CN117554533A - Gas chromatography-mass spectrometry combined instrument and combined method - Google Patents
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- 238000002290 gas chromatography-mass spectrometry Methods 0.000 title claims abstract description 19
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- 238000005040 ion trap Methods 0.000 claims abstract description 106
- 150000002500 ions Chemical class 0.000 claims abstract description 92
- 238000004817 gas chromatography Methods 0.000 claims abstract description 20
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- 239000000126 substance Substances 0.000 claims abstract description 17
- 238000012216 screening Methods 0.000 claims abstract description 8
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- 239000000523 sample Substances 0.000 claims description 50
- 238000004451 qualitative analysis Methods 0.000 claims description 15
- 238000004445 quantitative analysis Methods 0.000 claims description 13
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- 238000002546 full scan Methods 0.000 claims description 2
- 238000012764 semi-quantitative analysis Methods 0.000 claims description 2
- 238000004949 mass spectrometry Methods 0.000 abstract description 10
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- 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
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Abstract
The invention relates to the technical field of mass spectrometry, in particular to a gas chromatography-mass spectrometer and a gas chromatography-mass spectrometer combination method, which comprise a gas chromatography module, a gas chromatography-mass spectrometer and a gas chromatography-mass spectrometer, wherein the gas chromatography module is used for separating fed sample substances; the EI ion source is connected with the gas chromatography module and is used for ionizing the sample subjected to the substance separation and forming an ion flow; the quadrupole mass analyzer is connected with the EI ion source and is used for carrying out mass screening on the ion flow and transmitting the ion flow to the linear ion trap after screening; controlling the leaving direction of ions passing through the linear ion trap, and receiving the ions by an electron multiplier detector after the ions pass through the dynode; when passing through the transmission focusing lens and deflecting, the liquid enters the electrostatic ion trap mass analyzer. The invention solves the problems of weakening and insufficient quantitative capability of the conventional quadrupole GCMS under the conditions of large concentration gradient and complex samples by using a quadrupole mass analyzer, a linear ion trap, an electrostatic ion trap multi-detector and a multi-mode hybrid application, and simultaneously greatly enhances the qualitative capability of analyzing the samples.
Description
Technical Field
The invention relates to the technical field of mass spectrometry, in particular to a gas chromatography-mass spectrometry combined instrument and a combined method.
Background
Gas chromatography mass spectrometry (GC-MS, gas Chromatography-Mass Spectrometry) is an analytical technique that combines the separation capacity of Gas Chromatography (GC) with the qualitative and quantitative capacity of Mass Spectrometry (MS). Gas chromatography portion (GC): the device mainly comprises a carrier gas system, a sample injection system, a chromatographic column and a detector. The sample is first vaporized at high temperature and fed by a carrier gas into a chromatographic column, and the components are separated on the column by interactions in the column. Mass spectrometry section (MS): including an ion source, a mass analyzer, and a detector. The quadrupole mass spectrum is a common mass analyzer, and ions are selectively screened by using an alternating electric field on the quadrupole, so that mass spectrograms with different mass-to-charge ratios are obtained. Samples are identified by spectral analysis or spectral library search to identify locations, or qualitative and quantitative analysis is performed on known samples. The gas chromatograph-mass spectrometer, especially the GCMS with the quadrupole as a mass analyzer, is one of the instruments with the highest use frequency of the global basic mass spectrometer, and has wide application in the fields of environmental monitoring and research, food science, medicine analysis, medicine, petroleum and petrochemical industries, atmospheric chemistry and the like.
The gas chromatography mass spectrometry can obtain three-dimensional information of retention time, quality and strength, and can be matched with a database to finish qualitative and quantitative analysis, and the quadrupole mass analyzer has good quantitative effect, but in the case of metabonomics, petroleum or other complicated component analysis, the concentration of an analyte is greatly changed from mg/mL to pg/mL, and the components are very complicated. The challenges faced are: the conventional quadrupole rod is used as a mass analyzer of the GCMS, and because of resolution limitation, samples with complex components are easy to cause overlapping and interference of chromatographic peaks, substances with close mass numbers are difficult to distinguish, so that the recognition degree of a spectrum library is reduced, and the constant capability is weakened or even lost; the conventional quadrupole rod is used as a mass analyzer of the GCMS, and is faced to samples with large concentration variation, high-concentration sample chromatographic peaks easily interfere with adjacent low-concentration chromatographic peak channels, and also, if the concentration differences of samples with similar mass numbers are large, high-concentration sample peak lines can submerge low-concentration samples, and if the mass numbers are similar, the qualitative and quantitative identification of the low-concentration sample peaks can be seriously affected; quadrupole rods as mass analyzers for GCMS also face the challenges of isotope and homozygote recognition in conventional sample analysis; as a mass analyzer of GCMS, a high-resolution mass analyzer such as TOF has a problem of insufficient dynamic range, narrow linear range, and insufficient quantitative capability.
Disclosure of Invention
The invention aims to provide a gas chromatography-mass spectrometer and a method for combining the gas chromatography-mass spectrometer, which are used for solving the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a gas chromatography-mass spectrometry combined method comprising:
the sample to be tested enters a gas chromatography module to finish substance separation, and then enters an EI ion source to finish ionization to form an ion flow;
the ion flow is transmitted to the linear ion trap through the front end cover of the linear ion trap after being subjected to mass screening by the quadrupole mass analyzer, and the linear ion trap is connected with a buffer gas inlet;
the qualitative and quantitative analysis of the sample to be tested is completed when the quadrupole mass analyzer is used as a main mass analyzer;
when the electrostatic ion trap is used as a main mass analyzer, high-precision qualitative and semi-quantitative analysis is completed on the tested sample;
when the quadrupole mass analyzer and the electrostatic ion trap are used as mass analyzers, accurate qualitative and accurate quantitative analysis is realized on the measured sample.
Further, when the quadrupole mass analyzer is used as the main mass analyzer, the motion process of the ions is as follows: ions entering the linear ion trap pass through a rear end cover of the linear ion trap and a transmission lens, pass through a dynode and are received by an electron multiplier detector;
during the movement of the ions, the buffer gas inlet is closed, and the linear ion trap radio frequency amplitude follows the quadrupole mass analyzer radio frequency amplitude to perform synchronous mass scanning.
Furthermore, when the electrostatic ion trap is used as a main mass analyzer, a buffer gas inlet is opened, the quadrupole mass analyzer adopts an all-pass mode, a corresponding radio frequency amplitude is selected according to the mass range of a measured sample, the voltage of a rear end cover of the linear ion trap is raised, ions are trapped by the linear ion trap and cooled, the radio frequency amplitude of the linear ion trap is turned off, meanwhile, a gradient direct current pulse high voltage is increased, the ions are emitted under the gradient pulse high voltage and pass through a transmission focusing lens, and then deflect under the action of a deflection lens to enter the electrostatic ion trap.
Further, when the quadrupole mass analyzer and the electrostatic ion trap are used as mass analyzers, the quadrupole mass analyzer is used for carrying out qualitative and quantitative analysis on the sample, the intensity of selected ions or the full-scanning ion intensity is calculated when the quadrupole mass analyzer is used, if the intensity value exceeds a threshold value, the voltage of the rear end cover of the linear ion trap is raised, and a buffer gas inlet is opened, so that the ions enter the electrostatic ion trap to carry out high-resolution mass scanning, and a high-resolution mass spectrogram is obtained.
Further, when the quadrupole mass analyzer and the electrostatic ion trap are used as mass analyzers, the quadrupole mass analyzer is used for carrying out qualitative and quantitative analysis on samples, the quadrupole mass analyzer monitors the intensity of ions or the single-peak ion intensity of full scanning in real time, if the ion intensity exceeds a threshold value or the occurrence of an observation peak is identified, the voltage of the rear end cover of the linear ion trap is raised, and a buffer gas inlet is opened, so that the ions enter the electrostatic ion trap to carry out high-resolution mass scanning, and a high-resolution mass spectrogram is obtained.
In order to achieve the above purpose, the present invention further provides the following technical solutions:
a gas chromatography-mass spectrometer, comprising:
a gas chromatography module for separating the sample material fed in;
an EI ion source connected to the gas chromatography module for ionizing the mass separated sample and forming an ion stream;
the quadrupole mass analyzer is connected with the EI ion source and is used for carrying out mass screening on the ion flow and transmitting the ion flow to the linear ion trap after finishing screening;
controlling the leaving direction of ions passing through the linear ion trap, and receiving the ions by an electron multiplier detector after the ions pass through the dynode;
when passing through the transmission focusing lens and deflecting, the liquid enters the electrostatic ion trap mass analyzer.
Further, a transmission lens is located between the linear ion trap and the dynode.
Further, a deflection lens for deflecting ions is arranged between the transmission focusing lens and the electrostatic ion trap.
Further, a buffer gas inlet is connected to the linear ion trap, and a front end cover and a rear end cover of the linear ion trap are respectively arranged at two ends of the linear ion trap.
Further, the ion trap also comprises a vacuum pump which is respectively connected with the quadrupole mass analyzer, the deflection lens and the electrostatic ion trap.
Compared with the prior art, the invention has the beneficial effects that:
there are several modes of operation of sample materials after they enter mass spectrometry: the linear ion trap is adopted to carry out synchronous mass scanning by adopting a transmission mode, the radio frequency amplitude of the linear ion trap follows the radio frequency amplitude of the quadrupole mass analyzer, the mode takes the quadrupole mass analyzer as a main mass analyzer, and selective ion scanning (SIM mode) or full scanning (full scan) can be carried out, so that the excellent quantitative capability of the quadrupole mass analyzer is fully utilized to complete qualitative and quantitative analysis of substances.
The method adopts the mode that an electrostatic ion trap is used as a main mass analyzer, and fully utilizes the excellent full spectrum and high-resolution qualitative capability of the electrostatic ion trap to accurately and quantitatively analyze substances.
The mixed mode of the quadrupole mass analyzer and the electrostatic ion trap is adopted, so that the interference of high chromatographic peaks brought by high-concentration samples on nearby chromatographic peaks is solved, and the total ion quantity entering the electrostatic ion trap can be reduced by controlling the sample injection time of the ion trap, so that the ion trap obtains proper ion quantity.
And the sample injection time of the ion trap is controlled to perform full-spectrum high-resolution analysis on the sample injection ions, so that various substances can be easily identified qualitatively, and meanwhile, the isotope is utilized to perform qualitative analysis on the sample.
Drawings
FIG. 1 is a schematic diagram of a system according to the present invention.
Fig. 2 is a waveform diagram of a linear ion trap following quadrupole scanning voltage in an operational mode of the present invention.
FIG. 3 is a graph of waveforms of operating voltages of a dual quadrupole mass analyzer and a linear ion trap in accordance with the mode of operation of the present invention.
Fig. 4 is a mode three workflow diagram of the present invention.
Fig. 5 is a mode four workflow diagram of the present invention.
FIG. 6 is a graph showing the accuracy and qualitative accuracy of the mass number 131 isotope peak abundance ratio of a standard sample in the high resolution mode of the present invention.
Fig. 7 is a graph showing the actual effect of isotope peaks in the quadrupole mass analyzer mode 131 of the present invention.
In the figure: a 10-gas chromatography module, a 20-vacuum pump, a 30-EI ion source, a 40-quadrupole mass analyzer, a front end cap of a 50-linear ion trap, a rear end cap of a 60-linear ion trap, a 70-transmission lens, an 80-electron multiplier detector, a 90-dynode, a 100-deflection lens, a 110-electrostatic ion trap, a 120-linear ion trap, a 130-transmission focusing lens, and a 140-buffer gas inlet.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that the terms "upper end," "lower end," "inner," "outer," "front end," "rear end," "both ends," "one end," "the other end," and the like indicate an azimuth or a positional relationship based on that shown in the drawings, merely for convenience of description and simplification of the description, and do not indicate or imply that the apparatus or element to be referred to must have a specific azimuth, be configured and operated in a specific azimuth, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "configured," "sleeved," "connected," and the like are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
Referring to fig. 1 to 7, the present invention provides a technical solution:
a gas chromatography mixing mass spectrometer comprises a gas chromatography module 10 and a mass spectrometer at the rear end, wherein a vacuum pump (system) 20 is used for providing or maintaining vacuum for the whole machine, a quadrupole mass analyzer 40 and a linear ion trap 120 are positioned under the same vacuum, the first-stage vacuum pressure is near 1E-3pa, a deflection lens 100 is positioned at the second-stage vacuum, the vacuum degree is about 1E-5pa, an electrostatic ion trap 110 is positioned at the third-stage vacuum, and the vacuum degree is required to be maintained below 1E-7 pa; the working principle of the gas chromatography is as follows: the sample enters the gas chromatographic module 10 through the sample injection device, helium is used as a chromatographic mobile phase, sample molecules are pushed by the helium mobile phase to gradually move through the chromatographic column according to the interaction characteristics of the helium and the immobilized sample molecules, sample substances are gradually separated within a certain time to finish separation of the sample substances, then the sample substances enter the EI ion source 30, and the sample substances enter the following working modes after mass spectrometry:
operation mode one: the gas chromatography module 10 completes the separation of substances, then enters a mass spectrometry system, firstly enters an EI ion source 30 to complete ionization, and after mass screening of ion flow through a quadrupole mass analyzer 40, the ion flow is received by an electron multiplier detector 80 after passing through a front end cover 50 of a linear ion trap, a linear ion trap 120, a rear end cover 60 of the linear ion trap, a transmission lens 70 and a dynode 90 respectively. In this process, the buffer gas inlet 140 is closed, and the linear ion trap 120 performs synchronous mass scanning with the linear ion trap RF (radio frequency) amplitude following the quadrupole mass analyzer RF amplitude, using a transmission mode in which selective ion scanning (SIM mode) or full scanning (full scan) is performed using the quadrupole mass analyzer as a main mass analyzer, and the excellent quantitative capability of the quadrupole mass analyzer is fully utilized to perform qualitative and quantitative analysis of the substance.
And a second working mode: the gas chromatography module 10 completes substance separation, then enters a mass spectrometry system, firstly enters an EI ion source 30 to complete ionization, after the ion flow passes through a quadrupole mass analyzer 40, enters a linear ion trap 120 through a front end cover 50 of the linear ion trap, the mode needs to be opened to open a buffer gas inlet 140, the quadrupole mass analyzer 40 selects corresponding RF amplitude according to the mass range of a measured sample, an LMCO (low-mass-off value) mode is adopted, a rear end cover 60 of the linear ion trap is voltage-lifted, so that ions are trapped by the linear ion trap 120 (cannot pass through the rear end cover 60), the voltage timing of the front end cover 50 is controlled to control the sample injection time of the ions into the linear ion trap 120, after the ions are cooled in the linear ion trap 120, RF radio frequencies on four electrodes of the linear ion trap 120 are turned off, meanwhile, a group of gradient direct current pulse high voltage is added to the linear ion trap 120, ions are emitted under the gradient pulse high voltage and pass through the transmission focusing lens 130, the transmission focusing lens 130 is used for further focusing the ion beam emitted from the linear ion trap, then the deflection lens 100 deflects under the action of the deflection lens 100, the deflection lens 100 is in a Z shape, the purpose is to deflect the ion beam entering and leaving the deflection lens through the aperture, so that the air flow with higher pressure of the linear ion trap 120 cannot directly reach the electrostatic ion trap 110, the vacuum of the electrostatic ion trap reaches a better vacuum degree, and enters the mass analyzer of the electrostatic ion trap 110.
And a third working mode: mode three is a mixed mode of mode one and mode two, and the work flow is that the combined instrument starts with mode one and calculates the intensity of selected ions or the full-scanning TIC intensity in real time, if the intensity value exceeds a threshold value, the mode two is started, the voltage of the rear end cover 60 is raised, and the buffer gas inlet 140 is opened, so that the ions enter the electrostatic ion trap 110 to carry out high-resolution mass scanning, and a high-resolution mass spectrogram is obtained, and the main advantages of the mode are that: the interference of high chromatographic peaks on adjacent chromatographic peaks caused by high-concentration samples is solved, the total ion quantity entering the electrostatic ion trap 110 can be reduced by controlling the sample injection time of the linear ion trap 120, so that the ion trap obtains proper ion quantity, and the working flow is shown in figure 4.
Specifically, the combined instrument starts scanning in a mode, selects ions in real time to perform scanning or full scanning, judges whether the scanning is finished, if yes, finishes the scanning, if not, calculates the intensity of the ions or the ions and judges whether the intensity exceeds a set threshold, if yes, starts a mode II, and if not, returns to select the ions in real time to perform scanning or full scanning. And in the second mode, calculating and setting sample injection time through the ion intensity value, carrying out high-resolution full spectrum scanning, judging whether scanning is finished, if so, finishing scanning, and if not, restarting scanning in the first mode.
And a fourth working mode: in the first mode, the quadrupole mass analyzer 40 is used for qualitative and quantitative analysis of the sample, the intensity of the ions or the full-scan single-peak ion intensity can be monitored in real time during the analysis process, if the ion intensity exceeds a threshold value or the occurrence of an observation peak is identified, the second mode is started, the voltage of the rear end cover 60 is raised, and the buffer gas inlet 140 is made to make the ions enter the electrostatic ion trap 110 for high-resolution mass scanning, so as to obtain a high-resolution mass spectrogram, and the workflow is as shown in fig. 5, wherein the main advantages of the mode are that: the interference of high concentration signal peaks on adjacent mass numbers is solved, for example, if one chromatographic peak contains multiple substances in the scanning of the quadrupole mass analyzer 40, if the mass numbers are very close to each other, the adjacent channels can be mutually interfered due to insufficient resolution of the quadrupole mass analyzer 40, or noise increase caused by high concentration samples can cause the analysis of other channels to be affected, and the mode can easily and qualitatively identify multiple substances by controlling the sample injection time of the linear ion trap 120 and performing full-spectrum high-resolution analysis on sample injection ions, and meanwhile, the qualitative analysis of samples is performed by utilizing isotopes, and the working flow is shown in figure 5.
Specifically, the combined instrument sets an ion signal threshold value, sets an observation peak, performs selective ion scanning or full scanning in a first mode, judges whether scanning is finished, if so, finishes scanning, if not, calculates the ion peak signal intensity, judges whether the set threshold value is exceeded, starts a second mode if not, identifies the observation peak, judges whether the observation peak is identified, starts the second mode if so, and performs selective ion scanning or full scanning again if not, in the second mode, calculates and sets the sample introduction time through the intensity value, then performs high-resolution full scanning, judges whether scanning is finished, if so, finishes scanning, and performs selective ion scanning or full scanning again in the first mode if not.
Since in the third and fourth modes, the problem of the reduced quantification capability due to insufficient qualification of the quadrupole mass analyzer 40 can be enhanced or replaced by the high resolution mass spectrometry scan of the second mode, the shortfall of the quadrupole chromatograph mass spectrometer (quadrupole mass analyzer 40) can be compensated for.
The invention can work independently in mode one and mode two, can realize the quadrupole gas chromatograph mass spectrometer mainly based on quantification on a combination instrument, and can also realize the high-resolution electrostatic ion trap gas chromatograph mass spectrometer mainly based on qualitative and semi-quantitative.
The invention can effectively solve the problems of insufficient qualitative and quantitative determination and even failure of the sample caused by low resolution of the quadrupole mass analyzer 40 when the components of the sample are complex or the concentration difference of the sample is large, and greatly improves the spectrogram identification and analysis capability.
According to the invention, as shown in the above figures 6 and 7, a high-resolution enhanced quadrupole qualitative and quantitative comparison chart (working mode IV) is introduced, so that the problem of poor identification of isotopes and homoplasms of a sample in gas-phase mass spectrometry is solved.
The mass number 131 isotope peak abundance ratio of the standard sample in the high resolution mode in fig. 6 is accurate and qualitatively accurate, and the actual effect of the isotope peak in the quadrupole (quadrupole mass analyzer 40) mode 131 in fig. 7 is shown. In fig. 6 and 7, the abscissa is the mass number, and the ordinate is the signal intensity.
Other: because in mode three and mode four, the undetermined condition encountered by the quadrupole mass analyzer 40 can be enhanced or replaced by the high resolution mass spectrometry scan of mode two, as in fig. 6 and 7 above, the quadrupole mass analyzer 40 sees almost no isotope peak with a mass number 131 in the internal standard. Makes up for the deficiency of quadrupole chromatographic mass spectrometers.
In the present invention, the buffer gas introduced through the buffer gas inlet 140 is usually pure nitrogen; the gas chromatography module 10 is more particularly based on a chromatographic column; the front end cap 50 of the linear ion trap, the rear end cap 60 of the linear ion trap, the transfer lens 70, and the transfer focusing lens 130 are all aperture-bearing; fig. 2 is a basic operation principle of the quadrupole mass analyzer 40.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A gas chromatography-mass spectrometry combination method, comprising:
the sample to be tested enters a gas chromatography module (10) to finish substance separation, and then enters an EI ion source (30) to finish ionization to form ion flow;
the ion flow is subjected to mass screening or ion transmission through a quadrupole mass analyzer (40), and then is transmitted to a linear ion trap (120) through a front end cover (50) of the linear ion trap, and a buffer gas inlet (140) is connected to the linear ion trap (120);
the qualitative and quantitative analysis of the sample to be tested is completed when the quadrupole mass analyzer (40) is used as a main mass analyzer;
performing accurate qualitative and semi-quantitative analysis on the sample to be measured when the electrostatic ion trap (110) is used as a main mass analyzer;
when the quadrupole mass analyzer (40) and the electrostatic ion trap (110) are used as mass analyzers, accurate qualitative and accurate quantitative analysis is realized on the tested sample.
2. A gas chromatography-mass spectrometry combination according to claim 1, wherein when using a quadrupole mass analyzer (40) as the main mass analyzer, the movement process of the ions is: ions entering the linear ion trap (120) pass through a rear end cover (60) of the linear ion trap and a transmission lens (70), then pass through a dynode (90), and are received by an electron multiplier detector (80);
during the movement of the ions, the buffer gas inlet (140) is closed and the linear ion trap (120) radio frequency amplitude follows the quadrupole mass analyzer (40) radio frequency amplitude for simultaneous mass scanning.
3. A gas chromatography-mass spectrometry method according to claim 1, wherein when the electrostatic ion trap (110) is used as the main mass analyzer, the buffer gas inlet (140) is opened, the quadrupole mass analyzer (40) selects the corresponding radio frequency amplitude according to the mass range of the sample to be measured, the rear end cap (60) of the linear ion trap is voltage-lifted, so that ions are trapped by the linear ion trap (120) and cooled, the radio frequency amplitude of the linear ion trap (120) is turned off, and meanwhile, a gradient dc pulse high voltage is increased, the ions are emitted under the gradient pulse high voltage and pass through the transmission focusing lens (130) and then deflect under the action of the deflection lens (100) to enter the electrostatic ion trap (110).
4. A gas chromatography-mass spectrometry combination method according to claim 1, wherein when the quadrupole mass analyzer (40) and the electrostatic ion trap (110) are used as mass analyzers, qualitative and quantitative analysis of the sample is performed by the quadrupole mass analyzer (40), the intensity of selected ions or the full-scan ion intensity is calculated when the quadrupole mass analyzer (40), if the intensity value exceeds a threshold value, the voltage of the rear end cap (60) of the linear ion trap is raised, and a buffer gas inlet (140) is opened, and ions enter the electrostatic ion trap (110) to perform high-resolution mass scanning, so as to obtain a high-resolution mass spectrogram.
5. A gas chromatography-mass spectrometry combination method according to claim 1, wherein when the quadrupole mass analyzer (40) and the electrostatic ion trap (110) are used as mass analyzers, the quadrupole mass analyzer (40) is used for qualitative and quantitative analysis of the sample, the quadrupole mass analyzer (40) monitors the intensity of ions or the single peak ion intensity of full scan in real time, if the ion intensity exceeds a threshold value or the occurrence of an observation peak is identified, the voltage of the rear end cover (60) of the linear ion trap is raised, and a buffer gas inlet (140) is opened, and the ions enter the electrostatic ion trap (110) for high resolution mass scanning, so as to obtain a high resolution mass spectrogram.
6. A gas chromatograph-mass spectrometer, comprising:
a gas chromatography module (10) for separating the sample material fed in;
an EI ion source (30) connected to the gas chromatography module (10) for ionizing the mass separated sample and forming an ion stream;
a quadrupole mass analyzer (40) connected to the EI ion source (30) for mass screening the ion stream and transmitting the screened ion stream to a linear ion trap (120);
controlling the direction of exit of ions through the linear ion trap (120), as the flow passes through the dynode (90), and is then received by the electron multiplier detector (80);
when passing through the transmission focusing lens (130) and deflected, enters the electrostatic ion trap (110) mass analyzer.
7. A gas chromatograph-mass spectrometer as claimed in claim 6 wherein there is a transmission lens (70) between the linear ion trap (120) and the dynode (90).
8. A gas chromatograph-mass spectrometer as claimed in claim 6 wherein a deflection lens (100) for deflecting ions is provided between the transmission focusing lens (130) and the electrostatic ion trap (110).
9. The gas chromatography-mass spectrometer according to claim 6, wherein the buffer gas inlet (140) is connected to the linear ion trap (120), and both ends of the linear ion trap (120) are respectively provided with a front end cap (50) and a rear end cap (60) of the linear ion trap.
10. The gas chromatograph-mass spectrometer of claim 8, further comprising a vacuum pump (20), the vacuum pump (20) being configured to maintain vacuum for the quadrupole mass analyzer (40), the deflection lens (100) and the electrostatic ion trap (110), respectively.
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040108450A1 (en) * | 2001-03-23 | 2004-06-10 | Alexander Makarov | Mass spectrometry method and apparatus |
CN103548111A (en) * | 2011-05-20 | 2014-01-29 | 塞莫费雪科学(不来梅)有限公司 | Method and apparatus for mass analysis |
CN106169411A (en) * | 2016-07-13 | 2016-11-30 | 中国计量科学研究院 | New type series-parallel connected mass spectrometric apparatus system and parameter adjusting method thereof and using method |
US20200328073A1 (en) * | 2019-04-15 | 2020-10-15 | Thermo Fisher Scientific (Bremen) Gmbh | Mass Spectrometer Having Improved Quadrupole Robustness |
CN113948365A (en) * | 2020-07-15 | 2022-01-18 | 宁波大学 | Combined type mass spectrometer |
CN115015462A (en) * | 2022-07-01 | 2022-09-06 | 广西特色作物研究院 | Citrus huanglongbing detection method based on LC-MS (liquid chromatography-mass spectrometry) non-targeted analysis |
CN115097021A (en) * | 2022-05-27 | 2022-09-23 | 国家烟草质量监督检验中心 | Method for researching chemical component difference of cigarette smoke based on gas chromatography-quadrupole electrostatic field orbit trap high-resolution mass spectrometry |
-
2024
- 2024-01-11 CN CN202410040844.2A patent/CN117554533A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040108450A1 (en) * | 2001-03-23 | 2004-06-10 | Alexander Makarov | Mass spectrometry method and apparatus |
CN103548111A (en) * | 2011-05-20 | 2014-01-29 | 塞莫费雪科学(不来梅)有限公司 | Method and apparatus for mass analysis |
CN106169411A (en) * | 2016-07-13 | 2016-11-30 | 中国计量科学研究院 | New type series-parallel connected mass spectrometric apparatus system and parameter adjusting method thereof and using method |
US20200328073A1 (en) * | 2019-04-15 | 2020-10-15 | Thermo Fisher Scientific (Bremen) Gmbh | Mass Spectrometer Having Improved Quadrupole Robustness |
CN113948365A (en) * | 2020-07-15 | 2022-01-18 | 宁波大学 | Combined type mass spectrometer |
WO2022012701A1 (en) * | 2020-07-15 | 2022-01-20 | 宁波大学 | Composite mass spectrometer |
CN115097021A (en) * | 2022-05-27 | 2022-09-23 | 国家烟草质量监督检验中心 | Method for researching chemical component difference of cigarette smoke based on gas chromatography-quadrupole electrostatic field orbit trap high-resolution mass spectrometry |
CN115015462A (en) * | 2022-07-01 | 2022-09-06 | 广西特色作物研究院 | Citrus huanglongbing detection method based on LC-MS (liquid chromatography-mass spectrometry) non-targeted analysis |
Non-Patent Citations (2)
Title |
---|
"赛默飞世尔科技发布首台"三合一"LC-MS, 以创新性分析和适用性革新生命科学研究", 环境化学, no. 06, 15 June 2013 (2013-06-15) * |
"赛默飞推出众多色谱质谱新品", 环境化学, no. 07, 15 July 2013 (2013-07-15) * |
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