CN109326499B - Device for removing sample introduction crystals of mass spectrometer - Google Patents
Device for removing sample introduction crystals of mass spectrometer Download PDFInfo
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- CN109326499B CN109326499B CN201811149805.7A CN201811149805A CN109326499B CN 109326499 B CN109326499 B CN 109326499B CN 201811149805 A CN201811149805 A CN 201811149805A CN 109326499 B CN109326499 B CN 109326499B
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- 239000013078 crystal Substances 0.000 title claims description 12
- 239000007788 liquid Substances 0.000 claims abstract description 88
- 239000012159 carrier gas Substances 0.000 claims abstract description 83
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 238000001514 detection method Methods 0.000 claims abstract description 12
- 230000008878 coupling Effects 0.000 claims abstract 4
- 238000010168 coupling process Methods 0.000 claims abstract 4
- 238000005859 coupling reaction Methods 0.000 claims abstract 4
- 238000007664 blowing Methods 0.000 claims abstract 2
- 238000005070 sampling Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000004949 mass spectrometry Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000013067 intermediate product Substances 0.000 abstract 1
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0422—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for gaseous samples
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Sampling And Sample Adjustment (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The utility model provides a device for getting rid of mass spectrograph advance appearance crystallization, including carrier gas advance appearance pipe, liquid sample advance appearance pipe, tee bend cavity and connection mass spectrograph advance appearance pipe, carrier gas advance appearance union coupling tee bend cavity, liquid sample advance appearance union coupling tee bend cavity, it links to each other with tee bend cavity to connect mass spectrograph advance appearance pipe one end, the other end is used for linking to each other with mass spectrograph vacuum cavity, liquid sample advances appearance pipe and is used for carrying the liquid sample who waits to detect, carrier gas advances appearance pipe and is used for carrying the carrier gas, the export of carrier gas blowing liquid sample advances appearance pipe, carrier gas advances appearance pipe, liquid sample advances appearance pipe, the contained angle of connection mass spectrograph advance appearance pipe three extension line guarantees that liquid sample can be blown into by the carrier gas and connects mass spectrograph advance appearance pipe, and enter mass spectrograph vacuum cavity through connecting mass spectrograph advance appearance pipe. The device can effectively prevent, get rid of liquid sample and advance the appearance crystallization, prevents to block up the pipeline, improves and advances kind efficiency, still accessible make carrier gas and liquid sample reaction, detects some materials that are difficult for direct detection that react intermediate product.
Description
Technical Field
The invention relates to the field of analytical instruments, in particular to a device for removing sample introduction crystals of a mass spectrometer.
Background
The mass spectrometry has the characteristics of high sensitivity, high accuracy, high analysis speed, strong qualitative capability and the like, and is one of the most widely applied analysis techniques. The sample injection system is one of important technologies in substance detection and is also an important component in mass spectrometry. The quality of the sample introduction system directly influences whether the sample can smoothly enter the detection instrument and is detected by the detection instrument.
At present, in the process of utilizing mass spectrometry to detect, because liquid samples enter into the vacuum environment from atmospheric pressure and cause such as phase transition, the problem of crystallization can appear at the injection pipe mouth, and then causes the pipeline to block up for a long time, and some samples can't be detected. Therefore, it is necessary to research a sample injection method for removing the liquid sample crystals to improve the sample injection efficiency.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a device for removing sample introduction crystals of a mass spectrometer so as to ensure that a sample to be detected smoothly enters the mass spectrometer to be ionized, solves the problem that the traditional sample introduction mode is easy to generate crystals to block a pipeline, and improves the sample introduction efficiency; the detection of some substances which are not easy to be directly detected is realized by detecting reaction intermediate products.
In order to achieve the purpose, the invention adopts the following technical scheme:
a device for removing sample introduction crystals of a mass spectrometer comprises a carrier gas sample introduction pipe, a liquid sample introduction pipe, a three-way cavity and a sample introduction pipe connected with the mass spectrometer, the carrier gas sample inlet pipe is connected with the three-way cavity, the liquid sample inlet pipe is connected with the three-way cavity, one end of the sample inlet pipe connected with the mass spectrometer is connected with the three-way cavity, the other end of the sample inlet pipe is connected with the vacuum cavity of the mass spectrometer, the liquid sample inlet pipe is used for conveying a liquid sample to be detected, the carrier gas inlet pipe is used for conveying carrier gas, the carrier gas blows the export of liquid sample advances appearance pipe, carrier gas advances appearance pipe liquid sample advances appearance pipe the contained angle of connecting mass spectrograph advances appearance pipe three extension line guarantees that liquid sample can by the carrier gas blows in connect the mass spectrograph advances in the appearance pipe, and the process connect the mass spectrograph and advance appearance pipe and get into in the mass spectrograph vacuum cavity.
Further:
the included angle between the carrier gas sampling pipe and the extension line of the sample pipe connected with the mass spectrometer is (90 degrees and 180 degrees), and preferably, the included angle is 180 degrees.
The included angle between the liquid sample inlet pipe and the extension line of the sample inlet pipe connected with the mass spectrometer is not 0 degree, and preferably, the included angle is 90 degrees.
The liquid sample inlet pipe and the carrier gas sample inlet pipe are quartz capillary tubes or metal tubes or silicone tubes, and the connection mass spectrometer sample inlet pipe is a quartz capillary tube or a metal tube.
The carrier gas and the liquid sample enter the three-way cavity through a pump or enter the three-way cavity by self-absorption through air pressure difference; and the substance to be fed into the mass spectrometer enters the mass spectrometer through the sample feeding pipe of the connecting mass spectrometer by utilizing air pressure difference self-absorption.
Connect mass spectrograph advance appearance pipe one end and stretch into in the mass spectrograph, it is within 5cm to stretch into the distance, connect mass spectrograph advance appearance pipe other end and stretch into in the tee bend cavity, and contactless to the cavity wall, and with carrier gas advance appearance pipe with liquid sample advances appearance pipe keeps spacing distance, preferably, spacing distance is not more than 0.5 cm.
One end of the carrier gas sample inlet pipe extends into the three-way cavity and does not contact the wall of the cavity; one end of the liquid sample inlet pipe extends into the three-way cavity and cannot contact with the wall of the cavity.
The inner diameters of the carrier gas sample inlet pipe and the mass spectrometer sample inlet pipe are larger than the inner diameter of the liquid sample inlet pipe.
The carrier gas sampling pipe is connected with the gas heating device, so that the sampling carrier gas firstly passes through the heating device and then enters the carrier gas sampling pipe.
The carrier gas delivered by the carrier gas inlet pipe reacts with the liquid sample so as to detect the substances in the liquid sample by detecting reaction intermediate products.
A mass spectrum detection system comprises the device for removing the sample introduction crystallization of the mass spectrometer and the mass spectrometer matched with the device for use.
The invention has the beneficial technical effects that:
the invention provides a device for removing sample introduction crystals of a mass spectrometer, wherein a liquid sample to be detected passes through a liquid sample introduction pipe, gas passes through a carrier gas introduction pipe, the carrier gas blows the outlet of the liquid sample introduction pipe, and the carrier gas and the liquid sample to be detected simultaneously pass through a sample introduction pipe connected with the mass spectrometer and enter the mass spectrometer for detection. The sample introduction device has a simple structure, can effectively prevent and remove the sample introduction crystallization of the liquid sample, prevent the pipeline from being blocked and improve the sample introduction efficiency.
The invention can realize the reaction of the carrier gas and the liquid sample, and detect some substances which are not easy to be directly detected by detecting reaction intermediate products; the carrier gas can be detected independently; the liquid sample can be detected independently; provides a more effective sample introduction mode for the field of analytical instruments.
Drawings
FIG. 1 is a drawing of a liquid sample injection crystallized material.
FIG. 2 is a schematic structural diagram of an apparatus for removing mass spectrometer sample introduction crystals according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of a mass spectrometry detection system formed by the device and the mass spectrometer according to an embodiment of the present invention.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
As shown in fig. 1, crystallization occurs when a liquid sample is directly injected.
As shown in fig. 2 and fig. 3, in an embodiment, a device for removing sample crystals of a mass spectrometer includes a carrier gas sample inlet tube 1, a liquid sample inlet tube 2, a three-way cavity 3 and a connecting mass spectrometer sample inlet tube 4, where the carrier gas sample inlet tube 1 is connected to the three-way cavity 3, the liquid sample inlet tube 2 is connected to the three-way cavity 3, one end of the connecting mass spectrometer sample inlet tube 4 is connected to the three-way cavity 3, the other end of the connecting mass spectrometer sample inlet tube is connected to a vacuum cavity 6 of a mass spectrometer 5, the liquid sample inlet tube 2 is used to transport a liquid sample to be detected, the carrier gas sample inlet tube 1 is used to transport carrier gas, the carrier gas is blown to an outlet of the liquid sample inlet tube 2, and an included angle between extension lines of the carrier gas sample inlet tube 1, the liquid sample inlet tube 2 and the connecting mass spectrometer sample inlet tube 4 ensures that the liquid sample can be blown into the connecting mass spectrometer sample inlet tube 4 by the carrier, and enters the vacuum cavity 6 of the mass spectrometer 5 through the connecting mass spectrometer sample inlet pipe 4. The device can effectively prevent and remove the liquid sample introduction crystallization, prevent the pipeline from being blocked and improve the sample introduction efficiency; and can detect some substances which are not easy to be directly detected by detecting reaction intermediate products. The device is applicable to different sample types, can select different gas and pipeline according to the demand, realizes getting rid of liquid sample crystallization.
In a preferred embodiment, the carrier gas sample inlet 1 is at an angle (90 °, 180 °) to the extension of the sample inlet 4, and more preferably at an angle of 180 °.
In a preferred embodiment, the included angle between the liquid sample inlet tube 2 and the extension line of the sample inlet tube 4 connected to the mass spectrometer cannot be 0 degree, and more preferably, the included angle is 90 degrees.
In a preferred embodiment, the angle between the extension lines of the carrier gas inlet 1 and the liquid sample inlet 2 is required to ensure that the liquid sample can be blown into the sample inlet 4 of the connected mass spectrometer.
In a preferred embodiment, the liquid sample introduction tube 2 is a quartz capillary tube, a metal tube or a silicone tube.
In a preferred embodiment, the sample tube 4 is a quartz capillary or a metal tube.
In a preferred embodiment, the carrier gas sampling tube 1 is a quartz capillary tube or a metal tube or a silicone tube.
In a preferred embodiment, the carrier gas and liquid sample are pumped into the three-way chamber 3 or self-sucked into the three-way chamber 3 by means of a gas pressure differential.
In a preferred embodiment, the material to be introduced into the mass spectrometer is self-aspirated into the mass spectrometer by means of a gas pressure differential through the connecting mass spectrometer sample tube 4.
In a preferred embodiment, one end of the sample tube 4 extends into the mass spectrometer, more preferably within 5 cm.
In a preferred embodiment, the other end of the connecting mass spectrometer inlet 4 extends into the three-way cavity 3, and cannot contact the cavity wall, and is kept at a certain distance from the carrier gas inlet 1 and the liquid sample inlet 2, and more preferably, the distance is not more than 0.5 cm.
In a preferred embodiment, one end of the carrier gas sampling pipe 1 extends into the three-way cavity 3 and does not contact the cavity wall.
In a preferred embodiment, one end of the liquid sample inlet tube 2 extends into the three-way chamber 3 and can contact the wall of the chamber.
The distances of the carrier gas sample inlet pipe 1 and the liquid sample inlet pipe 2 extending into the three-way cavity 3 can be different.
In a preferred embodiment, the carrier gas inlet tube 1 is connected to a gas heating device (not shown), so that the carrier gas is heated before entering the carrier gas inlet tube 1.
In a preferred embodiment, the carrier gas delivered by the carrier gas inlet pipe 1 reacts with the liquid sample so as to detect substances in the liquid sample by detecting reaction intermediate products.
The structure of the three-way cavity 3 can be designed at will.
The three-way cavity 3 is made of stainless steel or Teflon.
In a preferred embodiment, the inner diameters of the carrier gas inlet tube 1 and the connecting mass spectrometer inlet tube 4 are larger than the inner diameter of the liquid sample inlet tube 2.
The carrier gas may be a single gas such as dry air or nitrogen, or may be a mixed gas.
In one embodiment, as shown in fig. 3, a mass spectrometry detection system comprises the apparatus for removing crystallization of a mass spectrometer sample and a mass spectrometer 5 used in cooperation with the apparatus. The mass spectrometer 5 may be a quadrupole mass spectrometer. Mass spectrometer 5 may include a vacuum chamber 6, an EI source 7, a quadrupole mass analyzer 8, and a detector 9.
The following further describes embodiments of the present invention, its principles and advantages, in conjunction with the drawings.
A sample introduction method for removing liquid sample crystals comprises a carrier gas sample introduction pipe 1, a liquid sample introduction pipe 2, a three-way cavity 3, a sample introduction pipe 4 connected with a mass spectrometer and the mass spectrometer, wherein the carrier gas sample introduction pipe 1 is connected with the three-way cavity 3, and the liquid sample introduction pipe 2 is connected with the three-way cavity 3; connect mass spectrograph advance appearance pipe 4 one end with tee bend cavity 3 links to each other, and the other end links to each other with the vacuum cavity of mass spectrograph. The liquid sample that awaits measuring passes through from inhaling or under other sampling device's drive liquid sample advances appearance pipe 2, and gaseous passing through from inhaling or under other sampling device's drive simultaneously carrier gas advances appearance pipe 1, and the carrier gas is blown liquid sample advances appearance pipe 2 export, and carrier gas and the liquid sample that awaits measuring pass through simultaneously connect mass spectrometer and advance appearance pipe 4, detect in getting into the mass spectrometer.
The liquid sample inlet pipe 2 and the carrier gas inlet pipe 1 are preferably quartz capillary tubes, and the connection mass spectrometer inlet pipe 4 is preferably a metal pipe. Preferably, the carrier gas sampling pipe 1 and the included angle of the extension line of the mass spectrometer sampling pipe 4 is 180 degrees, and the liquid sample sampling pipe 2 and the included angle of the extension line of the mass spectrometer sampling pipe 4 are 90 degrees.
Preferably, one end of the sample inlet pipe 4 connected with the mass spectrometer extends into the mass spectrometer within 5cm, and the other end of the sample inlet pipe extends into the three-way cavity 3 and does not contact with the wall of the cavity; preferably, one end of the carrier gas sampling pipe 1 extends into the three-way cavity 3 and does not contact with the wall of the cavity; one end of the liquid sample inlet pipe 2 extends into the three-way cavity 3 and does not contact with the wall of the cavity.
By the device, the crystallization of the detected sample can be removed by controlling the flow of the carrier gas, so that the liquid sample can smoothly enter the mass spectrum, and the sample introduction efficiency and the detection efficiency are improved; the simultaneous introduction of different carrier gases can react with the liquid sample, allowing some undetectable species to be detected through the reaction intermediate.
It should be noted that the present invention does not limit the specific implementation control manner of the sample injection method and the specific size of the sample injection channel.
Those skilled in the art will recognize that numerous variations are possible in light of the above description, and thus the examples are intended to describe one or more specific embodiments.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (14)
1. The utility model provides a device for getting rid of mass spectrograph advance appearance crystallization, its characterized in that advances appearance pipe, liquid sample advance appearance pipe, tee bend cavity and connects mass spectrograph advance appearance pipe including the carrier gas, carrier gas advances appearance union coupling the tee bend cavity, liquid sample advances appearance union coupling the tee bend cavity, connect mass spectrograph advance appearance pipe one end with the tee bend cavity links to each other, and the other end is used for linking to each other with mass spectrograph vacuum cavity, liquid sample advances appearance pipe and is used for carrying the liquid sample who treats the detection, carrier gas advances appearance pipe and is used for carrying the carrier gas, the export of carrier gas advances appearance pipe with the export of liquid sample advances appearance pipe all is located in the tee bend cavity, follow the export of carrier gas advances appearance pipe is blown the export of liquid sample advances appearance pipe, carrier gas advances appearance pipe liquid sample advance appearance pipe the liquid sample connect mass spectrograph advance appearance pipe three's contained angle guarantee that liquid sample can by the carrier gas blows in connect mass spectrograph advance appearance pipe three In the pipe, and pass through in connecting mass spectrometer and advancing the pipe and getting into mass spectrometer vacuum cavity, the liquid sample process connect mass spectrometer and advance the pipe and get into by the ionization in the vacuum environment of mass spectrometer vacuum cavity, wherein, through blowing in connect among the mass spectrometer advances the pipe the carrier gas is got rid of the liquid sample and is in connect the appearance crystallization of advancing in the mass spectrometer pipe.
2. The apparatus of claim 1, wherein the carrier gas sample introduction tube is at an angle (90 °, 180 °) to the extension of the connected mass spectrometer sample introduction tube.
3. The apparatus of claim 2, wherein the carrier gas sample inlet tube is at an angle of 180 degrees from the extension of the connecting mass spectrometer sample inlet tube.
4. The apparatus of any of claims 1 to 3, wherein the liquid sample inlet tube is at an angle other than 0 degrees to the extension of the connecting mass spectrometer inlet tube.
5. The apparatus of claim 4, wherein the liquid sample inlet tube is at a 90 degree angle to the extension of the connecting mass spectrometer inlet tube.
6. The device of any one of claims 1 to 3, wherein the liquid sample inlet tube and the carrier gas inlet tube are quartz capillary tubes or metal tubes or silicone tubes, and the connecting mass spectrometer inlet tube is a quartz capillary tube or a metal tube.
7. The device according to any one of claims 1 to 3, wherein the carrier gas and liquid sample are pumped into the three-way chamber or self-sucked into the three-way chamber by means of a gas pressure difference; and the substance to be fed into the mass spectrometer enters the mass spectrometer through the sample feeding pipe of the connecting mass spectrometer by utilizing air pressure difference self-absorption.
8. The device of any one of claims 1 to 3, wherein one end of the connecting mass spectrometer inlet tube extends into the mass spectrometer within 5cm of the mass spectrometer, and the other end of the connecting mass spectrometer inlet tube extends into the three-way cavity without contacting the wall of the cavity and is spaced apart from the carrier gas inlet tube and the liquid sample inlet tube.
9. The apparatus of claim 8, wherein the other end of the connecting mass spectrometer sample inlet is spaced from the carrier gas sample inlet and the liquid sample inlet by a distance of no more than 0.5 cm.
10. The device of any one of claims 1 to 3, wherein one end of the carrier gas sampling tube extends into the three-way cavity without contacting the cavity wall; one end of the liquid sample inlet pipe extends into the three-way cavity and does not contact with the wall of the cavity.
11. The apparatus of any of claims 1 to 3, wherein the carrier gas inlet and the connecting mass spectrometer inlet have an internal diameter greater than the internal diameter of the liquid sample inlet.
12. The apparatus of any one of claims 1 to 3, wherein the carrier gas inlet is connected to a gas heating device such that the carrier gas is heated before entering the carrier gas inlet.
13. The apparatus according to any one of claims 1 to 3, wherein the carrier gas fed from the carrier gas inlet tube reacts with the liquid sample to detect the substance in the liquid sample by detecting a reaction intermediate product.
14. A mass spectrometry detection system comprising an apparatus for removing crystals from a mass spectrometer sample according to any of claims 1 to 13 and a mass spectrometer for use in conjunction with the apparatus.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811149805.7A CN109326499B (en) | 2018-09-29 | 2018-09-29 | Device for removing sample introduction crystals of mass spectrometer |
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| CN201811149805.7A CN109326499B (en) | 2018-09-29 | 2018-09-29 | Device for removing sample introduction crystals of mass spectrometer |
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| CN109326499A CN109326499A (en) | 2019-02-12 |
| CN109326499B true CN109326499B (en) | 2020-06-02 |
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| CN111896438B (en) * | 2019-05-06 | 2025-02-18 | 中国科学院大气物理研究所 | Gas sample injection device, detection device and detection method containing ammonia and/or amine substances |
| CN111721832B (en) * | 2020-07-06 | 2022-12-30 | 广西壮族自治区亚热带作物研究所（广西亚热带农产品加工研究所） | Passiflora edulis pulp substance detection device and detection method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4968885A (en) * | 1987-03-06 | 1990-11-06 | Extrel Corporation | Method and apparatus for introduction of liquid effluent into mass spectrometer and other gas-phase or particle detectors |
| CN1830056A (en) * | 2003-07-24 | 2006-09-06 | 普渡研究基金会 | Electrosonic jet ionization method and atmospheric ionization device for molecules |
| CN104716003B (en) * | 2013-12-13 | 2017-09-29 | 中国科学院大连化学物理研究所 | One kind is used for mass spectrographic pulse nebulization technique formula film sampling device |
| CN106170844B (en) * | 2014-05-01 | 2019-11-12 | 珀金埃尔默健康科学公司 | System and method for detecting and quantifying selenium and silicon in sample |
| EP3166129A4 (en) * | 2014-07-03 | 2018-06-13 | Shimadzu Corporation | Mass spectrometer |
| CN104201086B (en) * | 2014-08-08 | 2016-09-14 | 中国计量科学研究院 | A kind of molecular ion reaction substance spectra system and molecular ion reaction, cleaning method |
| CN105632866B (en) * | 2014-10-27 | 2018-03-13 | 岛津分析技术研发（上海）有限公司 | Electron spray ionisation device and mass spectrograph |
| CN205582884U (en) * | 2016-04-19 | 2016-09-14 | 东华理工大学 | An ion mobility spectrometer |
| CN106198707A (en) * | 2016-07-08 | 2016-12-07 | 清华大学深圳研究生院 | A kind of mass spectrum sampling device and Mass Spectrometer Method equipment |
| CN206353519U (en) * | 2016-12-05 | 2017-07-25 | 中国水产科学研究院黑龙江水产研究所 | A kind of liquid mass spectrograph pretreating device |
| CN107039232B (en) * | 2017-04-12 | 2018-12-21 | 清华大学深圳研究生院 | A kind of vacuum electric spray ion source and mass spectrograph |
| CN107204275B (en) * | 2017-05-09 | 2018-11-16 | 清华大学深圳研究生院 | A kind of electron spray desorbing ionization device for mass spectrum imaging |
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