CN104201084A - Closed type molecular adduct isotope ion generator - Google Patents

Closed type molecular adduct isotope ion generator Download PDF

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Publication number
CN104201084A
CN104201084A CN201410261334.4A CN201410261334A CN104201084A CN 104201084 A CN104201084 A CN 104201084A CN 201410261334 A CN201410261334 A CN 201410261334A CN 104201084 A CN104201084 A CN 104201084A
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China
Prior art keywords
isotope
ion generator
capillary
taylor cone
container
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CN201410261334.4A
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CN104201084B (en
Inventor
朱一心
吕婷婷
葛林泽
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ZHEJIANG HAOCHUANG BIOTECHNOLOGY CO Ltd
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ZHEJIANG HAOCHUANG BIOTECHNOLOGY CO Ltd
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Publication of CN104201084A publication Critical patent/CN104201084A/en
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Abstract

The invention discloses an ion generator, and in particular to a closed type molecular adduct isotope ion generator. The closed type molecular adduct isotope ion generator comprises a Taylor cone generator, wherein a closed container for placing isotope gas or liquid steam is arranged at the capillary outlet of the Taylor cone generator, the Taylor cone generator comprises a capillary, the outer side of the capillary is connected to a high-pressure electric contact, and the high-pressure electric contact and the inner wall of the closed container for placing isotope gas or liquid steam form a circuit loop. The closed type molecular adduct isotope ion generator has the advantages that the current situation that enough molecular adduct isotope ion beams only can be generated by a lot of isotope sources can be effectively changed, thus enabling isotope ions to be popularized for application and greatly reducing production cost of the isotope ions; furthermore, the closed type molecular adduct isotope ion generator is convenient to use.

Description

A kind of enclosed type molecule adduction isotope ion generator
Technical field
The present invention relates to a kind of ion generating device, specifically refer to a kind of enclosed type generator for generation of molecule adduction isotope ion.
Background technology
Since the mid-80, since one of Nobel chemistry Prize winner in 2002 John B.Fenn is applied to large molecule mass spectral analysis by electric spray ion source, past more than 20 year, for electric spray ion source mechanism, still rest on two patterns: Ion Evaporation Model (IEM) ion evaporation, with the residual mechanism of Charged Residue Model (CRM) electric charge.The basic structure of electric spray ion source and the nineties there is no a difference in essence.
The basic structure of electric spray ion source is exactly in the middle of the metal of a hollow or capillary glass tube, to be full of liquid, facing to mass spectrometric ion entrance, on liquid, add plus or minus high voltage, in atmosphere, form negative ions, mass spectrometric vacuum system sucks mass spectrometric mass analyzer by a part of ion.
For electric spray ion source, although ionization probability is very high, almost reach 100%, molecular ion is transferred to the effective ion of mass spectrum mass detector, only have total number of ions 0.01% to 0.1% between.
In order to address the above problem, a lot of inventors have invented the electric spray ion source of different institutions, and referenced patent number is: U.S. US4861988, US5412208, US5432343, US6992299, US5504329.But all inventions are all that the transmitting needle point of electric spray ion source is among atmosphere, ion current and fluid flow are in close relations, cannot be in large range of flow 100 receive liter/min~100 microlitres/minute obtain stable emission of ions, and ion transmission efficiency is not significantly improved.
Formation for taylor cone, at < < computer and applied chemistry > > the 28th volume o. 11th, there is corresponding open explanation, wherein by controlling voltage swing, make solution form drop all the time and not drip at the capillary mouth of pipe, at this moment, the drop of capillary lower end is the hemispherical of convex, and " solution is subject to the effect of surface tension and electric field force simultaneously at the capillary mouth of pipe, along with electric field strength increases, same sex electric charge in solution is gathered in drop surface, the electric field that surface charge produces causes that drop deformation is " when voltage reaches a certain critical value Vc, the solution at mouth of pipe place gradually becomes taper by hemisphere, during balance, its angle, half top is approximately 493 ", this charged cone is called taylor cone (Tay lor Cone) by everybody ".
Electric spray ion source (ESI) is the most frequently used interface of current liquid chromatography-mass spectrography (LC-MS) coupling, belongs to soft ionization mode, can be used for studying thermally labile and the larger compound of polarity.Due to the molecular ion that can produce with multi-charge, electric spray ion source also can be used for the large biological molecules such as Study on Protein.The first provings such as Fenn ESI in the applicability that generates biomolecule ions, until the sixties in 20th century, Dole etc. produce the mass spectrometer of First based on electron spray.Afterwards, the use ESI series connection level Four bar detectors such as Fenn detect molecular beam, recognize that Dole ion source exists defect, and result is made an explanation, and have revised the distance between ion source nozzle needle and end plate, thereby have reduced nozzle needle voltage.The designed ion source of Fenn developed into Fenn-Whitehouse design afterwards.This design is used capillary glass tube that ion is delivered into the first vacuum chamber from atmospheric environment, can select according to demand different inner diameters capillary.1987, Bruins etc. introduced electrospray interface by Aeroassisted sprayer.Atomization gas contributes to stable electrical spraying, keeps flow velocity to approach 0.2mL/min, is applicable to liquid phase series connection ESI-MS. and allows nozzle and to there being larger distance between electrode, reduced the generation of corona discharge.Meanwhile, reduce the dependence of spray process to nozzle location, if place nozzle from axle, can obtain higher sensitivity.After this, electric spray ion source structural design has been passed through a series of improvement, and its operation principle has also been had to more and more deep understanding.
At present, technical staff emphasizes at taylor cone generator (in this application always, the device that forms taylor cone phenomenon is referred to as to taylor cone generator) in liquid in capillary be produce ion basic, and always unknown for phenomenons the such as whether liquid at capillary outlet place can be ionized.In current demand, in order to obtain isotopic ionization, the effect forming by taylor cone of the prior art, causes in isotope ion process can the needs very high cost that has, so, for the application of isotope ion, be subject to suitable restriction.
Summary of the invention
The present invention is directed to deficiency of the prior art, a kind of device that can conveniently prepare molecule adduction isotope ion is provided, can become possibility for the extensive use of isotope ion.
The present invention is achieved by following technical proposals:
An enclosed type molecule adduction isotope ion generator, is characterized in that a taylor cone generator has the placement isotope gas of a sealing or the container of liquid vapour at the capillary outlet place of taylor cone generator.
As preferably, in above-mentioned a kind of enclosed type molecule adduction isotope ion generator, taylor cone generator comprises capillary, in outside capillaceous, be connected to high-tension electricity joint, the placement isotope gas of high-tension electricity electric connection and sealing or the container inner wall of liquid vapour form a circuit loop.In order to realize better effect, between capillary and container inner wall, there is a gas flow void layer, gas flow void layer is in communication with the outside by several side openings.The body of ventilating is the mixing of several gases in nitrogen, oxygen, argon gas, hydrogen, air or above-mentioned gas, and the nitrogen in above-mentioned gas or air have better effect.
As preferably, the placement isotope gas sealing in above-mentioned a kind of enclosed type molecule adduction isotope ion generator or the container of liquid have an opening to be connected with mass spectrometer, and the import of taylor cone generator is connected with polar liquid; Guarantee to have continuous taylor cone phenomenon to exist in capillary.
As preferably, in above-mentioned a kind of enclosed type molecule adduction isotope ion generator, the capillary import of taylor cone generator is connected with chromatograph.
As preferably, the placement isotope gas sealing in above-mentioned a kind of enclosed type molecule adduction isotope ion generator or the container of liquid vapour are connected with isotopic source.
As preferably, above-mentioned a kind of enclosed type molecule adduction isotope ion generator, is characterized in that there is valve between the container of isotopic source and isotope gas or liquid vapour; Can effectively regulate the flow of isotope gas or liquid vapour like this, the handled easily such as control cost.
Beneficial effect: the present invention can effectively change the present situation that in the past needs a large amount of isotopic sources just can produce enough molecule adduction isotope ion bundle groups, makes applying of isotope ion become possibility, greatly reduces isotope ion production cost; And use this device convenient.Because isotope ion and molecule adduct ion bundle group have the industries such as biology, medicine, food to have purposes very widely, therefore the present invention can be realized this extensive use more fully.
Accompanying drawing explanation
Fig. 1 structural representation of the present invention
It in Fig. 2 embodiment of the present invention, near taylor cone, is the analysis of spectra of air
It in Fig. 3 embodiment of the present invention, near taylor cone, is the analysis of spectra of air and heavy water D2O mist
Embodiment
Below enforcement of the present invention is illustrated:
Embodiment 1
Structure shown in 1, makes an enclosed type molecule adduction isotope ion generator with reference to the accompanying drawings, comprising a taylor cone generator, in capillary 2 exits of taylor cone generator 1, has the placement isotope gas of a sealing or the container 4 of liquid vapour; In the outside of capillary 2, be connected to high-tension electricity joint, the placement isotope gas of high-tension electricity electric connection and sealing or the container of liquid vapour 4 inwalls form a circuit loop.
Import at taylor cone generator 1 is connected with polar liquid water, and then, under the effect of high-tension electricity, polar liquid is subject to electric field action, between the outlet of capillary 2 and the inwall of container 4, forms an electric field, has isotope heavy water (D simultaneously in container 4 2o), at the exit of capillary 2 heavy water (D 2o) be subject to electric field action and form ion.
By produced ion is analyzed, near taylor cone, measure, in order to obtain good contrast effect, first near air taylor cone is measured, gained collection of illustrative plates as shown in Figure 2, then near taylor cone being air and heavy water D 2o mist is measured, as shown in Figure 3 collection of illustrative plates.
Embodiment 2
Structure shown in 1, makes an enclosed type molecule adduction isotope ion generator with reference to the accompanying drawings, comprising a taylor cone generator, in capillary 2 exits of taylor cone generator 1, has the placement isotope gas of a sealing or the container 4 of liquid vapour; In the outside of capillary 2, be connected to high-tension electricity joint, the placement isotope gas of high-tension electricity electric connection and sealing or the container of liquid vapour 4 inwalls form a circuit loop.
Import at taylor cone generator 1 is connected with polar liquid water, and then, under the effect of high-tension electricity, polar liquid is subject to electric field action, between the outlet of capillary 2 and the inwall of container 4, forms an electric field, has isotope heavy water (D simultaneously in container 4 2o), at the exit of capillary 2 heavy water (D 2o) be subject to electric field action and form ion.And having a gas flow void layer between capillary 2 and container 4 inwalls, gas flow void layer is in communication with the outside by several side openings, can pass into N 2as assist gas.Then at the placement isotope gas of sealing or the container 4 of liquid, there is an opening to be connected with mass spectrometer 3, import connection and the chromatograph of taylor cone generator 1; Between isotopic source 6 and the container 4 of isotope gas or liquid vapour, there is valve 5, the control of more convenient like this dose of an isotope.
The present embodiment is carried out to data and record, also can obtain effect as shown in Figure 2 and Figure 3.

Claims (7)

1. an enclosed type molecule adduction isotope ion generator, it is characterized in that, a taylor cone generator, has the placement isotope gas of a sealing or the container (4) of liquid vapour in capillary (2) exit of taylor cone generator (1).
2. a kind of enclosed type molecule adduction isotope ion generator according to claim 1, it is characterized in that taylor cone generator (1) comprises capillary (2), outside at capillary (2) is connected to high-tension electricity joint, and container (4) inwall of the placement isotope gas of high-tension electricity electric connection and sealing or liquid vapour forms a circuit loop.
3. a kind of enclosed type molecule adduction isotope ion generator according to claim 2, it is characterized in that there is a gas flow void layer between capillary (2) and container (4) inwall, gas flow void layer is in communication with the outside by several side openings.
4. a kind of enclosed type molecule adduction isotope ion generator according to claim 1, it is characterized in that the placement isotope gas of sealing or the container (4) of liquid have an opening to be connected with mass spectrometer (3), the import of taylor cone generator (1) is connected with polar liquid.
5. a kind of enclosed type molecule adduction isotope ion generator according to claim 1, is characterized in that capillary (2) import of taylor cone generator (1) is connected with chromatograph.
6. a kind of enclosed type molecule adduction isotope ion generator according to claim 1, is characterized in that the placement isotope gas of sealing or the container (4) of liquid vapour are connected with isotopic source (6).
7. a kind of enclosed type molecule adduction isotope ion generator according to claim 1, is characterized in that there is valve (5) between the container (4) of isotopic source (6) and isotope gas or liquid vapour.
CN201410261334.4A 2014-06-12 2014-06-12 Closed type molecular adduct isotope ion generator Expired - Fee Related CN104201084B (en)

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CN104201084B CN104201084B (en) 2017-02-01

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050001162A1 (en) * 2002-10-29 2005-01-06 Target Discovery, Inc. Method for increasing ionization efficiency in mass spectroscopy
CN101464427A (en) * 2007-12-21 2009-06-24 清华大学 Open type atomizing field desorption ionization method and apparatus thereof
CN102142352A (en) * 2011-02-12 2011-08-03 浙江好创生物技术有限公司 Electro-spray ion generator
CN103035471A (en) * 2011-09-29 2013-04-10 江苏天瑞仪器股份有限公司 Electron spray ionization (ESI) source and controllable high-voltage direct current power supply for ESI source
CN204067299U (en) * 2014-08-21 2014-12-31 浙江好创生物技术有限公司 A kind of enclosed type molecule adduction isotope ion generator

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050001162A1 (en) * 2002-10-29 2005-01-06 Target Discovery, Inc. Method for increasing ionization efficiency in mass spectroscopy
CN101464427A (en) * 2007-12-21 2009-06-24 清华大学 Open type atomizing field desorption ionization method and apparatus thereof
CN102142352A (en) * 2011-02-12 2011-08-03 浙江好创生物技术有限公司 Electro-spray ion generator
CN103035471A (en) * 2011-09-29 2013-04-10 江苏天瑞仪器股份有限公司 Electron spray ionization (ESI) source and controllable high-voltage direct current power supply for ESI source
CN204067299U (en) * 2014-08-21 2014-12-31 浙江好创生物技术有限公司 A kind of enclosed type molecule adduction isotope ion generator

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Granted publication date: 20170201