CN111370289A - Ionization analysis system and method - Google Patents

Ionization analysis system and method Download PDF

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Publication number
CN111370289A
CN111370289A CN202010213816.8A CN202010213816A CN111370289A CN 111370289 A CN111370289 A CN 111370289A CN 202010213816 A CN202010213816 A CN 202010213816A CN 111370289 A CN111370289 A CN 111370289A
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China
Prior art keywords
cavity
sampling probe
analysis system
ionization
opening
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Pending
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CN202010213816.8A
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Chinese (zh)
Inventor
洪欢欢
闻路红
李文
余晓梅
赵鹏
史振志
毕磊
陈安琪
甘剑勤
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China Innovation Instrument Co ltd
Ningbo University
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China Innovation Instrument Co ltd
Ningbo University
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Priority to CN202010213816.8A priority Critical patent/CN111370289A/en
Publication of CN111370289A publication Critical patent/CN111370289A/en
Pending legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0409Sample holders or containers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • G01N27/68Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using electric discharge to ionise a gas
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0431Arrangements 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/04Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0468Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample
    • H01J49/049Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample with means for applying heat to desorb the sample; Evaporation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/10Ion sources; Ion guns
    • H01J49/16Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

The invention provides an ionization analysis system and method, wherein the ionization analysis system comprises an ion detector; the sampling probe is suitable for being inserted into the cavity; the adsorption substance is arranged on the outer wall of the part of the sampling probe, which is suitable for extending into the cavity; a first electrode disposed within the sampling probe; the two opposite ends of the cavity are provided with a first opening and a second opening, the sampling probe penetrates through the first opening to enter the cavity, and the interior of the cavity is communicated with the ion detector through the second opening; the medium barrier layer is arranged on the inner wall of the cavity; the second electrode is arranged on the outer side of the cavity; the gas channel is formed on the outer side of the sampling probe and extends along the length direction of the sampling probe; the gas channel has an inlet. The invention has the advantages of high efficiency of sampling and ionization, wide application range and the like.

Description

Ionization analysis system and method
Technical Field
The present invention relates to ionization, and more particularly to ionization analysis systems and methods.
Background
Pretreatment is an essential step for complicated sample analysis, but the time consumed by pretreatment often accounts for more than two-thirds of the analysis process. With the continuous development of the instrument level and the analysis technology, the sample pretreatment becomes a bottleneck restricting the rapid analysis and detection.
Solid Phase Microextraction (SPME) is a relatively new sample pretreatment technique that is based on the partitioning of target compounds between the extraction coating (stationary phase) and the solution. Compared with the traditional sample pretreatment technology such as liquid-liquid extraction, Soxhlet extraction and the like, the method has the advantages of less sample consumption, simple and convenient operation, no secondary pollution and the like. Currently, SPME is commonly used in conjunction with GC or LC for analysis of volatile or thermally labile substances. The disadvantages are that: the combination of GC or LC increases the complexity of the instrument to a certain extent, and is not suitable for rapid detection or in-situ detection.
Currently, researchers have attempted to use SPME directly in conjunction with an in situ ionization ion source. The patent TWI488215B proposes a mass spectrometry system based on a solid phase microextraction probe, wherein a heating unit instantaneously vaporizes a substance to be detected on the solid phase microextraction probe, and a charge generating unit sprays charged liquid drops to fuse with the vaporized substance to be detected, so as to form ions of the substance to be detected to enter mass spectrometry. However, the ionization process is in an open environment, the fusion of the vaporized to-be-detected object and the charged liquid drop is easily interfered by the environment, and experimental errors are caused.
The dielectric barrier discharge ion source (DBDI) is simple in structure and easy to manufacture, the typical density of generated high-energy electrons is 1010-1012 cm < -3 >, the ionization efficiency is high, the DBDI can be used for rapidly analyzing gaseous, liquid and solid samples, is suitable for samples with different polarities, and is wide in application range.
If the solid phase microextraction probe is combined with DBDI, the DBDI is used for directly bombarding the coating material and the sample of the sampling probe, the ionization effect is limited, the coating is easy to peel off, the detection noise is caused, and the signal to noise ratio is reduced.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the ionization analysis system which has high sampling and ionization efficiency, high signal-to-noise ratio and wide application range.
The purpose of the invention is realized by the following technical scheme:
an ionization analysis system comprising an ion detector; the ionization analysis system further comprises:
a sampling probe adapted to be inserted into a cavity;
an adsorbent material disposed on an outer wall of a portion of the sampling probe adapted to extend into the cavity;
a first electrode disposed within the sampling probe;
the sampling probe penetrates through the first opening to enter the cavity, and the interior of the cavity is communicated with the ion detector through the second opening;
the medium barrier layer is arranged on the inner wall of the cavity;
a second electrode disposed outside the cavity;
a gas channel formed outside the sampling probe and extending in a length direction of the sampling probe; the gas channel has an inlet.
The invention also aims to provide an ionization method based on the ionization analysis system, and the aim is realized by the following technical scheme:
the ionization analysis method based on the ionization analysis system comprises the following steps:
(A1) one end of the sampling probe extends into the sample solution, and the adsorption substance adsorbs the sample;
(A2) one end of the sampling probe with the adsorbed substances passes through the first opening to enter the cavity;
(A3) the gas enters the gas channel and flows out of the cavity;
the second electrode discharges, the sample is ionized, and the ions pass through the second opening and enter the ion detector; the first electrode is grounded.
Compared with the prior art, the invention has the beneficial effects that:
1. ionization is efficient, and the signal-to-noise ratio is high;
in the application, gas in the gas channel is firstly ionized by the second electrode to form plasma, the plasma acts on a sample adjacent to the first electrode on the sampling probe, and adsorbed substances on the sampling probe are firm and do not fall off, so that the signal-to-noise ratio is high;
a grounded first electrode is arranged in the sampling probe, so that a discharge area is concentrated in a sample area adjacent to the first electrode, and the adsorbed sample is desorbed and then ionized, so that the ionization process is more efficient;
the heated gas is more beneficial to the desorption of a sample on the sampling probe, and the ionization process is more efficient;
2. sampling is efficient;
the operation can be completed only by inserting the sample probe stained with the sample into an analysis system, so that the operation is efficient and rapid;
3. the application range is wide;
the method can be freely switched between dielectric barrier discharge and proton transfer reaction, so that the application range of the sample is expanded;
the discharge, ionization and transmission are all completed in a closed cavity, the environmental interference is small, and the method is suitable for various analysis occasions.
Drawings
The disclosure of the present invention will become more readily understood with reference to the accompanying drawings. As is readily understood by those skilled in the art: these drawings are only for illustrating the technical solutions of the present invention and are not intended to limit the scope of the present invention. In the figure:
FIG. 1 is a simplified schematic diagram of an ionization analysis system according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of another configuration of an ionization analysis system according to an embodiment of the present invention;
FIG. 3 is a mass spectrum of caffeine obtained according to example 3 of the present invention.
Detailed Description
Fig. 1-3 and the following description depict alternative embodiments of the invention to teach those skilled in the art how to make and use the invention. Some conventional aspects have been simplified or omitted for the purpose of teaching the present invention. Those skilled in the art will appreciate that variations or substitutions from these embodiments will be within the scope of the invention. Those skilled in the art will appreciate that the features described below can be combined in various ways to form multiple variations of the invention. Thus, the present invention is not limited to the following alternative embodiments, but is only limited by the claims and their equivalents.
Example 1:
fig. 1 schematically shows a schematic view of an ionization analysis system according to example 1 of the present invention, which, as shown in fig. 1, includes:
a sampling probe 12, for example in a tubular configuration, said sampling probe 12 being adapted to be inserted into the cavity 2;
an adsorbent (not shown) disposed on an outer wall of a portion of the sampling probe adapted to protrude into the cavity, the adsorbent adapted to adsorb a sample to be measured;
a first electrode (not shown) adapted to be grounded and disposed within the sampling probe and adjacent to the adsorbate;
the cavity 2 is in a cylindrical structure, two opposite ends of the cavity 2 are provided with a first opening and a second opening, the sampling probe 12 penetrates through the first opening to enter the cavity 2, and the interior of the cavity 2 is communicated with the ion detector 3 through the second opening;
the dielectric barrier layer 21, the said dielectric barrier layer 21 is set up in the inboard wall of the said cavity 2;
a second electrode 22, the second electrode 22 being disposed outside the cavity 2;
a gas channel formed outside the sampling probe and extending in a length direction of the sampling probe; the gas channel has an inlet such that gas within the gas channel flows along the outer wall of the sampling probe towards the end having the adsorbent material.
To form a stable gas flow, further, the ionization analysis system further comprises:
a sleeve 11, wherein the sleeve 11 is fixed on the outer side of the sampling probe 12 and enters the cavity 2 along with the sampling probe 12 passing through the first opening; or the sleeve 11 is fixed in the cavity 2, and the sampling probe 12 passes through the first opening and enters the sleeve 11;
the gas passage forms a space between the sampling probe and the sleeve.
To evacuate the effects of the sleeve on ionization, further, one end of the sampling probe within the cavity extends outside the sleeve.
In order to reduce the influence of the external environment on the ionization in the cavity, further, the ionization system further comprises:
a seal 4, 24 arranged at the first and/or second opening.
In order to increase the intensity of the detection signal, the chamber has a steam inlet 31 through which steam such as water vapor or methanol is introduced as needed.
In order to improve the desorption capability of the gas in the gas channel on the sample on the sampling probe, further, the ionization analysis system further comprises:
a heating unit for increasing the temperature within the gas passage within the cavity.
In order to prevent the adsorbed substances from falling off and improve the ionization efficiency of the sample, further, the sampling probe adopts a hollow pipe with a closed end, the adsorbed substances are arranged on the outer wall of the closed end, and the first electrode is arranged inside the closed end.
In order to adapt to various samples to be detected, the adsorption substance is any one of polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, acrylamide, polyethylene glycol/polydimethylsiloxane, molecularly imprinted polymer or carbon nanotube, mesoporous material and graphene.
The ionization analysis method of the embodiment of the present invention, that is, the working mode of the ionization analysis system of the embodiment of the present invention, includes the following steps:
(A1) one end of the sampling probe extends into the sample solution, and the adsorption substance adsorbs the sample;
(A2) one end of the sampling probe with the adsorbed substances passes through the first opening to enter the cavity;
(A3) the gas enters the gas channel and flows out of the cavity to purge the sample on the sampling probe;
the second electrode discharges, the sample is ionized, and the ions pass through the second opening and enter the ion detector; the first electrode is grounded.
In order to improve the signal intensity, water vapor or methanol vapor is further introduced into the cavity.
Example 2:
an application example of the ionization analysis system and method according to embodiment 1 of the present invention.
In the present application example, as shown in fig. 1, the sampling probe 12 is a hollow tube with one end closed, the hollow tube is made of insulating materials such as glass, quartz, and ceramics, and the closed end has an adsorbing substance such as polydimethylsiloxane; the first electrode which is grounded and takes the shape of a needle is arranged in the closed end of the hollow pipe and is adjacent to the adsorption substance; the sleeve 11 is fixed on the outer side of the sampling probe 12, a gas channel is formed between the sampling probe 12 and the sleeve 11, a gas inlet 13 and a gas outlet 14 are formed in the sleeve, and the gas inlet 13 and the gas outlet 14 are far away from the closed end; the closed end of the sampling probe 12 extends out of the casing 11;
the hollow cavity 2 is provided with a medium barrier layer 21, and an annular second electrode 22 is arranged on the outer side of the medium barrier layer 21; the steam inlet 31 is arranged on the medium barrier layer 21 and communicated with the inside of the cavity 2; a sealing gasket 24 is arranged at the first opening of the cavity, and the sleeve 11 is inserted into the cavity 2 through the sealing gasket 24; the annular electrode 22 is connected with an alternating current high-voltage power supply, the power of the alternating current is 5-30W, the voltage is 1-20kV, and the frequency is 10-1000 Hz; the second opening of the cavity 2 is provided with a sealing element 4, the ion detector 3 is connected with the sealing element 4 and is provided with a vacuum pumping system, the internal pressure of the vacuum pumping system is far less than the internal pressure of the cavity 2, most of the gas entering from the gas inlet 13 enters the cavity 2 under the action of pressure difference, and a small part of the gas is discharged through the gas outlet 14.
The ionization analysis method provided by the embodiment of the invention comprises the following steps:
(A1) the sampling probe 12 is immersed in the sample solution for a period of time while the solution is stirred to accelerate the two phases to reach equilibrium;
(A2) the closed end of the sampling probe 12 passes through the sealing washer 24, and part of the sampling probe and the sleeve are inserted into the cavity 2;
(A3) introducing gas such as nitrogen, helium, argon and the like into the gas inlet 13, wherein the flow rate of the gas is 0.03-5L/min; part of gas enters a gas channel between the sleeve 11 and the sampling probe due to the low-pressure environment in the cavity 2, flows towards the closed end of the sampling probe 12 and takes away a sample adsorbed on the sampling probe;
the second electrode 22 is connected with an alternating current high voltage power supply, the first electrode 122 in the sampling probe 12 is grounded, and discharges gas flow carrying the sample at the closed end of the sampling probe 12, so that ion beams are formed;
under the action of the pressure difference, the ion beam enters the ion detector 3 through the sealing piece 4 for analysis;
when the detection signal is weak, the steam passes through H from the steam inlet 312O or methanol (will be ionized by plasma and converted into proton transferReaction ionization) and increases the detection signal intensity.
Example 3:
an application example of the ionization analysis system and method according to embodiment 1 of the invention in the detection of caffeine is shown in fig. 2, which is different from embodiment 2 in that:
1. the sleeve 11 is fixed in the cavity 2, when the sampling probe 12 is inserted into the cavity 2, the sampling probe is positioned in the sleeve 11, and the closed end of the sampling probe 12 inserted into the cavity 2 extends out of the sleeve 11; the gas inlet 13 of the sleeve 11 extends out of the cavity 2;
2. a heating element 23 is arranged in the cavity 2 to increase the temperature of the gas between the sleeve 11 and the sampling probe 12.
The ionization analysis method provided by the embodiment of the invention comprises the following steps:
(A1) the sampling probe 12 is immersed in a methanol solution of caffeine for a period of time while the solution is stirred to accelerate the two phases to reach equilibrium;
(A2) the closed end of the sampling probe 12 penetrates through the sealing washer 24, part of the sampling probe is inserted into the cavity 2 and is positioned in the sleeve, and the closed end extends out of the sleeve;
(A3) helium is introduced into the gas inlet 13 at the flow rate of 3.5L/min; the gas entering between the sleeve 11 and the sampling probe is heated to 200 ℃ and flows towards the closed end of the sampling probe 12, and meanwhile, the gas takes away the sample adsorbed on the sampling probe;
the second electrode 22 is connected with an alternating current high voltage power supply, the first electrode 122 in the sampling probe 12 is grounded, and discharges gas flow carrying the sample at the closed end of the sampling probe 12, so that ion beams are formed;
the ion beam enters the ion detector 3 through the sealing member 4 under the action of the pressure difference, and the mass spectrum obtained is shown in fig. 3.

Claims (10)

1. An ionization analysis system comprising an ion detector; the method is characterized in that: the ionization analysis system further comprises:
a sampling probe adapted to be inserted into a cavity;
an adsorbent material disposed on an outer wall of a portion of the sampling probe adapted to extend into the cavity;
a first electrode disposed within the sampling probe;
the sampling probe penetrates through the first opening to enter the cavity, and the interior of the cavity is communicated with the ion detector through the second opening;
the medium barrier layer is arranged on the inner wall of the cavity;
a second electrode disposed outside the cavity;
a gas channel formed outside the sampling probe and extending in a length direction of the sampling probe; the gas channel has an inlet.
2. The ionization analysis system of claim 1, wherein: the ionization analysis system further comprises:
the sleeve is fixed on the outer side of the sampling probe and enters the cavity along with the sampling probe passing through the first opening; or the sleeve is fixed in the cavity, and the sampling probe passes through the first opening and enters the sleeve;
the gas passage forms a space between the sampling probe and the sleeve.
3. The ionization analysis system of claim 2, wherein: one end of the sampling probe in the cavity extends out of the sleeve.
4. The ionization analysis system of claim 1, wherein: the ionization system further comprises:
a seal disposed at the first opening and/or the second opening.
5. The ionization analysis system of claim 1, wherein: the first electrode is grounded.
6. The ionization analysis system of claim 2, wherein: the ionization analysis system further comprises:
a heating unit for increasing the temperature within the gas passage within the cavity.
7. The ionization analysis system of claim 1, wherein: sampling probe adopts the hollow tube that has the blind end, absorbent sets up the blind end outer wall, first electrode setting is in inside the blind end.
8. The ionization analysis system of claim 1, wherein: the adsorption substance is any one of polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, acrylamide, polyethylene glycol/polydimethylsiloxane, molecularly imprinted polymer or carbon nanotube, mesoporous material and graphene.
9. A method of ionization analysis based on the ionization analysis system of any one of claims 1 to 8, comprising the steps of:
(A1) one end of the sampling probe extends into the sample solution, and the adsorption substance adsorbs the sample;
(A2) one end of the sampling probe with the adsorbed substances passes through the first opening to enter the cavity;
(A3) the gas enters the gas channel and flows out of the cavity;
the second electrode discharges, the sample is ionized, and the ions pass through the second opening and enter the ion detector; the first electrode is grounded.
10. The ionization analysis method according to claim 9, wherein: and introducing water vapor or methanol vapor into the cavity.
CN202010213816.8A 2020-03-24 2020-03-24 Ionization analysis system and method Pending CN111370289A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113252767A (en) * 2021-05-13 2021-08-13 杭州谱育科技发展有限公司 Analysis system and method based on evaporation technology

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CN102353799A (en) * 2011-07-25 2012-02-15 中国地质大学(武汉) Method of evaporating sample injecting inducted by dielectric barrier discharge microplasma
CN202196744U (en) * 2008-04-04 2012-04-18 安捷伦科技有限公司 Ion source and mass spectrum system
CN102762022A (en) * 2011-04-26 2012-10-31 中国科学院化学研究所 Method for generating glow discharge plasma and special device for method
US20150144777A1 (en) * 2013-11-28 2015-05-28 National Sun Yat-Sen University Multiple solid phase micro-extraction thermal desorption ionization device, mass spectrometer and analytical method for mass spectrometry
CN107561151A (en) * 2017-09-22 2018-01-09 山东国投鸿基检测技术股份有限公司 A kind of quick instrument for detecting pesticide residue through based on analytical technique of mass spectrum
CN109545648A (en) * 2018-12-27 2019-03-29 昆山禾信质谱技术有限公司 A kind of compound ionization device
CN211455643U (en) * 2020-03-24 2020-09-08 宁波大学 Ionization analysis system
CN211877862U (en) * 2020-03-24 2020-11-06 宁波大学 Ionization analysis system

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN202196744U (en) * 2008-04-04 2012-04-18 安捷伦科技有限公司 Ion source and mass spectrum system
CN102762022A (en) * 2011-04-26 2012-10-31 中国科学院化学研究所 Method for generating glow discharge plasma and special device for method
CN102353799A (en) * 2011-07-25 2012-02-15 中国地质大学(武汉) Method of evaporating sample injecting inducted by dielectric barrier discharge microplasma
US20150144777A1 (en) * 2013-11-28 2015-05-28 National Sun Yat-Sen University Multiple solid phase micro-extraction thermal desorption ionization device, mass spectrometer and analytical method for mass spectrometry
CN107561151A (en) * 2017-09-22 2018-01-09 山东国投鸿基检测技术股份有限公司 A kind of quick instrument for detecting pesticide residue through based on analytical technique of mass spectrum
CN109545648A (en) * 2018-12-27 2019-03-29 昆山禾信质谱技术有限公司 A kind of compound ionization device
CN211455643U (en) * 2020-03-24 2020-09-08 宁波大学 Ionization analysis system
CN211877862U (en) * 2020-03-24 2020-11-06 宁波大学 Ionization analysis system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113252767A (en) * 2021-05-13 2021-08-13 杭州谱育科技发展有限公司 Analysis system and method based on evaporation technology
CN113252767B (en) * 2021-05-13 2023-09-15 杭州谱育科技发展有限公司 Analysis system and method based on evaporation technology

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