CN217544538U - Secondary electrospray ionization source device, gas sample introduction system and reagent atomizer - Google Patents

Secondary electrospray ionization source device, gas sample introduction system and reagent atomizer Download PDF

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CN217544538U
CN217544538U CN202221097164.7U CN202221097164U CN217544538U CN 217544538 U CN217544538 U CN 217544538U CN 202221097164 U CN202221097164 U CN 202221097164U CN 217544538 U CN217544538 U CN 217544538U
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sample
atomizer
reagent
ionization source
capillary
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张建勋
徐珩琦
孙世豪
赵无垛
曾世通
席辉
王丁众
李鹏
付英杰
卢斌斌
宗永立
刘珊
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Zhengzhou Tobacco Research Institute of CNTC
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Zhengzhou Tobacco Research Institute of CNTC
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Abstract

The utility model provides a secondary electrospray ionization source device, which comprises a vacuum ionization source cavity, a vacuum ultraviolet lamp, a mass spectrum sampling taper hole, a reagent atomizer and a gas sample introducing system; the reagent atomizer comprises an atomizer, a high-voltage power supply, a reagent supply capillary tube and a first high-voltage gas tube, wherein the reagent supply capillary tube is communicated with the atomizer, the first high-voltage gas tube is communicated with the gas inlet end of the atomizer, and the high-voltage power supply acts on the atomizer to form a reagent ion flow; the gas sample introducing system comprises a sample capillary tube, a sample transmission tube and a second high-pressure gas tube, wherein the sample capillary tube is connected with the sample transmission tube, and the second high-pressure gas tube is connected with the side end inlet of the sample transmission tube; the vacuum ultraviolet lamp is arranged in the vacuum ionization source cavity. The device can detect polarity and non-polarity sample simultaneously, and two ionization processes are mutually noninterference, improve ion ionization efficiency, are fit for the on-line research of complicated component, utilize the venturi effect to realize the self-driven no pump of sample and advance the appearance simultaneously.

Description

Secondary electrospray ionization source device, gas sample introduction system and reagent atomizer
Technical Field
The utility model relates to a mass spectrometry instrument technical field, specific theory has related to a secondary electrospray ionization source device to and gaseous sample introducing system and reagent atomizer.
Background
The mass spectrometry technology has the advantages of high sensitivity, strong specificity, high response speed and the like, and is widely applied to the fields of organic synthesis, pharmaceutical analysis, life science, food safety, environmental analysis, public safety and the like. The development of ion sources, which serve as one of the core components of mass spectrometry instruments, has driven the progress and development of mass spectrometry. In order to simplify the sample pretreatment step and realize the purpose of in-situ real-time analysis, the analysis method based on the atmospheric open ionization Mass Spectrometry (AMS) is rapidly developed, and the key for realizing the Mass spectrum direct sample injection analysis under the atmospheric pressure is to select a proper ionization source according to the physicochemical property of an analyte.
At present, the developed atmospheric pressure open ion source mainly originates from electrospray technology and plasma technology. The atmospheric open ion source based on the electrospray technique is suitable for the ionization of polar compounds, and the atmospheric open ion source based on the plasma technique is suitable for the ionization of medium-polarity and weak-polarity compounds.
The secondary electrospray ionization source (SESI) is an atmospheric pressure soft ionization technology derived from an electrospray technology, and the principle is that a sample to be detected is introduced into a charged liquid drop and a reactive reagent ion region generated by electrospray to react and ionize.
The utility model discloses a current CN109360781A patent utility model discloses a secondary electrospray ion source device for gas detection such as volatile gas, human respiratory gas, but the range of application of single ionization source technique receives the restriction of ionization source self ionization mechanism and target object polarity, produces ionization discrimination effect easily in ionization process, is difficult for realizing the synchronous ionization of polarity and non-polar compound, has restricted the application of mass spectrometry technique in the synchronous detection field of different polarity target objects.
In order to realize synchronous detection of targets with different polarities, a technical means of compounding ion sources suitable for different polarity ranges is mainly adopted at the present stage. A Vacuum Ultraviolet (VUV) ionization source is a soft ionization source capable of emitting ultraviolet photons, which has a simple spectrum and can be used for ionization of nonpolar compounds. Meanwhile, the device has small volume, simple structure, low power consumption and easy integration with other ionization technologies.
The existing patent CN113539784A, the utility model discloses a combined type ion source, mass spectrometer, combine photoionization and electron ionization together, but it is not real combined ionization source, only switches between the two, and the interference is serious.
Therefore, there is a need for a new composite ion source that combines the secondary electrospray technique with the photoionization technique to solve the above-mentioned problems.
SUMMERY OF THE UTILITY MODEL
The utility model aims at prior art not enough to provide a but simultaneous detection polarity and non-polar sample, two ionization process mutual noninterference improve ion ionization efficiency, are fit for the online research of complicated component, utilize the secondary electrospray ionization source device that the self-driven no pump of venturi effect realization sample advanced simultaneously, and gaseous sample introducing system and reagent atomizer.
In order to realize the purpose, the utility model discloses the technical scheme who adopts is: a secondary electrospray ionization source device comprises a vacuum ionization source cavity, a vacuum ultraviolet lamp, a mass spectrum sample injection taper hole, a reagent atomizer and a gas sample introduction system;
the reagent atomizer comprises an atomizer, a high-voltage power supply, a reagent supply capillary and a first high-voltage gas pipe, wherein the reagent supply capillary is communicated with a liquid inlet end of the atomizer to provide a reagent, the first high-voltage gas pipe is communicated with a gas inlet end of the atomizer to provide high-voltage nitrogen and is used for atomizing the reagent, and the high-voltage power supply acts on the atomizer to form a reagent ion flow;
the gas sample introduction system comprises a sample capillary, a sample transmission pipe and a second high-pressure gas pipe, wherein the sample capillary is connected with a rear end inlet of the sample transmission pipe to provide a sample gas flow, and the second high-pressure gas pipe is connected with a side end inlet of the sample transmission pipe to generate negative pressure at a pipe orifice at an outlet end of the sample capillary as an introduction power of the sample gas flow;
the reagent ion flow and the sample gas flow are converged at the mass spectrum sample introduction taper hole and are subjected to primary ionization;
the mass spectrum sample injection taper hole is communicated with the vacuum ionization source cavity, and the vacuum ultraviolet lamp is arranged in the vacuum ionization source cavity or in a space between the mass spectrum sample injection taper hole and the vacuum ionization source cavity and is used for carrying out secondary ionization on the sample gas flow.
Basically, the direction of the light emitted by the vacuum ultraviolet lamp is perpendicular to the central axis of the flow direction of the mixed fluid of the reagent ion flow and the sample gas flow.
Basically, the atomizer and the sample transmission pipe are fixed through the angle regulator, the outlet end of the atomizer and the outlet end of the sample transmission pipe are both provided with needle-shaped outlets, and the included angle between the outlet end of the atomizer and the outlet end of the sample transmission pipe is 30-60 degrees.
Basically, the rear end of the reagent supply capillary is connected with an injector and an injection pump in sequence, and the rear end of the sample capillary is connected with a sample injection container; the included angle between the second high-pressure gas pipe and the sample transmission pipe is 90 degrees, and the included angle between the first high-pressure gas pipe and the atomizer is 90 degrees.
And heating jackets are arranged outside the sample transmission pipe and the atomizer.
Basically, the vacuum ultraviolet lamp is installed on an isolation valve base which is arranged in the vacuum ionization source cavity and is positioned between the mass spectrum sample introduction taper hole and the transmission six-stage rod.
Basically, the atomizer and the sample transmission pipe are both made of metal materials, the atomizing pipe in the atomizer is an electrospray metal capillary or an inert quartz capillary, and the sample capillary is an inert quartz capillary.
Basically, the distance between the outlet end of the atomizer and the outlet end of the sample transmission pipe and the mass spectrum sample injection taper hole is respectively 2 mm to 40mm, the inner diameter of the sample capillary is 5 to 150 μm, the sample capillary is arranged in the sample transmission pipe, the distance between the tail end of the sample capillary and the outlet end of the sample transmission pipe is 0 to 10mm, the electrospray metal capillary extends out of the outlet end of the atomizer, and the distance between the end surface of the electrospray metal capillary and the outlet end surface of the atomizer is 2 to 3mm.
The voltage range of the high-voltage power supply is 3-5 kV.
Basically, the first high-pressure gas pipe and the second high-pressure gas pipe are respectively connected with a high-pressure nitrogen source through a mass flow controller.
A gas sample introduction system of a secondary electrospray ionization source device comprises a sample capillary, a sample transmission pipe and a second high-pressure gas pipe, wherein the sample capillary is connected with a rear end inlet of the sample transmission pipe to provide a sample gas flow, and the second high-pressure gas pipe is connected with a side end inlet of the sample transmission pipe to generate negative pressure at a pipe orifice at an outlet end of the sample capillary to serve as introduction power of the sample gas flow; the second high-pressure gas pipe is externally connected with a high-pressure gas source.
Basically, the included angle between the second high-pressure gas pipe and the sample transmission pipe is 90 degrees.
Basically, a gas flow control valve is connected between the second high-pressure gas pipe and the high-pressure gas source.
The utility model provides a reagent atomizer of secondary electrospray ionization source device, includes atomizer, high voltage power supply, reagent supply capillary and first high-pressure gas pipe, reagent supply capillary intercommunication atomizer feed liquor end is in order to provide reagent, the inlet end of first high-pressure gas pipe intercommunication atomizer is in order to provide high-pressure nitrogen gas and be used for the atomizing of reagent, high voltage power supply acts on the atomizer in order to form the reagent ion flow.
Basically, the inlet end of the reagent supply capillary is connected with an injector, and the inlet end of the injector is connected with a syringe pump.
Basically, the included angle between the first high-pressure gas pipe and the atomizer is 90 degrees.
Basically, a gas flow control valve is connected between the first high-pressure gas inlet pipe and the high-pressure gas source.
The utility model discloses relative prior art has substantive characteristics and progress, specific theory, the utility model discloses concatenate secondary electron spray and low pressure VUV light ionization source, fuse the structure of both and mass spectrograph, realize detecting polarity and non-polar sample simultaneously, and two ionization processes go on simultaneously under atmospheric pressure and vacuum condition, mutual noninterference has widened the detection range of sample, has improved ion ionization efficiency.
The ionization source has universality and universality, is suitable for the prior research of complex components, and realizes the functions of in-situ, multi-target, synchronous, high-sensitivity analysis and the like of volatile organic compounds with different polarities in the environment.
And simultaneously, the utility model discloses a venturi effect that high-speed air current produced realizes sample under the atmospheric pressure environment and advances the appearance to the self-driven no pump of atmospheric pressure ionization source, and the introduction in-process does not need extra valve and pump, effectively reduces the volume, reduces gaseous residual to the influence of analysis.
The utility model discloses but wide application in fields such as atmospheric quality monitoring, medical diagnosis.
Furthermore, the outlet end of the atomizer, the outlet end of the sample transmission pipe and the mass spectrum sample injection taper hole are arranged according to a certain angle, so that the reagent ion flow and the sample gas flow are conveniently and fully contacted and interacted.
Furthermore, a heating jacket is added outside the atomizer and the sample conveying pipe to ensure that the temperature of the reagent ion flow and the sample gas flow is in a stable range.
Furthermore, the vacuum ultraviolet lamp is installed on the isolation valve base and integrally fixed with the mass spectrometer, so that the working stability of the vacuum ultraviolet lamp is ensured.
Drawings
Fig. 1 is a schematic structural diagram of a secondary electrospray ionization source device of the present invention.
In the figure: 1. a vacuum ionization source cavity; 2. a vacuum ultraviolet lamp; 3. mass spectrum sample introduction taper holes; 4. an atomizer; 5. a high voltage power supply; 6. a reagent supply capillary; 7. a first high pressure gas pipe; 8. an injector; 9. an injection pump; 10. a sample capillary; 11. a sample transfer tube; 12. a second high pressure gas pipe; 13. a sample introduction container; 14. an angle adjuster; 15. a mass flow controller.
Detailed Description
The technical solution of the present invention is further described in detail through the following embodiments.
Example 1
As shown in fig. 1, a secondary electrospray ionization source device includes a vacuum ionization source cavity 1, a vacuum ultraviolet lamp 2, a mass spectrometry sample injection taper hole 3, a reagent atomizer, and a gas sample introduction system.
The reagent atomizer comprises an atomizer 4, a high-voltage power supply 5, a reagent supply capillary 6 and a first high-pressure gas pipe 7, wherein the outlet end of the reagent supply capillary 6 is communicated with the liquid inlet end of the atomizer 4 to provide a reagent, the inlet end of the reagent supply capillary 6 is sequentially connected with an injector 8 and an injection pump 9, the first high-pressure gas pipe 7 is communicated with the gas inlet end of the atomizer 4 to provide high-pressure nitrogen gas for atomizing the reagent, the included angle between the first high-pressure gas pipe 7 and the atomizer 4 is 90 degrees, the gas inlet end of the first high-pressure gas pipe 7 is connected with a high-pressure nitrogen gas source, and the flow rate are controlled by a mass flow controller 15; the voltage range of the high-voltage power supply 5 is 3-5 kV, the high-voltage power supply acts on the atomizer 4, and a reagent is driven by high voltage to form a reagent ion flow.
The gas sample introducing system comprises a sample capillary tube 10, a sample transmission tube 11 and a second high-pressure gas tube 12, wherein the sample capillary tube 10 is connected with an inlet at the rear end of the sample transmission tube 11 so as to provide a sample gas flow, the tail end of the sample capillary tube 10 is connected with a sample introduction container 13 such as an air collecting bag or an air collecting tank, the second high-pressure gas tube 12 is connected with an inlet at the side end of the sample transmission tube 11, the air inlet end of the second high-pressure gas tube 12 is connected with a high-pressure nitrogen source, the flow and the flow speed are controlled through a mass flow controller, the connection angle is 90 degrees, negative pressure is generated at a tube opening at the outlet end of the sample capillary tube by utilizing the Venturi effect, and negative pressure power is used as introduction power of the sample gas flow.
The atomizer 4 and the sample transmission pipe 11 are both fixed through an angle adjuster 14, the outlet end of the atomizer 4 and the outlet end of the sample transmission pipe 11 are both provided with needle-shaped outlets, the included angle between the outlet end of the atomizer 4 and the outlet end of the sample transmission pipe 11 is 30-60 degrees, and the angle can be adjusted according to requirements.
And heating sleeves are arranged outside the sample transmission pipe and the atomizer so as to ensure the stability of temperature.
The reagent ion flow and the sample gas flow are converged at the mass spectrum sample injection taper hole 3 and are subjected to primary ionization, the primary ionization is secondary electrospray ionization, and the primary ionization and the secondary electrospray ionization are performed under normal pressure to generate initial ions and sample gas flow which is not ionized.
The mass spectrum advances kind taper hole 3 intercommunication vacuum ionization source cavity 1, vacuum ultraviolet lamp 2 sets up in vacuum ionization source cavity or is located the mass spectrum advances kind taper hole and transmits on the isolation valve base between the six grades of poles, the light direction that the vacuum ultraviolet lamp jetted out is perpendicular with the axis of the mixed fluid's of reagent ion flow and sample gas stream flow direction for carry out secondary ionization to sample gas stream, secondary ionization is the photoionization, goes on under vacuum environment.
And the ions after the second ionization and the initial ions are converged into a total ion flow, and the total ion flow enters a mass analyzer for analysis.
The atomizer 4 and the sample transmission pipe 11 are both made of metal materials, the atomizing pipe inside the atomizer 4 is an electrospray metal capillary or an inert quartz capillary, and the sample capillary is an inert quartz capillary.
The distance between the outlet end of the atomizer 4 and the outlet end of the sample transmission pipe 11 and the mass spectrum sample injection taper hole 3 is 20-40 mm, the inner diameter of the sample capillary is 5-150 mu m, the sample capillary 10 is arranged in the sample transmission pipe 11, the distance between the tail end of the sample capillary 10 and the outlet end of the sample transmission pipe 11 is 0-10mm, the electrospray metal capillary extends out of the outlet end of the atomizer, and the distance between the end face of the electrospray metal capillary and the outlet end face of the atomizer 4 is 2-3mm.
The working principle is as follows:
the atmospheric pressure secondary electrospray ionization source mainly comprises an atmospheric pressure gas sample introduction system and a reagent atomizer. The gas sample and charged liquid drops generated by electrospray are mixed in front of a mass spectrum taper hole to generate charge exchange or molecular ion reaction, under the action of gas flow and an electric field, part of charged ions and neutral gas enter a photoionization source and a mass spectrum, the gas sample passing through a secondary electrospray ionization source enters a photoionization region under the carrying of the gas flow, and the ultraviolet light emitted by a VUV lamp enables the sample to generate single photon ionization, and finally the sample enters a mass analyzer for analysis.
Application example:
ionization of small molecule carbonyl compound. The method is characterized in that a derivatization reagent generates charged liquid drops through an ionization source of a reagent atomizer, and the ions of the derivatization reagent in the charged liquid drops and a gas sample introduced through a sample introduction system undergo chemical reaction and charge exchange to realize the ionization of the small-molecule carbonyl compound.
The volatile benzene series ionizes. The gas sample reaches a secondary electrospray ionization region through a sample introduction system, volatile benzene series cannot be ionized due to weak polarity, enters a VUV photo-ionization region under the carrying of gas flow, and generates single photon ionization under the irradiation of VUV light.
Through a two-step ionization mode, the mutual noninterference of the two ionization processes is realized, and the defect of low benzene series ionization efficiency of a secondary electrospray ionization source is overcome. And (3) building a mass spectrum platform for synchronous detection of volatile organic compounds, and building an in-situ, multi-target, synchronous and high-sensitivity analysis method for small molecular carbonyl compounds and volatile benzene compounds. The distribution characteristics and the evolution process of small molecular carbonyl compounds and volatile benzene series compounds in the ambient air are researched.
In other embodiments, the reagent flow in the reagent atomizer can also be induced by the venturi effect generated by the first high pressure gas tube, which serves as a main power source and can greatly reduce the complexity of the device.
In other embodiments, the sample introduction end of the sample transmission pipe can also be connected with a syringe, so that the detection and analysis of the liquid sample are realized, and the detection range of the sample is expanded.
It should be finally noted that the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, it should be understood by those skilled in the art that: the invention can be modified or equivalent substituted for some technical features; without departing from the spirit of the present invention, it should be understood that the scope of the claims is intended to cover all such modifications and variations.

Claims (17)

1. A secondary electrospray ionization source device is characterized in that: comprises a vacuum ionization source cavity, a vacuum ultraviolet lamp, a mass spectrum sample injection taper hole, a reagent atomizer and a gas sample introducing system;
the reagent atomizer comprises an atomizer, a high-voltage power supply, a reagent supply capillary and a first high-voltage gas pipe, wherein the reagent supply capillary is communicated with a liquid inlet end of the atomizer to provide a reagent, the first high-voltage gas pipe is communicated with a gas inlet end of the atomizer to provide high-voltage nitrogen and is used for atomizing the reagent, and the high-voltage power supply acts on the atomizer to form a reagent ion flow;
the gas sample introduction system comprises a sample capillary, a sample transmission pipe and a second high-pressure gas pipe, wherein the sample capillary is connected with a rear end inlet of the sample transmission pipe to provide a sample gas flow, and the second high-pressure gas pipe is connected with a side end inlet of the sample transmission pipe to generate negative pressure at a pipe orifice at an outlet end of the sample capillary as an introduction power of the sample gas flow;
the reagent ion flow and the sample gas flow are converged at the mass spectrum sample introduction taper hole and are subjected to primary ionization;
the mass spectrum sample injection taper hole is communicated with the vacuum ionization source cavity, and the vacuum ultraviolet lamp is arranged in the vacuum ionization source cavity or in a space between the mass spectrum sample injection taper hole and the vacuum ionization source cavity and is used for carrying out secondary ionization on the sample gas flow.
2. A secondary electrospray ionization source device according to claim 1, wherein: the direction of the light emitted by the vacuum ultraviolet lamp is vertical to the central axis of the flow direction of the mixed fluid of the reagent ion flow and the sample gas flow.
3. A secondary electrospray ionization source device according to claim 1, wherein: the atomizer and the sample transmission pipe are both fixed through an angle regulator, the outlet end of the atomizer and the outlet end of the sample transmission pipe are both provided with needle-shaped outlets, and the included angle between the outlet end of the atomizer and the outlet end of the sample transmission pipe is 30-60 degrees.
4. A secondary electrospray ionization source device according to claim 1, wherein: the rear end of the reagent supply capillary is connected with the injector and the injection pump in sequence, and the rear end of the sample capillary is connected with the sample injection container; the included angle between the second high-pressure gas pipe and the sample transmission pipe is 90 degrees, and the included angle between the first high-pressure gas pipe and the atomizer is 90 degrees.
5. A secondary electrospray ionization source device according to claim 1, wherein: and heating jackets are arranged outside the sample transmission pipe and the atomizer.
6. A secondary electrospray ionization source device according to claim 1, wherein: the vacuum ultraviolet lamp is arranged on an isolation valve base which is arranged in the vacuum ionization source cavity and is positioned between the mass spectrum sample injection taper hole and the transmission six-stage rod.
7. A secondary electrospray ionization source device according to claim 1, wherein: the atomizer and the sample transmission pipe are both made of metal materials, the spray pipe in the atomizer is an electrospray metal capillary or an inert quartz capillary, and the sample capillary is an inert quartz capillary.
8. A secondary electrospray ionization source device according to claim 1, wherein: the distance between the outlet end of the atomizer and the outlet end of the sample transmission pipe and the mass spectrum sample injection taper hole is respectively 2 to 40mm, the inner diameter of the sample capillary is 5 to 150 mu m, the sample capillary is arranged in the sample transmission pipe, the distance between the tail end of the sample capillary and the outlet end of the sample transmission pipe is 0 to 10mm, the electrospray metal capillary extends out of the outlet end of the atomizer, and the distance between the end face of the electrospray metal capillary and the outlet end face of the atomizer is 2 to 3mm.
9. A secondary electrospray ionization source device according to claim 1, wherein: the voltage range of the high-voltage power supply is 3-5kV.
10. A secondary electrospray ionization source device according to claim 1, wherein: and the first high-pressure gas pipe and the second high-pressure gas pipe are respectively connected with a high-pressure nitrogen source through a mass flow controller.
11. A gas sample introduction system for a secondary electrospray ionization source device, comprising: the device comprises a sample capillary tube, a sample transmission tube and a second high-pressure gas tube, wherein the sample capillary tube is connected with a rear end inlet of the sample transmission tube to provide a sample gas flow, and the second high-pressure gas tube is connected with a side end inlet of the sample transmission tube to generate negative pressure at a tube orifice at an outlet end of the sample capillary tube as an introduction power of the sample gas flow; the second high-pressure gas pipe is externally connected with a high-pressure gas source.
12. A gas sample introduction system for a secondary electrospray ionization source device according to claim 11, wherein: the included angle between the second high-pressure gas pipe and the sample transmission pipe is 90 degrees.
13. A gas sample introduction system for a secondary electrospray ionization source device according to claim 12, wherein: and a gas flow control valve is connected between the second high-pressure gas pipe and the high-pressure gas source.
14. A reagent atomizer of a secondary electrospray ionization source device is characterized in that: the reagent supply capillary is communicated with a liquid inlet end of the atomizer to provide a reagent, the first high-pressure gas pipe is communicated with a gas inlet end of the atomizer to provide high-pressure nitrogen and used for atomizing the reagent, the high-pressure power supply acts on the atomizer to form a reagent ion flow, and the reagent ion flow is used for converging with a sample gas flow at a mass spectrum sample injection taper hole and carrying out primary ionization;
the mass spectrum sample injection taper hole is communicated with the vacuum ionization source cavity, and the vacuum ultraviolet lamp is arranged in the vacuum ionization source cavity or in a space between the mass spectrum sample injection taper hole and the vacuum ionization source cavity and is used for carrying out secondary ionization on the sample gas flow.
15. The reagent nebulizer of a secondary electrospray ionization source device of claim 14, wherein: the inlet end of the reagent supply capillary is connected with an injector, and the inlet end of the injector is connected with a syringe pump.
16. The reagent atomizer of a secondary electrospray ionization source device of claim 15, wherein: the included angle between the first high-pressure gas pipe and the atomizer is 90 degrees.
17. The reagent nebulizer of a secondary electrospray ionization source device of claim 16, wherein: and a gas flow control valve is connected between the first high-pressure gas inlet pipe and the high-pressure gas source.
CN202221097164.7U 2022-05-09 2022-05-09 Secondary electrospray ionization source device, gas sample introduction system and reagent atomizer Active CN217544538U (en)

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