WO2021033318A1 - ガスクロマトグラフ質量分析計および質量分析方法 - Google Patents

ガスクロマトグラフ質量分析計および質量分析方法 Download PDF

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Publication number
WO2021033318A1
WO2021033318A1 PCT/JP2019/032873 JP2019032873W WO2021033318A1 WO 2021033318 A1 WO2021033318 A1 WO 2021033318A1 JP 2019032873 W JP2019032873 W JP 2019032873W WO 2021033318 A1 WO2021033318 A1 WO 2021033318A1
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Prior art keywords
filament
mass spectrometer
gas chromatograph
ionization
opening
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Ceased
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English (en)
French (fr)
Japanese (ja)
Inventor
誠人 ▲高▼倉
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Shimadzu Corp
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Shimadzu Corp
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Priority to JP2021540612A priority Critical patent/JPWO2021033318A1/ja
Priority to CN201980099014.4A priority patent/CN114207427A/zh
Priority to PCT/JP2019/032873 priority patent/WO2021033318A1/ja
Priority to US17/597,015 priority patent/US20220317089A1/en
Publication of WO2021033318A1 publication Critical patent/WO2021033318A1/ja
Anticipated expiration legal-status Critical
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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
    • H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
    • H01J49/147—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers with electrons, e.g. electron impact ionisation, electron attachment
    • 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
    • H01J49/02—Details
    • H01J49/022—Circuit arrangements, e.g. for generating deviation currents or voltages ; Components associated with high voltage supply

Definitions

  • the present invention relates to a gas chromatograph mass spectrometer and a mass spectrometry method.
  • the sensitivity can be increased by efficiently ionizing the sample separated by the gas chromatograph (GC).
  • GC gas chromatograph
  • EI electron impact ionization method
  • the sample introduced into the ionization chamber is irradiated with thermions emitted from the filaments arranged outside the ionization chamber, and the sample is ionized by the reaction with the thermions. .. If the current flowing through the filament is increased and the amount of thermions is increased for efficient ionization, there is a problem that the life of the filament is shortened.
  • Patent Document 1 A device configuration that improves the performance of GC-MS using EI has been proposed.
  • the thermionic inlet for EI is formed larger than the thermionic inlet for chemical ionization (CI).
  • Patent Document 2 proposes to install the filament away from the ionization chamber until the influence of the electric field formed between the filament and the electron incident port does not reach the inside of the ionization chamber.
  • a first aspect of the present invention is a gas chromatograph mass spectrometer including a separation unit for separating a sample and a mass spectrometer for mass spectrometry of the sample introduced from the separation unit.
  • the ionization chamber or the ionization chamber and the ionization chamber which comprises a filament and an ionization chamber into which the thermoelectrons from the filament and the sample from the separation portion are introduced, and through which the thermions emitted from the filament pass.
  • the present invention relates to a gas chromatograph mass spectrometer in which the maximum diameter of an opening formed in a member arranged between the filament and the filament is less than 3 mm.
  • a second aspect of the present invention is to separate a sample by a separation unit of a gas chromatograph mass spectrometer, and to perform mass spectrometry of the sample introduced from the separation unit by the mass spectrometer of the gas chromatograph mass spectrometer.
  • mass spectrometry in the mass spectrometry, a current is passed through the filament to emit thermoelectrons from the filament, and the emitted thermions are referred to an ionization chamber or the ionization chamber and the filament.
  • the present invention relates to a mass spectrometric method in which an opening formed in a member installed between the two is passed through and introduced into the ionization chamber to be ionized, and the maximum diameter of the opening is less than 3 mm.
  • the efficiency of ionization can be increased in GC-MS.
  • FIG. 1 is a conceptual diagram showing the configuration of GC-MS of one embodiment.
  • FIG. 2 is a conceptual diagram showing an ionization unit according to an embodiment.
  • FIG. 3 is a flowchart showing the flow of the mass spectrometry method according to the embodiment.
  • FIG. 4 is a conceptual diagram showing the configuration of the ionized portion according to the modified example.
  • FIG. 5 is a chromatogram obtained in Comparative Example 1.
  • FIG. 6 is a chromatogram obtained in Comparative Example 2.
  • FIG. 7 is a chromatogram obtained in the examples.
  • FIG. 1 is a conceptual diagram showing the configuration of a gas chromatograph-mass spectrometer (GC-MS) 1 of the present embodiment.
  • the GC-MS1 includes a measuring unit 100 and an information processing unit 40.
  • the measuring unit 100 includes a gas chromatograph (GC) 10, a sample introduction tube 20, and a mass spectrometer 30.
  • the mass spectrometer 30 includes a vacuum vessel 31, an exhaust port 32, an ionization unit 33 that ionizes the sample S to generate ions In, an ion adjustment unit 34, a mass separation unit 35, a detection unit 36, and a vacuum. It includes an exhaust system 300.
  • the ionization unit 33 includes an ionization chamber 331, a filament 332, and a trap electrode 333.
  • the measuring unit 100 separates each component of the sample (hereinafter referred to as a sample component) and detects each separated sample component.
  • the GC10 separates the sample S introduced into the GC10 by gas chromatography.
  • a separation column (not shown) is attached to the GC10, and the sample S is separated in the separation column.
  • the sample S is in the form of a gas or a gas, which is appropriately referred to as a sample gas.
  • the type of separation column is not particularly limited, and any column such as a capillary column can be used.
  • Each component of the sample gas separated in the GC 10 is eluted from the separation column at different times and introduced into the ionization section 33 of the mass spectrometry section 30 through the sample introduction tube 20.
  • the bonding method between the GC 10 and the mass spectrometer 30 is not particularly limited, and a direct bonding method, an open split method, a jet separator method, or the like can be used.
  • the mass spectrometer 30 includes a mass spectrometer and ionizes the sample S introduced into the ionization unit 33, separates the mass, and detects the sample S.
  • the ion In derived from the sample S generated by the ionization unit 33 moves along the ion optical axis Ax1.
  • the type of the mass spectrometer constituting the mass spectrometer 30 is not particularly limited, and one or more masses of any kind are used. Those including an analyzer can be used.
  • the vacuum container 31 of the mass spectrometer 30 includes an exhaust port 32.
  • the exhaust port 32 is connected to the vacuum exhaust system 300 so as to be exhaustable.
  • the vacuum exhaust system 300 includes a pump capable of realizing a high vacuum of 10-2 Pa or less, such as a turbo molecular pump, and an auxiliary pump thereof.
  • a pump capable of realizing a high vacuum of 10-2 Pa or less such as a turbo molecular pump, and an auxiliary pump thereof.
  • FIG. 1 the points at which the gas inside the vacuum vessel 31 is discharged are schematically indicated by arrows A10.
  • the ionization unit 33 of the mass spectrometry unit 30 ionizes the sample S introduced into the ionization unit 33 by electron impact ionization (EI).
  • EI electron impact ionization
  • a sample introduction tube 20 is connected to the ionization chamber 331 so that the sample gas can be introduced into the ionization chamber.
  • the sample S introduced into the ionization chamber 331 is irradiated with thermions emitted from the filament 332.
  • the flow of thermions is schematically shown by arrow A20.
  • the amount of thermions to be irradiated is detected by a trap electrode 333 arranged on the opposite side of the filament 332 with the ionization chamber 331 in between.
  • Ions In derived from sample S including molecular ions or fragment ions, are emitted from the ionization chamber 331 by a voltage-based electromagnetic action based on a voltage applied to an electrode arranged outside the ionization chamber 331. For example, a voltage having a polarity opposite to that of the ion In to be detected is applied to the ion adjusting unit 34, and the ion In is accelerated by a drawing electric field based on the voltage.
  • FIG. 2 is a conceptual diagram showing the configuration of the ionization unit 33.
  • a first opening 321 is formed in the first side wall 311 of the ionization chamber 331.
  • the second side wall 312 of the ionization chamber 331 is formed with a second opening 322.
  • the second side wall 312 is formed at a position facing the first side wall 311 with the ion optical axis Ax1 interposed therebetween.
  • the third side wall 313 of the ionization chamber 331 is formed with a third opening 323 through which the ions In generated in the ionization chamber 301 are emitted.
  • a sample introduction tube 20 is installed on the fourth side wall 314 of the ionization chamber 331.
  • the first side wall 311 and the second side wall 312, the third side wall 313 and the fourth side wall 314 are made of a metal such as stainless steel.
  • a voltage of + several tens of volts is applied to the filament 332 in the ionization chamber 331 including the first side wall 311. This voltage is appropriately set from the viewpoint of increasing the efficiency of ionization.
  • the ionization chamber 331 can be grounded and the filament 332 can have a potential of approximately ⁇ 70 V.
  • the ionization chamber 301 can be, for example, a rectangular parallelepiped or a cylinder.
  • the shape of the ionization chamber 331 is not particularly limited as long as the thermions emitted from the filament 332 can be passed through the first opening 321 to irradiate the sample S and the ions In obtained by the irradiation can be emitted from the ionization chamber. ..
  • the first opening 321 is an opening through which thermions emitted from the filament 332 pass when entering the inside of the ionization chamber 331.
  • the second opening 322 is an opening through which thermions emitted from the filament 332 pass when they are emitted from the ionization chamber 331.
  • the first opening 321 and the second opening 322 are formed with the axis Ax2 as the central axis. It is preferable that the axis Ax2 is substantially orthogonal to the flow of the sample gas from the sample introduction tube 20 and the ion optical axis Ax1.
  • the sample introduction tube 20 is arranged so that the flow of the sample S discharged from the sample introduction tube 20 passes through the intersection of the axis Ax2 and the ion optical axis Ax1.
  • the shapes of the first opening 321 and the second opening 322 are not particularly limited as long as ionization can be performed with a desired efficiency.
  • the first opening 311 and the second opening 321 can be circular, elliptical, square or rectangular.
  • the maximum value of the inner diameter of the first opening 321 is defined as the first maximum diameter L1.
  • the first maximum diameter L1 is perpendicular to the axis Ax2 and can be the length of the longest line segment among the line segments passing through the two points of the axis Ax2 and the inner wall of the first opening 321.
  • the first maximum diameter L1 is preferably less than 3 mm, more preferably less than 2 mm, and even more preferably 1.5 mm or less.
  • the first maximum diameter L1 of the first opening 321 is preferably 1 mm or more. Further, it is preferable that the first maximum diameter L1 is larger than the inner diameter of the column to be used so as not to reduce the ionization efficiency.
  • the first maximum diameter L1 is preferably larger than the maximum value of the inner diameter of the thermoelectron incident port for CI.
  • the length from the first opening 321 to the filament 332 measured along the axis Ax2, which is the central axis of the first opening 321 is defined as the first filament distance L2.
  • the first filament distance L2 is preferably 1 mm or more.
  • the ratio of the first maximum diameter L1 to the first filament distance L2 is L1 / L2. Similar to the case where the first maximum value L1 is appropriately set, the L1 / L2 is preferably less than 3 and more preferably less than 2 from the viewpoint of increasing the density of thermions introduced into the ionization chamber 331. It is more preferably 1.5 or less. Further, L1 / L2 is preferably 1 or more from the viewpoint of suppressing a decrease in ionization efficiency due to a shift in the position of each portion of the ionization portion 33 during assembly.
  • the current flowing through the filament 332 can be adjusted to an appropriate value in order to prevent the ionization efficiency from being lowered due to the above-mentioned displacement of each portion of the ionization portion 33. it can.
  • the manufacturer or repairer or the like analyzes an arbitrary sample such as a standard sample by mass spectrometry of the mass spectrometer 30 while changing the current flowing through the filament 332. To detect.
  • the first current value which is the current value flowing through the filament 332 when the sensitivity is the highest in this detection, is acquired.
  • the first current value is transmitted to the user of GC-MS1 (hereinafter, simply referred to as "user") by any means such as document or communication.
  • the user adjusts the current flowing through the filament 332 to be the same as or close to the first current value. As a result, it is possible to suppress the influence on the ionization efficiency due to the displacement of the positions of the ionization portions 33 during assembly.
  • the second current value which is the current value flowing through the trap current 333 when the sensitivity is the highest, may be acquired.
  • the second current value is transmitted to the user by any means such as writing or communication.
  • the user monitors the current flowing through the trap electrode 333 and adjusts the current flowing through the filament 332 so that the current is equal to or close to the second current value. Even in this case, it is possible to suppress the influence on the ionization efficiency due to the displacement of the positions of the ionization portions 33 during assembly.
  • the trap electrode 333 can be any electrode capable of detecting thermions, but preferably contains a filament.
  • the trap electrode 333 is electrically connected to an ammeter or the like (not shown), and is configured to be able to measure the amount of thermions reaching the trap electrode.
  • EI can be performed using the filament as a thermionic source and the filament 332 as a trap electrode.
  • the filament 332 and the trap electrode 333 have the same shape.
  • the maximum value of the inner diameter of the second opening 322 and the distance between the second opening 322 and the trap electrode 333 which is a filament the first maximum diameter L1 and the first filament distance L2 of the first opening 321 described above are also obtained. It is preferable to set in the same manner as.
  • the thermions emitted from the filament 332 move along a spiral orbit due to the magnetic field generated by the magnets 334a and 334b arranged in the ionization unit 33. As a result, the thermions and the sample S can be easily reacted, and the ionization efficiency is enhanced.
  • the thermal conductor 301 contains a conductive substance such as metal as a main component, and is, for example, an aluminum block.
  • the heat conductor 301 functions as a temperature adjusting unit for adjusting the temperature of the ionization chamber 331.
  • the heat conductor is arranged in contact with the ionization chamber 331 and a heat source such as a heater (not shown). By controlling the temperature of the heat source, the temperature of the ionization chamber 331 is configured to approach the set temperature.
  • the ion adjusting unit 34 of the mass spectrometry unit 30 is provided with an ion transport system such as a lens electrode or an ion guide, and adjusts by converging the flux of ions In by an electromagnetic action.
  • the ion In emitted from the ion adjusting unit 34 is introduced into the mass separating unit 35.
  • the mass separation unit 35 of the mass spectrometry unit 30 includes a quadrupole mass filter and mass-separates the introduced ion In.
  • the mass separation unit 35 selectively passes the ion In based on the value of m / z by the voltage applied to the quadrupole mass filter.
  • the ion In obtained by the mass separation of the mass separation unit 35 is incident on the detection unit 36.
  • the detection unit 36 of the mass spectrometry unit 30 includes an ion detector and detects the incident ion In.
  • the information processing unit 40 is provided with an information processing device such as a computer, serves as an interface with a user, and performs processing such as communication, storage, and calculation related to various data.
  • the information processing unit 40 acquires information on analysis conditions and the like from the user via an input device such as a keyboard or a touch panel.
  • the information processing unit 40 includes a processing device such as a CPU (Central Processing Unit) and a storage medium.
  • the processing device executes a program stored in the storage medium, controls the measuring unit 100, processes measurement data, and is the main body of the operation of the GC-MS1.
  • the method of processing the measurement data is not particularly limited, and data corresponding to the chromatogram in which the retention time of the ion In detected by the detection unit 36 and the intensity of the detection signal are associated can be created, or the molecule contained in the sample S can be produced. Can be identified or quantified.
  • the information processing unit 40 includes a display device such as a display monitor, and displays information obtained by processing by the processing device.
  • the measuring unit 100 and the information processing unit 40 may be configured as an integrated device.
  • FIG. 3 is a flowchart showing the flow of the mass spectrometry method according to the present embodiment.
  • the information processing unit 40 acquires the first current value or the second current value.
  • the first current value or the second current value may be stored in the storage medium of the information processing unit 40 in advance, or may be input by the user.
  • step S103 is started.
  • step S103 the information processing unit 40 adjusts the amount of current flowing through the filament 332 based on the first current value or the second current value, as described above.
  • step S105 is started.
  • step S105 GC-MS1 performs mass spectrometry of sample S.
  • step S105 the process is completed.
  • a member may be arranged between the filament 332 and the ionization chamber 331 to make it difficult to transfer the heat of the filament 332 to the ionization chamber 331.
  • a member may be arranged between the filament 332 and the ionization chamber 331 to make it difficult to transfer the heat of the filament 332 to the ionization chamber 331.
  • this member is referred to as a shielding member.
  • the shielding member also refer to the document of Japanese Patent No. 4793440.
  • FIG. 4 is a conceptual diagram showing the configuration of the ionization unit 33a of this modified example.
  • the ionization unit 33a is different from the ionization unit 33 in the above-described embodiment in that it includes a shielding unit 400.
  • the shielding portion 400 is composed of a conductive substance such as stainless steel, and includes a first shielding member 411 and a second shielding member 412 arranged substantially in parallel.
  • the shielding portion 400 is arranged in contact with the heat conductor 301. Since the shielding portion 400 is electrically connected to the ionization chamber 331, it has the same potential as the ionization chamber 331.
  • the first shielding member 411 and the second shielding member 412 are arranged so as to face each other with the ionization chamber 331 interposed therebetween.
  • a fourth opening 421 is formed in the first shielding member 411, and a fifth opening 422 is formed in the second shielding member 412.
  • the fourth opening 421 and the fifth opening 422 are formed with the axis Ax2 as the central axis.
  • the shapes of the fourth opening 421 and the second opening 422 are not particularly limited as long as ionization can be performed with a desired efficiency.
  • the fourth opening 421 and the fifth opening 422 can be circular, elliptical, square or rectangular.
  • the maximum value of the inner diameter of the fourth opening 421 is defined as the second maximum diameter L10.
  • the second maximum diameter L10 can be the length of the longest line segment that is perpendicular to the axis Ax2 and passes through the two points of the axis Ax2 and the inner wall of the fourth opening 421.
  • the inventor has found that ionization can be performed more efficiently by setting the second maximum diameter L10 to an appropriate value.
  • the second maximum diameter L10 is preferably less than 3 mm, more preferably less than 2 mm, and even more preferably 1.5 mm or less. When the second maximum diameter L10 is reduced, the density of thermions introduced into the ionization chamber 331 increases, and more efficient ionization is realized.
  • the second maximum diameter L10 is preferably 1 mm or more.
  • the second maximum diameter L10 is preferably larger than the maximum value of the inner diameter of the opening through which thermions for CI pass.
  • the length from the fourth opening 421 to the filament 332 measured along the axis Ax2 is defined as the second filament distance L20.
  • the second filament distance L20 is preferably 1 mm or more.
  • the ratio of the second maximum diameter L10 corresponding to the second filament distance L2 is L10 / L20. Similar to the case where the second maximum diameter L10 is appropriately set, the L10 / L20 is preferably less than 3 and more preferably less than 2 from the viewpoint of increasing the density of thermions introduced into the ionization chamber 331. 5 or less is more preferable. Further, L10 / L20 is preferably 1 or more from the viewpoint of suppressing a decrease in ionization efficiency due to a displacement of each portion of the ionization portion 33a during assembly.
  • the current flowing through the filament 332 is appropriately used in order to prevent the ionization efficiency from being lowered due to the displacement of the positions of the ionization portions 33a described above. Can be adjusted to any value.
  • the trap electrode 333 is also used as a filament for emitting thermions in the EI
  • the maximum value of the inner diameter of the fifth opening 422 and the distance from the fifth opening 422 to the trap electrode 333 are also the second. It is preferable to set the maximum diameter L10 and the second filament distance L20 in the same manner.
  • the shape of the shielding portion 400 and the first shielding member 411 may be such that the fourth opening 421 is formed in the first shielding member 411, making it difficult to transfer the heat from the filament 332 to the ionization chamber 331 to a desired degree.
  • the shape of the shielding portion 400 and the first shielding member 411 may be such that the fourth opening 421 is formed in the first shielding member 411, making it difficult to transfer the heat from the filament 332 to the ionization chamber 331 to a desired degree.
  • the gas chromatograph mass spectrometer is a gas chromatograph mass spectrometer including a separation unit for separating a sample and a mass spectrometer for mass spectrometry of the sample introduced from the separation unit.
  • the mass spectrometer includes a filament and an ionization chamber into which the thermions from the filament and the sample from the separation section are introduced, and the thermions emitted from the filament pass through the ionization.
  • the maximum diameter of the opening formed in the chamber or the member arranged between the ionization chamber and the filament is less than 3 mm. This makes it possible to increase the efficiency of ionization in GC-MS.
  • the maximum diameter of the opening is 1 mm or more.
  • the opening of the gas chromatograph with respect to the distance from the filament to the opening is less than 3. As a result, the efficiency of ionization can be increased more reliably.
  • the ratio of the maximum diameter of the opening to the distance from the filament to the opening. Is 1 or more.
  • the opening is formed during electron impact ionization. It is configured so that the thermions irradiated to the sample pass through. Compared with other ionizations, in EI, the amount of thermions irradiated to the sample tends to affect the ionization efficiency, so that the ionization efficiency can be increased more effectively.
  • the mass spectrometric method is to separate the gas phase sample by the separation part of the gas chromatograph mass spectrometer and to introduce from the separation part by the mass spectrometer of the gas chromatograph mass spectrometer.
  • a current is passed through the filament to emit thermoelectrons from the filament, and the emitted thermions are emitted into an ionization chamber.
  • an opening formed in a member installed between the ionization chamber and the filament is passed through and introduced into the ionization chamber for ionization, and the maximum diameter of the opening is less than 3 mm. This makes it possible to increase the efficiency of ionization in GC-MS.
  • the current set based on the sensitivity of the mass spectrometry performed after the assembly of the gas chromatograph mass spectrometer is performed. It comprises adjusting the current flowing through the filament based on the value.
  • the present invention is not limited to the contents of the above embodiment. Other aspects conceivable within the scope of the technical idea of the present invention are also included within the scope of the present invention.
  • the model of the GC-MS used in the following examples is GCMS-TQ8050 (Shimadzu Corporation), and has the same configuration as in FIG.
  • a shielding member is arranged between the filament that emits thermions and the ionization chamber, and the shielding member is formed with an opening through which thermions pass.
  • the distance between the opening and the filament was 1 mm.
  • the maximum inner diameter of the opening of the shielding member was 3 mm.
  • Comparative Example 2 the same GC-MS as in Comparative Example 1 was used, and the analysis was performed by increasing the current flowing through the filament so that the current detected by the trap electrode (hereinafter referred to as emission current) was doubled. went.
  • emission current the current detected by the trap electrode
  • the measurement mode for mass spectrometry in the following examples was Multiple Reaction Monitoring (MRM).
  • MRM Multiple Reaction Monitoring
  • one fragment ion (referred to as the first fragment ion) was mass-separated at m / z of 319.90 in the first step and 256.90 in the second step.
  • other fragment ions (referred to as second fragment ions) were mass-separated at m / z of 321.90 in the first step and 258.90 in the second step.
  • FIGS. 5, 6 and 7 are diagrams showing chromatograms obtained by mass spectrometry of Comparative Example 1, Comparative Example 2 and Example, respectively.
  • the data for the first fragment ion is shown by a solid line
  • the data for the second fragment ion is shown by a broken line.
  • the horizontal axis shows the retention time
  • the vertical axis shows the intensity of the detection signal of the ion detected during the retention time. Since the intensities are not standardized in FIGS. 5, 6 and 7, it is possible to directly compare the amount of ions detected by the values shown on the vertical axis of each chromatogram.
  • the emission currents were 150 ⁇ A, 300 ⁇ A and 150 ⁇ A
  • the currents flowing through the filaments were 3.29 A, 3.49 A and 3.40 A.
  • the maximum intensity (unit: AU) of the peak corresponding to the sample was about 800 to 1200.
  • the maximum intensity of the peak corresponding to the sample was about 1250 to 1700, and an increase in sensitivity was observed due to an increase in the current flowing through the filament.
  • the maximum intensity of the peak corresponding to the sample was about 3500 to 3800.
  • the emission current was the same as that of Comparative Example 1, the sensitivity was significantly increased as compared with Comparative Example 1, and a further greater effect was observed as compared with Comparative Example 2.

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PCT/JP2019/032873 2019-08-22 2019-08-22 ガスクロマトグラフ質量分析計および質量分析方法 Ceased WO2021033318A1 (ja)

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JP2021540612A JPWO2021033318A1 (https=) 2019-08-22 2019-08-22
CN201980099014.4A CN114207427A (zh) 2019-08-22 2019-08-22 气相色谱质量分析仪以及质量分析方法
PCT/JP2019/032873 WO2021033318A1 (ja) 2019-08-22 2019-08-22 ガスクロマトグラフ質量分析計および質量分析方法
US17/597,015 US20220317089A1 (en) 2019-08-22 2019-08-22 Gas chromatograph mass spectrometer and mass spectrometry method

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Citations (3)

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Publication number Priority date Publication date Assignee Title
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