placed in a vacuum state.
  • the gas chromatograph unit 2 includes an injector 8, a sample vaporization unit 10, and a separation column 12.
  • the injector 8 collects a sample from a sample vial (not shown) and injects it into the sample vaporizer 10.
  • the sample vaporization unit 10 vaporizes the sample injected by the injector 8 to generate a sample gas, and conveys the sample gas to the separation column 12 by the carrier gas.
  • the separation column 12 the components in the sample gas are separated.
  • the outlet 12a of the separation column 12 is arranged in the ion source box 18 of the ionization unit 14 described later, and the components separated in the separation column 12 are discharged into the space inside the ion source box 18.
  • the ionization unit 14 of the mass spectrometry unit 4 includes an ion source box 18, a filament 20, an emission electrode 22, an ammeter 23, an ionization power supply 24, a temperature sensor 26, and a heater 28.
  • the ion source box 18 is a metal box, and components are discharged from the outlet 12a of the separation column 12 into the space inside the ion source box 18.
  • the filament 20 and the emission electrode 22 are arranged outside the ion source box 18 so as to sandwich the ion source box 18 between them.
  • the ionization power supply 24 is for applying a voltage to the filament 20.
  • the temperature sensor 26 and the heater 28 are attached to the ion source box 18 in order to adjust the temperature of the ion source box 18.
  • the filament 20 is for generating electrons for ionizing the component molecules emitted from the outlet 12a of the separation column 12.
  • the electrons generated in the filament 20 pass through the space in the ion source box 18 toward the emission electrode 22 and collide with the component molecules released from the outlet 12a of the separation column 12 to ionize the component molecules.
  • the ammeter 23 is for detecting the amount of electrons reaching the emission electrode 22 as an emission current.
  • the voltage applied to the filament 20 by the ionization power supply 24 is controlled so that the emission current detected by the ammeter 23 becomes constant at a predetermined value.
  • the detection unit 16 of the mass spectrometry unit 4 includes an ion lens 30, a quadrupole mass filter 24, and an ion detector 34.
  • the components ionized in the ion source box 18 of the ionization unit 14 are introduced into the quadrupole mass filter 32 via the ion lens 30 and have a mass electrification ratio according to the voltage applied to the quadrupole mass filter 32. Only the ions having pass through the quadrupole mass filter 32 and are detected by the ion detector 34.
  • the control device 6 is for controlling the operation of the gas chromatograph unit 2 and the mass spectrometry unit 4, and is realized by a computer circuit including a CPU (central processing unit) and an information storage device.
  • the control device 6 includes a control unit 36 and a correlation data holding unit 38.
  • the control unit 36 is a function obtained by the CPU executing a program
  • the correlation data holding unit 38 is a function realized by a part of the storage area of the information storage device.
  • the control unit 36 controls the voltage applied to the filament 20 by the ionizing power supply 24 (current flowing through the filament 20) and the output of the heater 28 in consideration of the influence of the heat generated from the filament 20, so that the ion source box 18 can be used. It is configured to maintain the temperature of the above at a predetermined temperature.
  • the correlation between the magnitude of the current flowing through the filament 20 and the correction amount of the output of the heater 28 required to cancel the influence of the temperature of the ion source box 18 from the filament 20 is determined by an experiment performed in advance. It is defined, and the correlation data is held in the correlation data holding unit 38.
  • control unit 36 controls the output of the heater 28 so that the temperature of the ion source box 18 becomes the set temperature, and the voltage is not applied to the filament 20. It controls the ionization power supply 24. The output of the heater 28 is controlled by adjusting the effective voltage applied to the heater 28.
  • the control device 6 sends an instruction to inject the sample into the injector 8, and the injector 8 injects the sample into the sample vaporization chamber 10 (step 101).
  • the control unit 36 starts applying a voltage to the filament 20 after a predetermined time has elapsed after the sample injection is executed (steps 102 and 103).
  • the time until the voltage application to the filament 20 is started after the sample injection is executed is the time until all the solvent components contained in the injected sample are released from the outlet 12a of the separation column 12. It is determined by the internal capacity from the sample vaporization chamber 10 to the outlet 12a of the separation column 12 and the flow rate of the carrier gas.
  • the control unit 36 monitors the magnitude of the current flowing through the filament 20, and the magnitude of the current flowing through the filament 20 and the correlation data held in the correlation data holding unit 38. Is used to obtain a correction amount for temperature control of the ion source box 18 necessary for canceling the rising temperature of the ion source box 18 due to heat generated from the filament 20 (step 104). Then, the control unit 36 corrects the temperature control control amount (output of the heater 28) of the ion source box 18 by using the obtained correction amount (step 105). Actually, the temperature of the ion source box 18 gradually rises for a certain period of time after the voltage application to the filament 20 is started. Therefore, the control unit 36 gradually reduces the effective voltage applied to the heater 28 so as to cancel the temperature rise of the ion source box 18 by using the correction amount obtained from the magnitude of the current flowing through the filament 20.
  • the correction of the output of the heater 28 is the voltage applied to the filament 20 related to the calorific value of the filament 20. It can also be performed based on the magnitude of the emission current or the magnitude of the emission current. In particular, since the current flowing through the filament 20 is controlled so that the emission current, which is the amount of electrons emitted from the filament 20, is constant, the emission current detected by the ammeter 23 is used to correct the output of the heater 28. be able to. In that case, the correlation data holding unit 38 holds the correlation data between the magnitude of the emission current acquired in advance by the experiment and the correction amount of the temperature control necessary for canceling the influence on the ion source box 18.
  • the temperature stability of the ion source box 18 can be improved as compared with the simple feedback control of the output of the heater 28.
  • the temperature of the ion source box 18 drops, contrary to the case when the voltage application to the filament 20 is started.
  • the output of the heater 28 can be corrected by predicting the temperature drop of the ion source box 18 and keeping the temperature of the ion source box 18 constant, as in the case of starting the voltage application to the filament 20. ..
  • the correlation data holding unit 38 has the magnitude of the applied voltage to the filament 20, the magnitude of the current flowing through the filament 20, and the magnitude of the emission current immediately before the voltage application to the filament 20 is stopped.
  • a gas chromatograph unit that generates a sample gas from an injected sample and separates components in the sample gas by a separation column, and the separation of the gas chromatograph unit.
  • the ionization unit of the mass spectrometric unit has an ion source box having a space inside for ionizing the components coming out from the outlet of the separation column, and for adjusting the temperature of the ion source box.
  • the control unit includes a heater and a filament that is arranged outside the ion source box and generates electrons for ionizing components coming out of the outlet of the separation column, and the control unit applies a voltage to the filament. Later, by controlling the output of the heater in relation to the magnitude of heat generation of the filament, the temperature of the ion source box affected by the heat emitted from the filament is adjusted to a predetermined temperature. Has been done.
  • any one of the magnitude of the voltage applied to the filament, the magnitude of the current flowing through the filament, and the emission current which is the amount of electrons emitted from the filament, and the ion source box is provided, and the control unit is held by the correlation data holding unit.
  • the correlation data is used to correct the output of the heater so as to cancel the influence of the filament on the temperature of the ion source box. According to such an embodiment, the output of the heater is corrected before the temperature of the ion source box actually changes, so that the temperature stability of the ion source box is improved.
  • control unit is configured to start applying a voltage to the filament after the outflow of the solvent from the outlet of the separation column is completed. According to such an embodiment, it is possible to prevent the filament from being deteriorated by the vaporized solvent.
  • This second aspect can be combined with the first aspect.
  • control unit is configured to detect that the outflow of the solvent from the outlet of the separation column is completed based on the elapsed time from the injection of the sample in the gas chromatograph unit. It may have been done.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electron Tubes For Measurement (AREA)
PCT/JP2021/016773 2020-07-14 2021-04-27 ガスクロマトグラフ質量分析装置 Ceased WO2022014119A1 (ja)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2022536141A JP7414146B2 (ja) 2020-07-14 2021-04-27 ガスクロマトグラフ質量分析装置
US18/015,887 US20230243787A1 (en) 2020-07-14 2021-04-27 Gas chromatograph mass spectrometer
CN202180049657.5A CN115836220B (zh) 2020-07-14 2021-04-27 气相色谱质量分析装置

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Application Number Priority Date Filing Date Title
JP2020-120450 2020-07-14
JP2020120450 2020-07-14

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WO2022014119A1 true WO2022014119A1 (ja) 2022-01-20

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US (1) US20230243787A1 (https=)
JP (1) JP7414146B2 (https=)
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WO (1) WO2022014119A1 (https=)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5163683A (https=) * 1974-11-11 1976-06-02 Hitachi Ltd
JP2002329475A (ja) * 2001-05-01 2002-11-15 Shimadzu Corp ガスクロマトグラフ質量分析装置
WO2007102224A1 (ja) * 2006-03-09 2007-09-13 Shimadzu Corporation 質量分析装置
WO2016092696A1 (ja) * 2014-12-12 2016-06-16 株式会社島津製作所 質量分析装置
WO2017086393A1 (ja) * 2015-11-17 2017-05-26 アトナープ株式会社 分析装置及びその制御方法
JP2018032481A (ja) * 2016-08-23 2018-03-01 株式会社島津製作所 質量分析装置及び質量分析装置用ソフトウエア
US10497548B1 (en) * 2019-05-01 2019-12-03 Aviv Amirav Method and apparatus for electron ionization liquid chromatography mass spectrometry

Family Cites Families (9)

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JPS5697865A (en) * 1980-01-07 1981-08-06 Hitachi Ltd Ionization detector
US5218203A (en) * 1991-03-22 1993-06-08 Georgia Tech Research Corporation Ion source and sample introduction method and apparatus using two stage ionization for producing sample gas ions
JP2001357816A (ja) 2000-06-13 2001-12-26 Shimadzu Corp 質量分析計
JP4123135B2 (ja) * 2003-11-11 2008-07-23 株式会社島津製作所 熱イオン化検出器
JP2010251718A (ja) * 2009-03-27 2010-11-04 Canon Anelva Corp 加熱装置の温度制御方法及び記憶媒体
US10262848B2 (en) * 2015-01-21 2019-04-16 Shimadzu Corporation Mass spectrometer
JP6432404B2 (ja) * 2015-03-18 2018-12-05 株式会社島津製作所 液化二酸化炭素送液ポンプとそれを備えた超臨界流体クロマトグラフ
CN108233759B (zh) * 2017-12-29 2020-03-03 北京市北分仪器技术有限责任公司 一种具有温度补偿系统的质谱仪射频电源
JP6843817B2 (ja) * 2018-11-21 2021-03-17 日本電子株式会社 質量分析装置、ガスクロマトグラフ質量分析装置及び焼き出し電流制御装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5163683A (https=) * 1974-11-11 1976-06-02 Hitachi Ltd
JP2002329475A (ja) * 2001-05-01 2002-11-15 Shimadzu Corp ガスクロマトグラフ質量分析装置
WO2007102224A1 (ja) * 2006-03-09 2007-09-13 Shimadzu Corporation 質量分析装置
WO2016092696A1 (ja) * 2014-12-12 2016-06-16 株式会社島津製作所 質量分析装置
WO2017086393A1 (ja) * 2015-11-17 2017-05-26 アトナープ株式会社 分析装置及びその制御方法
JP2018032481A (ja) * 2016-08-23 2018-03-01 株式会社島津製作所 質量分析装置及び質量分析装置用ソフトウエア
US10497548B1 (en) * 2019-05-01 2019-12-03 Aviv Amirav Method and apparatus for electron ionization liquid chromatography mass spectrometry

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CN115836220A (zh) 2023-03-21
US20230243787A1 (en) 2023-08-03
JPWO2022014119A1 (https=) 2022-01-20
CN115836220B (zh) 2025-01-17
JP7414146B2 (ja) 2024-01-16

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