CN101606219B - Ion transfer arrangement - Google Patents
Ion transfer arrangement Download PDFInfo
- Publication number
- CN101606219B CN101606219B CN2007800490085A CN200780049008A CN101606219B CN 101606219 B CN101606219 B CN 101606219B CN 2007800490085 A CN2007800490085 A CN 2007800490085A CN 200780049008 A CN200780049008 A CN 200780049008A CN 101606219 B CN101606219 B CN 101606219B
- Authority
- CN
- China
- Prior art keywords
- ion
- electrode
- transference tube
- tube road
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
A method of transferring gas and ions between a relatively higher pressure region and a relatively lower pressure region of a mass spectrometer comprises: providing an ion conduit (60) between the relatively higher pressure region and the relatively lower pressure region. The ion conduit (60) includes an electrode assembly (300) defining an ion transfer channel. The electrode assembly (300) has a first group of ring electrodes (305) with a first width D1, and a second group of ring electrodes alternately with the first ring electrodes (305) with a second width D2 (>=D1). A DC voltage with a V1 voltage and a first polarity is supplied to the first ring electrodes (205) and a DC voltage with a V2 (may be less than or equal to V1) voltage and an opposite polarity is applied to the second ring electrodes (310). The pressure of the ion conduit (60) is controlled to facilitate to maintain the viscous flow of the gas and ion in the ion transfer channel.
Description
Invention field
The present invention relates to be used for the ion transfer arrangement of transmission ion in mass spectrometer, relate in particular to the ion transfer arrangement that is used for ion is transferred to from atmospheric pressure ionization source the high vacuum of mass spectrometer vacuum chamber.
Background of invention
Transference tube is also referred to as capillary, knownly in the mass spectrometer field is used for maintaining or near atmospheric ionization chamber and maintain between second Room that reduces pressure and transmit ion.Generally speaking, the ion migrating channels adopts the form of elongated narrow pipe (capillary) usually, and it has arrival end that ionization chamber is opened and the port of export that second Room is opened.Ion and charged and uncharged particle (for example, from the part desolvation drop of electrostatic spray or APCI probe, or from ion and the neutron and the matrix/matrix in laser desorb or MALDI source) and background gas get into ion together and move arrival end capillaceous and under the influence of barometric gradient, cross its length.Ion flow/air-flow withdraws from transference tube as free jet expansion (free jetexpansion) then.Ion can pass the aperture of skimming tool awl (skimmer cone) and after this be delivered to mass analyzer through the zone of continuous low pressure subsequently and obtain mass spectrum.
In existing ion transfer arrangement, have remarkable loss, thereby so that the great majority that produce those ions by ion source can't successfully arrive and pass the follow-up phase that ion transfer arrangement gets into mass-spectrometer measurement.
Taked several different methods to solve this problem.For example, transference tube can be heated with evaporation of residual solvent (thereby improving ion output) and isolate the dissolved adduct.The adverse current of the gas that has proposed to be heated increased desolvation before getting into migrating channels in spraying.The various technology that realized being used for aligning and the location of sample spraying, capillary and skimming tool manage to maximize the amount of ions from the source of the mass spectrometric ion optics in actual arrival ion migrating channels downstream.
Observe (referring to, people such as Sunner for example, American society's magazine, Mass Spectrometry (mass spectrometer), the 5th volume, the 10th phase, 873-885 page or leaf (in October, 1994)) get into transference tube ion a big chunk because of with tube wall collision loss.This has reduced the number of ions that is delivered to mass analyzer and instrumental sensitivity has been had a negative impact.In addition, for the pipe that is made up of dielectric substance, the collision of ion and tube wall can cause electric charge to gather and suppress ion getting into and this pipe of flowing through.Prior art comprises the interaction that it is said through reducing ion and tube wall or designs through reducing a plurality of transference tubes that charge effects reduces ion loss.For example, the United States Patent (USP) of Franzen proposes for 5,736, No. 740 to come with respect to the air-flow decelerate ions through using the axial dc field.According to this list of references, the parabolic velocity curve of air-flow (with respect to ion) produces the aerodynamic force of ion focusing to the tube hub line.
Other prior art list of references No. 6,486,469, United States Patent (USP) (for example, Fischer) relates to the conductive material layer that for example is used for being connected to through use the electric charge groove and applies the technology that the inlet region minimizes the charging of dielectric tube.
Another kind method is to make ion from atmosphere towards central shaft " funneling compiling ".The notion of the ion funnel of work under vacuum condition that is used for after ion migration capillary is at first set forth at US6107628, and is rolled up at the magazine Mass Spectrom of American society 200, the 11 by people such as Belov then, describes in detail in the 19-23 page or leaf.Nearest ion funnel is compiled technology has description in following patent: people such as Tang, that be entitled as " Independent Control of Ion transmission in ajet disrupter Dual-Channelion funnel electrospray ionization MS interface " (independent control that the ion in spraying interrupter binary channels ion funnel electrostatic spray ionization MS interface transmits), analytical chemistry 2002; The 74th volume; The U.S. Patent number 6 of 5431-5437 page or leaf; 107; 628, it illustrates two funnels and arranges; People such as Page " An electrodynamic ion funnel interface for greater sensitivity and higherthroughput with linear ion trap mass spectrometers " (using the electrodynamics ion funnel interface that is used for bigger sensitivity and higher yield of linear ion trap mass spectrometer); International magazine MassSpectrometry 265 (2007) 244-250 pages or leaves, its description are applicable to the ion funnel of in linear trap quadrupole rod (LTQ) device, using.Unfortunately, effective work of ion funnel only extends to the air pressure of about 40mbar, and promptly atmospheric 4%.
Have to the infundibulate equipment of atmospheric opening people such as Kremer, physical magazine: open in " A novel method for the collimation of ions atatmospheric pressure " (a kind of novel method that is used at the ion collimation of atmospheric pressure) in Applied Physics the 39th volume (2006) 5008-5015 page or leaf, it adopts the passive ion lens of float element to come static ground focused ion (collimation they).Yet this does not solve the problem of focused ion in the pressure area between atmosphere and forevacuum.
Another alternative is set forth in No. 6,943,347, people's such as Willoughby United States Patent (USP), and it provides the tubular construction of the stratification with the conductive electrode layer that axially replaces.Accelerating potential is applied in conductive electrode and penetrates to minimize the field that gets into the inlet region, and a delay dispersion more can overcome because of reducing the dispersion effect that electric field produces up to viscous force.Though possibly help to reduce ion loss, ion needs the constantly axial field of increase to the actual focusing of central shaft, and this under low pressure becomes technical impossible because puncture.
Another prior art list of references No. 6,486,469, United States Patent (USP) (for example, Fischer) relates to and being used for for example through applying the technology that the inlet region minimizes the charging of dielectric tube with the conductive material layer that is connected to the electric charge groove.
Though some can partly successfully be used to certain in the above method to reduce ion loss and/or be alleviated the adverse effect that the collision because of ion and tube wall causes; But being far from, focusing force is enough to keep ion, especially under the situation in the ion beam than large space electric charge and bigger length of tube away from wall.Back one requires because of needing desolvation bunch to be occurred by what electrostatic spray or APCI ion source formed.In alternative, pipe can must be arranged on the front in this aperture by the replacement of simple aperture and the district of desolvating then.Yet, gas velocity inboard much lower than at pipe in this zone, and the therefore higher loss of space charge effect generation.Therefore, still there are the needs that the further reduction that realizes ion loss and the transference tube that can on wider experiment condition and specimen types, work are designed in the art.
Summary of the invention
Under this background, and according to a first aspect of the invention, provide
A kind of ion transfer arrangement, it is used between relatively high pressure zone and relatively low pressure zone, transmitting ion, comprising:
The transference tube road, it has towards the inlet opening of relatively high pressure chamber, towards the exit opening of relatively low pressure chamber and at least one sidewall that centers on the ion migrating channels, and this sidewall is along the extension of central axis between the arrival end and the port of export; And
A plurality of apertures, these apertures along vertical formation of sidewall so that allow from the gas in the ion migrating channels flow to pipeline outside than the area of low pressure.
According to a second aspect of the invention, provide a kind of method of transmitting ion first, between the relatively high pressure zone and second, relatively low pressure zone, this method may further comprise the steps:
Permission gets into the inlet opening that has or limit the transference tube road of ion migrating channels from the ion in relatively high pressure zone and the mixture of gas;
Through a plurality of passageways of the duct wall in the middle of inlet opening that is arranged in the transference tube road and exit opening, remove the part of the gas in the ion migrating channels; And
Make ion and residual gas withdraw from the transference tube road through exit opening towards the relatively low pressure zone.
In a kind of simple form, be used for mass spectrometric interface according to various embodiments of the present invention and comprise having towards the arrival end opening in hyperbaric chamber and towards the transference tube of the port of export opening of low-pressure chamber.High and low-pressure chamber can be by relative to each other having higher relatively and any zone lower pressure provides.For example, the hyperbaric chamber can be a source housing and low-pressure chamber can be first vacuum chamber.Transference tube has around interior zone and along at least one sidewall of the extension of central axis between the arrival end and the port of export.Transference tube has a plurality of passageways that are formed in the sidewall.The passageway allows gas to flow in the outside step-down zone of sidewall in the zone internally.
In another simple form, various embodiments of the present invention comprise transference tube, and this transference tube is used for receiving from the ion in the source of high-pressure area and with it and is transferred to the ion optics in mass spectrometric step-down zone.This transference tube comprises arrival end, the port of export and around interior zone and along at least one sidewall of the extension of central axis between the arrival end and the port of export.Transference tube also can comprise the integration vacuum chamber pipe that at least partly centers on and be connected to transference tube.This is integrated vacuum chamber pipe and isolates the volume that directly centers at least a portion of transference tube down at the pressure with respect to the reduction of interior zone.Sidewall has the structure that at least one passageway that is formed in the sidewall is provided.At least one passageway allows gas to flow at the outside volume of sidewall in the zone internally.This structure and passageway are in the inboard of integrating the vacuum chamber pipe.The structure of this sidewall can comprise a plurality of passageways.
In another simple form, various embodiments of the present invention comprise a kind of method that ion is transferred to first vacuum chamber from the ion source zone.This method comprises the arrival end of permission from the mixture entering transference tube of the ion in ion source zone and gas.This method also comprises a part of removing gas through a plurality of passages of the centre of the arrival end that is positioned at transference tube and the port of export.This method comprises that also making ion and residual gas withdraw from transference tube through the port of export enters into first vacuum chamber.This method also can comprise the minimizing by at least one latent heat that causes in the removal of the part of background gas and the evaporation that is associated in the sensing transference tube, and under the control of software or firmware, is applied to the heat of transference tube through the heater increase.
Various embodiments of the present invention have the advantage of the gas flow that reduces the port of export that passes through transference tube.Some advantages that are associated have also been supposed.For example, the port of export that passes through transference tube of minimizing mobile reduced the gas that carries ion and when it leaves transference tube, has been used for the energy that expands.Thereby ion has aperture that bigger chance comes the skimming tool through direct downstream to advance on the straight line.In addition, the minimizing of flowing at least a portion of transference tube can have the effect of the laminar flow amount of increase in this part of transference tube.Laminar flow is more stable so that ion can keep focus on and the relative small-bore through skimming tool on the passageway with straightaway.Along with the sidewall of gas through transference tube is drawn out of, the pressure in the transference tube is lowered.The pressure that reduces can cause the desolvation that increases.In addition, latent heat is removed when gas is extracted out through sidewall.Therefore, more heat can be by migration through transference tube, and gets into remaining sample in the interior zone, thereby the desolvation that causes increasing and actual arrives the number of increase of the ion of ion optics.
Further characteristics of the present invention and advantage will become obvious from appended claims and following description.
The accompanying drawing summary
Fig. 1 illustrates the sectional view according to the ion transfer arrangement of the first embodiment of the present invention;
Fig. 2 illustrates the example of the ion entrance area of the ion transfer arrangement that is used for Fig. 1;
Fig. 3 illustrates the ion entrance area with the Fig. 2 that optimizes flow air dynamics lens;
Fig. 4 a, 4b and 4c illustrate the example of envelope of setting embodiment of the ion entrance area of Fig. 2 and 3 together.
Fig. 5 illustrates in greater detail the ion entrance area with the shape shown in Fig. 4 b;
Fig. 6 illustrates first embodiment of alternating voltage pipeline of the part of the ion transfer arrangement that forms Fig. 1;
Fig. 7 illustrates second embodiment of alternating voltage pipeline,
The vertical view that the replacement of Fig. 8 depiction 7 and 8 alternating voltage pipeline realizes;
Fig. 9 a, 9b, 9c and 9d illustrate each alternative embodiment according to ion transfer arrangement of the present invention; And
Figure 10 illustrates the exemplary ion track through ion transfer arrangement.
Detailed description of preferred embodiment
Fig. 1 illustrates the ion transfer arrangement that adopts each side of the present invention, and it is used between atmospheric pressure ionizationion (for example, electrostatic spray) and one or more stages that mass-spectrometer measurement the arranged high vacuum at wherein follow-up vacuum chamber, transmitting ion.In Fig. 1, be arranged in atmospheric pressure such as (but being not limited to) electrostatic spray source, atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization (APPI) source plasma source 10.This produces ion with known manner, and ion gets into ion transfer arrangement (the generally indication at Reference numeral 20 places) via entrance hole diameter 30.Ion gets into second vacuum chamber 50 that comprises ion pipeline 60 through first pump transmission chamber 40 (after this being called expanding chamber 40) and continuation then.Ion withdraws from pipeline 60 and the outlet aperture 70 through ion transfer arrangement, and their get into the phase I (below be called MS1) 80 of (via a series of ion lens-not shown) mass spectral analysis in this position.As the technical staff easily understand, MS1 connects the follow-up phase (MS2, MS3...) of mass spectral analysis after will be usually, but these stages do not form a part of the present invention and therefore for clarity sake not shown in Fig. 1.
The more detailed explanation of the configuration of each assembly in the ion transfer arrangement 20 of Fig. 1 below will be provided.Yet, should dispose in order to understand better, at first will be provided at the general discussion of the ion transfer mode in the different pressures zone between atmosphere and the forevacuum (such as under about 1-10mbar).
Ion transfer in the ion 20 of Fig. 1 be different on characteristic on every side the different pressures zone.Though in fact surely not any some moment change between ion source and MS1 80 of pressure, five different pressure spans of definable, and different ion transfer characteristics is arranged in each zone.These five zones are labeled in Fig. 1 and as follows:
Zone 1.This be pressure under about 1-10mbar, the zone at the entering ion optics of MS1 place.This zone is not by involved in the present invention.
Zone 5.This is atmospheric pressure region and mainly receives kinetic current and electrostatic spray or other atmospheric pressure ion source domination itself.The same as zone 1, it is not that the present invention is directly related.
Remaining zone 2,3 and 4.
Zone 4: this is near the ingate 30 of arriving ion 20.
Zone 2: this is the zone at pipeline 60 places, and its outlet aperture 70 with ion 20 is contiguous to MS1.At last,
Zone 3: this is ingate 30 (zone 4) and the zone between aforesaid regional 2 in ion 20.
To the measurement indication of the ionic current that gets into the ion capillaceous (30 places) that can buy on the typical market in the ingate it at I
0In the scope of ≈ 2.5nA.Therefore, known introducing air flow value Q=8atmcm
3The internal diameter of/S and pipeline is 0.5mm, then the scope of initial charge density
0Can be estimated as 0.3-1*10
-9C/cm
3=(0.3...1) * 10
-3C/m
3The time of staying of known ion in insides of pipes, t=0.113m/50m/s ≈ 2*10
-3S, and the average ion mobility value K=10 under the atmospheric pressure
-4m
2/ s, then transmission efficiency can be confirmed from following formula because of the restriction of space charge repulsion:
Thereby, preferably optimize the ducted ionic mobility and the ion time of staying for improving ionic current (this is the purpose of each side of the present invention).
The major part of the ion loss in atmospheric pressure ionization (API) source takes place in the ionization chamber of 30 fronts, ingate of interface.The ratio of this ion loss is confirmed by ion/drop that the Taylor from the API source bores ingate 30 drift time.Near ingate 30 Velocity Profiles is
wherein d be the diameter of pipeline; And R be from this to the ingate 30 distance, C is that constant and Δ P are pressure drops.Ion velocity is V
Ion=V
Gas+ KE, wherein K is that ionic mobility and E are electric field strength.Suppose K～10
-4m
2/ s and E～510
5V/m then by the speed that electric field causes is～50m/s.Air velocity in 0.5mm ID insides of pipes is same value approximately, but apart from the ingate 30 apart from the 5mm place, slow 10 times approximately in the ion of advancing with gas than its drift in electric field.Therefore, the ion time of staying in this zone is 10
-4In the scope of s, this causes about 50% ion loss because of the space charge repulsion according to above equation (2).
In other words, the analysis of ion transfer arrangement considers that the proposition space charge repulsion is main ion loss mechanism.The major parameter of confirming the ion transmission efficiency is at ducted ion time of staying t and ionic mobility K.Thereby a kind of mode of improving ion transmission efficiency is to reduce t.Yet, there are a series of restrictions to the unlimited increase of t:
1. evaporate the required time of drop;
2. layer air-flow converts the critical speed of disorderly air-flow to; And
3. the appearance of shock wave when air-flow accelerates to the velocity of sound.This is especially in big pressure drop be exposed at 1 o'clock from zone 5 situation of (about 1000 to 1mbar).
Turn back to accompanying drawing 1 now, will describe the preferred embodiment of ion now in more detail.The characteristic that is adopted manages to solve the restriction to above-mentioned ion transmission efficiency with configuration.
The zone of at first considering is zone 4 and 3, and they limit the near zone of entrance hole diameter 30 and expanding chamber 40 respectively.
In order to solve the ion loss of 30 fronts in the ingate, it is desirable increasing the introducing air-flow that gets into ingate 30.This be with above analysis corresponding to-to given ionic current, allow to catch more substantial gas in higher airflow rate to the porch of ion, and supposition gas is filled into saturatedly by ion, more polyion is then arranged.The time of staying in the reduction zone 3 and 4 reaches high with ion flow but non-ultrasonic velocity is a condition.
Thereby through optimizing or comprising API source 10 and arrive the assembly between the inlet of pipeline 60, it is possible in zone 4 and 3, improving.The zone 4 and 3 of interface provides the aerodynamic force of ion to focus on ideally between zone 5 in atmosphere and the zone 2, and these ions heavily surpass 4-10 doubly than the nitrogen molecular that is used for most interested analytes usually.
First purpose is to avoid the hypersonic flow pattern of zone between 5 and 2, because this can cause the ion loss that can not expect.This purpose can realize through the buccal funnel 48 of going into that use is arranged in expanding chamber 40.This funnel 48 is shown the series of parallel plate with different center bores in Fig. 1; Purposes contact Fig. 2-4 of this device (and some alternative) sets forth hereinafter.Ideally, funnel 48 is short (in fact, for the sectioning shown in Fig. 1,3mm is short as much as possible approximately), and long less than 1cm ideally.
Barrier film, extraction or the vortex pump (not shown) of the pumping mouth 45 of expanding chamber 40 through being connected to expanding chamber preferably by pumping to about 300-600mbar.Through suitable setting ion funnel 48, their expansion when ion gets into expanding chamber 40 can be arranged to be convenient to control or avoid shock wave to form fully.
As by shown in people's such as Sunner the above-mentioned document, even when hanging down the spraying electric current, atmosphere potential source (for example, electrostatic spray or API) is the space charge restriction.The inventor confirms that through experiment even apply the highest electric field, does not carry above 0.1-0.5*10-9 coulomb (atm.cm3) in API source yet ability.Even in order to be the major part that this electric current is caught in nanometer spraying source, this also requires entrance hole diameter 30 to have the diameter of 0.6-0.7mm at least, and be subsequently force speed and focusing electric field (though total be necessary with pressure drop remain under the generation of electric field breakdown).
Fig. 2 realizes this to force the indicative icon of the simple mechanism of speed and focusing electric field.At this, in expanding chamber 40 but be adjacent to the inlet of pipeline 60, entrance hole diameter 30 be maintained at the first direct voltage V1 simultaneously plate electrode 90 be maintained at voltage V2.After applying voltage, ingate 30 constitutes simple ion funnel 48 together with plate electrode 90.Plate electrode among Fig. 2 has usually with the similar diameter of the internal diameter of pipeline 60 and with it to be aimed at, but still play with the ion funnel formula converge to the center bore of the effect of pipeline 60.Electric field between aperture 30 and dull and stereotyped 90 makes charged particle quicken effectively, and pulls charged particle into pipeline at the fringing field of opening part, advances because these often are parallel to electric field line, even also be like this in viscous flow.This is normally preferred to the auxiliary acceleration of the electricity in the conduit region.
As the development to the simple mechanism of Fig. 2, ingate 30 and the space in the expanding chamber 40 between the plate electrode under the voltage V2 under voltage V1 can comprise other ion lens or air force lens or their both combinations.Schematically illustrated this structure of Fig. 3: the array of plate electrode 100 is installed between ingate 30 and the plane electrode 90 to constitute ion funnel 48.But each of the electrode of composition plate electrode array 100 has coaxial each center bore for different diameters in common those apertures with ingate 30 and plate electrode 90.
Various shape can be described through plate electrode array 100: in the simplest situation, be only flared (linear taper) towards the funnel of pipeline.This is schematically illustrated in Fig. 4 a; " Incorporation of a Flared Inlet Capillary tube on a FourierTransform Ion Cyclotron Resonance Mass Spectrometer " (on Fourier transform ion cyclotron resonant mode spectrometer, combining flared inlet capillary) describes in the magazine MassSpectrom.2006 of American society the 17th volume, the 772-779 page or leaf in more detail and people's such as Wu.The replacement shape is equally highly schematically shown in Fig. 4 b and the 4c, and is respectively nozzle (venturi (Venturi) equipment-referring to people such as Zhou (Zhou, L.; Yue, B; Dearden, D.; Lee, E.; Rockwood, A.&Lee, M.Incorporation of a Venturi Device in Electrospray Ionization (in the electrostatic spray ionization, combining Venturi equipment); Analytical chemistry; 2003,75,5978-5983) and loudspeaker or index shape inlet.
Thereby the effect of the device of Fig. 2 to 4 (and the device shown in the expanding chamber 40 of Fig. 1) is to have created the segmentation funnel inlet of pipeline 60.In each situation, but entrance hole diameter 30 can be less than the diameter of focus channel enough greatly to allow mass air flow.To the purpose of ion funnel setting be with the volume between the inlet of hopper outlet and pipeline 60 convert to equipment in the mass spectrometer relevant of jet separator-still be widely used in gas chromatographic analysis-simulation.Because the molecule of the molecular proportion carrier gas (normally nitrogen) of analyte wants recuperation many, so their dispersing after expanding are also much little than carrier gas, air force focusing takes place promptly.This effect can be come further the promotion through forming carrier gas from helium at least in part, especially under the enough low situation about limiting with the low glow discharge of dealing with inert gas of required voltage.As a result, ion is maintained near the axle, and can be moved to the core of focus channel, though channel diameter big a lot of unlike funnel, for example, 0.8-1.2mm ID.Even this diameter is greater than tradition diameter capillaceous, but the little 2-3 of starting pressure doubly, so that it still possibly adopt vacuum pump with the end of the funnel of the similar pumping capacity of for example 28-40m3/h of those current uses.Simultaneously, the active of the ion of funnel 48 inboards focuses on and allows the follow-up length of pipeline 60 under loss-free situation, to increase.This improve again any residue drop and bunch desolvation.As a result, the sample flow velocity can be expanded higher scope, far surpasses nanometer spraying flow velocity.
Only be that very simple some embodiment of example in following contact Fig. 9 a-d that the jet of an example of air force lens separates discusses.
As the further additional or replacement to the device of the zone 4 of preferred embodiment and 3, ion funnel 48 can comprise the auxiliary pumping in boundary layer at the inboard one or more somes place of passage, can be limited or the like along the pressure drop of passage.In order to keep highfield along this funnel 48, these pumping grooves can be used as the gap between the thin plate under the different electromotive forces.
Refer again to Fig. 1, will more describe the configuration of zone 2 (that is, expanding chamber 40 and the zone of arriving between the outlet opening 70 of MS1 80) now in detail.
The pipeline 60 that is arranged in vacuum chamber 50 and limits the zone 2 of ion transfer arrangement is formed by three independent assemblies: heater 110, one group of DC electrode 120 and generally illustrate at 130 places and differential pumping device in greater detail hereinafter.Each that should be understood that these assemblies has their independent function and advantage, but they have mutual synergy advantage in addition when being adopted together.In other words, use any one or two in these three assemblies to cause the improvement to the clean ion flow that gets into MS1 simultaneously, all these threes' combination often provides maximum improvement therein.
Add thermion migrating channels 115 its temperature of air-flow of flowing through that raises, thus promote residual solvent evaporation and lyate ion bunch decomposition and increase the number of the analyte ions that is delivered to MS1 80.
Fig. 5 will be shown the entrance area of the pumping pipeline that piles up plate electrode at the embodiment of shape depicted in figure 4, and have device 48 and be used to improve pumping.To understand, shown in plate electrode can be at direct current, alternately work on direct current or the RF, and the pumping of inlet opening and suitably shape all improve transmission in all cases.
Each embodiment of one group of DC electrode 120 will be described now.These can and be seen in the longitudinal cross-section of Fig. 1 with the form of sketch map again, but in Fig. 6 and 7, illustrate in greater detail alternative embodiment.In each situation, the identical identical parts of Reference numeral indication.
With reference to figure 1 and 6, the purpose of DC electrode 120 is to reduce the reciprocation of ion and the wall of the passages 115 that limited DC electrode 120 itself.This is tending towards ion is realized away from the inner surface of conduit wall and towards the space-alternating asymmetric electric field that channel centerline focuses on through generation.Fig. 1 and 6 shows with longitudinal cross-section and can how to use one group of DC electrode 120 to construct the example of particle migrating channels 115 so that this electric field to be provided.Ion migrating channels 115 (is called " low field intensity electrode " or LFE) (owing to will become obviously, is called " high field intensity electrode " or HFE) limits at this for more than first electrode 205 of relation alternately at this by being arranged in more than second electrode 210.Each HFE 205 has annular with LFE 210, and the inner surface of HFE 205 and LFE 210 defines the inner surface of ion migrating channels wall jointly.Adjacent electrode by the mode of following discussion through gap or insulating barrier electrically insulated from one another so that apply different voltages with different.In concrete a realization, electric insulation can through a plurality of electrodes (for example, on one of LEF) the outer surface or near formation insulation (for example, aluminium oxide) layer realize.As shown in Figure 6, HFE 205 and LFE210 can be by outer tubular structure 215 around to provide structural intergrity, air-tightness and auxiliary assembling.Yet in the preferred embodiment of Fig. 1, the outer tubular structure can be omitted or utilize hole or hole to adjust so that can be along its interior zone of length pumping (via the gap between the adjacent electrode) of ion migrating channels-following with the process that further describes.
To understand, though Fig. 1 and 6 for clarity sake describes relatively small number purpose electrode, the typical case of ion migrating channels 115 realizes will comprising tens of or hundreds of electrodes.Notice that further though Fig. 1 and 6 illustrates the basic electrode that extends along the total length of ion migrating channels 115, other realization can have the one or more parts that do not have the ion of electrode migrating channels length fully.
Electrode is arranged with cycle H (interval between LFE or the HFE continuously).The width of HFE 205 (longitudinal extent) is much smaller than the width of corresponding LFE 210, and HFE constitutes about 20-25% of cycle H usually.The HFE width can be expressed as H/p, and wherein p can be usually in the scope of 3-4.Selection cycle H so that the ion that passes ion migrating channels 115 with the asymmetric ionic mobility spectrometry of conventional High-Field (FAIMS) equipment in the approximate frequency of the frequency of radio frequency restricted area under experience height and low field intensity alternately.For example, suppose the mean air flow speed of 500 meter per seconds, 500 microns cycle H produces the frequency of 1 megahertz.Cycle H can remain unchanged along the total length of pipe, is perhaps replacedly adjusted (with the mode of continuous or stepping) to reflect the variation in the speed that is caused by barometric gradient along passage length.The internal diameter of ion migrating channels 115 (ID) (inner surface LFE 205 and HFE 210 limits) will preferably have the value greater than cycle H.
One or more direct voltage sources (not describing) are connected to electrode with the first voltage V
1Be applied to HFE205 and with the second voltage V
2Be applied to LFE 210.V
2Have and V
1Antipole property and much smaller than V
1Size.Preferably, ratio V
1/ V
2Equal-p, wherein p (shown in above) is mark reciprocal of the interval H that occupied by the LFE width and usually in the scope of 3-4, so that electric field space/time integral that ion experienced in the whole cycle equals zero.V
1And V
2Size should be enough greatly realizing the required focusing effect of following detailed description, but can not be greatly to causing between the adjacent electrode the perhaps discharge between the electrode and neighbouring surface.Believe that 50 to 500V big young pathbreaker satisfies aforesaid standards.
The direct voltage that applies regulation to HFE 205 and LFE 210 generates space-alternating pattern high and the low field intensity zone in ion migrating channels 115 inside, each zone and respective electrode are roughly longitudinally with prolonging.In each zone, field intensity is zero or near zero and increase with the radial distance apart from the center in the stream centerline, so that the attraction that the ion experience increases near the inner surface of transference tube along with ion in size or repel radial load.Height/low field intensity the mode producing that should replace is in the conceptive and similar ion behavior of behavior that in the asymmetric ionic mobility spectrometry of conventional High-Field (FAIMS) equipment, take place; Asymmetric waveform is applied to a right electrode of the opposite electrode in limiting analysis device zone (for example referring to people's such as Guevremont United States Patent (USP) 7 in this routine FAIMS equipment; 084, No. 394).
Fig. 6 is illustrated in the track of the cation of locating away from the stream center line under the influence that replaces asymmetric electric field.Ion in the high field intensity zone away from the inner surface of ion migrating channels; And (it is electronegative (once more that this hypothesis HFE 205 has the positive voltage that is applied on it and LFE 210 in the low field intensity zone, to shift to inner surface; Note polarity should be with reference to the warp in the moving path of longshore current level and smooth (promptly; Average on space periodic) Potential Distributing distributes, as previously discussed), thereby produce the zigzag path.
As in the FAIMS field, described in detail, clean the moving of the ion in the viscous flow zone of standing alternately high/low field will be depended on the variation of ionic mobility with field intensity.For A type ion, its ionic mobility increases with the field intensity that increases, and the radial distance of in the high field intensity part of circulation, passing through will be above the radial distance of during the low field intensity part, passing through.For in Fig. 6, describing and example described above, A type ion will show towards the moving radially only of stream center line, thereby prevent and the collision of ion migrating channels 115 inner surfaces and thereby the neutralization that produces.Along with the approaching stream of ion center line, field intensity significantly reduces, and ion stops to experience the strong radial load that produces from electrode.On the contrary, for C type ion (ionic mobility reduces with the field intensity that increases), the radial distance that ion is passed through in the low field intensity zone will be above the distance of in the high field intensity zone, being passed through, thus if V
1With the polarity of ion is that identical then producing towards the clean of ion migrating channels 115 inner surfaces moved.This behavior can be used between A and C type ion, distinguish because C type ion will be preferentially the collision of quilt and conduit wall damage, and A type ion will focus on the stream center line.If the prioritised transmission of C type ion is expected, then commutative V
1And V
2Polarity.
The ion of the track above-mentioned technology that DC electric field alternately is provided makes to(for) aerodynamic force therein becomes from pure longitudinal path deflection or mean free path, and focused ion possibly be unsuitable in the zone of long enough (that is, wherein no longer arranging ion motion with the collision of gas atom or molecule).For example; In ion migrating channels 115 owing under atmospheric pressure API source and high vacuum (gas that the pressure differential between＜1mbar) the MS1 80 causes expands and quickens and can cause producing one or more shock waves in ion migrating channels inside near its port of export place, thus deflection Ion paths sharp.For the electrode of the distal portions that is arranged on ion migrating channels 115, have necessity and apply RF voltage (with direct voltage or replace direct voltage) and avoid ion-conduit wall reciprocation so that enough focusing to be provided.In this situation, the RF voltage of anti-phase will be applied to adjacent electrode.
The replacement method that suppresses shock wave is a differential ground pumping pipeline 60 (Fig. 1), and this will be in following description.
Fig. 7 describes the ion focusing/guide frame 300 according to second embodiment of the invention, its can be used to ion transfer through mass spectrometer near atmosphere or than the area of low pressure.Under this pressure, ion is gone in the air-flow and therefore to have and the similar speed of the speed of air-flow by " embedding " owing to the high viscosity friction.
Be in a ratio of hour in the mean free path of ion and device size, it has been generally acknowledged that and flow and the molecule flowing opposite is a viscosity.In this case, between the molecule or the collision between molecule and the ion in transport phenomena, play an important role.
For according to of the present invention have several millimeters or to one centimetre representative diameter and several centimetres or decimeter total length and be pressed onto the device of the barometric gradient of about 1hpa pressure from about atmosphere, have the VISCOUS FLOW condition that spreads all over device of the present invention.
In fact; VISCOUS FLOW condition Knudsen number (Knudsen number) K=lambda/D is less than 1; Have down to the VISCOUS FLOW of about pressure of 1 to 10pa, this depends on analyte and size (micromolecule for the metabolin in the similar 1mm diameter capillary is 1pa).
Focusing/guide frame 300 constitutes by being placed to more than first annular electrode alternately arranging with more than second annular electrode (below be called " second electrode ") 310 (below be called " first electrode ") 305.Adjacent electrode is through gap or insulating material or layer electrically insulated from one another.With the embodiment contrast of Fig. 5, first and second electrodes 305 and 310 have basic equal widths.Similar on annular electrode 305 and 310 the configuration surface with the configuration of known RF annular electrode ion guide in the mass spectrometer field.Yet, be not the RF voltage that applies anti-phase to adjacent electrode, but 300 employings of focusing/guide frame are applied to the contrary sign of adjacent click and the direct voltage of equal sizes.Through suitably selecting electrode cycle D with respect to gas (ion) speed, the ion of inside that traverses guiding/focusing structure is at the electric field of going up the experience alter polarity near the frequency of the conventional RF field magnitude of 1 megahertz (for example).Alternately electric field comprises and focused ion with the mode identical with the RF electric field.To depend on various how much (electrode internal diameter and width) and work (gas pressure) parameter to the selection that is applied to the suitable direct voltage on first click, 305 and second electrode 310; In typical a realization, the direct voltage of 100V to 500V will enough generate required field intensity and not cause electric discharge between electrodes.In addition, additional RF voltage can apply (thereby focousing field is provided effectively) with these direct voltages under independent frequency.
At this device and in other device of the present invention, running length H is preferably little, and size is 0.1 to 20mm, and about usually 1mm is so that the mean free path of ion is shorter than the relevant size of pipeline usually.
But the device that preferentially transmits A or C type ion with the furnishing of Fig. 6 is opposite, and Fig. 7 will not illustrate the remarkable deviation about the differentiated ionic mobility characteristic of ion than simple mechanism, but only improves the transmission of all charged particles.
Similar effects can realize (that is, voltage being set, so that can not create different height and low field) through the device of Fig. 6 being adjusted to the condition that is used to transmit the Type B ion.
In the replacement working method; The device of Fig. 7 can directly use an alternately high and low waveform to come work; Thereby generation RF FAIMS equipment; In this RF FAIMS equipment, change the field be converted in time and change with the field in space, this change when the moving coordinate system of charged particle is observed about equally.
The arrangement of first and second electrodes of focusing/guide frame can be modified to realize some purpose.For example, the vertical view of focusing/guide frame 400 that Fig. 8 describes to be made up of first electrode 405 and second electrode 410, wherein the adjacent annular electrode laterally each other skew to limit crooked ion trajectory (describing) by mirage line 415.Alternatively, the axle of this structure can be crooked by gradually.Crooked through in ion trajectory, creating, can realize that certain ion-neutral particle separates (because the differential effect of electric field causes), thereby strengthen the concentrated of the ion/ion stream in the gas.In another variant of focusing/guide frame; First and second electrodes with the internal diameter that reduces size gradually can be used to create the U.S. Patent number 6 with people such as Smith; The ion funnel structure of disclosed similar in 583,408, DC electric field replaces conventional RF field but it adopts alternately.
Turn back to Fig. 1, will describe differential pumping device 130 in more detail now.
As discussed, get into the particle optics device with before being transferred to mass spectrometric filtering and analysis part at ion, the loss of most of ions that the conventional intake section with atmospheric pressure ionization source suffers in the source, to produce.Believe that the high gas flow that withdraws from end at ion transfer arrangement is the factor of facilitating for this big figure ion loss.Neutral gas experiences the energy expansion when it leaves transference tube.In this expansion area flow and for transference tube middle and upper reaches distance to flow usually be turbulent in conventional intake section.Thereby, only focus on limited extent in the ion ion intake section in the past by gas delivery.On the contrary, many ions move in the volume of whole flowing gas high energy.Suppose that the ion out-focus arrives desirable degree, and is difficult under these flox condition, make ion to separate with neutral gas because of the melange effect of this high energy with turbulent flow and the gained on ion.Thereby, when neutral gas is detached, be difficult to isolate most ion and they are mobile downstream.On the contrary, many ions are pulled away and loss with neutral gas.On the other hand, the hypothesis that is associated with various embodiments of the present invention is to make that flowing along the more most of of transference tube is that ion can be held and focus on more on the meaning of layering.A kind of method provides required laminar flow removing the neutral gas through the sidewall of transference tube, so that the inflow in axially and be reduced from the outflow of the port of export of transference tube.In addition, through neutral gas being extracted out sidewall to moderate, to the attenuation of the boundary layer of airflow flowing, it is fuller that VELOCITY DISTRIBUTION becomes at the transference tube inner shafts, and flow and become more stable.
It is a kind of that in the atmospheric pressure ionization interface, to increase the mode of ion through amount or efficiency of transmission be through the one or more conductibility that increase in internal diameter that increases transference tube and the length that reduces transference tube.Like common knowledge, wideer and shorter transference tube has been arranged, the ion optics that polyion more is transferred to downstream will be possible.Yet the capacity limit diameter of available pump pumping system has much and total conc can have much.Therefore; According to various embodiments of the present invention; The internal diameter of ion migrating channels 115 (Fig. 1) can be done greatly relatively, and simultaneously, the air-flow that leaves the port of export of ion migrating channels 115 can be lowered to improve flow behavior and keep the centre focus of ion towards air-flow.In this way, neutral gas can by more easily with ion isolation, and ion can more always be led through outlet opening 70 to get into the MS1 in downstream.The result is the device sensitivity of improved efficiency of transmission and increase.
Even find that in some or all situations turbulent flow causes the ion transmission efficiency that increases, should understand the pressure of the reduction in the downstream of ion migrating channels and the desolvation of the increase that caused by the pressure that reduces can be the incidental advantage of various embodiments of the present invention under laminar flow and turbulent-flow conditions.In addition, even under turbulent-flow conditions, certain some the removal at least of the neutral gas of the sidewall through transference tube can play a part to make effectively ion to separate with neutral gas.Even in turbulent flow, drop and the ion with their big quality with most probable axial flow through during the pipeline 60 more in the heart distribution.Thereby the removal of the neutral gas of expectation through sidewall will make neutral gas and ion isolation effectively and have less relatively ion loss under laminar flow and turbulent-flow conditions.Further, remove the desolvation that latent heat allows additional heating to increase through charging under laminar flow and turbulent-flow conditions through the neutral gas of sidewall.
The zone 2 that comprises pipeline 60 is preferentially from pump ports 55 pumpings.As can be from seen in fig. 1, differential pumping device 130 comprises a plurality of passageways 140 that are used in interior zone that comprises passage 115 and the fluid communication between the vacuum chamber that comprises pipeline 60 50 in zone 2.Regional internally 115 pumpings of neutral gas and extract out to get into the vacuum chamber 50 that it is drawn out of therein through the passageway in the differential pumping device 130 140.
Transducer can be connected to the signal of temperature that transference tube road 60 and controller 58 be used for indication ion is moved sidewall or a certain other part of pipeline 60 and beam back controller 58.Should be understood that a plurality of transducers can be placed on diverse location to obtain temperature profile.Thereby one or more transducers can be connected to the minimizing that transference tube road 60 is used for detecting the heat when a plurality of passageway 140 of the sidewall of gas pumping through transference tube road 60.
In alternative, shown in Fig. 9 a, the 3rd vacuum chamber 150 that pipeline 60 can be closed centers on.This can be used to through 140 draw gas of the passageway in the wall of differential pumping device 130.Yet it can be used to equally the passage 115 in passageway 140 and entering transference tube road 60 is passed through in the air-flow guiding but not remove background gas, as previously discussed.This can realize through the pressure in the 3rd vacuum chamber 150 is adjusted between the pressure in atmospheric pressure and the passage 115.Through passageway 140 admission passages 115 are passed through in the air-flow guiding, can create the more turbulent-flow conditions that can destroy the sample drop therein.More turbulent-flow conditions can thereby make the sample drop be divided into littler drop.The division of this drop is the external force division, but not divides the COULOMB EXPLOSION type division of drop equally.In the embodiment of Fig. 9 a, also show and get into the additional pump ports 56 of choosing wantonly of expanding chamber 40.Pump ports 45 is towards location, the front portion of plate electrode 48, and pump ports 56 pumping plate electrodes 48 and to the zone between the inlet of the 3rd vacuum chamber 150.
In the application of external force and enclosed pasture blast division, the removal of gas and interpolation can be used in a transference tube.For example, shown in Fig. 9 b, the 3rd vacuum chamber 150 is shortened and only seals the zone of second vacuum chamber 50.Through this mode, gas can via inlet 150 or enter the mouth 156 be added to second vacuum chamber 50 any part.Thereby, can realize that a series of external force that replace and enclosed pasture blast divide the drop of sample.
The wall of the differential pumping device 130 in each embodiment of Fig. 1 and 9a, 9b, 9c and 9d can form from the one or more material that comprises metal melt, metal sponge, permeable pottery and permeable polymer.Passageway 140 can be limited in hole in the material or void space.Hole in the material of sidewall or space can be little and can form usually continuous porous member and the aperture that not have to disperse.Alternatively, discrete aperture or the form of perforation in the sidewall that is formed at differential pumping device 130 can be adopted in the passageway.The passageway can dispose through the one or more opening that passes through that has in circle, straight line, elongated, the even and non-homogeneous structure.
As further details, Fig. 9 c illustrates the device that improves the ion flow in the critical entrance area.Expansion area 90 in the hole 30 provides a kind of jet of simple form to separate, and it preferentially transmits the paraxial heavier particle that connects, and is diffused on every side and is not accepted by follow-up aperture than lepton, and accelerator card plays the effect of collection of ions.Fig. 9 d illustrates wherein that nozzle plate 48 overturns on direction, and they itself create the breathing space, is the embodiment of extremely thin access panel subsequently.Sufficient pressure drop has been arranged, and heavy (that is, heavier than carrier gas) charged particle will easily get into conduit region, and a large amount of carrier bundle and light (solvent) ion are by skim.
A plurality of pump arrangements shown in Fig. 9 a, c and the d (and they also can be applicable to the embodiment of Fig. 9 b) can help to reduce interface cost, because the early stage minimizing of gas load reduces the pumping requirement to next stage.Especially, the top stage 45 reduces the gas load in the stage of back above 2, even when it only is air blast.
Figure 10 illustrate the simulation of using SIMION (RTM) software ion trajectory (r, z).The ID of the passage that is limited DC electrode 120 is 0.75mm, and long DC electrode section 210 is 0.36mm, and noncontinuous electrode section 205 is 0.12mm, and between the gap be 0.03mm.Air velocity is 200m/S, and the voltage that is applied to this group section be+/-100V.Ion is from moving left the right side.The ion of inboard that this simulation is presented at 1/3 place of the channel diameter that is limited DC electrode is limited and focuses on along passage.The maximum radial coordinate of vibration ion is reduced to the 0.07mm of outlet from the 0.16mm of beginning along the length of about 20mm.In Figure 10, observe, not the radius of passage 1/3 in ion be depleted because they do not move to such an extent that enough overcome the opposite direct DC electric field near conduit wall soon.This simulation confirms that this confinement depends on pressure and air velocity in the inboard of pipeline 60.This effect at atmospheric pressure and corresponding to the speed (about 60m/s) of this pressure under very weak (focusing on 0.126mm) from 0.174mm.Yet, when adopting aforesaid DC electrode device 120, at lower pressure (less than several times in atmospheric pressure), and～during the air velocity of 200m/s, see the much bigger improvement in the confinement.This is because be limited at the maximum airflow of pressure for entering MS1 80 under about 1mbar situation.
Thereby; Though when only adopting DC electrode device 120, in zone 2, there are some improvement in confinement; And dividually; Though improvement is arranged when under not to the situation of the radially static of DC electrode device restriction, using differential pumping device 130, the two adopted together in a preferred embodiment so that when creating optimum pressure state (being lower than about 300-600mbar) radially static limit ion.
To notice from above introductory discussion that the various piece of ion transfer arrangement seeks from the withdrawing from of pipeline 60 time, to keep air velocity below horizontal so that avoid shock wave in supersonic speed.A result is not so needing skimming tool to the inlet of MS180, that is, the outlet aperture 70 from regional 2 can be simple aperture.Observe, the existence of the skimming tool on the outlet aperture can cause reducing of ionic current, in fact has further desirable result (not needing skimming tool) so leave the supersonic velocity of the gas of pipeline 60.
Though the great majority of the above embodiment preferably adopt the transference tube road (that is, pipe) of circular cross section, the invention is not restricted to pipe.For example ellipse or rectangle or even other cross section of plane (that is, having the rectangle or the ellipse of very high aspect ratio) can become and be more preferably, especially when adopting macroion electric current or a plurality of nozzle (nozzle array).The increase that the air-flow of following enlarges markedly by the number of stages of differential pumping compensates.This can for example realize through the interstage of using those pumps that adopted.
Under the situation of aforesaid pumping adjustment, causing their multipath conversion own at the ion migrating channels described in this application is array.This device can be best for multiple capillary or many sprayers ion source.
Claims (17)
1. ion transfer arrangement that is used between atmospheric pressure ionizationion (10) and relatively low nip territory the transmission ion, it comprises:
Expanding chamber (40), it has inlet (30), and this inlet (30) is to said atmospheric pressure ionizationion (10) opening;
Transference tube road (60); It has towards the inlet opening of said expanding chamber (40), towards the exit opening (70) in said relatively low nip territory and at least one duct wall (130) that centers on ion migrating channels (115); Said duct wall (130) is along the extension of central axis between said inlet opening and the said exit opening (70), and wherein said relatively low nip territory is lower than the pressure of said expanding chamber (40);
Vacuum chamber (50), said transference tube road (60) is positioned at this vacuum chamber (50);
A plurality of apertures (140), said aperture is along vertical formation of the duct wall (130) of said transference tube road (60);
Pump arrangement; Said vacuum chamber (50) is used to find time; Thereby the part of the interior gas of said ion migrating channels (115) is moved to said vacuum chamber (50) through the said a plurality of apertures (140) in the said transference tube road (60); Said pump arrangement is configured to said vacuum chamber (50) is evacuated to pressure below atmospheric pressure, but this pressure is high simultaneously to enough keeping through the gas of said ion migrating channels (115) and the VISCOUS FLOW of ion; And
Air force and/or electron lens (48); Be positioned between the inlet in inlet (30) and said transference tube road (60) of said expanding chamber (40), said expanding chamber, be used for the ion from said atmospheric pressure ionizationion (10) is focused on towards the longitudinal axis of said ion migrating channels (115).
2. ion transfer arrangement as claimed in claim 1 is characterized in that, also comprises heater (11), said heater (11) be used for heat conduction, convection current and/or to be radiated the transference tube road (60) of said ion migrating channels (115) adjacent.
3. according to claim 1 or claim 2 ion transfer arrangement; It is characterized in that; Said duct wall (130) is by comprising that at least one the material in metal melt, metal sponge, permeable pottery and the permeable polymer forms, and the aperture (140) in the wherein said duct wall (130) is limited in hole in the said material or clearance space.
4. according to claim 1 or claim 2 ion transfer arrangement is characterized in that, also comprises:
Electrode assemblie (120); Said electrode assemblie (120) has along first group of electrode (205) of first width D 1 of the longitudinal direction of said transference tube road (60); Said first group of electrode (205) replaces with the second group of electrode (210) with second width D 2 of the said longitudinal direction in edge, wherein D2 >=D1; And
The direct voltage generator, it is used for to said first group of electrode (205) big or small V being provided
1With the direct voltage of first polarity and to said second group of electrode (210) big or small V is provided
2With distribute with respect to the average voltage on the longitudinal direction second, the direct voltage of opposite polarity, wherein | V
2|≤| V
1|;
Wherein, said electrode assemblie (120) is formed in the duct wall (130) in said transference tube road (60) at least in part and limits said ion migrating channels (115).
5. ion transfer arrangement as claimed in claim 4, it is characterized in that D2＞D1 and | V
2|＜| V
1|.
6. ion transfer arrangement as claimed in claim 4 is characterized in that, each electrode in said first group of electrode (205) separates through the follow-up and previous electrode of gap or insulating barrier and said second group of electrode (210).
7. ion transfer arrangement as claimed in claim 4 is characterized in that, also comprises the device that is used for RF voltage is applied to said first group of electrode (205) and said second group of electrode (210).
8. ion transfer arrangement as claimed in claim 1 is characterized in that, said air force and/or electron lens (48) have crooked envelope.
9. like claim 1 or 8 described ion transfer arrangements; It is characterized in that; Said air force and/or electron lens (48) comprise a plurality of discrete lens ring electrodes, and wherein it has than away from the little aperture of lens electrode in said transference tube road (60) near the lens electrode in said transference tube road (60).
10. ion transfer arrangement as claimed in claim 9 is characterized in that, the radial dimension in the aperture in the most approaching lens electrode in said transference tube road (60) is less than the radial dimension of the said ion migrating channels (115) in the said transference tube road (60).
11., it is characterized in that said air force and/or electron lens (48) are positioned at another vacuum chamber like each described ion transfer arrangement in the claim 1,8 and 10, this another vacuum chamber separates with said vacuum chamber (50).
12. the method for a transmission ion between atmospheric pressure ionizationion (10) and relatively low nip territory may further comprise the steps:
Permission gets into the inlet opening of expanding chamber (40) from the mixture of the ion of said atmospheric pressure ionizationion (10) and gas; This expanding chamber (40) comprises air force and/or electron lens (48); This air force and/or electron lens (48) were used for before the mixture that allows ion with gas gets into the inlet opening in transference tube road (60) will be from the ion of said atmospheric pressure ionizationion (10) towards the longitudinal axis focusing of inlet opening that has or limit the said transference tube road (60) of ion migrating channels (115); Wherein, said transference tube road (60) is positioned at a vacuum chamber (50);
The said vacuum chamber (50) of finding time; Thereby a plurality of apertures (140) of the duct wall (130) in the middle of inlet opening through being arranged in said transference tube road (60) and the exit opening (70); Remove the part of the gas in the said ion migrating channels (115); Said vacuum chamber (50) is evacuated to pressure below atmospheric pressure, but this pressure is high simultaneously to enough keeping through the gas of said ion migrating channels (115) and the VISCOUS FLOW of ion; And
Make said ion and residual gas withdraw from said transference tube road (60) through exit opening (70) towards said relatively low nip territory.
13. method as claimed in claim 12 is characterized in that, also comprises heating said ion migrating channels (115) so that promote the evaporation of the residual liquid solvent in said ion migrating channels (115).
14. method as claimed in claim 12; It is characterized in that, said transference tube road (60) is positioned at step that wherein vacuum chamber (50) is evacuated to pressure below atmospheric pressure comprises said vacuum chamber (50) is evacuated to the pressure between 600mbar and 1mbar.
15. like claim 12 or 14 described methods, it is characterized in that, also comprise vacuum chamber (50) with backfill gas backfill at least a portion.
16. like each described method in the claim 12 to 14, it is characterized in that, also comprise:
In said duct wall (130) inboard electrode assemblie (120) is provided; Said electrode assemblie (120) limit said ion migrating channels (115) and its have along first group of electrode (205) of first width D 1 longitudinally of said transference tube road (60) and along said vertically and second group of electrode (210) of second width D 2 that replaces with said first group of electrode (205), wherein D2 >=D1; And
To said first group of electrode (205) big or small V is provided
1With the direct voltage of first polarity, and big or small V is provided to said second group of electrode (210)
2With with respect to said electrode assemblie vertically on average voltage distribute second, the direct voltage of opposite polarity, wherein | V
2|≤| V
1|.
17. method as claimed in claim 16 is characterized in that, also comprises RF voltage is applied to said first group of electrode (205) and said second group of electrode (210).
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85773706P | 2006-11-07 | 2006-11-07 | |
| US60/857737 | 2006-11-07 | ||
| US60/857,737 | 2006-11-07 | ||
| US11/833209 | 2007-08-02 | ||
| US11/833,209 | 2007-08-02 | ||
| US11/833,209 US20090283674A1 (en) | 2006-11-07 | 2007-08-02 | Efficient Atmospheric Pressure Interface for Mass Spectrometers and Method |
| PCT/EP2007/009642 WO2008061628A2 (en) | 2006-11-07 | 2007-11-07 | Ion transfer arrangement |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210111145XA Division CN102768936A (en) | 2006-11-07 | 2007-11-07 | Ion transfer arrangement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101606219A CN101606219A (en) | 2009-12-16 |
| CN101606219B true CN101606219B (en) | 2012-06-20 |
Family
ID=41470987
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800490189A Expired - Fee Related CN101606220B (en) | 2006-11-07 | 2007-11-07 | Ion transfer arrangement |
| CNA2007800490352A Pending CN101606221A (en) | 2006-11-07 | 2007-11-07 | Ion transfer arrangement |
| CN2007800490085A Expired - Fee Related CN101606219B (en) | 2006-11-07 | 2007-11-07 | Ion transfer arrangement |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800490189A Expired - Fee Related CN101606220B (en) | 2006-11-07 | 2007-11-07 | Ion transfer arrangement |
| CNA2007800490352A Pending CN101606221A (en) | 2006-11-07 | 2007-11-07 | Ion transfer arrangement |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN101606220B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101606220B (en) * | 2006-11-07 | 2012-08-29 | 塞莫费雪科学（不来梅）有限公司 | Ion transfer arrangement |
| CN102221576B (en) * | 2010-04-15 | 2015-09-16 | 岛津分析技术研发（上海）有限公司 | The method and apparatus of a kind of generation, analysis ion |
| GB201021360D0 (en) * | 2010-12-16 | 2011-01-26 | Thermo Fisher Scient Bremen Gmbh | Apparatus and methods for ion mobility spectrometry |
| CN102157329B (en) * | 2011-02-20 | 2013-08-14 | 汪小知 | Method for realizing spatially-asymmetric ionic migration spectrum based on discrete electrodes |
| CN108511315B (en) * | 2011-12-28 | 2021-01-08 | 英国质谱有限公司 | Collision ion generator and separator |
| CN104160474A (en) * | 2012-02-01 | 2014-11-19 | Dh科技发展私人贸易有限公司 | Method and apparatus for improved sensitivity in a mass spectrometer |
| CN103107060A (en) * | 2013-01-18 | 2013-05-15 | 中国科学院大连化学物理研究所 | Ionic migration spectrum with radio frequency confinement function |
| JP6093861B2 (en) * | 2013-08-02 | 2017-03-08 | 株式会社日立ハイテクノロジーズ | Mass spectrometer |
| CN103592335A (en) * | 2013-11-29 | 2014-02-19 | 北京东创旭新测控技术有限公司 | Air ion detection apparatus |
| WO2015101821A1 (en) * | 2013-12-31 | 2015-07-09 | Dh Technologies Development Pte. Ltd. | Vacuum dms with high efficiency ion guides |
| CA2932672A1 (en) * | 2013-12-31 | 2015-07-09 | Dh Technologies Development Pte. Ltd. | Lens pulsing apparatus and method |
| US9921195B2 (en) * | 2014-01-27 | 2018-03-20 | Hitachi High-Technologies Corporation | Liquid chromatography-mass spectrometry device |
| CN105632874B (en) * | 2014-11-07 | 2017-09-26 | 中国科学院大连化学物理研究所 | A kind of direct current inhomogeneous field transference tube |
| CN106783466B (en) * | 2016-12-27 | 2019-04-02 | 四川智研科技有限公司 | A kind of accelerated electron beam stream optical texture |
| CN108807132B (en) | 2017-04-28 | 2021-06-25 | 株式会社岛津制作所 | Ion guiding device and guiding method |
| CN109841489B (en) * | 2017-11-27 | 2020-07-07 | 中国科学院大连化学物理研究所 | Device for reducing discrimination of transmission quality of radio frequency quadrupole rods |
| CN109236300B (en) * | 2018-07-30 | 2020-05-05 | 中煤科工集团西安研究院有限公司 | Electromigration method for preventing mine concrete well bore from being damaged by ion erosion |
| CN110783165A (en) * | 2019-11-01 | 2020-02-11 | 上海裕达实业有限公司 | End cover electrode structure of ion introduction side of linear ion trap |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6483109B1 (en) * | 1999-08-26 | 2002-11-19 | University Of New Hampshire | Multiple stage mass spectrometer |
| US6504150B1 (en) * | 1999-06-11 | 2003-01-07 | Perseptive Biosystems, Inc. | Method and apparatus for determining molecular weight of labile molecules |
| US6781117B1 (en) * | 2002-05-30 | 2004-08-24 | Ross C Willoughby | Efficient direct current collision and reaction cell |
| US6906322B2 (en) * | 2001-03-29 | 2005-06-14 | Wisconsin Alumni Research Foundation | Charged particle source with droplet control for mass spectrometry |
| CN1672238A (en) * | 2002-07-31 | 2005-09-21 | 美国瓦里安澳大利亚有限公司 | Mass spectrographic analysis equipment and method |
| CN101606221A (en) * | 2006-11-07 | 2009-12-16 | 塞莫费雪科学（不来梅）有限公司 | Ion transfer arrangement |
-
2007
- 2007-11-07 CN CN2007800490189A patent/CN101606220B/en not_active Expired - Fee Related
- 2007-11-07 CN CNA2007800490352A patent/CN101606221A/en active Pending
- 2007-11-07 CN CN2007800490085A patent/CN101606219B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6504150B1 (en) * | 1999-06-11 | 2003-01-07 | Perseptive Biosystems, Inc. | Method and apparatus for determining molecular weight of labile molecules |
| US6483109B1 (en) * | 1999-08-26 | 2002-11-19 | University Of New Hampshire | Multiple stage mass spectrometer |
| US6906322B2 (en) * | 2001-03-29 | 2005-06-14 | Wisconsin Alumni Research Foundation | Charged particle source with droplet control for mass spectrometry |
| US6781117B1 (en) * | 2002-05-30 | 2004-08-24 | Ross C Willoughby | Efficient direct current collision and reaction cell |
| CN1672238A (en) * | 2002-07-31 | 2005-09-21 | 美国瓦里安澳大利亚有限公司 | Mass spectrographic analysis equipment and method |
| CN101606221A (en) * | 2006-11-07 | 2009-12-16 | 塞莫费雪科学（不来梅）有限公司 | Ion transfer arrangement |
Non-Patent Citations (1)
| Title |
|---|
| Shenheng Guan, Alan G. Marshall.Stacked-Ring Electrostatic Ion Guide.《Journal of the American Society for Mass Spectrometry》.ELSEVIER SCIENCE INC, US,1996,第7卷(第1期),101-106. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101606221A (en) | 2009-12-16 |
| CN101606220A (en) | 2009-12-16 |
| CN101606219A (en) | 2009-12-16 |
| CN101606220B (en) | 2012-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101606219B (en) | Ion transfer arrangement | |
| CN102768936A (en) | Ion transfer arrangement | |
| US20090321655A1 (en) | Ion Transfer Tube with Spatially Alternating DC Fields | |
| US11631577B2 (en) | Ion focusing | |
| EP1856714B1 (en) | Method and apparatus for improved sensitivity in a mass spectrometer | |
| US8373120B2 (en) | Method and apparatus for ion manipulation using mesh in a radio frequency field | |
| US7256395B2 (en) | Method and apparatus for improved sensitivity in a mass spectrometer | |
| US20150014525A1 (en) | Systems and methods for transfer of ions for analysis | |
| US20100276584A1 (en) | Method and Apparatus for an Ion Transfer Tube and Mass Spectrometer System Using Same | |
| US10395914B2 (en) | Efficient ion trapping | |
| CN113496866B (en) | Counterflow uniform field ion mobility spectrometer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120620 Termination date: 20201107 |