CN106373857A - Laser desorption ionization ion source assisted by protonated reinforcement matrix - Google Patents
Laser desorption ionization ion source assisted by protonated reinforcement matrix Download PDFInfo
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- CN106373857A CN106373857A CN201610967193.7A CN201610967193A CN106373857A CN 106373857 A CN106373857 A CN 106373857A CN 201610967193 A CN201610967193 A CN 201610967193A CN 106373857 A CN106373857 A CN 106373857A
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- protonation
- desorption ionization
- ion source
- dichloromethane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/16—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission
- H01J49/161—Ion sources; Ion guns using surface ionisation, e.g. field-, thermionic- or photo-emission using photoionisation, e.g. by laser
- H01J49/164—Laser desorption/ionisation, e.g. matrix-assisted laser desorption/ionisation [MALDI]
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- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
Abstract
The invention relates to an ion source. The ion source is a new ion source used for ionizing macromolecular organics and biomolecules, the ion source is combined with the proton transfer reaction technology and the traditional matrix assisted laser desorption ionization technology to realize efficient desorption and ionization of analytes, and after the traditional matrix assisted laser desorption ionization is implemented, the protonation of the analytes is reinforced by adding a protonation reaction; and the protonation reaction is added by a proton transfer reaction between a dichloromethane protonation agent excited by vacuum ultraviolet and unionized gaseous analyte molecules. By means of the application of the technology, the ionization of the analytes does not depend on the matrix at all, thereby reducing the requirements for the physical and chemical properties of the matrix, reinforcing the protonation efficiency of the analytes and improving the strength of the ion source.
Description
Art
The present invention relates to a kind of ion source, be a kind of for realize larger molecular organicses and biomolecular ions new from
Component, can strengthen traditional matrices assisted laser desorption ionisation technology protonation efficiency.
Background technology
Substance assistant laser desorpted ionized technology is the important means of ionization organic macromolecule and biomolecule, and it utilizes base
Energy, to absorb the energy of laser beam, is then passed to analyzed material by substrate by matter, makes analyte desorption, passes through simultaneously
Gaseous analytes produce analyte ions with the chemical reaction of matrix ion, and wherein protonation reaction is the one of analyte ions
Individual important channel.The method avoids light laser direct irradiation and analyze the serious dissociation that sample brings, such that it is able to ionizing
Organic macromolecule and biomolecule.For the analyte having suitable matrix coupling, substance assistant laser desorpted ionized analytical technology
Sensitivity very high by (10-15Mol), it can be analyzed to micro-example.The limitation of this technology is to lack wide model effective
Substrate mating different analytes and make analyte desorbing simultaneously and effective to ionize.Additionally, the chemistry for the matching analysis thing
Composition, a lot of substrate (as alpha-cyano -4- hydroxycinnamic acid) of selection have certain carcinogenecity or chemical toxicity, constrain substrate auxiliary
Help the application of laser desorption ionisation technology.
For substance assistant laser desorpted ionized technical deficiency, we have invented a kind of new protonation and strengthen Matrix-assisted
Laser desorption ionisation ion source, implement traditional substance assistant laser desorpted ionized after, it utilize additional protonation reaction Lai
Strengthen the protonation of analyte, reduce the requirement to substrate.Additional protonation reaction is by light activated by VUV
Dichloromethane (ch2cl2) protonating agent realized with the reaction of unionized gaseous analytes molecule.
Proton-Transfer Reactions technology is a kind of Soft ionization techniques developed in recent years, and it passes through protonating agent and analysis
Proton-Transfer Reactions between thing molecule is realizing the protonation of analyte molecule.Water (h2O) it is a kind of common protonating agent,
The method of the electric discharge hydrone to prepare protonation commonly used by business-like Proton transfer reaction mass spectrometry instrument.Dichloromethane is a kind of wide
The halogenated alkane of general use.Recently, our experimental result showed that by the light activated dichloromethane of VUV to polar substancess
(inclusion hydrone) has very strong protonation, because the proton affinity (6.5ev) of dichloromethane is more affine than the proton of water
Gesture (7.2ev) is also low, and therefore the light activated dichloromethane of VUV is a kind of good protonating agent.
This protonation of our inventions strengthens MALDI by Proton-Transfer Reactions technology
Combine with substance assistant laser desorpted ionized technology, analyte is strengthened by the light activated dichloromethane of VUV
Protonation, makes the ionization of analyte not exclusively rely on the effect of substrate, it is possible to achieve to wide larger molecular organicses and life
Thing related substanceses ionizing, increased ionogenic intensity, reduces the difficulty of substrate selection, thus greatly improving correlation analysiss
The efficiency of work.
Content of the invention
In order to overcome existing substance assistant laser desorpted ionized technical deficiency, the present invention combines Proton-Transfer Reactions
With substance assistant laser desorpted ionized technology, there is provided a kind of new protonation strengthens substance assistant laser desorpted ionized ion
Source.This ion source employs multiple advanced technology, excites including vacuum-ultraviolet light, Proton-Transfer Reactions and ground substance assistant laser
Desorption ionization techniques.
Patent of the present invention the technical scheme is that 1, produces vacuum-ultraviolet light by krypton lamp；2nd, vacuum-ultraviolet light irradiates two
Chloromethanes generate excited state dichloromethane protonating agent；3rd, the analyte of mixed-matrix is deposited on desorption ionization substrate, by passing
Defeated system transfers are to desorption ionization hole；4th, the analyte of pulsed laser irradiation mixed-matrix；5th, the gas desorbing through laser pulse
State analyte and excited state dichloromethane protonating agent react generation protonation analyte；6th, protonation analyte is gone out by ion source
Mouth is drawn the various ion analyzers of entrance and is carried out quality analysiss.
The invention has the beneficial effects as follows: implement traditional substance assistant laser desorpted ionized after, then by additional proton
Change reaction to strengthen the protonation of analyte；Additional protonation reaction is by by VUV light activated dichloromethane proton
Agent is reacted with unionized gaseous analytes molecule and is realized.The application of this technology makes the ionization of analyte not exclusively rely on base
The effect of matter, reduces the requirement to substrate physics and chemical characteristic, enhances the protonation efficiency of analyte, increases ion source
Intensity.
Brief description
Fig. 1 is the outside drawing of present configuration, respectively 1, vacuum-ultraviolet light source chamber, 2, desorption ionization room, 3, sample room,
4th, pulse laser, 5, dichloromethane gas sampling valve.
Fig. 2 is the sectional structural map of the present invention, and critical piece has: 6, VUV krypton lamp, 7, vacuum-ultraviolet light, 8, fluorination
Magnesium lens, 9, dichloromethane gas, 10, pulse laser, 11, the automatic transmitter of substrate, 12, sample substrate, 13, laser desorption electricity
From mouth, 14, the combination of ion migration electric field electrode, 15, ion outlet.
Specific embodiment
Protonation strengthens the main part of MALDI by vacuum ultraviolet light source (1), desorbing
Ionization chamber (2), sample room (3), and pulse laser (4) four part are constituted.Specific embodiment is:
First, VUV krypton lamp (6) produces vacuum-ultraviolet light (7) and enters desorption ionization room by Afluon (Asta) lens (8)
(2)；
2nd, dichloromethane gas (9) enters desorption ionization room (2) by dichloromethane gas sampling valve (5)；
3rd, vacuum-ultraviolet light (7) irradiates dichloromethane gas (9) generation excited state dichloromethane protonating agent；
4th, the substrate (12) depositing mixed-matrix and sample is sent to laser desorption ionisation by the automatic transmitter of substrate (11)
Mouth (13)；
5th, pulse laser (10) irradiating sample substrate (12), the sample on desorbing sample substrate, have certain kinetic energy
Hybrid ionic and unionized sample molecule air mass；
6th, sample molecule air mass is in motor process upwards, unionized sample molecule and excited state dichloromethane proton
Agent collision occurs Proton-Transfer Reactions to generate the sample ions of protonation；
7th, the sample ions of protonation combine, by ion migration electric field electrode, the electric field extraction ion outlet that (14) produce
(15), form ion source.
Claims (5)
1. protonation strengthens MALDI by vacuum-ultraviolet light source chamber, desorption ionization room, sample room
With pulse laser forms it is characterised in that being connected by aperture between sample room and desorbing ionization chamber, vacuum ultraviolet light source is from one
Side lower position is connected with desorption ionization room by Afluon (Asta) lens, pulse laser from opposite side with 45 degree pass through flange with
Desorption ionization room is connected, and vacuum-ultraviolet light source chamber is provided with a VUV krypton lamp and a dichloromethane gas sampling valve,
Desorption ionization room is provided with one group of ion migration electric field electrode combination, and the automatic transmitter of a set of substrate is installed in sample room.
2. protonation according to claim 1 strengthens MALDI, it is characterized in that adopting two
Chloromethanes are protonating agent precursor.
3. protonation according to claim 1 strengthens MALDI, it is characterized in that adopting krypton
The vacuum-ultraviolet light that lamp produces, to excite dichloromethane, produces excited state dichloromethane protonating agent.
4. protonation according to claim 1 strengthens MALDI, it is characterized in that mixed base
The sample of matter is by the analyte of pulse laser desorption ionization mixed-matrix.
5. protonation according to claim 1 strengthens MALDI, it is characterized in that by swashing
Send out state dichloromethane protonating agent to strengthen analyte with unionized analyte molecule through the protonation reaction that collision occurs
Protonation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610967193.7A CN106373857B (en) | 2016-10-28 | 2016-10-28 | Protonation enhancing MALDI |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610967193.7A CN106373857B (en) | 2016-10-28 | 2016-10-28 | Protonation enhancing MALDI |
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| CN106373857A true CN106373857A (en) | 2017-02-01 |
| CN106373857B CN106373857B (en) | 2017-12-08 |
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| CN201610967193.7A Active CN106373857B (en) | 2016-10-28 | 2016-10-28 | Protonation enhancing MALDI |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195529A (en) * | 2017-07-07 | 2017-09-22 | 中国科学院生态环境研究中心 | A kind of ioning method and its device based on excitation state proton-electron collaboration transfer reaction |
| CN107342210A (en) * | 2017-07-07 | 2017-11-10 | 中国科学院生态环境研究中心 | The Proton-Transfer Reactions ion gun of protonation water is provided using excitation state proton-electron collaboration transfer reaction |
| CN109887831A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A method of slowing down the decaying of mass spectrum ionized region ion source |
| CN112240849A (en) * | 2019-07-16 | 2021-01-19 | 哈米尔顿森德斯特兰德公司 | Thermal desorption device |
| CN114252502A (en) * | 2020-09-22 | 2022-03-29 | 中国科学院大学 | Method for detecting acetonitrile and derivatives thereof in real time by excited methylene chloride induced proton transfer reaction mass spectrum |
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| CN102221576A (en) * | 2010-04-15 | 2011-10-19 | 岛津分析技术研发（上海）有限公司 | Method and device for generating and analyzing ions |
| CN205542701U (en) * | 2016-03-23 | 2016-08-31 | 中国科学院生态环境研究中心 | Protonation enhancement mode low pressure vacuum ultraviolet electro -dissociator |
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| US20060097143A1 (en) * | 2004-10-25 | 2006-05-11 | Bruker Daltonik Gmbh | Protein profiles with atmospheric pressure ionization |
| CN101216459A (en) * | 2007-12-28 | 2008-07-09 | 中国科学技术大学 | Infrared laser desorption/vacuume ultraviolet single photon ionization mass spectrometry analytical equipment |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195529A (en) * | 2017-07-07 | 2017-09-22 | 中国科学院生态环境研究中心 | A kind of ioning method and its device based on excitation state proton-electron collaboration transfer reaction |
| CN107342210A (en) * | 2017-07-07 | 2017-11-10 | 中国科学院生态环境研究中心 | The Proton-Transfer Reactions ion gun of protonation water is provided using excitation state proton-electron collaboration transfer reaction |
| CN107342210B (en) * | 2017-07-07 | 2024-01-26 | 中国科学院生态环境研究中心 | Proton transfer reaction ion source for providing protonated water by utilizing excited proton electron cooperative transfer reaction |
| CN107195529B (en) * | 2017-07-07 | 2024-01-26 | 中国科学院生态环境研究中心 | Ionization method and device based on excited proton electron cooperative transfer reaction |
| CN109887831A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A method of slowing down the decaying of mass spectrum ionized region ion source |
| CN112240849A (en) * | 2019-07-16 | 2021-01-19 | 哈米尔顿森德斯特兰德公司 | Thermal desorption device |
| CN112240849B (en) * | 2019-07-16 | 2024-03-19 | 哈米尔顿森德斯特兰德公司 | Thermal desorber |
| CN114252502A (en) * | 2020-09-22 | 2022-03-29 | 中国科学院大学 | Method for detecting acetonitrile and derivatives thereof in real time by excited methylene chloride induced proton transfer reaction mass spectrum |
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| CN106373857B (en) | 2017-12-08 |
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