CN104124131A - Mass spectrum ion source and mass spectrometer - Google Patents
Mass spectrum ion source and mass spectrometer Download PDFInfo
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- CN104124131A CN104124131A CN201310143337.3A CN201310143337A CN104124131A CN 104124131 A CN104124131 A CN 104124131A CN 201310143337 A CN201310143337 A CN 201310143337A CN 104124131 A CN104124131 A CN 104124131A
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Abstract
The invention provides a mass spectrum ion source and a mass spectrometer. The mass spectrum ion source includes a sampling device, a spray needle and a capillary pipe. The sampling device includes a T-junction, and a liquid sample inlet pipe, a liquid sample outlet pipe and a waste-liquid pipe, which are connected to the T-junction, and a constant-pressure valve installed at the waste-liquid pipe. The spray needle enables a liquid sample to become charged ions through an electrospray process. The capillary pipe guides the charged ions to a mass analyzer. When the quantity of the liquid sample which enters the T-junction via the liquid sample inlet pipe is overly large, the constant-pressure valve is started so that redundant liquid sample flows out from the waste-liquid pipe and thus the pressure and flow of the liquid sample outlet pipe are maintained at set values. In the mass spectrum ion source and mass spectrometer, the flow rate of only a specific quantity of liquid sample which enters the spray needle via the liquid sample outlet pipe is constant without changing with the flow rate of the injected sample. Therefore, the spray needle is kept at an optimal flow rate, an atomization effect is great and charged ions which are smaller in size can be formed without using an atomized gas or a blowback gas and thus the use cost of the mass spectrum ion source is low.
Description
Technical field
The present invention relates to a kind of mass ion source for field of analytic instrument and mass spectrometer.
Background technology
Application of gas chromatorgraphy/mass instrument is widely used in scientific research and biological detection analysis field, and its structure mainly comprises liquid chromatograph and mass spectrometer.Wherein liquid chromatograph is for preliminary treatment fluid sample to be detected, to form comparatively pure fluid sample.Mass spectrometer mainly comprises mass ion source and mass analyzer etc.Mass ion source is divided into again a lot of different kinds, wherein electric spray ion source comprises a charged nozzle needle, capillary and the heater to capillary heating, charged nozzle needle is arranged in atmosphere, for receiving the purer fluid sample of processing through liquid chromatograph, and by the charged ion of fluid sample ionization gasification formation gaseous state; Capillary one end extend in mass spectrometer, and the other end is arranged in atmosphere, and the sample ions of the air pressure official post in described mass spectrometer and between atmosphere after ionization gasification forms sample ions stream, and by described capillary suction in mass spectrometer.In traditional mass ion source, the mass analyzer in capillary and mass spectrometer is arranged on same center line, so ion current flies into mass analyzer with form of straight lines.
As shown in Figure 1, the voltage on capillary 2 and nozzle needle 1 have a high-tension electricity potential difference, can utilize a high-voltage suppling power to make to keep this high-tension electricity potential difference between capillary 2 and nozzle needle 1, can certainly between the two, keep by other means high-tension electricity potential difference.The nozzle of nozzle needle 1 forms taylor cone by electric field action, makes fluid sample convert a large amount of drops with electric charge to, and charged drop generation COULOMB EXPLOSION effect, evaporates partial solvent, becomes less Charged Droplet; These little droplets in the guiding of air-flow, wrap up in and under the effect of taking, form sample ions and flow to into capillary 2, solvent under the high temperature action of capillary 2 in little droplet is further evaporated, therefore little droplet, by can be more and more less in the process of capillary 2, finally enters in mass analyzer 4.
In application of gas chromatorgraphy/mass instrument, too many owing to entering the fluid sample of nozzle needle 1, the liquid gushing out is too large, drop initial particle is large, atomizing effect is poor, therefore the size of the Charged Droplet forming is larger, therefore in order to make mass analyzer can obtain the charged ion that more size is less, in traditional mass ion source, be provided with blowback air flue 5 in capillary 2 peripheries, some mass ion sources are also provided with atomization gas around nozzle needle 1, in atomization gas and blowback air flue 5 such as nitrogen of gas etc. the drop of atomization is smashed, with by ion desolventizing, thereby obtain the less charged ion of size.But, in experiment each time or using, all need to consume a lot of nitrogen as blowback air and atomization gas, increase experiment or use cost.In prior art, another method of obtaining the Charged Droplet that size is less is to take what is called to receive liter the mode of spraying (Nanospray), realize electron spray with very thin capillary, but because too thin capillary easily stops up, the more difficult realization of this mode.Receive and rise spraying and can only be used for tiny flow quantity sample introduction, be difficult for mating with conventional liquid chromatograph.
Summary of the invention
The object of the present invention is to provide a kind of mass ion source and mass spectrometer that can form reduced size charged ion without blowback air and atomization gas, to solve in above-mentioned prior art owing to needing blowback air and atomization gas to cause the technical problem of waste.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
The invention provides a kind of mass ion source, for mass spectrometer, described mass spectrometer comprises mass analyzer.Described mass ion source comprises sampling device, nozzle needle and capillary.Sampling device is for receiving and shunt fluid sample, and this sampling device comprises: three-way connection, fluid sample feed tube, fluid sample drain pipe and sewer pipe, and wherein three-way connection has first interface, the second interface, the 3rd interface and constant pressure valve; Fluid sample feed tube is connected in described first interface; Fluid sample drain pipe is connected in described the second interface, and sewer pipe is connected in described the 3rd interface, and constant pressure valve is installed on described sewer pipe.Nozzle needle is connected in described fluid sample drain pipe, makes fluid sample become charged ion by electron spray process; One end capillaceous is exposed in atmosphere, and aims at the outlet of described nozzle needle, and the other end, in mass spectrometric vacuum cavity, and is directed to described mass analyzer by charged ion.When being entered the fluid sample amount of described three-way connection by described fluid sample feed tube when excessive, described constant pressure valve is opened, and unnecessary fluid sample is flowed out by described sewer pipe, thereby make the pressure of described fluid sample drain pipe and flow maintain set point.
According to an embodiment of the present invention, described constant pressure valve comprises: valve body, valve plate and spring.Wherein said valve body is installed on described sewer pipe; Valve plate is connected in described valve body rotationally; One end of spring is connected in described valve body, and the other end is connected in described valve plate.Wherein, described constant pressure valve is normal closed gate, and when the pressure being subject to when valve plate is greater than the elastic force of described spring, valve plate is opened.
According to an embodiment of the present invention, wherein said mass ion source also comprises: the waste liquid collecting box that is connected in described sewer pipe end.
According to an embodiment of the present invention, wherein said fluid sample feed tube is connected in described first interface by connecting hose; And/or described fluid sample drain pipe is connected in described the second interface by connecting hose; And/or described sewer pipe is flexible pipe.
According to an embodiment of the present invention, the pressure of wherein said fluid sample drain pipe maintains within the scope of 20～40 pounds/square inch.
According to an embodiment of the present invention, in wherein said fluid sample drain pipe, fluid sample flow per minute is 0.5～10 microlitre.
The invention provides a kind of mass spectrometer, comprise mass analyzer and mass ion source, wherein said mass ion source is mass ion source of the present invention.
As shown from the above technical solution, mass ion source of the present invention and mass spectrometric advantage and good effect are: in the present invention, be provided with sampling device and constant pressure valve for receiving and shunt fluid sample, under the control action of constant pressure valve, entered the fluid sample of three-way connection by fluid sample feed tube, only have the fluid sample of specified quantitative to enter nozzle needle by fluid sample drain pipe, and unnecessary fluid sample is flowed out by sewer pipe.A small amount of fluid sample atomization more fully, more complete, can form the electricity band ion that size is less, therefore these electricity band ions, flying in process capillaceous, make its size decreases without re-using purge gas, therefore reduction use cost of the present invention is low.
By referring to accompanying drawing description of a preferred embodiment, above-mentioned and other objects, features and advantages of the present invention will be more obvious.
Brief description of the drawings
Fig. 1 represents the structural representation of traditional mass ion source, and it is expressed fluid sample simultaneously and is ionized the change procedure in the rear flight course of gasification;
Fig. 2 represents the structural representation of mass ion source of the present invention;
Fig. 3 represents the structural representation of the sampling device in mass ion source of the present invention;
Fig. 4 represents to use mass spectrometer of the present invention reserpine sample to be carried out to the mass signal figure of analytical test.
Embodiment
Describe specific embodiments of the invention in detail below in conjunction with accompanying drawing.It should be noted that the embodiments described herein, only for illustrating, is not limited to the present invention.
As shown in Figure 2, Figure 3 and Figure 4, mass ion source of the present invention, for mass spectrometer, mass spectrometer comprises mass analyzer 4.Mass ion source mainly comprises charged nozzle needle 1, capillary 2, heater (not shown) and sampling device 6 to capillary heating.
Charged nozzle needle 1 can be identical with the charged nozzle needle in the mass ion source of traditional structure.
Referring to Fig. 3, sampling device 6 is for receiving and shunt fluid sample.This sampling device comprises: three-way connection 7, fluid sample feed tube 71, fluid sample drain pipe 72, sewer pipe 73, waste liquid collecting box 74 and constant pressure valve 76.Three-way connection 7 can adopt any traditional structure, and three-way connection 7 has first interface, the second interface and the 3rd interface.Fluid sample feed tube 71 is connected in first interface; Fluid sample drain pipe 72 is connected in the second interface; Sewer pipe 73 is connected in the 3rd interface, and waste liquid collecting box 74 is connected in the other end of sewer pipe 73; Constant pressure valve 76 is installed on sewer pipe 73.Fluid sample feed tube 71 wherein and fluid sample drain pipe 72 are connected in first interface, second interface of three-way connection 7 separately by connecting hose 75, be conducive to like this structural configuration compactness of mass ion source.Equally, sewer pipe 73 also can adopt flexible pipe.
Nozzle needle 1 is connected in fluid sample drain pipe 72, for ionizing the fluid sample of fluid sample drain pipe 72, makes it to become charged ion by electron spray process.
One end of capillary 2 is exposed in atmosphere, and aims at the outlet of nozzle needle 1, and the other end is in mass spectrometric vacuum cavity, and alignment quality analyzer, and charged ion is directed to mass analyzer 4.
Constant pressure valve 76 is normal closed gates, its role is to: when being entered the fluid sample amount of described three-way connection 7 by described fluid sample feed tube 71 when excessive, constant pressure valve is opened, unnecessary fluid sample is flowed out by described sewer pipe 73, thereby make the pressure of fluid sample drain pipe 72 and flow maintain set point, for example pressure is maintained 20PSI～40PSI (pound/square inch) arbitrary set point in scope.
The structure of constant pressure valve 76 comprises valve body, valve plate and spring.Valve body is installed on described sewer pipe 73; Valve plate, is connected in valve body rotationally; One end of spring is connected in valve body, and the other end is connected in valve plate.When the pressure being subject to when valve plate is greater than the elastic force of spring, valve plate is opened, and unnecessary fluid sample can flow into exhausted bath box 74 by constant pressure valve 76, constant thereby the flow velocity of fluid sample drain pipe 72 keeps, not sample introduction flow rate effect in liquid body sample feed tube 71.
In mass ion source of the present invention, constant pressure valve regulates split ratio automatically according to the flow of fluid sample feed tube 71, the fluid flow that control enters nozzle needle 1 reaches constant current, and for example controlling fluid sample flow per minute in fluid sample drain pipe 72 is micro updating, for example 0.5～10 microlitre.
Mass ion source of the present invention can solve liquid chromatograph and mass spectrometric connection problem in application of gas chromatorgraphy/mass instrument, for example solve the sampling device flow velocity of liquid phase inhomogeneous with the unmatched problem of ion source optimum flow rate, the flow of general liquid phase is that flow per minute is milliliter (ml/min) magnitude, is that the flow of microlitre (ul/min) magnitude is sprayed but the best sample introduction flow velocity of mass spectrometer only needs flow per minute.By mass ion source of the present invention, can be liquid phase automatic current limiting at the little flow velocity of some specific ul/min magnitudes, thereby and do not need to add again any blowback air and atomization gas, greatly saved experiment and use cost.
Mass spectrometer of the present invention, comprises mass ion source and mass analyzer 4.Mass ion source is wherein aforementioned mass ion source of the present invention, repeats no more here.
The sensitivity determination of general application of gas chromatorgraphy/mass instrument often adopts reserpine as test sample, method of testing is as follows: configure certain density reserpine (as 10pg/ μ l), enter a certain amount of sample by liquid chromatograph, taking water and methyl alcohol each 50% as mobile phase (adding 1% acetic acid), then do full scan.As shown in Figure 4, it represents to use mass spectrometer of the present invention reserpine sample to be carried out to the mass signal figure of analytical test.The main peak structure that mass number is 609 is as can be seen from Figure 4 very clear, and resolution reaches more than 2000.Near 610,607 peaks 609 may be unstable the causing of radio-frequency voltage on impurity or mass analyzer, do not form substantive obstacle concerning understanding whole spectrogram.This has absolutely proved that mass ion source of the present invention and mass spectrometer are effective.
Although described the present invention with reference to several exemplary embodiments, should be appreciated that term used is explanation and exemplary and nonrestrictive term.Because can specifically implementing in a variety of forms, the present invention do not depart from spirit or the essence of invention, so be to be understood that, above-described embodiment is not limited to any aforesaid details, and explain widely in the spirit and scope that should limit in the claim of enclosing, therefore fall into whole variations in claim or its equivalent scope and remodeling and all should be the claim of enclosing and contain.
Claims (9)
1. a mass ion source, for mass spectrometer, described mass spectrometer comprises mass analyzer, it is characterized in that, described mass ion source comprises:
Sampling device (6), for receiving and shunt fluid sample, this sampling device comprises:
Three-way connection (7), it has first interface, the second interface and the 3rd interface;
Fluid sample feed tube (71), is connected in described first interface;
Fluid sample drain pipe (72), is connected in described the second interface;
Sewer pipe (73), is connected in described the 3rd interface; And
Constant pressure valve (76), is installed on described sewer pipe (73);
Nozzle needle (1), is connected in described fluid sample drain pipe (72), makes fluid sample become charged ion by electron spray process; And
Capillary (2), its one end is exposed in atmosphere, and aims at the outlet of described nozzle needle (1), and the other end, in mass spectrometric vacuum cavity, is directed to described mass analyzer (4) by charged ion;
When being entered the fluid sample amount of described three-way connection (7) by described fluid sample feed tube (71) when excessive, described constant pressure valve is opened, unnecessary fluid sample is flowed out by described sewer pipe (73), thereby make pressure and the flow of described fluid sample drain pipe (72) maintain set point.
2. mass ion source as claimed in claim 1, is characterized in that, described constant pressure valve (76) comprising:
Valve body, is installed on described sewer pipe (73);
Valve plate, is connected in described valve body rotationally; And
Spring, one end is connected in described valve body, and the other end is connected in described valve plate;
Wherein, described constant pressure valve (76) is normal closed gate, and when the pressure being subject to when valve plate is greater than the elastic force of described spring, valve plate is opened.
3. mass ion source as claimed in claim 1 or 2, is characterized in that, described mass ion source also comprises: the waste liquid collecting box (74) that is connected in described sewer pipe (73) end.
4. mass ion source as claimed in claim 1 or 2, is characterized in that, described fluid sample feed tube (71) is connected in described first interface by connecting hose.
5. mass ion source as claimed in claim 1 or 2, is characterized in that, described fluid sample drain pipe (72) is connected in described the second interface by connecting hose.
6. mass ion source as claimed in claim 1 or 2, is characterized in that, described sewer pipe (73) is flexible pipe.
7. mass ion source as claimed in claim 1 or 2, is characterized in that, the pressure of described fluid sample drain pipe (72) maintains within the scope of 20～40 pounds/square inch.
8. mass ion source as claimed in claim 1 or 2, is characterized in that, in described fluid sample drain pipe (72), fluid sample flow per minute is 0.5～10 microlitre.
9. a mass spectrometer, comprises mass analyzer (4) and mass ion source, it is characterized in that: described mass ion source is the mass ion source as described in any one in claim 1-8.
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| CN201310143337.3A CN104124131A (en) | 2013-04-23 | 2013-04-23 | Mass spectrum ion source and mass spectrometer |
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| CN201310143337.3A CN104124131A (en) | 2013-04-23 | 2013-04-23 | Mass spectrum ion source and mass spectrometer |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105845540A (en) * | 2016-03-28 | 2016-08-10 | 复旦大学 | Desolvation and ionizationoun method through heating and apparatus |
| CN106841459A (en) * | 2017-03-31 | 2017-06-13 | 北京雪迪龙科技股份有限公司 | A kind of gas chromatography combined with mass spectrometry interface, system and flow matches method |
| CN106896089A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of photoelectronic imaging device based on electric spray ion source |
| CN107389831A (en) * | 2017-09-26 | 2017-11-24 | 中国检验检疫科学研究院 | The quick determination method of banned substance oestrone in a kind of spraying cosmetics |
| CN108831819A (en) * | 2018-04-20 | 2018-11-16 | 中国药科大学 | A kind of equipment and its application in ortho states-denaturation conversion ions source |
| CN110455972A (en) * | 2019-08-21 | 2019-11-15 | 哈尔滨阿斯顿仪器有限公司 | Analysis method associated with a kind of liquid chromatography mass and its use interface arrangement |
| CN112885702A (en) * | 2021-04-12 | 2021-06-01 | 杭州安誉科技有限公司 | Sampling device of mass spectrometer |
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| WO2012167183A1 (en) * | 2011-06-03 | 2012-12-06 | Perkinelmer Health Sciences, Inc. | Direct sample analysis ion source |
| CN203300595U (en) * | 2013-04-23 | 2013-11-20 | 北京普析通用仪器有限责任公司 | Mass spectrum ion source and mass spectrometer |
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| CN101206197A (en) * | 2006-12-22 | 2008-06-25 | 中国科学院大连化学物理研究所 | System for on-line desalinization, enrichment and mass spectrum of double split flow noy upgrade liquid chromatogram |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106896089A (en) * | 2015-12-17 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of photoelectronic imaging device based on electric spray ion source |
| CN105845540A (en) * | 2016-03-28 | 2016-08-10 | 复旦大学 | Desolvation and ionizationoun method through heating and apparatus |
| CN106841459A (en) * | 2017-03-31 | 2017-06-13 | 北京雪迪龙科技股份有限公司 | A kind of gas chromatography combined with mass spectrometry interface, system and flow matches method |
| CN107389831A (en) * | 2017-09-26 | 2017-11-24 | 中国检验检疫科学研究院 | The quick determination method of banned substance oestrone in a kind of spraying cosmetics |
| CN107389831B (en) * | 2017-09-26 | 2020-01-21 | 中国检验检疫科学研究院 | Method for rapidly detecting forbidden substance estrone in spray cosmetics |
| CN108831819A (en) * | 2018-04-20 | 2018-11-16 | 中国药科大学 | A kind of equipment and its application in ortho states-denaturation conversion ions source |
| CN110455972A (en) * | 2019-08-21 | 2019-11-15 | 哈尔滨阿斯顿仪器有限公司 | Analysis method associated with a kind of liquid chromatography mass and its use interface arrangement |
| CN110455972B (en) * | 2019-08-21 | 2022-01-14 | 哈尔滨阿斯顿仪器有限公司 | Liquid chromatography-mass spectrometry combined analysis method and interface device used by same |
| CN112885702A (en) * | 2021-04-12 | 2021-06-01 | 杭州安誉科技有限公司 | Sampling device of mass spectrometer |
| CN112885702B (en) * | 2021-04-12 | 2022-09-16 | 杭州安誉科技有限公司 | Sampling device of mass spectrometer |
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Application publication date: 20141029 |