CN109872940A - A kind of ion source device using dielectric barrier discharge assist ionization - Google Patents

A kind of ion source device using dielectric barrier discharge assist ionization Download PDF

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CN109872940A
CN109872940A CN201711263765.4A CN201711263765A CN109872940A CN 109872940 A CN109872940 A CN 109872940A CN 201711263765 A CN201711263765 A CN 201711263765A CN 109872940 A CN109872940 A CN 109872940A
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hole
way
electrode
ion source
inner catheter
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CN109872940B (en
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关亚风
李盛红
杨航
高岩
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a kind of mass ions source devices using dielectric barrier discharge assist ionization.The device is by dielectric barrier discharge device, electrospray ionisation ion source device composition, dielectric barrier discharge device is by two conduits, two electrodes, ac high voltage source and two-way composition, two conduits are coaxially fixed in two-way, and electrode is separately fixed on the outer wall of inside and outside conduit, and two electrodes are connect with high voltage power supply respectively.For electrospray ionisation ion source by nozzle needle, threeway, DC high-voltage power supply and electrode composition, nozzle needle is fixed on the center of dielectric barrier discharge device conduit, and the positive and negative anodes of high voltage power supply are connected with nozzle needle and MS acquisition cone respectively.The plasma that the neutral molecule that electrospray ionisation process is not ionized is generated by dielectric barrier discharge ionizes, to greatly improve Ionization Efficiency.

Description

A kind of ion source device using dielectric barrier discharge assist ionization
Technical field
The present invention relates to field of mass spectrometry, the specifically ion source device of dielectric barrier discharge assisted electrospray ionization.
Background technique
Mass spectral analysis is one and object is introduced into ion source, is transferred to detector after being ionized again, according to its matter lotus The process that the difference of ratio is separated.During this, Ionization mode not only determines sample incorporation way, has an effect on mesh The final appearance form of object is marked, such as whether have fragment, electrically charged situation etc..Therefore, ion source is mass spectrometer " heart ".Electricity Spraying ionization is widely used for the ionization of large biological molecule as a kind of common atmospheric pressure mass ions method.EFI Mist ionization makes its electrification by applying a voltage on liquid, and charged liquid forms taylor cone in capillary outlet, works as electric field force Overcome surface tension, charged liquid sprays to form charged drop, generates ion by ion evaporation.But electrospray ionisation exists The low problem of Ionization Efficiency.
Researchers also exploitation other forms ion source, such as using gas discharge technology generation plasma come Ionize object, be applied at present gas discharge technology on mass ion source mainly have glow discharge (Glow Discharge, GD), corona discharge (Corona Discharge, CD), dielectric barrier discharge (Dielectric Barrier Discharge, DBD) etc., wherein dielectric barrier discharge is a kind of nonequilibrium state gas discharge for having dielectric insertion discharge space, and electric discharge produces Raw low temperature plasma can not form electricity compared to other discharge type dielectric barrier discharges due to there is the presence of dielectric Road is flowed back to, is a kind of very advantageous gas discharge technology to avoid overheating.
Summary of the invention
For the low problem of electrospray ionisation Ionization Efficiency, the present invention proposes a kind of ion source device, by dielectric impedance Electric discharge device is coupled with electrospray ion source device, while utilizing dielectric barrier discharge and electrospray ionisation compound, is mentioned significantly The Ionization Efficiency of high-intensity ion source.
The technical scheme is that
A kind of ion source device using dielectric barrier discharge assist ionization, by dielectric barrier discharge device, electron spray Ionization ion source device composition, it is characterised in that: dielectric barrier discharge device is by inner catheter, outer catheter, interior electrode, external electrode, Ac high voltage source and two-way composition;Two-way is the column having through circular through hole, and through-hole side open end edge is axially arranged with Two-stage step hole, wherein first step bore dia is greater than second step bore dia;Through-hole other side open end is equipped with internal screw thread, shape At threaded hole;There is L shape through-hole inside two-way, two open ends of L shape through-hole respectively lead to two-way side wall surface and first step Hole bottom surface;Inner catheter arrival end insertion second step hole is simultaneously sealed with it, and outer catheter arrival end is inserted into first step hole and its is close Envelope, inner catheter and outer catheter coaxially wear to form cannula structure;Outer catheter outer wall is equipped with a connection fairlead, puts for introducing Electrical body;Cylindrical internal electrode is closely arranged in the outside wall surface for being fitted in inner catheter, and tubular external electrode, which is closely arranged, is fitted in outer lead In the outside wall surface of pipe;Interior electrode outlet line is drawn by L-type through-hole from the side wall of two-way, drawing on blend compounds sealing through-hole side wall Outlet;The interior electrode outlet line that ac high voltage source is connected with interior electrode respectively and the external electrode lead-out wire being connected with external electrode Connection;Electrospray ionisation ion source is by nozzle needle, DC high-voltage power supply, threeway, electrode and electron spray fluid supply composition;Nozzle needle passes through The circular through hole of inner catheter and two-way, arrival end are connected with a connector of threeway, and inner catheter is stretched out far from second in outlet end The exit end face of stepped hole, and will be on threaded hole of the nozzle needle fixed to the other side open end of two-way with nut;Threeway other two A connector is connected with electrode and electron spray fluid supply respectively;The anode of DC high-voltage power supply is connect with electrode, DC high-voltage The cathode in source is connect with mass spectrographic sampling spiroid;Entire ion source device is placed in sampling spiroid front end, and needle outlets are towards sampling spiroid Entrance, inner catheter exit end face are located inside outer catheter.
The inner catheter, outer catheter, two-way and threeway are made of insulating material;The inner catheter and outer catheter material are glass Glass, quartz or ceramics;The two-way and the material of threeway are peek, polyethersulfone ketone or polytetrafluoroethylene (PTFE).
The inner and outer electrodes are conductive metal annular electrode.
The nozzle needle is an internal diameter 0.01-1mm, and outlet end internal diameter is contracted to the quartz ampoule of 0.01-0.15mm;Outlet end with Exit end face of the inner catheter far from second step hole is at a distance of 1-10mm;Between outer catheter exit end face and inner catheter exit end face Distance is 0-20mm.
The distance between the outer catheter exit end face and sampling spiroid are 1-20mm.
The outlet end of the outer catheter is equipped with the closing in that diameter becomes smaller.
The two-way is cylindrical body, and the side end face Yu Qiyi is equipped with cylindrical first groove, is equipped with circle in the first groove floor The second groove of cylindricality is equipped with circular through hole in the second groove floor, and the first groove, the second groove, circular through hole and two-way are coaxial, Upper surface successively has two-stage step hole along axial direction, and wherein first step bore dia is greater than second step bore dia;The two-way other side End face circular through hole is equipped with internal screw thread, forms threaded hole;L shape through-hole, L shape are equipped between the first groove floor and two-way side wall surface Through-hole respectively leads to side wall surface and first step hole.
Ion source device of the invention is organic by the original electrospray ion source device of mass spectrum and dielectric barrier discharge device In conjunction with two kinds of Ionization modes carry out simultaneously.In structure of the invention, nozzle needle is in catheter center, avoids spraying by not Uniform air flow influences;Meanwhile this coaxial configuration can guarantee the plasma of dielectric barrier discharge generation in discharge gas atmosphere Middle ionization object is enclosed, avoids and object is ionized in air atmosphere to blowing structure plasma, leads to air acceleration etc. The problem of active component is quenched in gas ions.Therefore ion source device of the invention can utilize dielectric barrier discharge and EFI simultaneously Mist ionization generates ion, substantially increases Ionization Efficiency, improves sensitivity of mass spectrometry.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes part of this application, not Inappropriate limitation of the present invention is constituted, in the accompanying drawings:
Fig. 1 is the ion source device schematic diagram of dielectric barrier discharge assist ionization.
Wherein: 1- inner catheter, 2- outer catheter, electrode in 3-, 4- external electrode, 5- ac high voltage source, 6- two-way, 7- are drawn It manages, 8-L type aperture, electrode outlet line in 9-, 10- external electrode lead-out wire, 11- nozzle needle, 12- DC high-voltage power supply, 13- threeway, 14- electrode, 15- electron spray source of solvent, 16- sampling spiroid
Fig. 2 is the ion source device schematic diagram of the dielectric barrier discharge assist ionization of embodiment 5
Wherein: 1- inner catheter, 2- outer catheter, electrode in 3-, 4- external electrode, 5- ac high voltage source, 6- two-way, 7- are drawn It manages, 8-L type aperture, electrode outlet line in 9-, 10- external electrode lead-out wire, 11- nozzle needle, 12- DC high-voltage power supply, 13- threeway, 14- electrode, 15- electron spray source of solvent, 16- sampling spiroid.
Specific embodiment
With reference to the accompanying drawing and specific embodiment illustrates the present invention, herein illustrative examples and explanation of the invention For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1
A kind of ion source device using dielectric barrier discharge assist ionization, by dielectric barrier discharge device, electron spray Ionization ion source device composition.Dielectric barrier discharge device is by inner catheter 1 (internal diameter 6mm, outer diameter 8mm), 2 (internal diameter of outer catheter 10mm, outer diameter 12mm), interior electrode 3 (copper material), external electrode 4 (copper material), ac high voltage source 5 and two-way 6 (peek material) Composition;Two-way 6 is the column having through circular through hole, and through-hole side open end edge is axially arranged with two-stage step hole, First Rank bore dia 12mm, second step bore dia 8mm;Through-hole other side open end is equipped with internal screw thread, forms threaded hole;In two-way 6 There is the L shape through-hole 8 of diameter 1mm in inside, and two open ends of L shape through-hole 8 respectively lead to two-way side wall surface and first step bottom hole Face;1 arrival end of inner catheter insertion second step hole is simultaneously sealed with it, and outer catheter 2 is inserted into first step hole and seals with it, is inside led Pipe 1 and outer catheter 2 coaxially wear to form cannula structure, outer catheter outlet end and inner catheter outlet end at a distance of 4mm, and outer catheter away from It is closer from sampling spiroid 16;2 outer wall of outer catheter is equipped with a connection fairlead 7, for introducing discharge gas;Cylindrical internal electrode 3 is tight Close to be arranged in the outside wall surface for being fitted in inner catheter 1, tubular external electrode 4 is closely arranged in the outside wall surface for being fitted in outer catheter 2;Interior electricity Pole lead-out wire 9 is drawn by L-type through-hole 8 from 6 side wall of two-way, and blend compounds seal the outlet on through-hole side wall;AC high voltage Source 5 is connect with the interior electrode outlet line 9 being connected with interior electrode and the external electrode lead-out wire 10 being connected with external electrode respectively;Electron spray Ionization ion source is by nozzle needle 11, DC high-voltage power supply 12, threeway 13 (peek material), electrode 14 (platinum filament) and electron spray fluid supply 15 compositions;Nozzle needle 11 is internal diameter 0.075mm, and outlet end is contracted to the quartz ampoule of internal diameter 0.01mm, and nozzle needle 11 passes through 1 He of inner catheter The circular through hole of two-way 6, arrival end are connected with a connector of threeway 13, and inner catheter 1 is stretched out far from second step in outlet end The exit end face 2mm in hole, and will be on threaded hole of the nozzle needle 11 fixed to the other side open end of two-way 6 with nut;Threeway 13 is another Outer two connectors are connected with electrode 14 and electron spray fluid supply 15 respectively;The anode of DC high-voltage power supply 12 connects with electrode 14 It connects, the cathode of DC high-voltage power supply 12 is connect with mass spectrographic sampling spiroid 16.Entire ion source device is placed in sampling spiroid front end, leads outside Pipe exit end face distance samples bore 5mm, and nozzle needle 11 exports the entrance towards sampling spiroid 16, and 1 exit end face of inner catheter is located at leads outside Inside pipe 2.The schematic diagram of device is shown in Fig. 1.
Embodiment 2
As described in Example 1, wherein in 1 and outer catheter 2 be ceramic material;Interior electrode 3 and external electrode 4 are platinum product matter, two Logical 6 and threeway 13 be polyethersulfone ketone material.
Embodiment 3
As described in Example 1, wherein two-way 6 is stretched out in 11 outlet end of nozzle needle, close to inner catheter (1) far from second step hole Exit end face 2mm, and nozzle needle 11 1 inner distance sampling spiroid 16 of inner catheter from the near to the distant be 2 exit end face of outer catheter according to this, Exit end face and nozzle needle 11 outlet end of the inner catheter 1 far from second step hole.
Embodiment 4
As described in Example 1, wherein 1 exit end face of inner catheter is located at outside outer catheter 2, and distance samples cone 16 is from the near to the distant Be 11 outlet end of nozzle needle, exit end face and outer catheter 2 exit end face of the inner catheter 1 far from second step hole according to this.
Embodiment 5
A kind of ion source device using dielectric barrier discharge assist ionization, by dielectric barrier discharge device, electron spray Ionization ion source device composition.Dielectric barrier discharge device is by inner catheter 1 (internal diameter 6mm, outer diameter 8mm), 2 (internal diameter of outer catheter 10mm, outer diameter 12mm, outlet end is contracted to internal diameter 2mm), interior electrode 3 (copper material), external electrode 4 (copper material), AC high voltage Source 5 and two-way 6 (peek material) composition;Two-way 6 is the column having through circular through hole, and through-hole side open end is set along axial direction There are two-stage step hole, first step bore dia 12mm, second step bore dia 8mm;Two through-hole other side open ends are equipped with interior spiral shell Line forms threaded hole;There is the L shape through-hole 8 of diameter 1mm inside two-way 6, two open ends of L shape through-hole 8 respectively lead to two-way Side wall surface and first step hole bottom surface;1 arrival end of inner catheter insertion second step hole is simultaneously sealed with it, the insertion of outer catheter 2 first Stepped hole is simultaneously sealed with it, and inner catheter 1 and outer catheter 2 coaxially wear to form cannula structure, and outer catheter outlet end goes out with inner catheter Mouth end is at a distance of 8mm, and inner catheter outlet end is located inside outer catheter outlet end;2 outer wall of outer catheter is equipped with a connection fairlead 7, for introducing discharge gas;Cylindrical internal electrode 3 is closely arranged on the outer wall for being fitted in inner catheter 1, and tubular external electrode 4 closely covers If being fitted on the outer wall of outer catheter 2;Interior electrode outlet line 9 is drawn by L-type through-hole 8 from 6 side wall of two-way, and blend compounds sealing is logical Outlet on the side wall of hole;Interior electrode outlet line 9 that ac high voltage source 5 is connected with interior electrode respectively and it is connected with external electrode External electrode lead-out wire 10 connects;Electrospray ionisation ion source is by nozzle needle 11, DC high-voltage power supply 12, threeway 13 (peek material), Electrode 14 (platinum filament) and electron spray fluid supply 15 form;Nozzle needle 11 is internal diameter 0.25mm, and outlet end is contracted to internal diameter 0.15mm's Quartz ampoule, nozzle needle 11 pass through the circular through hole of inner catheter 1 and two-way 6, and arrival end is connected with a connector of threeway 13, export Exit end face 2mm of the inner catheter 1 far from second step hole is stretched out at end, and nozzle needle 11 is fixed to the other side of two-way 6 with nut On the threaded hole of open end;Other two connector of threeway 13 is connected with electrode 14 and electron spray fluid supply 15 respectively;Direct current is high The anode of voltage source 12 is connect with electrode 14, and the cathode of DC high-voltage power supply 12 is connect with mass spectrographic sampling spiroid 16.Entire ion Source device is placed in 16 front end of sampling spiroid, and outer catheter exit end face distance samples bore 2mm.The schematic diagram of device is shown in Fig. 2.

Claims (7)

1. a kind of ion source device using dielectric barrier discharge assist ionization, by dielectric barrier discharge device, electron spray electricity Luxuriant source arrangement composition, it is characterised in that: dielectric barrier discharge device is by inner catheter (1), outer catheter (2), interior electrode (3), External electrode (4), ac high voltage source (5) and two-way (6) composition;Two-way (6) is the column having through circular through hole, through-hole one Side opening end is along two-stage step hole is axially arranged with, and wherein first step bore dia is greater than second step bore dia;The through-hole other side Open end is equipped with internal screw thread, forms threaded hole;There are L shape through-hole (8), two open ends of L shape through-hole (8) inside two-way (6) Respectively lead to two-way side wall surface and first step hole bottom surface;Inner catheter (1) arrival end insertion second step hole is simultaneously sealed with it, outside Conduit (2) arrival end is inserted into first step hole and its sealing, and inner catheter (1) and outer catheter (2) coaxially wear to form cannula structure; Outer catheter (2) outer wall is equipped with connection fairlead (7), for introducing discharge gas;Cylindrical internal electrode (3) is closely arranged fitting In the outside wall surface of inner catheter (1), tubular external electrode (4) is closely arranged in the outside wall surface for being fitted in outer catheter (2);Interior electrode draws Outlet (9) is drawn by L-type through-hole (8) from the side wall of two-way (6), and blend compounds seal the outlet on through-hole side wall;Exchange is high The interior electrode outlet line (9) that voltage source (5) is connected with interior electrode respectively and the external electrode lead-out wire (10) being connected with external electrode Connection;Electrospray ionisation ion source is by nozzle needle (11), DC high-voltage power supply (12), threeway (13), electrode (14) and EFI spray film Body source (15) composition;Nozzle needle (11) passes through the circular through hole of inner catheter (1) and two-way (6), and one of arrival end and threeway (13) Connector is connected, and the exit end face of inner catheter (1) far from second step hole is stretched out in outlet end, and with nut that nozzle needle (11) are fixed Onto the threaded hole of the other side open end of two-way (6);Threeway (13) other two connector respectively with electrode (14) and EFI Mist fluid supply (15) is connected;The anode of DC high-voltage power supply (12) is connect with electrode (14), the cathode of DC high-voltage power supply (12) It is connect with mass spectrographic sampling spiroid (16);Entire ion source device is placed in sampling spiroid (16) front end, and nozzle needle (11) is exported towards sampling The entrance of (16) is bored, it is internal that inner catheter (1) exit end face is located at outer catheter (2).
2. ion source device according to claim 1, it is characterised in that: the inner catheter (1), outer catheter (2), two-way (6) it is made of insulating material with threeway (13);The inner catheter (1) and outer catheter (2) material are glass, quartz or ceramics;Institute The material for stating two-way (6) and threeway (13) is peek, polyethersulfone ketone or polytetrafluoroethylene (PTFE).
3. the apparatus according to claim 1, it is characterised in that: the interior electrode (3) and external electrode (4) are conductive metal ring Shape electrode.
4. ion source device according to claim 1, it is characterised in that: nozzle needle (11) is an internal diameter 0.01-1mm, outlet End internal diameter is contracted to the quartz ampoule of 0.01-0.15mm;The exit end face of outlet end and inner catheter (1) far from second step hole is apart 1-10mm;The distance between outer catheter (2) exit end face and inner catheter (1) exit end face are 0-20mm.
5. ion source device according to claim 1, it is characterised in that: outer catheter (2) exit end face and sampling spiroid The distance between be 1-20mm.
6. ion source device according to claim 1, it is characterised in that: the outlet end of the outer catheter (2) is equipped with diameter The closing in become smaller.
7. ion source device according to claim 1, it is characterised in that: two-way (6) is cylindrical body, and the side end face Yu Qiyi is set There is cylindrical first groove, be equipped with cylindrical second groove in the first groove floor, be equipped with circular through hole in the second groove floor, First groove, the second groove, circular through hole and two-way are coaxial, and upper surface successively has two-stage step hole along axial direction, wherein First Rank bore dia is greater than second step bore dia;Another side end face circular through hole of two-way (6) is equipped with internal screw thread, forms threaded hole;In L shape through-hole (8) is equipped between first groove floor and two-way (6) side wall surface, L shape through-hole (8) respectively leads to side wall surface and First Rank hole.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113205997A (en) * 2021-05-06 2021-08-03 南京同歌网络科技有限公司 Efficient ionization device for mass spectrometer

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Publication number Priority date Publication date Assignee Title
CN103260329A (en) * 2013-04-23 2013-08-21 华中科技大学 Plasma jet device with suspension electrode
CN104111282A (en) * 2013-04-18 2014-10-22 谢建台 Mass spectrum ionization device with multiple ionization sources and mass spectrum analysis system
WO2016163046A1 (en) * 2015-04-09 2016-10-13 旭サナック株式会社 Electrical discharge nozzle to be used in electrospray ionization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104111282A (en) * 2013-04-18 2014-10-22 谢建台 Mass spectrum ionization device with multiple ionization sources and mass spectrum analysis system
CN103260329A (en) * 2013-04-23 2013-08-21 华中科技大学 Plasma jet device with suspension electrode
WO2016163046A1 (en) * 2015-04-09 2016-10-13 旭サナック株式会社 Electrical discharge nozzle to be used in electrospray ionization

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113205997A (en) * 2021-05-06 2021-08-03 南京同歌网络科技有限公司 Efficient ionization device for mass spectrometer
CN113205997B (en) * 2021-05-06 2024-04-26 南京品生医疗科技有限公司 Efficient ionization device for mass spectrometer

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