CN101449355A - A sampling system for use with surface ionization spectroscopy - Google Patents
A sampling system for use with surface ionization spectroscopy Download PDFInfo
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- CN101449355A CN101449355A CNA2007800159745A CN200780015974A CN101449355A CN 101449355 A CN101449355 A CN 101449355A CN A2007800159745 A CNA2007800159745 A CN A2007800159745A CN 200780015974 A CN200780015974 A CN 200780015974A CN 101449355 A CN101449355 A CN 101449355A
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Abstract
In various embodiments of the invention, a device permits more efficient collection and transmission of ions produced by the action of a carrier gas containing metastable neutral excited-state species into a mass spectrometer. In one embodiment of the invention, the device incorporates the source for ionization in combination with a jet separator to efficiently remove excess carrier gas while permitting ions to be more efficiently transferred into the vacuum chamber of the mass spectrometer. In an embodiment of the invention, improved collection of ions produced by the carrier gas containing metastable neutral excited-state species at greater distances from between the position of the analyte and the position of the mass spectrometer are enabled.
Description
Technical field
The present invention relates to the collection of improved analyte ions and neutral molecule and transmission and be used for the more efficiently sampling undertaken by spectral measurement system.
Background technology
Invent out gaseous diffusion separator by Watson and Biemann and it is made improvements since the sixties in 20th century, can be effectively remove carrier gas from discharging in the gas molecule of the end of gas-chromatography (GC) post by the jet separator of Ryhage invention.Normally used gas comprises helium, hydrogen and nitrogen in the GC experiment.In whole examples of Miao Shuing, the particle of process jet separator exists as neutral atom and molecule in the literature.The molecule that leaves jet separator directly enter mass spectrometer (MS, massspectrometer), their ionization in ionization source here, operation is carried out under the condition of high vacuum degree state.The major function of the jet separator that uses among the GC/MS is that the neutral molecule of removing carrier gas while enriching analyte molecule enters mass spectrometric flowing.
In contrast to the GC device, atmospheric pressure ionization (API) device generates ion outside the mass spectrometer high vacuum system.Such is the fact, and most of API source MS device generates ion existing under the situation of electric field.Electric field is the ion in order to be generated in the inlet guiding ionization process of MS also.In electron spray ionisation (DESI) and other desorption ionization techniques, the generation of the ion under atmospheric pressure can be finished with sample under earth potential.For example, not having the parts of system can be applied in electromotive force usually enters the mouth towards mass spectrometer with focused ion optionally.In these situations, the inlet that ion transfer enters MS depends on the effect that the attraction ion enters the vacuum of MS inlet to a great extent.The MS source comprises a plurality of pumping stages of being separated by little aperture usually, the aperture is used to reduce make the ion of being paid close attention to march to the acceptable level that is used for quality analysis along the gas pressure in path, and operate as the ion focusing lens when electromotive force is applied to they surperficial in these apertures.
Allow molecule to develop by Cody et al recently from the desorption ionization source of the ionization of the direct ionization of surface desorption and ionization, liquid and gaseous molecular.This method has been utilized low quality atom or the molecule that comprises helium, nitrogen and other gas that can exist to long-time metastable state as carrier gas.These carrier gas particles exist with high nargin in the atmosphere that ionization takes place.
Although this ionization method for the rapid analysis of analyte sample provides some advantages, adopts this technology to be used for several samples and the kinds of experiments environment still keeps to some extent.For example, its help by improve the relevant ion of sample from they generation point extremely the efficiency of transmission of mass spectrometric mass spectrometer increase the sensitiveness of desorption ionization techniques.And, can be with hope in the desorption ionization source at distance mass spectrometer distance guiding analyte sample place significantly far away.In addition, if can utilize this technology, desorption ionization will have more influence for the traditional high vacuum ionization source that is run in most of mass spectrometer.
Summary of the invention
Embodiments of the invention comprise and are used to collect and transmit the analyte ions that is formed in the carrier gas apparatus and method to mass spectrometric inlet.In an embodiment of the present invention, carrier gas comprises: metastable neutral excited state particle; Charged and neutral molecule.In other embodiments of the invention, jet separator enters mass spectrometric high vacuum region in order to more effectively to transmit ion and molecule.In contrast to previous technology, previous technology has only been described and has been used jet separator to be used for the transmission that the enriching molecule enters MS; In an embodiment of the present invention, jet separator is in order to the optionally transmission of enriching ion by these ions of separation from carrier gas.Use jet separator, can carry out the sensitiveness that the significantly sampling of bigger carrier gas volume increases desorption ionization techniques by allowing time per unit, wherein carrier gas is uniform in the nargin of the ion of the per unit volume of its porch.And, use jet separator to allow at distance mass spectrometer distance significantly far away collection analysis thing more effectively as first vacuum zone of pumping desorption ionization source.In addition, adopt jet separator, desorption ionization source can be coupled to traditional high vacuum ionization source mass spectrometer.
When externally ion source becomes known for MS, transmit enough ions to the problem of MS and can cause the sensitiveness that reduces usually.Make problem worse at atmospheric pressure or near the external ionization source of operating under the atmospheric pressure, because MS typically operates under high vacuum degree.Jet separator is before in order to separate the analyte of being paid close attention to from carrier gas before entering MS at neutral analyte molecule.But jet separator uses with external ion source did not behave good in order to introduce the principle that ion enters MS in the past.Thus in one embodiment of the invention, gas separator comprises external ion source and jet separator.In an embodiment, such separator is used among the MS.In various embodiments of the present invention, gas separator can be any device that can enter the little neutral atom of extraction the charged particle of high vacuum region from transmission.In optional embodiment of the present invention, electric field can be applied to the surface of gas separator to improve the transmission that ion enters MS.
In various embodiments of the present invention, gas separator comprises: ion source; The a plurality of pipes that between pipe and vacuum tube, have the gap.Typically, gas separator comprises inlet tube and outlet, and wherein the near-end of inlet tube approaches external ionization source and far-end most apart from external ionization source farthest.Vacuum can be applied to the exit of at least one distal tube and can be applied to one or more gap locations between a plurality of pipes.In a plurality of embodiment, the silk screen screen can be closed the gap between a plurality of pipes.
The near-end of inlet tube generally apart from external ionization source about 10
-3The lower limit of m and about 10
-1Z-wheelbase between the upper limit of m from.The near-end and/or the far-end of the heater that is used to heat, the near-end of inlet tube and/or far-end and outlet can be used in gas separator.In optional embodiment of the present invention, can apply one or more capacitive characters (capacitive) surface of one or more electromotive forces to one or more inlets and/or the outlet.
Description of drawings
Various embodiments of the present invention will be described in detail based on following chart, wherein:
Fig. 1 is the sketch that the jet separator of prior art is used for traditional GC/MS device;
Fig. 2 is the schematic diagram of jet separator that has the prior art of traditional GC/MS high vacuum ionization source;
Fig. 3 is the schematic diagram of the typical API-MS of prior art;
Fig. 4 (A) enters the schematic diagram that has based on the jet separator of the device of the MS of knockout API according to the conduct of one embodiment of the present of invention transmission ion;
Fig. 4 (B) is the schematic diagram of jet separator that enters the device of the MS that has capillary type API according to the conduct of one embodiment of the present of invention transmission ion;
Fig. 4 (C) is the schematic diagram according to the jet separator that is integrated in traditional API-MS of one embodiment of the present of invention;
Fig. 5 is the schematic diagram according to the jet separator that is equipped with inlet tube and outlet of one embodiment of the present of invention;
Fig. 6 shows the schematic diagram of embodiments of the invention, and wherein jet separator is connected in sampling pipe;
Fig. 7 shows the schematic diagram that has the jet separator of grid in its porch according to embodiments of the invention;
Fig. 8 shows the schematic diagram that has the jet separator of grid according to the porch at sampling pipe of embodiments of the invention;
Fig. 9 shows the schematic diagram that has the jet separator of grid between inlet tube and outlet according to embodiments of the invention;
Figure 10 is the schematic diagram according to the jet separator of one embodiment of the present of invention, and this jet separator has the sample that sampling pipe and grid and the position between grid and jet separator are connected to sampling pipe;
Figure 11 shows the schematic diagram according to the diffusion separator of one embodiment of the present of invention;
Figure 12 has shown according to the merging of one embodiment of the present of invention the schematic diagram of the diffused separator of the metal wire mesh cage that can be applied in electromotive force;
Figure 13 has shown according to the merging of one embodiment of the present of invention the schematic diagram of the diffused separator of the perforated cage that can be applied in electromotive force;
Figure 14 has shown according to the assembling of one embodiment of the present of invention the schematic diagram of the jet separator of inlet tube with pipe of comparing thicker diameter with Fig. 4 (C) and outlet;
Figure 15 has shown according to the assembling of one embodiment of the present of invention the schematic diagram of the jet separator of inlet tube with pipe of comparing thicker diameter with Fig. 4 (C) and outlet;
Figure 16 has shown according to the assembling of one embodiment of the present of invention the schematic diagram of the jet separator of inlet tube with different length and outlet;
Figure 17 shows the schematic diagram according to the jet separator of one embodiment of the present of invention, and wherein the outlet of gas separator crosses more than a knockout;
Figure 18 (i)-(vi) be the mass spectrogram trace of function of the electromotive force on conduct from the ion of the relative nargin of the ionized region sampling surface that is applied to the inlet tube of gas separator and outlet;
Figure 19 (i)-(vi) be total chromatography of ions figure trace that conduct from the ion of the relative nargin of ionized region sampling is applied to the function of relative vacuum degree between the inlet tube of gas separator and the outlet; With
Figure 20 shows from using vacuum (i) and use vacuum to gas separator (ii) the resulting mass spectrogram of ionization of ambient air before to gas separator.
Embodiment
The term jet separator will be with referring to prior art.The term gas separator will can be in order to not refer to prior art.The term jet separator also can be in order to refer to charged particle and/or neutral molecule separator.The term gas separator will be in order to refer to electrically charged and/or neutral molecule separator.Term ' inlet tube ' will be in order to refer to the low vacuum, side of gas separator.Term ' outlet ' will be in order to refer to the high vacuum, side of gas separator.Term ' outlet ' will be in order to refer to the high vacuum, side of gas separator.
Nearest development as on-radiation atmospheric pressure ionization (MI) method of the ionization that is used for analyte described in No. the 6th, 949,741, the United States Patent (USP) sequence number allows directly analyzing in real time for analyte
The United States Patent (USP) sequence number is referenced as ' 741 patent for the 6th, 949, No. 741 hereinafter and clearly incorporates its full content here according to the scope of authority into.' 741 patents announced use comprise metastable neutral excited state particle be used for to from surface, liquid and the device of desorption ionization of molecule.The device of describing in the patent of ' 741 has utilized a large amount of carrier gas that typically is helium and/or nitrogen, though can use other can produce the inert gas of metastable neutral excited state particle.
Invented gaseous diffusion separator by Watson and Biemann and made improvements since the sixties in 20th century, jet separator (United States Patent (USP) sequence number 3 by the Ryhage invention, 633,027, clearly incorporate its full content here into according to the scope of authority) can be effectively remove carrier gas from the molecular flow of gas of the end of discharging gas-chromatography (GC) post.Jet separator device makes the business development of gas chromatography/mass spectrometry (GC/MS) system become possibility.In GC/MS, the air-flow that passes heavy caliber GC post is 20 to 30 milliliters of per minutes.The widely-used of these equipment starts from the seventies in 20th century, and up to the eighties in 20th century, low discharge GC post equipment was used as industrial standard at that time, did not need jet separator thus.Normally used gas comprises in the GC experiment: helium; Hydrogen; And nitrogen.The molecule of discharging from jet separator directly enters mass spectrometer, and they are by ionization source ionization in mass spectrometer, and it is operated under the state of high vacuum.Atmospheric vacuum degree is 760 holder ears (torr).Usually, ' approx ' comprises from being lower than 10 in this pressure limit
1Atmospheric pressure (7.6 x 10
3Torr) to 10
-1Atmospheric pressure (7.6 x10
1Torr) pressure limit.Be lower than 10
-3The vacuum of torr will constitute condition of high vacuum degree.Usually, this pressure limit ' approx ' comprises from 5 x 10
-3Torr to 5 x 10
-6The pressure limit of torr.Be lower than 10
-6The vacuum of torr will constitute the very high vacuum degree.Usually, this pressure limit ' approx ' comprises from being lower than 5 x 10
-6Torr to 5 x 10
-9The pressure limit of torr.Below, phrase ' condition of high vacuum degree ' comprises condition of high vacuum degree and very high vacuum degree.The major function of jet separator is to remove carrier gas to increase the neutral molecule that comprises analyte molecule simultaneously and enter mass spectrometric efficiency of transmission.In jet separator, introduce improvement by Ryhage after, Dawes et al. is in United States Patent (USP) sequence number the 5th, 137, describing molecular separator in 553 in detail reaches in United States Patent (USP) sequence number the 4th, 654, describe variable molecular separator in 052 in detail, clearly incorporate their full content here according to the scope of authority into.
In contrast to GC/MS equipment, API-MS provides in order to generate the device of ion outside mass spectrometer condition of high vacuum degree system.Such is the fact, and most API source device produces ion in the situation that electric field exists.Electric field is also in order to the inlet of the ion that forms during ionization process of guiding towards mass spectrometer (MS).Electric field is typically by arranging that electromotive force is on the pin or arrange that solution that electromotive force is comprising analyte molecule passes on the pipe that wherein flows and set up.In these API-MS equipment, high vacuum inlet is by the design of set access arrangement, and this design is feasible to reduce air-flow and focused ion enters mass spectrometric high vacuum chamber easily.Focused ion enters the mass spectrometric electromotive force synergy that acts on the electromotive force that is applied to inlet and be applied to the pin that ionization takes place and is accomplished when ion enters mass spectrometer optionally to transmit, and most of neutral molecule and atmospheric gases diffuse are left and entered into ambient air simultaneously.
Develop and in the patent of ' 741, describe by Cody et al.
Ionization source is the method that is used for the desorb of the ion under the atmospheric pressure.
The low quality atom or the molecule that comprise that helium, nitrogen and other can metastable existence as carrier gas have been utilized.These carrier gas particles are taking place
Exist with high nargin in the atmosphere of ionization.
Fig. 1 shows the jet separator 120 of prior art, and it includes oral-lateral 130 and outlet side 140.Being dispersed in analyte a fluid stream in the carrier gas molecules a fluid stream advances and passes internal diameter 112, the entrance side of 114 place's discharging jet separators 110 in the aperture.Analyte molecule passes gap 105 and is inhaled into and passes the internal diameter 122 that aperture 124 enters the outlet side of jet separator 117.Lower relative pressure institute pumping is compared in zone 155 with outside chamber 162 in the zone 160 that is formed by vacuum 180 in case the lighter mass carrier gases molecule is discharged arrival end 114.
The ion that Fig. 2 shows prior art directly transfers to mass spectrometric source region 240, and wherein the zone around traditional ionization source 252 is under the condition of high vacuum degree.Typically, neutral molecule and gas are discharged 230 chromatographic columns and are entered conventional jet separator 220, gas is able to optionally to remove simultaneously in vacuum 280 times heavy molecules enters source 252 herein, and they are in source 252 places ionization and subsequently because the effect of electric field in the source 252 and being pushed is passed a series of lens 254 is used for being used to analyze prefocusing entering mass spectrometer 248.
Fig. 3 show prior art be used for directly transmit the device that ion enters the mass spectrometer vacuum inlet of atmospheric pressure ionization mass spectrometer (API-MS) equipment.The ionization source that is used for API-MS typically comprises the pin that has applied electromotive force 322 or manages 326.Pin 326 aligns with the aperture 328 of a series of one or more knockouts 332,334, and aperture 328 operation when electromotive force 336,338 is applied to knockout 332,334 surperficial enters the mass spectrometer 342,344 of one or more alignment to allow the transmission ion to ion detector 352 with the guiding ion as the ion focusing lens.The aperture provides the border in addition between the pumping stage, it is in order to reduce being used for mass spectrometer 348 and ion detector 352 with suitably effect along the air pressure in the path that relevant ions is advanced to acceptable level.
Conventional jet separator in the GC/MS experiment uses vacuum to isolate analyte molecule from carrier gas.
In the experiment, analyte ions is present in carrier gas.Jet separator typically design with optionally from analyte molecule, remove carrier gas at gas the same as or similar to
The typical carrier gas of using in the experiment.
Experiment has available vacuum.Unpredictably, find that jet separator can do in order to not only separating the analyte molecule in the carrier gas air-flow, but also be charging positive charge of the analyte molecule in the carrier gas air-flow or negative electrical charge.
In an embodiment of the present invention, the ion that forms by the desorption ionization in the air-flow of carrier gas is directed toward the target that comprises analyte molecule.In an embodiment of the present invention, target can comprise the object of one or more following kinds: solid; Liquid; And gas.Fig. 4 (A) shows embodiments of the invention, wherein the analyte ions that generates from target passes jet separator 420, enter aperture 428, and a series of one or more knockouts 432,434 that focus on electromotive force 436,438 that applied, enter mass spectrometer 448, and have influence on ion detector 452.
In an embodiment of the present invention, the analyte ions that illustrates of Fig. 4 (B) is formed on the near-end of the entrance side of jet separator 430.In an embodiment of the present invention, ion will be inhaled into jet separator owing to vacuum 480.In an embodiment of the present invention, equipment can be operated jet separator entrance side 430 under atmospheric pressure.In additional embodiments of the present invention, entrance side 430 can be operated under elevated pressure.In optional embodiment of the present invention, entrance side 430 can be operated under the pressure that reduces.
In one embodiment of the invention,
The source produces the helium of a large amount of volumes, the gas molecule with equal volume and analyte of interest ion.Difference between the quality of carrier gas quality and analyte of interest can be one to the several number magnitude.Thus lighter mass carrier gases can be fully by jet separator based on the difference of relative momentum and from the lightweight analyte ions, separate.In additional embodiments of the present invention, jet separator is the heavy ion flow in the enriching atmosphere preferably, removes simultaneously to have formed with lightweight solution molecule and the solution relevant ions of influence from the ionization of the sample on surface.In additional embodiments of the present invention, jet separator is the heavy ion flow in the enriching atmosphere preferably, removes simultaneously to have formed with influence to come from lightweight solution molecule and solution relevant ions in order to the ionization of the sample of the initial source that generates reagent ion.In one embodiment of the invention, following being selected from comprises methyl alcohol, dimethyl sulfoxide (DMSO), water (H
2O) one or more carrier gas in the group of solvent molecule are used for
And isolate with jet separator.
In an embodiment of the present invention, incorporate the gas that comprises ion that jet separator makes it possible to collect large volume into and be used to transmit these ions to mass spectrometric high vacuum chamber.As shown in Fig. 4 (B), in an embodiment of the present invention, the gas of large volume enters the inlet 430 of jet (gas) separator and exports gap 405 between 440 sides, and heavy ion and unionized molecule pass from entering the mouth to the gap of outlet side with the efficient that is higher than light gas molecule and atom.In an embodiment of the present invention, jet (gas) separator comprises two or more coaxial substantially pipes that have internal diameter 412 and 422 410 and 417.In an embodiment of the present invention, pipe can have the outside diameter that reduces in its end 414 and 424 separately.Jet (gas) separator is positioned at regional 462 places, because the effect of vacuum 480, and the pressure 460 times that it is compared with exterior lateral area 455 and is in reduction.In one embodiment of the invention, the jet separator inlet that acts on traditional non-API-MS equipment.In additional embodiments of the present invention, the jet separator inlet that acts on API-MS equipment.
In an embodiment of the present invention, mass spectrometer source can be operated without ionization device.In optional embodiment of the present invention, the ionization device that mass spectrometer has is including, but not limited to adopting positive ionization or negative electricity electron bombard, chemi-ionization and the DCI desorption chemical ionization from pattern.
Fig. 4 (C) shows embodiments of the invention, wherein the ionization source among Fig. 3 has been modified and has made the vacuum stages 450 of equipment comprise that the outlet side inner orifice mouth 422 of using jet (gas) separator 420 replaces its knockout 442 type apertures like this, in order to be formed up to the inlet in the first medium vacuum district 450, region of no pressure 450 is separated with the high vacuum region of the mass spectrometer 460 that comprises mass spectrometer with knockout 444 by other aperture 432.In an embodiment of the present invention, the entrance side 430 of jet separator can be under atmospheric pressure and vacuum be applied to 480.
Figure 17 shows embodiments of the invention, wherein the high vacuum region that makes the outlet 1740 of gas separator directly be coupled to mass spectrometer 1760 has been revised in the API district of the equipment shown in Fig. 3, and bypass two knockouts 1742,1744 make the gas that enters gas separator and molecule bear vacuum from gas separator vacuum pump 1780 and spectrometer system 1760.
Gas separator can comprise the jet separator that is combined in external ion source.Gas separator has advantage, and it can increase from external ion source transmission and enters mass spectrometric amount of ions, and can not have influence on mass spectrometric performance with worsening.By increasing, can transmit more ion in order to enter the diameter of mass spectrometric pipe from external ion source transmission ion.Enter pipe to transmit ion by merging gas separator, can minimize interference (perhaps other situation is undisturbed) for mass spectrometric high vacuum region to mass spectrometer.Gas separator can act in order to detach just to be present in from external ion source and transfer to neutral atom and micromolecule the mass spectrometric ion flow.
Example 1-applies electromotive force to jet separator
Fig. 5 shows embodiments of the invention, and wherein the entrance side of jet separator and outlet side can be operated with earth potential, positive potential or negative potential.In an embodiment of the present invention, the one or more pipes that constitute jet separator can optionally charge, and jet separator can design and have inlet 530 and outlet 540 to allow evenly to apply electromotive force 522 and 524 and apply uniform field in the gap 505 under the vacuum 580 thus.In an embodiment of the present invention, the electromotive force that is applied to the metal surface of entrance and exit pipe can be that identical electromotive force is to provide maximized ion transfer.In optional embodiment of the present invention, the electromotive force that is applied to the metal surface of inlet 522 and egress line 524 can be different from mutually maximized ion transfer to be provided.In optional embodiment of the present invention, gap 505 can increase length so that maximized ion transfer to be provided.In optional embodiment of the present invention, inlet 530 and outlet 540 diameter can have the internal diameter 512,522 that differs from one another so that maximized ion transfer to be provided.
Figure 14 shows embodiments of the invention, and wherein inlet tube 1430 and outlet 1440 have the big diameter of the internal diameter 1412,1422 of relative each pipe.In additional embodiments of the present invention, Figure 15, the internal diameter 1512 of 1530 pipes that enter the mouth can be different with the internal diameter 1522 of outlet 1540 pipes.In additional embodiments of the present invention, Figure 16, inlet 1630 pipes can differently be used for analyzing with the more efficiently collection that gas and molecule are provided with the length that exports 1640 pipes.
In example 1, jet separator can replace by enough gas separators.
Example 2-handles high carrier gas volume
Fig. 6 shows embodiments of the invention with jet separator entrance extension sampling pipe 690.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 has improved from longer distance suction and has comprised that the carrier gas of metastable neutral excited state particle, gas molecule, ion that the molecule that sample is relevant is relevant with sample enters mass spectrometric ability.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 is linear.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 is crooked.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 is Yi Qu.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 is heated.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 is operated at ambient temperature.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 is metal, easy bent metal, pottery, plastics, easy bent plastics or their combination.In an embodiment of the present invention, the length of jet separator entrance extension sampling pipe can be in 10 millimeters to 10 meters or bigger scope.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 can be made of the non-knitting material.In an embodiment of the present invention, jet separator entrance extension sampling pipe 690 can by a kind of or what time knit materials constitute.In the prior art, the capillary transfer line with limited diameter and short length has been used to realize by the compound action of electromotive force and vacuum that the ion that generates during the directly transfer surface ionization enters mass spectrometer.In an embodiment of the present invention, the jet separator that has narrow entrance side internal diameter 612 is used to limit air-flow and enters mass spectrometer 622, thus allow jet separator 620 best enriching be used to transfer to mass spectrometric ion.In an embodiment of the present invention, the jet separator that has wide internal diameter 612 is used in the air-flow that enters jet separator 620 on the entrance side with raising, no matter and whether it act as jet separator ideally, this is to pass jet separator entrance extension sampling pipe 690 owing to can accept to be lower than the best enriching that is used to transfer to mass spectrometric ion with the air-flow that improvement comprises ion.In an embodiment of the present invention, jet separator entrance extension sampling pipe inlet internal diameter 692 can differently transmit the efficient of crossing certain distance in order to improve ion with outlet internal diameter 694 in carrier gas and atmosphere.
In example 2, jet separator can be replaced by enough gas separators.
The wire netting of example 3-jet separator strengthens
Fig. 7 shows embodiments of the invention, is wherein improved by the grid that interpolation is looped around the ionized region of desorption ionization experiment via the collection for the ion that is used for sampling that jet separator carries out by mass spectrometer.In an embodiment of the present invention, grid is made by the cylinder mould 70 of an end opening.In an embodiment of the present invention, cylinder mould is a cylindrical shape.In an embodiment of the present invention, style is made of metal.In an embodiment of the present invention, cylinder mould is a silk.In an embodiment of the present invention, metal wire mesh cage can be operated under earth potential.In an embodiment of the present invention, metal wire mesh cage can be in positive potential 772 times operation, as it is desired to be used to suppress the relevant ions that generates from sample.In an embodiment of the present invention, metal wire mesh cage can be in negative potential 772 times operation, as it is desired to be used to suppress the relevant ions that generates from sample.In an embodiment of the present invention, metal wire mesh cage is contacted with the inlet tube of jet separator and in the outlet one or two.In an embodiment of the present invention, metal wire mesh cage is not contacted with the inlet tube or the outlet of jet separator.In an embodiment of the present invention, the cylinder mould 770 of silk surrounds and extends the efficient that is collected in the ion that the porch of jet separator 720 generates in order to raising from the end of jet separator inlet 730.In an embodiment of the present invention, cylinder mould can 705 be supported fully to build bridge in the gap by overlapping inlet tube or outlet, and the physics of perhaps installing as pipe extends.
Fig. 8 shows embodiments of the invention, wherein removes from jet separator 820 around the grid of the ionized region in the desorption ionization experiment.In an embodiment of the present invention, grid is made by the cylinder mould 870 of open end.In an embodiment of the present invention, cylinder mould is a cylindrical shape.In an embodiment of the present invention, grid is made of metal.In an embodiment of the present invention, cylinder mould is a silk.In an embodiment of the present invention, metal wire mesh cage can be operated under earth potential.In an embodiment of the present invention, metal wire mesh cage can be in positive potential 872 times operation, as it is desired to be used to suppress the relevant ions that generates from sample.In an embodiment of the present invention, metal wire mesh cage can be in negative potential 872 times operation, as it is desired to be used to suppress the relevant ions that generates from sample.In an embodiment of the present invention, metal wire mesh cage is contacted with the inlet tube of jet separator and in the outlet one or two.In an embodiment of the present invention, metal wire mesh cage is not contacted with the inlet tube or the outlet of jet separator.In an embodiment of the present invention, the cylinder mould of silk surrounds and extends the efficient that is collected in the ion that the position of the inlet that is away from jet separator 820 generates in order to raising from the end of jet separator entrance extension sampling pipe 890.In an embodiment of the present invention, cylinder mould can be installed in the position between the inlet 894 of jet separator entrance extension sampling pipe 892 and jet separator 820.In an embodiment of the present invention, wire mesh cage acts is to strengthen the transmission of ion between inlet tube 812 and outlet 822.In an embodiment of the present invention, cylinder mould can 805 be supported fully to build bridge in the gap by overlapping inlet tube or outlet, and the physics of perhaps installing as pipe extends.
In example 3, jet separator can be substituted by gas separator
Example 4-applied field is to wire netting
Fig. 9 shows embodiments of the invention, wherein the entrance side 930 of jet separator 920 and and outlet side 940 between the gap stretched by grid 970.In an embodiment of the present invention, electromotive force 932 and 942 is applied to the entrance side 930 and the outlet side 940 of jet separator 920 respectively.In an embodiment of the present invention, grid is made by the cylinder mould 970 of open end, to allow gas atom and neutral molecule by the low-voltage vacuum district 980 to jet separator 920.In an embodiment of the present invention, cylinder mould is a cylindrical shape.In an embodiment of the present invention, grid is made of metal.In an embodiment of the present invention, cylinder mould is a silk.In an embodiment of the present invention, metal wire mesh cage can be in 972 times operations of earth potential.In an embodiment of the present invention, metal wire mesh cage can be in positive potential 972 times operation, as it is desired to be used to suppress the relevant ions that generates from sample.In an embodiment of the present invention, metal wire mesh cage can be in negative potential 972 times operation, as it is desired to be used to suppress the relevant ions that generates from sample.In an embodiment of the present invention, metal wire mesh cage electrically and or physically be contacted with the inlet tube of jet separator and in the outlet one or two.In an embodiment of the present invention, metal wire mesh cage is not contacted with the inlet tube or the outlet of jet separator electrically and/or physically.In an embodiment of the present invention, the electric field in the metal wire mesh cage is uniform.In an embodiment of the present invention, the electric field in the metal wire mesh cage is heterogeneous.In an embodiment of the present invention, magnetic field is created in the cylinder mould.Be created in the interior long time of volume that the interior ion of cylinder mould is limited in cylinder mould, improve electromotive force thus and be used for collecting their gas at certain volume, gas is inhaled into the inlet of jet separator.In optional embodiment of the present invention, metal wire mesh cage did not stretch the entrance side 930 of jet separator 920 and the gap between the outlet side 940.
In example 4, jet separator can be substituted by gas separator
The application of example 5-ion guide
In additional embodiments of the present invention, ion guide stretched the entrance side of jet separator and the gap between the outlet side.In an embodiment of the present invention, direct voltage is applied to ion guide.In additional embodiments of the present invention, radio-frequency voltage is applied to ion guide.
In example 5, jet separator can be substituted by gas separator.In an embodiment of the present invention, gas separator also comprises ion guide.The advantage of ion guide be ion along the guiding length transmit effectively be both atom and neutral molecule is unaffected and thus vacuum will trend towards peeling off neutral molecule dramatically, avoid it to enter the outlet side of gas separator.Ion guide has increased the transmission of ion from the inlet tube of gas separator to outlet thus.
Example 6-is by the vaporization of the molecule of heating
In an embodiment of the present invention, collecting molecule, to be used to transfer to ionized region be that the zone of the end by making the inlet suction pipe is comprised thermolamp, flame, polytype laser, finishes by thermal source and other effect that can execute the high temperature source of the thermal source that is heated to the surface of using circuit to activate.In an embodiment of the present invention, the effect of the vacuum that is provided by jet separator and the sample molecule ionization by the effect of desorption ionization source subsequently of collecting comprise the carrier gas, air molecule of metastable neutral excited state particle, the molecule ion relevant with sample that sample is relevant mixes along transfer tube simultaneously.
In example 6, jet separator can be substituted by gas separator.
The vaporization of the molecule in the example 7-closed system
In an embodiment of the present invention, the molecule of volatilization is dispersed in the atmosphere of sample in even, non-focusing mode.The gas a fluid stream enters sampling pipe in order to force the gas that comprises vaporized molecules to pass outlet, exists to comprise by desorption ionization source in sampling pipe to generate and be sucked metastable neutral excited state particle towards the inlet of jet separator.The interaction of vaporized molecules and desorption ionization carrier gas causes ionization and the subsequently transmission inlet that enter jet separator of these molecules in sampling pipe to be used for enriching when they transmission enter mass spectrometer.
In example 7, jet separator can be substituted by gas separator.
The vaporization of the molecule in the example 8-closed system
Figure 10 shows embodiments of the invention, and wherein sample is enclosed in the chamber 1092, and the volatilization molecule avoids disperseing in chamber 1092 in the atmosphere of volume of inlet chamber.The sample room can be fully around sample or constitute by this way and make it be placed on such as time on the object of plane surface to form enclosure.Sample can be under the ambient temperature, bears to comprise thermolamp, flame, polytype laser, the effect by using thermal source that circuit activates and other high temperature source that can execute the thermal source that is heated to the surface or be frozen in the situation of the sample of highly volatile.Vaporized molecules or by they effect or can pass pipe 1098 and discharge and to leave chamber 1092 and pass pipe 1094 inlet chambers and discharge owing to the air-flow that is derived from device 1096 forces to pass pipe 1098, a bit entering the volume of transfer tube 1090 in place along the source 1070 of transfer tube 1090 and between the jet separator 1020 certain.Pipe 1090 is attached to source 1070, and source 1070 produces the carrier gas that comprises metastable neutral excited state particle, carrier gas flow in its end attached transfer tube 1090.The sample molecule of the volatilization in the sampling pipe 1090 causes the ionization of sample molecule along the volume of sampling pipe with the interaction that comprises metastable neutral excited state particle.Be formed on the inlet 1012 that ion in 1090 the volume enters jet separator and be used for enriching when they transmission enter mass spectrometer.
In optional structure, Figure 11, we have imagined the use of diffused gas separator 1120.In this device, the inlet tube 1130 with inside diameter-variable is attached to porous glass tube 1183, and outlet 1140 is attached to the length that porous glass tube 1183 passes gas separator with the air-flow that allows to comprise ion.Porous glass tube is surrounded by the vacuum chamber 1162 that is connected to vacuum pump 1180.Gas and ion pass inlet 1130 and enter gas separator and advance towards mass spectrometer.When the gas that comprises sample passed through porous region, less gas molecule and atom penetrated into low vacuum district 1162 owing to spreading to be removed.
In optional structure, Figure 12, the wire netting cylinder 1283 that can apply electromotive force 1224 is positioned in the volume of antipriming pipe so that can keep ion by the electromotive force that keeps equating around ion when the gas separator in ion is advanced the volume that passes pipe, allow neutral carrier gas to diffuse into pumping area 1262 simultaneously.
In optional embodiment of the present invention, Figure 13, porous glass tube, plastics sieve, glass, workable glass and pottery and porous ceramic, wire netting, glass-lined metal tube, metal coating fused silica, metal coating workable glass and the electromotive force 1324 that can apply metal film and coating can be applied to metal coating pottery 1343 on its inner diameter surface and be used to keep these ions when ions diffusion is passed antipriming pipe and entered pumping area 1362 when detaching neutral particle.
In example 8, jet separator can be substituted by gas separator.
The transmission that example 9-ion passes gas separator
Using the electromotive force that equates must be to the inlet tube of gas separator and the results are shown among Figure 18 of outlet, and the mass spectrogram of wherein protonated quinine molecular ion is drawn out as the function of the electromotive force of inner surface that is applied to the gas separations organ pipe and outer surface.The 1ng quinine sample that is inserted in the glass melting point tube is introduced in DART
Before and ionization under atmospheric pressure.The electromotive force that is applied to inlet tube and outlet raises and measures the nargin of molecule in time.The voltage that is used for every kind of sample that is applied to pipe indicates at each serial peak, and wherein the 0V voltage that applied of (i) expression is (ii) represented 50V, (iii) represents 200V, (iv) represents 300V, (v) represents 400V and (vi) represents 500V.This has shown unexpected result, and (high relatively) electromotive force that promptly is applied to gas separator can increase the number that enters the ion in spectrometer analysis device district from the atmospheric ionization sources transmission.Experiment also shows, reduces to some extent with respect to the relative nargin at higher protonated molecule in 100 to 400V potential range in lower relative nargin from the protonated molecule in 0 to 50V the potential range.
Placement two pipes coaxially to each other cause these overall ion transfer to enter mass spectrometer and are used for analysis between atmospheric pressure ionization district and mass spectrometric high vacuum inlet.In experiment, we understand two different vacuum sources of existence in gas separator.At the carrier gas neutral atom and the branch period of the day from 11 p.m. to 1 a.m, charged atom and molecule and metastable atom and molecule are discharged inlet tube, and they can or be drawn into outlet and transfer to mass spectrometer or be drawn into the low-pressure area of separator and discharge and enter vacuum pump.The pressure reduction combination in each district is to empty inlet tube.Being plotted in experimental result among Figure 19 shows the vacuum that increases in the zone that is applied between inlet tube and the outlet and enters mass spectrometric influence for ion transfer.Valve is used to regulate the vacuum degree that is applied to gas separator.In Figure 19, the TIC trace in regional (i) changes corresponding to 0 of valve, and (ii) change corresponding to 1 of valve in the zone, and (iii) corresponding to 2 commentaries on classics of valve, (iv) change corresponding to 3 of valve in the zone in the zone, and (v) change corresponding to 4 of valve and regional (vi) the commentaries on classics corresponding to 5 of valve in the zone.Experiment has shown unexpected result, and the vacuum that promptly is applied to gas separator can increase the number that transfers to the ion in spectrometer analysis district from atmospheric ionization sources.The result also illustrates, and along with valve is opened and the vacuum degree increase, ion transfer enters mass spectrometer increases (seeing that the zone (ii), (iii) and (iv)).But further the opening of valve can cause transmission to reduce, as in the zone (v) and (vi).Data show also that along with vacuum degree further increases its influence makes more sample ions turn to and leaves mass spectrometer.Viewed valve is as the function of the inlet tube of gas separator and the distance between the outlet and change.For particular geometric shapes, can regulate vacuum degree and enter mass spectrometric best transmission with the outlet that ion passes gas separator.
The source makes the ionization of material can be away from mass spectrometric API inlet to carry out, but in the situation that for example distance increases, and the nargin of the ion that obtains from ambient air is significant with respect to the nargin of the ion that obtains from associated sample.By extending
The operating space, source leaves immediate mass spectrometric API-entrance area and makes it possible to use the long inlet tube remote zone that is used for sampling to be present in the effect of the molecule of ambient air with reduction, as shown in Figure 20, wherein show and have (i) and do not have the (ii) comparison of the mass spectrogram that is generated of gas separator function.Figure 20 (ii) in, the ion that obtains from the standard laboratory air occupies critical positions mass spectrogram, in case and vacuum (Figure 20 (i)) is applied to the zone between inlet tube and the outlet with the vacuum open mode, these ions exist with the level that reduces.Experiment has shown unexpected result, promptly increase the gas of being sampled the volume of the opening part of inlet tube can increase from the atmospheric ionization sources transmission enter the spectrometer analysis district ion number and increase the overall sensitivity of analyzing thus.
Advantage
The advantage of gas separator can be the volume that increases the gas of the high vacuum region of being sampled and can introduce MS.Because atom and little central element can be peeled off by the ion from gas separator, condition of high vacuum degree is unaffected, increases the sensitiveness of analyzing simultaneously.
Use
Gas separator can be combined in multiple atmospheric ionization sources, and it comprises:
DESI; With the atmospheric pressure MALDI that is used among the MS.In each example, by increasing the number of the ion of introducing MS, the sensitiveness of technology can increase.Gas separator also can be used in some other depend on to be transmitted in and be similar to the device that ion to the high vacuum region that forms under atmospheric pressure or the low vacuum is used for detecting.Gas separator also can be used in the Surface Science spectroscopic apparatus, and it is preferably operated under ultra high vacuum, and by handle forming ion, introducing gas in processing will be harmful in ultra high vacuum, and therefore to remove gas will be favourable.Gas separator also can be used in other suitable detector, and it comprises: Raman spectrometer (raman spectrometer); Electromagnetic absorption spectrometer (electromagneticabsorption spectrometer); Electromagnetic emission spectrometer (electromagnetic emissionspectrometer); Detect spectrometer (surface detection spectrometer) with the surface.The analyte detection kind that can be used in gas separator is not limited to particular types, and comprise personnel to imagine with ordinary skill and invariably when the experiment those detectors.
Metal wire mesh cage comprises antipriming pipe, and its mesopore can machine work or is porous ceramic etc. alternatively.As used herein, if not in addition explanation, term "based" represent " to small part based on ".
Capacitive surface is can charge with having the surface of electromotive force.If the electromotive force that is applied to the surface keeps the typical duration of experiment, can be charged in the surface has electromotive force, and wherein the electromotive force of surface is greater than 50% of the electromotive force that is applied to the surface.
The one exemplary embodiment of method of the present invention, system and parts here is described.As mentioning in other place, these one exemplary embodiment have been described only is used for illustrative purpose, and is not restrictive.Other embodiment is fine and is included by the present invention.Such embodiment is cheer and bright based on the technology that is comprised here for the technical staff in the association area.For example, it is contemplated that although described actual shape in above-described a plurality of drawings and Examples, the male-tapered or non-taper and the external diameter that enter outlet that withdraw from inlet tube can be taper or non-taper.
Thus, range of the present invention and scope should not be limited to any exemplary embodiment recited above, and should be only according to claim and the definition of their equivalent text.
The application requires the priority of following application: U.S. Provisional Patent Application sequence number the 60/778th, No. 874, title is " sampling system (A Sampling System for Use withSurface Ionization Spectroscopy) that is used for surface ionization spectroscopy ", inventor: Brian D.Musselman, (the attorney's procuration's application case numbering: IONS-01000USO) of filing on March 3rd, 2006; With U.S. Provisional Patent Application sequence number the 11/580th, No. 323, title is " sampling system (ASampling System for Use with Surface Ionization Spectroscopy) that is used for surface ionization spectroscopy ", inventor: BrianD.Musselman, (the attorney's procuration's application case numbering: IONS-01000US1) of filing on October 13rd, 2006.
The full content of these applications here is incorporated herein by reference.
Claims (14)
1, a kind of gas separator, it comprises:
(a) external ion source, it generates analyte ions; With
(b) jet separator, wherein said ion enters this jet separator.
2, gas separator as claimed in claim 1 wherein, also comprises the capacitive surface on the described jet separator.
3, a kind of mass spectrometer, it comprises gas separator as claimed in claim 1.
4, a kind of gas separator, it comprises:
(a) external ion source;
(b) coaxial substantially a plurality of pipes, wherein, described a plurality of pipes are partitioned into and make have the gap between described a plurality of pipes; With
(c) region of no pressure, wherein, at least a portion of coaxial a plurality of pipes is arranged in described region of no pressure.
5, gas separator as claimed in claim 4 wherein, also comprises the one or more metal wire mesh cage graticule mesh in a plurality of gaps that are looped around between coaxial substantially a plurality of pipes.
6, gas separator as claimed in claim 1, wherein, described gas separator is made by inlet tube with near-end and far-end and the outlet with near-end and far-end; The far-end that the near-end of wherein said inlet tube approaches external ionization source and described inlet tube most apart from external ionization source farthest; The near-end of wherein said inlet tube is positioned at a certain distance apart from external ionization source, and the scope of described distance exists:
About 10
-3The lower limit of m and about 10
1Between the upper limit of m.
7, gas separator as claimed in claim 6 wherein, also comprises heater, and it is directed in the far-end of the near-end of the far-end of the near-end to described inlet tube, described inlet tube, described outlet and described outlet at least one.
8, gas separator as claimed in claim 4 wherein, also is included in the one or more capacitive surface on one or more coaxial substantially pipes, and wherein one or more electromotive forces are applied to described one or more capacitive surface.
9, gas separator as claimed in claim 8, wherein, one or more in described coaxial substantially a plurality of pipes comprise glass, impedance cladding glasses, glass-lined metal tube by being selected from, the material that applies in the group of fused silica, metal coating fused silica, workable glass, metal coating workable glass, pottery, metal coating pottery and metal makes.
10, gas separator as claimed in claim 8, wherein, described coaxial substantially a plurality of pipes are positioned at the zone of approx atmospheric press and the zone between the zone of approximate high vacuum.
11, a kind of mass spectrometer, it comprises:
(a) external ion source, wherein said external ion source generates analyte ions;
(b) jet separator, wherein said ion cross described jet separator under vacuum; With
(c) mass spectrometer/ion detector, the described ion of wherein discharging described jet separator enters described mass spectrometer/ion detector.
12, a kind of method of check and analysis thing, it comprises:
(a) provide a device, described device comprises: mass spectrometer; External ion source; And jet separator;
(b) generate analyte ions from described external ion source; With
(c) the described analyte ions of transmission passes described jet separator and enters described mass spectrometer.
13, a kind of system that is used for the check and analysis thing, it comprises:
(a) be used for the ionization source of ionization of analytes;
(b) have the inlet side pipe of two ends, wherein, described ionization source is approached in an end, and described analyte ions passes this end and enters, and the other end is away from described ionization source, and described analyte ions passes this other end and discharges;
(c) region of no pressure, described analyte ions crosses wherein;
(d) have the outlet side pipe of two ends, wherein, described region of no pressure is approached in an end, and described analyte ions passes this end and enters, and the other end is away from described region of no pressure, and described analyte ions passes this other end and discharges; With
(e) detector of analyte ions.
14, system as claimed in claim 13, wherein, described detector is selected from the group that comprises mass spectrometer, Raman spectrometer, electromagnetic absorption spectrometer, electromagnetic emission spectrometer and surface detection spectrometer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77887406P | 2006-03-03 | 2006-03-03 | |
| US60/778,874 | 2006-03-03 | ||
| US11/580,323 | 2006-10-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101449355A true CN101449355A (en) | 2009-06-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007800159745A Pending CN101449355A (en) | 2006-03-03 | 2007-02-28 | A sampling system for use with surface ionization spectroscopy |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103959428A (en) * | 2011-11-21 | 2014-07-30 | Dh科技发展私人贸易有限公司 | System and method for applying curtain gas flow in a mass spectrometer |
| CN110391129A (en) * | 2018-04-20 | 2019-10-29 | 岛津分析技术研发（上海）有限公司 | Ionization apparatus, mass spectrograph, ionic migration spectrometer and ioning method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957470A (en) * | 1973-10-18 | 1976-05-18 | Ernest Fredrick Dawes | Molecule separators |
| US4144451A (en) * | 1976-01-28 | 1979-03-13 | Hitachi, Ltd. | Mass spectrometer |
| US4542293A (en) * | 1983-04-20 | 1985-09-17 | Yale University | Process and apparatus for changing the energy of charged particles contained in a gaseous medium |
| US5448062A (en) * | 1993-08-30 | 1995-09-05 | Mims Technology Development Co. | Analyte separation process and apparatus |
| US20050151074A1 (en) * | 2002-05-31 | 2005-07-14 | Rohan Thakur | Focusing ions using gas dynamics |
-
2007
- 2007-02-28 CN CNA2007800159745A patent/CN101449355A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3957470A (en) * | 1973-10-18 | 1976-05-18 | Ernest Fredrick Dawes | Molecule separators |
| US4144451A (en) * | 1976-01-28 | 1979-03-13 | Hitachi, Ltd. | Mass spectrometer |
| US4542293A (en) * | 1983-04-20 | 1985-09-17 | Yale University | Process and apparatus for changing the energy of charged particles contained in a gaseous medium |
| US5448062A (en) * | 1993-08-30 | 1995-09-05 | Mims Technology Development Co. | Analyte separation process and apparatus |
| US20050151074A1 (en) * | 2002-05-31 | 2005-07-14 | Rohan Thakur | Focusing ions using gas dynamics |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103959428A (en) * | 2011-11-21 | 2014-07-30 | Dh科技发展私人贸易有限公司 | System and method for applying curtain gas flow in a mass spectrometer |
| CN103959428B (en) * | 2011-11-21 | 2016-12-21 | Dh科技发展私人贸易有限公司 | For applying the system and method for heavy curtain air-flow in a mass spectrometer |
| CN110391129A (en) * | 2018-04-20 | 2019-10-29 | 岛津分析技术研发（上海）有限公司 | Ionization apparatus, mass spectrograph, ionic migration spectrometer and ioning method |
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Application publication date: 20090603 |