CN103367090B - ion analyzer and ion analysis method - Google Patents
ion analyzer and ion analysis method Download PDFInfo
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- CN103367090B CN103367090B CN201210090875.6A CN201210090875A CN103367090B CN 103367090 B CN103367090 B CN 103367090B CN 201210090875 A CN201210090875 A CN 201210090875A CN 103367090 B CN103367090 B CN 103367090B
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
- G01N27/624—Differential mobility spectrometry [DMS]; Field asymmetric-waveform ion mobility spectrometry [FAIMS]
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- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
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Abstract
The present invention relates to a kind of ion analyzer and ion analysis method associated with difference ion mobility spectrometry analyzer array and mass analyzer array.This ion analyzer comprises the ion source being sequentially connected or ion source array, difference ion mobility spectrometry analyzer array, ion transfer passage array, mass analyzer array and ion detector or ion detector array.Each two or more passages self-contained of difference ion mobility spectrometry analyzer array, ion transfer passage array, mass analyzer array, the port number in these arrays is equal and one_to_one corresponding.The ion that ion source or ion source array produce is introduced each passage of difference ion mobility spectrometry analyzer array by this ion analysis method, after each passage carries out selection based on ionic mobility, after ion transfer passage array, enter mass analyzer array and finally detected by ion detector or ion detector array.
Description
Technical field
The present invention relates to the device and method of ion isolation and detection, particularly relate to use difference ion mobility spectrometry analyzer
Array and mass analyzer array carry out high efficiency separation and detection to the complex sample from chromatographic isolation or direct sampling process
Ion analyzer and ion analysis method.
Background technology
Along with countries in the world are to public safety and the attention of anti-terrorism ability, have and can quick and precisely identify target compound
Analytical tool and method increasingly become each research institution and instrument company research and development object.Ionic migration spectrometer is as one
Opposed configuration compared with simple, cost is relatively low but speed is higher and the ion analysis method of wide spectrum, in the anti-terrorism work in various countries
Play important role.The instrument being currently based on ionic migration spectrometer has been widely used in airport, station, convention
The place that the crowd is dense such as the heart and mechanism, also include explosive, drugs and other contraband for target determinand.
Meanwhile, gas phase and liquid chromatograph still take advantage status at each analysis field, and based on ion mobility spectrometry
Ion analyzer is also being subject to more with its comparatively faster speed and relatively independent separation principle as chromatographic detector
Carry out the most attention.It is, of course, also possible to ion analyzer based on ion mobility spectrometry is contained between chromatograph and mass spectrograph, with
Improve the peak capacity of system further, alleviate the mass spectrometric burden of rear class.
Ion mobility spectrometry quasi-instrument is generally divided into three classes, i.e. ionic migration spectrometer (Ion from structurally and operationally principle
Mobility Spectrometer, IMS), difference ion mobility spectrometry analyzer (Differential Mobility
Analyzer, DMA), and difference ionic migration spectrometer (Differential Mobility Spectrometer, DMS) or
Claim High-Field asymmetric waveform ion mobility spectrometer (High Field Asymmetric Waveform Ion Mobility
Spectrometer, FAIMS).Wherein, IMS and DMA two class ionic migration spectrometer is all with the different mobilitys of ion as foundation
And ion is separated and detects, DMS/FAIMS is then to migrate rate variance under high electric field and under low electric field with different ions
Other difference (differential mobility spectrum rate) and carry out separation and the detection of ion.
Detecting instrument with IMS as principle is usually operated under pulse mode, is i.e. introduced by the high-speed switch of ion gate
Simultaneously enter the ion of drift region on a small quantity, and then judge its ion structure by detecting these ions through the time of drift tube
Type.This kind of detector can be found in paper: Eiceman, G.A.and Karpas, Z., Ion Mobility Spectrometry,
CRC Press, 2005,119pp..This kind of detector the most both can work and under atmospheric pressure can also work under partial vacuum,
Its simple in construction, it is thus achieved that data relatively direct and be prone to explain.But, under most atmospheric pressure/coarse vacuum, ion source is equal
Work (time especially with the combination of the separating tool such as chromatograph), therefore uses the sample introduction of pulse mode in a continuous mode for IMS
Mode can make the dutycycle of instrument the lowest, and this greatly reduces the utilization ratio to sample.
Compared with IMS, the mode of operation of DMA is different.The relative theory of DMA can be found in paper: Panich Intra
Et al., Songklanakarin J.Sci.Technol.30 (2), 243-256, Mar.-Apr.2008.In the dma, with all
The channel flow that even high velocity air is formed along pair of parallel battery lead plate；The ion stream continuously generated is positioned at this to parallel by one
Slit on one electrode of battery lead plate enters flow area and with air current flow downstream.Owing to this is to parallel electrode plate
On be perpendicular to the DC voltage (migration voltage) of airflow direction added with an electric field force direction, ion while with air current flow also
Migrate under conditions of same air velocity and electric field force intensity to face electrode under the effect of electric field force, ionic mobility
Size determines this ion and is taken time in uprush direction, also determines this kind of ion simultaneously and the most finally moves
Dynamic distance.By regulating the size of electric field force between two battery lead plates, the ion with a certain ionic mobility can be made from being positioned at
The slit in airflow downstream somewhere is drawn, thus realizes the detection to this ion.For DMA, sampling process is continuous print, this
The biggest advantage is had for carrying out mating with the ion source worked in a continuous mode under various atmospheric pressure.But, in order to obtain
One full time spectrum also needs to be scanned the migration voltage on analyzer, and this can make dutycycle during analysis be substantially reduced.But
It should be noted that for some on-line checking or monitoring process, target compound may only have several or ten several,
One of this field potential method solving this problem can be after for the first time scanned, several or ten several different
Migrate and switch between voltage, thus improve the detection efficiency of DMA to a certain extent.
Although having certain advantage compared with DMA with IMS in ion utilization ratio, but it being the most excellent in resolution
Gesture, for little molecule, strong spreading effect makes its resolution generally all below tens, and more difficult carries
High.Therefore, for as an on-line monitoring equipment, producing false positive results is also a DMA institute facing challenges.For solving
This problem, can be by DMA with detect the combination of character is relatively independent and resolution is higher mass spectrograph with it.
From with the matching degree of difference ion mobility spectrometry analyzer prime for, owing to obtain a complete ion migration
Spectrum needs the step-scan cycle of part to several seconds, and this operation time range pair and direct analysis are (straight under atmospheric pressure
Connect sample desorption ionization) or carry out being combined with chromatograph and all seem slightly slow, particularly with the liquid chromatograph or very of speed
For high desorption temperature, sample appearance time, the most just within several seconds, the most easily misses preferable sampled point.
Solve this problem and to improve an important way of ion utilization ratio be by using frequency multiplexing technique, i.e. using
Multiple ion mobility spectrometry passages and corresponding mass spectrograph passage detect simultaneously.If Ionwerks company is in United States Patent (USP)
Method associated with the use multiple IMS passage mentioned in US7482582 B2 and ion trap and time of-flight mass spectrometer.Side at this
In method, multiple passages receive after the ion that ion trap is injected, and work asynchronously under identical voltage, each passage stream afterwards
The ion gone out is detected by the respective channel in the multianode detector of a flight time.This patent has used multi-way detecting skill
Art, but owing to each passage is operated under the pulse mode of synchronization, and the problem that unresolved whole detection process dutycycle is low,
Therefore the utilization ratio of ion still can not be largely increased.
Chen et al. mentions the same DMA channel of use in the article of multi-stage DMA, but different at DMA
Channel position carries out synchronous detecting (Aerosol Science and Technology, 41:217-230,2007).Similar side
Method is also described (J.Aerosol Res., 21 (4), 329-340 (2006)) in the article of Intra et al..This kind of method
Advantage be that the analysis efficiency of system is the highest, detector everywhere can continuously detect ion.But shortcoming exists
In, the electric field of the most whole passage determines, each detector can only the ion of corresponding a certain fixing mobility.Especially examine when needs
During the mobility not even variation of various ions surveyed, the relative position of detector is more difficult to be determined.Divide simultaneously for different
Analysis sample, whole instrument will lack motility.
Another use frequency multiplexing technique example be Owlstone company use FAIMS technology (US7714277 B2) by micro-
The ion transfer arrangement that electric system is made.In this technique, multichannel FAIMS analyzer is by two microelectromechanical-systems
The unit composition that processing obtains.Ion enters analyzer from multichannel one end, passes through multichannel under the driving of axial electric field
Region.Simultaneously because be all applied with same radio frequency and the DC voltage carrying out difference ionic mobility selection on each passage, because of
This only has the ion of suitable differential mobility to pass through, thus reaches the purpose of ion isolation and detection.With US7482582
B2 patent is similar, uses multichannel purpose also for the flux increasing whole system in US7714277 B2 patent.Right
In detecting a range of ionic mobility, the voltage on FAIMS need nonetheless remain for scanning, and the dutycycle of whole instrument is the most not
High.
In another is about the U.S. Patent application of use multichannel FAIMS technology (US2008/0067350 A1), Li
Gangqiang proposes and uses multichannel FAIMS to carry out sample analysis simultaneously, but the compensation voltage (CV) of each paths can not
With, therefore can improve the analysis speed of whole instrument.But multichannel DMA technology do not discussed by this document.
It is worthy of note simultaneously, when using multichannel ion analyser to carry out ion detection, if each passage
It is required for independent detector and follow-up amplification Acquisition Circuit carries out ion detection, the one-tenth of analytical tool will be greatly increased
This.For such issues that, in the United States Patent (USP) 7157699 of Ou Yangzheng also refer to use array mass spectrograph especially array
Formula ion trap carries out quality analysis, and the ion detection method being applied in combination by multiple discrete ion detectors to ion.This
Being limited in that of one method, although use by the combination of multiple ion detectors being decreased to rear class collection amplifying circuit
Quantitative requirement, but the number of ion detector can not reduce.For another example, fourth army equality people " mass spectrum journal, Vol22, No.3,
29-35. " propose use one ion detector and the follow-up amplification Acquisition Circuit array to being formed by multiple level Four bars after
Ion carry out the scheme that detects.But, each mass analyzer Channel Synchronous can only be used, therefore when in this matter by this scheme
When adding the ion mobility spectrometry selection device that can each work alone before spectrometer array, the function of the latter cannot be complete
Embody.
Summary of the invention
The technical problem to be solved is to provide a kind of use difference ion mobility spectrometry analyzer array and mass spectrum
Ion analyzer associated with instrument array, and a kind of ion using this ion detection device to carry out quick and precisely sample analysis divides
Analysis method, in order to solve the shortcoming that when currently used ion mobility spectrometry quasi-instrument detects, efficiency is low, false positive is high.
The present invention solves that above-mentioned technical problem employed technical scheme comprise that a kind of ion analyzer of proposition, comprise successively
The ion source being connected or ion source array, difference ion mobility spectrometry analyzer array, ion transfer passage array, mass analyzer
Array and ion detector or ion detector array, wherein said difference ion mobility spectrometry analyzer array, described ion
Each two or more passages self-contained of transfer passage array, described mass analyzer array, and each described difference ion
Migrate a passage of at least corresponding described mass analyzer array of a passage of spectralyzer array.
In one embodiment of this invention, described mass analyzer array is level Four bar array or ion trap array.
In one embodiment of this invention, ion analyzer may also include ionic dissociation device, is located at the conveying of described ion
Between channel array and described mass analyzer array.
In one embodiment of this invention, described ionic dissociation device is gas collisions room or photodissociation room or electricity
Son capture dissociation chamber.
In one embodiment of this invention, described difference ion mobility spectrometry analyzer array is planar structure, ion entrance
It is positioned at the relatively the same position of each passage, and the relative position of each channel ions exit slit is identical.
In one embodiment of this invention, the described difference each passage of ion mobility spectrometry analyzer array is centrosymmetric knot
Structure, each passage correspondence centrage is distributed in radial symmetric.
In one embodiment of this invention, each unit of described mass analyzer array is equipped with independent ion
Detector and data acquisition amplification system.
In one embodiment of this invention, each unit of described mass analyzer array is centrosymmetric structure, and each list
Unit shares an ion detector and data collecting system.
In one embodiment of this invention, described difference ionic migration spectrometer array is to be operated in synchronous mode or asynchronous mould
Under formula, described mass spectrograph array is to be operated under synchronous mode or asynchronous mode.
In one embodiment of this invention, described difference ion mobility spectrometry analyzer array works under atmospheric pressure.
In one embodiment of this invention, described difference ion mobility spectrometry analyzer array be operated in subatmospheric but not
In the environment of 0.1torr.
In one embodiment of this invention, the airflow direction in described differential mobility spectralyzer array is defeated with described ion
Send the axially vertical of channel array.
In one embodiment of this invention, be provided with at each feeder connection of described differential mobility spectralyzer array one from
Subflow detector, and described ion current detector is connected with outside current sensing means.
In one embodiment of this invention, described ion source comprises an isotopic ion source, and described isotopic ion
Source can need by machinery the most open or close according to experiment.
In one embodiment of this invention, described ion analysis method includes producing ion source or ion source array
Ion introduces each passage of difference ion mobility spectrometry analyzer array, carries out selection based on ionic mobility through each passage
After, after ion transfer passage array, enter mass analyzer array and finally by ion detector or ion detector array
Detected.
In one embodiment of this invention, described method also includes making ion enter described mass analyzer array
Before each passage, it is introduced into an ionic dissociation device, so that ion can described dissociate in ionic dissociation device.
In one embodiment of this invention, described difference ionic migration spectrometer array is to be operated in synchronous mode or asynchronous mould
Under formula, described mass spectrograph array is to be operated under synchronous mode or asynchronous mode, and described method includes with signal in sampling process
Change and the mode of operation of described difference ionic migration spectrometer array and/or described mass spectrograph array is switched over.
In one embodiment of this invention, described method comprises use level Four bar array or ion trap array as described
Mass analyzer array.
In one embodiment of this invention, when using a described ion detector, described method includes using timesharing
The mode that scanning is evicted from detects the ion information of each passage.
In one embodiment of this invention, described method also comprises use one and is positioned at difference ion mobility spectrometry analyzer
Ion current detector at each feeder connection of array, is monitored the ion introduction volume of each passage, obtained each passage
After the intensity normalization of described ion stream, it is used for calibrating the object ion intensity finally recorded in each passage.
In one embodiment of this invention, described method comprise one radioactivity being positioned in described ion source of use from
Component, and by certain specific ion using each passage of described ion analyzer respectively described isotopic ion source to be produced
Carry out periodic detection, after the ionic strength normalization that final each passage is obtained on described ion detector, be used for calibrating respectively
The object ion intensity finally recorded in passage.
Ion analyzer proposed by the invention and ion analysis method are owing to using multichannel difference ion mobility spectrometry with many
Road mass spectrograph and the combination of single or multiple ion detector, thus improve detection efficiency and the accuracy of instrument；Difference simultaneously
Ion migration spectrum array can work in different modes with the combination of mass spectrograph array, thus improves this device public
The application power in the field such as safety and environmental monitoring.
Accompanying drawing explanation
For the above-mentioned purpose of the present invention, feature and advantage can be become apparent, below in conjunction with the accompanying drawing tool to the present invention
Body embodiment elaborates, wherein:
Figure 1A illustrates ion source and plate difference ion mobility spectrometry analyzer array, plate ion guides array, puts down
The structure that template ion trap analyzer array is contacted mutually.
Figure 1B illustrates the basic structure of a unit in differential mobility spectralyzer array.
Fig. 2 A illustrates ion source and difference ion mobility spectrometry analyzer array axisymmetricly, quadrupole rod ion guides battle array
The structure that row, ion trap analyzer are contacted mutually.
Fig. 2 B illustrates that the ion trap in Fig. 2 A analyzes the cross-section structure of array.
Fig. 3 illustrates ion source and plate difference ion mobility spectrometry analyzer array, plate ion guides array, quadrupole
The structure that bar mass analyzer array is contacted mutually.
Fig. 4 A illustrates ion source and the structure that difference ion mobility spectrometry analyzer array is connected axisymmetricly, its intermediate ion warp
Evict to an ion detector array after crossing quadrupole rod mass analyzer array, to reach the purpose of multichannel quality analysis.
Fig. 4 B illustrates ion source and the structure that difference ion mobility spectrometry analyzer array is connected axisymmetricly, its intermediate ion warp
Evict to same ion detector after crossing quadrupole rod mass analyzer array quality analysis, to reach to be enriched with quality analysis or timesharing
The purpose of shunting quality analysis.
Fig. 5 A illustrates a kind of differential mobility spectralyzer and next stage ion conveyer device mutually perpendicular instrument configuration, from
Son is upwards distributed at one-dimensional square at the entrance of differential mobility spectralyzer.
Fig. 5 B illustrates a kind of differential mobility spectralyzer and next stage ion conveyer device mutually perpendicular instrument configuration, its
Intermediate ion is distributed on two-dimensional direction at the entrance of differential mobility spectralyzer.
Fig. 5 C illustrates the sectional view of the ion trap array with central ion detector.
Fig. 5 D illustrates the sectional view of the ion trap array with shunting ion detector.
Fig. 6 illustrates ion source and difference ion mobility spectrometry analyzer array axisymmetricly, ion guides array, ion trap
The structure that analyzer array is contacted mutually, in the most each array channel by ion radially outgoing, quilt in ion trap analyzer
It is positioned at this ion trap and analyzes the detector array shunting detection of array periphery.
Fig. 7 illustrates structure associated with the ion detection device of the present invention and desorbing corona beam ion source.
Fig. 8 illustrates synchronization (DMAA)-asynchronous (ITA) pattern diagram according to an embodiment of the invention.
Fig. 9 illustrates the most asynchronous (DMAA)-asynchronous (ITA) pattern diagram.
Figure 10 illustrates ion analysis and the schematic diagram of timesharing outgoing of ion trap array according to an embodiment of the invention.
Detailed description of the invention
Summarily saying, embodiments of the invention relate to a kind of by difference ion mobility spectrometry analyzer array
(Differential Mobility Analyzer Array, DMAA) and mass analyzer array (Mass Spectrometer
Array, MSA) associated with thus improve the device of ion analyzer unitary analysis efficiency and in order to improve ion analysis efficiency
Method.
Embodiment one
As it was previously stated, when using difference ion mobility spectrometry analyzer to carry out ion detection, there is different ion migration
The ion of rate selects by changing difference ion mobility spectrometry analyzer migration voltage.Whole when going for one
During spectrogram in the range of ionic mobility, just the migration voltage of this analyzer need to be carried out step-by-step movement scanning.This process is usual
Quite time-consuming, in order to reach balance when stepping each time, the single pass time is generally the time of several seconds to tens seconds.In order to
Increase the efficiency of this analysis process, the method that multi-way detecting can be used.Figure 1A illustrates ion source and plate difference ion
Migrate the structure that spectralyzer array is connected.As shown in Figure 1A, an ion source array 1 and a plate difference ion mobility spectrometry
Analyzer array (F-DMAA) 2 is connected, and the ion drawn from F-DMAA 2 can be entered by an ion transfer passage array 3
The plate ion trap array of next stage (F-ITA) 4, evicts to an ion detector array 5, to reach matter after quality analysis
The purpose of component analysis.
In the present embodiment, each unit in F-DMAA 2, the structure of the most each passage is identical, its cross section such as Figure 1B institute
Show.Ion entrance 2a is positioned at the relatively the same position of each passage, and the relative position of each channel ions exit slit is identical.From
Son enters via the bottom slit 6 of F-DMAA passage, moves to passages downstream with an air-flow being parallel to channel direction.Meanwhile,
Ion under the effect of a DC electric field being perpendicular to airflow direction to the top movements of parallel plate electrode.Owing to different ions migrates
The ion of rate movement velocity under same electric field action is different, only makes that those have after ion both direction speed superposition
The ion of specific ion mobility can leave migration area from top slit 7.
Above ion migration zone both may operate under atmospheric pressure, it is also possible to operates in background gas pressure the most as little as 0.1torr
Under the coarse vacuum of (≈ 13.3322Pa) left and right, but the resolution capability analyzed for ion migration considers, usual ion migration zone
Average gas pressure is not less than 0.1Torr.Therefore need through an ion before entering F-ITA 4 after ion leaves F-DMAA 2
Transfer passage array 3, its effect is to provide a pressure differential extraction district placed in the middle, and that improves ion passes through efficiency.Such
Ion transfer passage array can be a multistage bar array, an ion funnel array, or one by multiple electrode slices or
The array of the multipole fields that wire electrode is formed.By the ion of ion transfer passage array 3, next stage can be entered axially into
F-ITA 4.Ion after entrance F-ITA 4, after supercooling and scanning are evicted from, enters the ion detector in direction on the side
The corresponding unit of array 5 detects.
For this structure, can there is multiple-working mode.Such as, each passage of F-DMAA 2 can be operated in
Synchronous mode, on the most each passage, institute's making alive is equal, and the mobility of the ion that property selected by the most each passage is passed through is equal.At this
Under pattern, F-DMAA 2 only monitors the ion of a kind of ionic mobility at synchronization.As monitored different kinds of ions, this array needs
It is operated under step mode, i.e. changes between different migration voltage；Meanwhile, the F-ITA 4 being attached thereto is also
Can work in synchronous mode, quality or mass range that the most each ion trap unit is detected are equal.This pattern is suitable
F-DMAA 2 and F-ITA 4 is used respectively as an overall analyzer.Thus the main purpose of this kind of pattern is to carry
The overall sensitivity of high score parser, but the speed of analysis can not be improved.
Certainly, ion trap array can also work in asynchronous mode, quality that the most each unit is detected or quality model
Enclose；Or, several unit can form one group, detects identical quality or mass range.Usual this pattern main
Purpose is the component with several different karyoplasmic ratio included in detection same ionic mobility ion.This is for F-DMAA
The 2 scanning speeds different component that in the case of faster, quick examination has analog structure compound has Special Significance.This same
The pattern of step (F-DMAA 2)-asynchronous (F-ITA 4) is as shown in Figure 8.In Fig. 8, V1 to V5 represents each at F-DMAA 2 the most in the same time
The migration voltage that passage applies simultaneously, m1, m2, the quality that m3, m4 etc. represent each Channel scan of mass spectrograph respectively is interval.For
For mass spectrum asynchronous mode, these intervals are different, it might even be possible to make each passage lock a certain special quality and supervise
Depending on.When F-DMAA 2 sweep speed very fast time, for ion trap or quadrupole rod, scan a complete mass range become ten
Dividing difficulty, above subchannel segmentation is scanned just highlighting its advantage.
For the synchronous mode of F-DMAA 2, it is more suitable for monitoring some sample concentration and changing over is not very
Fast sampling process.But, when the prime analyzer (such as liquid phase or gas chromatogram) of F-DMAA 2 go out peak very fast time, use F-
DMAA 2 carries out the scanning of complete spectrogram and also becomes difficulty.At this moment can the mode of operation of F-DMAA 2 be changed into different by synchronization
Step, makes the channels operation of each F-DMAA 2 at different migration voltage or migrate under voltage range, thus monitors multiple simultaneously
Determinand, greatly reduces the time of the full spectrum of scanning.Certainly, channel selecting each for F-DMAA under asynchronous mode 2 having out
The ion of different ions mobility, continue after a procedure F-ITA 4 carry out karyoplasmic ratio analyze time, for F-ITA 4, the most permissible
Take synchronous mode, it is also possible to take asynchronous mode.For the synchronous mode of F-ITA 4, analyst can more concerned with monitoring
Can have the same class ion of different spaces geometric configuration；And for the asynchronous mode of F-ITA 4, analyst then more concerned with
Karyoplasmic ratio is used to confirm, to reduce false-positive appearance in each ion with special ion mobility.The latter is more
It is suitable for replacing the ionic migration spectrometer only carrying out qualitative ion with ionic mobility that current public safety field is conventional.This process
Requirement as of both meaningful needs meet, first, this ionic species interested to detection process is not (the most no
Exceed overall channel number), and the mobility known (monitoring to known sample) of all kinds of ions before detection.Therefore, this process
It is more suitable for conventional for some and needs certain process detecting speed, as the field such as on-line monitoring and airport security carries out answering
With.Fig. 9 describes the process of asynchronous (F-DMAA)-asynchronous (F-ITA) mode of operation.The each passage of F-DMAA 2 is 0 to t1's
In sweep time, each passage correspondence of the mass analyzer array of its correspondence is operated in m1 to m2, m3 to m4, waits different works
In the range of work.In such a mode, F-DMAA 2 can monitor the ion of multiple different ions mobility at synchronization；Monitor ion
Kind number is determined by channel number in described array；Now the migration voltage of each passage of F-DMAA 2 can be as shown in Figure 9
It is maintained at a fixed value (V1, V2, V3, and V4), persistently to monitor a certain ion.The migration voltage of each passage of F-DMAA2
Also can be a different narrow range interscan, with the ion information in the range of the quickly whole mobility of acquisition.
Additionally, the ion source in the present embodiment is alternatively isotopic ion source, this isotopic ion source can be according to reality
Test need by machinery the most open or close.So, by using each passage of ion analyzer respectively to putting
Penetrating property ion source produce certain specific ion carry out periodic detection, final each passage on described ion detector obtained by
After ionic strength normalization, can be used to calibrate the object ion intensity finally recorded in each passage.
Embodiment two
The ultimate principle of the ion analyzer in the present embodiment is similar to embodiment one, but difference is in the present embodiment
Difference ion mobility spectrometry analyzer array (DMAA) and ion trap array (ITA) all use drum type brake, are called for short C-DMAA 11 respectively
With C-ITA 13, connected, as shown in Figure 2 A by cylindric ion transfer passage array 12 therebetween.In this embodiment,
Each passage of C-DMAA 11 is centrosymmetric structure, and each passage correspondence centrage is distributed in radial symmetric.Fig. 2 B illustrates further
The cross-section structure of C-ITA 13, in array, each analytic unit is a complete circumference type distribution around same axis, and this can
So that the ion of multiple analytic unit institute outgoing focuses on outgoing further on the axis of device from array.
Furthermore, it is possible to outlet on C-ITA 13 end cap etc. sets up axial outgoing ion detector etc. respectively, point
Do not detect the ion that each ion analysis unit is evicted from, or with the detector of a big receptor area come same detection all of from
Son.
The structure of the present embodiment has some advantages compared with the slab construction in a upper embodiment.Such as, tie due to cylinder
Structure is symmetrical for axis, therefore can by ion source array and ion detector array reduction be single ion source 10 and from
Sub-detector 14, ensures that each passage has simultaneously and responds the most uniformly.Moreover, for the letter of ion detector 14
Change can reduce the quantity of follow-up signal amplifier and data acquisition channel further so that whole instrument cost reduces.
Under this instrument configuration structure, the various work in a upper embodiment synchronize and asynchronous pattern is all suitable for.When
So, while ion detector quantity is reduced to one, to comprising asynchronous mode during ion detection, (DMAA and ITA is extremely
Few one is asynchronous mode) sequential be also required to adjust.Figure 10 have expressed under asynchronous (DMAA)-asynchronous (ITA) pattern
Special sequencing contro to ITA when using an independent ion detector.As shown in Figure 10, each channels operation of DMAA is not
Under same migration voltage (V1 to V4), and the ITA unit of corresponding each DMAA passage can be cut between substantially 3 working stages
To change, ion trap empties-and ion introduces and is enriched with-Ion Extraction.In the these three stage, ion introduces and concentration stage required time
The longest, generally can continue tens to hundreds of millisecond, and ion trap to empty required time the shortest, usual tens microseconds just foot
Enough.And for the time in Ion Extraction stage, need to determine according to the scope of concrete quality of scanning, if carrying out total quality scope
Interior scanning is evicted from, needs at least ten several milliseconds.But, owing to ion is moved by each passage of DMAA according to different
Shifting rate has carried out certain differentiation, therefore, it can combine the ion selected by each DMAA passage and certain mass scope,
The most corresponding special karyoplasmic ratio of the most each passage.The time of each ion trap unit scan in so C-ITA 13 can
To foreshorten to hundreds of microsecond, only accounting for share the least in ion trap analysis time, this is just for each ion trap units shared one
Individual ion detector creates condition.As long as therefore the scanning time of evicting from of each ion trap unit being staggered, it becomes possible to fully
Utilize the use time of ion detector, so that the dutycycle of whole system is visited as ion with using ion detector array
Survey device phase difference little.
Certainly, for C-ITA 13, it is also possible to for each ion trap passage, one ion detector is installed, and is equipped with
Independent amplifier and data collecting system.At this moment the operation of each passage will be completely self-contained, this and F-DMAA and F-ITA
Combination pattern in running be duplicate.This pattern is more suitable for that each ion trap is carried out total quality and sweeps
Retouch.
Embodiment three
The ultimate principle of the ion analyzer in the present embodiment is quite similar with embodiment one, but difference is in this enforcement
In example, mass analyzer array uses level Four bar array.As it is shown on figure 3, in plane level Four bar array (F-QA) 15 each four
Level bar is connected by a plate ion transfer passage array 3 with a F-DMAA unit in F-DMAA 2.With precedent
Similar, the unit of F-QA 15 can optionally work in different modes, enters with the different working modes with F-DMAA 2
Row combination, thus adapt to different application demands.Such as, when F-DMAA 2 each channels operation in synchronous mode time, F-
All unit of QA 15 also work in synchronous mode, to increase sensitivity when a certain ion is monitored and is confirmed.
Or, the different units of F-QA 15 can also be divided into several groups, thus to the ion of analog structure in different possible mass ranges
It is monitored.When each channels operation of F-DMAA 2 in asynchronous mode time, then the purpose that F-QA 15 works in synchronous mode is
Multiple isomers is monitored, it is thus achieved that its relative and absolute content information.Finally, when F-DMAA 2 and F-QA 15 all
When being operated in asynchronous mode, different passages are by for different, proprietary ionic mobility ion karyoplasmic ratios pair, thus effectively
Different types of ion is screened on ground.
As shown in Figure 4 A, it is possible to use the difference ion mobility spectrometry analyzer array of similar embodiment two cylindrical structure
(C-DMAA) combination of the 11 level Four bar arrays (C-QA) 16 being distributed with cylindrical shape carries out ion analysis.Draw from C-DMAA 11
Ion can enter next stage C-QA 16, after quality analysis by a cylindric ion transfer passage array 12
Evict to ion detector array 17, to reach the purpose of quality analysis.The advantage using this structure is that total is with circle
Cylinder axle center is symmetrical, is consequently adapted to import the generation ion of independent ion source 10.At this moment, the operation of whole ion analyzer
Pattern is identical with the operational mode of aforementioned slab construction.
Furthermore, as shown in Figure 4 B, each unit of the level Four bar array 16 of cylindric distribution also can be close to each other, logical
Cross and exported by a cylinder conversion dynode 18.Then the ion detector array at rear portion is further simplified as one individually
Ion detector 14, to reduce the cost that detector and rear class signals collecting are amplified.But, due to the level Four usual work of bar mass spectrum
Make in a continuous mode, use level Four bar array to be that ion will not carry out richness during detection with the difference of ion trap array
Collection (by contrast, in ion trap array, evict time of time relative ion cooling enrichment etc. from and to be so short that by the ion of each unit
Many), therefore use independent ion detector that each passage of level Four bar array carries out timesharing detection and can be substantially reduced instrument and divide
Analysis efficiency.So, the most whole ion detector is preferably operated under full synchronous mode.
It is worthy of note, even if whole ion analyzer is operated in (either difference ion migration under full synchronous mode
Spectralyzer and ion trap array still with the combination of quadrupole rod array), use multichannel mode also to have its advantage.Former
Because being, the amount of ions that ion source produces under normal circumstances can be far longer than the ion that ion analyzer can introduce and utilize
Quantity, for difference ion mobility spectrometry analyzer, increases ion intake size and can increase the journey that stream field destroys
Degree, thus affect resolution and the stability of instrument.And for the mass analyzer of rear class, for identical ionic flux,
Multi-channel structure can reduce the size of every channel quality analyzer, thus reduces the voltage request of mass analyzer, and this is also
Miniaturization, portability for ion analyzer provide prerequisite.
Embodiment four
For the combination of F-DMAA Yu F-ITA or F-QA in embodiment one and three, it is also possible to there is other geometry.As
Shown in Fig. 5 A, the plate ion transfer passage array of F-DMAA 2 (i.e. airflow direction shown in figure) and next stage can be allowed
3 are disposed vertically so that air-flow front and back is imported and exported and is easier to place.
Such displacement structure can also have a kind of variant, as shown in Figure 5 B by the intake 2a of each passage of F-DMAA 2
Arranging according to centrosymmetric mode, Ion Extraction mouth 2b correspondingly is also by identical structural arrangement.C-ITA 13 simultaneously
Periphery shunting ion detector 19 radially is set.The benefit of this arrangement mode is that such F-DMAA 2 just can be with enforcement
Ion source 10 and C-ITA 13 in example two is combined, and reduces desired ion source and detector and the number of subsequent acquisition amplifying device
Amount.
Fig. 5 C, 5D illustrate the profile of ion trap array.As shown in Figure 5 C, can set at the axis of ion trap array
Putting a common ion detector 14 evicting total ion current for detecting each passage from, this detector 14 also can be with one by being somebody's turn to do
The first dynode on axis replaces so that detector body can be arranged into other correct positions, the so central authorities of design
Ion detection system can be used for collectiong focusing outgoing ion stream on the axis of device and delivering to analog digital conversion collection dress
Put the enhancing that takes a step forward.When ion trap array is longer, drawing ion can be subject to due to ion detector extraction electric field from axis
Difficulty is become to the shielding of ion trap array body electrode.In this case can arrange multiple on axis as shown in Figure 5 D
Shunting ion detector 19 or their multiple first dynodes, the most certain model of each of which ion detector correspondence detection
The ion radially evicted from by each analytic unit in enclosing.
Embodiment five
For the combination of difference ion mobility spectrometry analyzer array Yu mass analyzer array in the various embodiments described above, it is all
Ion qualitative information is obtained based on the ion obtained after selecting according to ionic mobility is directly carried out quality analysis
Concept.But, for most of isomerss, the difference of its molecular structure is likely to be not so large as to be enough to by difference
Ion mobility spectrometry analyzer separates.Therefore, between difference ion mobility spectrometry analyzer and mass analyzer, an ion is increased
Device for dissociation, such that it is able to enable ion analyzer to carry out for a certain daughter ion of the ion with a certain ionic mobility
Monitoring becomes necessary to.Ion Selective reaction monitoring (SRM) pattern that this process is similar in triple quadrupole mass spectrum.At this
Under pattern, the chemical noises that the weakness of the lack of resolution coming from difference ion mobility spectrometry analyzer is caused can be by prison
Survey the peculiar daughter ion of certain isomers and significantly suppressed.Be on duty ion mobility spectralyzer array each unit work
Time in asynchronous mode, this ion analyzer can be operated in and be similar to triple quadrupole mass spectrographic ion multiple-reaction monitoring
(MRM) under pattern.Owing in asynchronous mode, each passage is each independent and works simultaneously, therefore each reaction monitoring can be led to
Road accomplishes to monitor simultaneously, it is to avoid needs for the process that each interchannel switches one by one, can be greatly improved whole instrument
Detection efficiency.
One simple case of ionic dissociation device is a collision cell being filled with certain pressure collision gas.Such as Fig. 6 institute
Showing, one is placed between C-DMAA 11 and C-ITA 13 with the collision cell array 21 of cylindrical shape distribution, and it can be relatively low
Under vacuum, by the ion introduced from each passage of C-DMAA by dissociating with neutral gas collision.The mother that obtains after dissociating,
Daughter ion can be focused on and be eventually entered into the mass analyzer array of rear class under the auxiliary of alternating electric field and be carried out karyoplasmic ratio
Analyze.Mass spectrograph described here both can be quadrupole rod array 16 (C-QA) can also be ion trap array 13 (C-ITA).
In other embodiments, ionic dissociation device can also is that a photodissociation room, at the laser of this ion Yu high energy
Collide and dissociate.Ionic dissociation device can also is that an electron capture dissociation room, at this ion and electron beam interaction
Dissociated.
Embodiment six
For aforementioned each structure, its purpose is provided to come from the complicated ions mixing after liquid chromatograph separates
Thing is effectively separated and detects.Owing to difference ion mobility spectrometry analyzer itself just has certain separation energy to complex sample
Power, therefore can also use a kind of atmospheric pressure direct analysis ion source to be directly combined with described ion analyzer, to exempt use
The analysis speed that liquid chromatograph is brought is slow and numerous and diverse shortcoming prepared by sample.
Fig. 7 illustrates a kind of desorbing corona beam used disclosed by Chinese patent application 200810188989.8 to carry out sample
The direct desorption ionization of product, then uses above-mentioned ion analyzer to carry out the device of ion analysis.In this device, desorbing corona beam
Ion source is added heat pipe 31, spray point 32, ground connection to electrode 33, high voltage power supply 34, heating power supply 35 by gas, and the solution produced
Suction corona beam forms.The ion 36 being desorbed corona beam ion source desorption ionization is uniformly introduced each of C-DMAA 11 as far as possible
Individual passage is separated further and detects.The detection signal of channel ions detector 19 through channel amplifier 22 amplify after,
Send into collecting device 23.
Embodiment seven
For aforementioned each structure, owing to each entrance present position of difference ion mobility spectrometry analyzer array is each not
Identical, it is thus possible to the population of ions amount that each passage entered can be caused different, thus cause in each passage measured from
The signal proportion distortion of son.In order to solve this problem, can visit at one ion stream of connection of each ion intake rear end
Survey device and form array, and ion current detector array is connected with outside current sensing means, and the sign that will record in real time
The current signal of the ion introduction volume of each passage imports data collecting system and contrasts.The most simply tying of this ion current detector
Structure can realize with the little metallic plate array of an additional bias voltage.When ion stream source is chromatograph isopulse form ion
During source, the top crown voltage that bias voltage can be made to be difference ion mobility spectrometry analyzer, detect that this is total by image current method
Ion stream situation of change.When ion stream changes by force slow or constant, it would however also be possible to employ this ion current detector and rear class mass spectrum
The method of detector time-sharing multiplex, such as, in every 20ms, take the 0.5ms time therein, during this period of time by array 20
The current potential of interior each discrete Detection electrode draws to be born to electronegative potential such as-200V so that all cation streams are directed on this pole plate,
And the current potential of the discrete Detection electrode of other times can recover to the normal value needed for difference ion mobility spectrometry analyzer.Due to ion
The strong change of stream slowly, always detects electricity with each unit Detection electrode gained in this 0.5ms and does a simple transformation of scale and many
Item formula interpolation can represent the curent change data flowing into this passage.
Alternating current impression method or time-sharing multiplex method is either used to obtain ion current letter before integral array analytical equipment
Number, owing to this current signal reflects the ion that will enter in each passage total amount before separation, this value is in preferable feelings
Should be independent of the channel position used under condition.According to the current value measured by different Channel front end, can to each passage
Ionic strength measured by end is normalized, and is used for calibrating the object ion intensity finally recorded in each passage, each to ensure
Proportionate relationship component each with the reality ion concentration ratio of ion channel object ion intensity is consistent.
Further, it is also possible to by each passage in the combination of aforesaid any DMAA Yu MSA periodically to coming from one
The same material in individual stabilizing ion source detects respectively, in order to revise the difference of each channel transfer ion efficiency.
As the summary of the mode of operation for the ion detector array described in various embodiments above, table 1 below illustrates root
Sum up chart according to the combination of the various mode of operation of DMAA Yu ITA of one embodiment of the invention, make embodiments of the invention brighter
?.
Table 1
Owing to difference ionic migration spectrometer array can be operated under synchronous mode or asynchronous mode, mass spectrograph array also may be used
To be operated under synchronous mode or asynchronous mode.The ion analysis method of the present invention include with in sampling process signal change and
The mode of operation of difference ionic migration spectrometer array and/or mass spectrograph array is switched over, to obtain desired performance, example
Such as high-resolution, high sensitivity, high efficiency etc..
Additionally it is worthy of note, in addition to the structure disclosed by above-described embodiment, the present invention can also use existing
Ion trap analyzer array uses with ion mobility spectrometry array coupling.Such as, Fudan University's fourth passes all et al. at Chinese patent
The ion storage proposed in application 200610001017.4 and U.S. Patent application 2009/0294655 A1 and analytical equipment battle array
Row.And for example, the column type ion trap array and afterwards that in United States Patent (USP) US6762406, RG Cook seminar of Purdue University proposes
The column type ion trap array mass analyzer chip based on micromechanics Yu micro-processing technology (MEMS) that Ramsy et al. makes.
Or in Chinese patent application 200910054963.9, Fudan University Pan Xin deep pool et al. simplifies from electrode structure further
Above-mentioned fourth passes all et al. designed PCB electrode runs parallel array structure ion traps.
The present invention is used as other quadrupole rod analyzer arrays and to use with ion mobility spectrometry array coupling.Such as,
Ferran et al. is in United States Patent (USP) 5401962 and J.Vac.Sci.Technol.A, described in 1996, Vol 14 (3), p1258
, and the ten six types of severe debility disease array matter that fourth army equality people (mass spectrum journal, Vol22, No.3,29-35.) develops on this basis
Spectrometer.For relatively common quadrupole rod analyzer, such mass spectrograph array has the features such as volume is little, quality is clear, low in energy consumption.
Although the present invention discloses as above with preferred embodiment, so it is not limited to the present invention, any this area skill
Art personnel, without departing from the spirit and scope of the present invention, when making a little amendment and perfect, the therefore protection model of the present invention
Enclose when with being as the criterion that claims are defined.Such as, ion source used is not electron spray, but atmosphere pressure chemical ion source；
It not desorbing corona beam ion source, but desorption electrospray source (DESI) or directly analyze ion source (DART) in real time.For another example, institute
State ion analyzer to be possible not only to and liquid chromatograph or direct analyzing method coupling, it is also possible to and capillary electrophoresis or gas chromatogram
Coupling.
Claims (21)
1. an ion analyzer, comprises the ion source being sequentially connected or ion source array, difference ion mobility spectrometry analyzer battle array
Row, ion transfer passage array, mass analyzer array and ion detector or ion detector array, wherein:
Described difference ion mobility spectrometry analyzer array, described ion transfer passage array, described mass analyzer array are each
Comprise two or more passage, and a passage of each described difference ion mobility spectrometry analyzer array is at least described in corresponding one
One passage of mass analyzer array.
Ion analyzer the most according to claim 1, it is characterised in that described mass analyzer array is level Four bar array
Or ion trap array.
Ion analyzer the most according to claim 1, it is characterised in that also include ionic dissociation device, be located at described from
Between sub-transfer passage array and described mass analyzer array.
Ion analyzer the most according to claim 3, it is characterised in that described ionic dissociation device be gas collisions room,
Or photodissociation room or electron capture dissociation room.
Ion analyzer the most according to claim 1, it is characterised in that described difference ion mobility spectrometry analyzer array is
Planar structure, ion entrance is positioned at the relatively the same position of each passage, and the relative position phase of each channel ions exit slit
With.
Ion analyzer the most according to claim 1, it is characterised in that described difference ion mobility spectrometry analyzer array is each
Passage is centrosymmetric structure, and each passage correspondence centrage is distributed in radial symmetric.
Ion analyzer the most according to claim 1, it is characterised in that each unit of described mass analyzer array
It is equipped with independent ion detector and data acquisition amplification system.
Ion analyzer the most according to claim 1, it is characterised in that each unit of described mass analyzer array in
Heart symmetrical structure, and each unit shares an ion detector and data acquisition amplification system.
Ion analyzer the most according to claim 1, it is characterised in that described difference ion mobility spectrometry analyzer array is
Being operated under synchronous mode or asynchronous mode, described mass analyzer array is to be operated under synchronous mode or asynchronous mode.
Ion analyzer the most according to claim 1, it is characterised in that described difference ion mobility spectrometry analyzer array
Work is under atmospheric pressure.
11. ion analyzers according to claim 1, it is characterised in that described difference ion mobility spectrometry analyzer array
In the environment of being operated in subatmospheric but being not less than 0.1torr.
12. ion analyzers according to claim 1, it is characterised in that described difference ion mobility spectrometry analyzer array
In airflow direction and described ion transfer passage array axially vertical.
13. ion analyzers according to claim 1, it is characterised in that described difference ion mobility spectrometry analyzer array
Each feeder connection at be provided with an ion current detector, and described ion current detector and outside current sensing means phase
Even.
14. ion analyzers according to claim 1, it is characterised in that described ion source comprises an isotopic ion
Source, and described isotopic ion source can need by machinery the most open or close according to experiment.
The ion analysis method of 15. 1 kinds of ion analyzers using claim 1, produces including by ion source or ion source array
Raw ion introduces each passage of difference ion mobility spectrometry analyzer array, carries out choosing based on ionic mobility through each passage
After selecting, after ion transfer passage array, enter mass analyzer array and finally by ion detector or ion detector battle array
Row are detected.
16. methods according to claim 15, it is characterised in that also include making ion enter described mass analyzer battle array
Before each passage of row, it is introduced into an ionic dissociation device, so that ion can dissociate in described ionic dissociation device.
17. methods according to claim 15, it is characterised in that described difference ion mobility spectrometry analyzer array is work
Under synchronous mode or asynchronous mode, described mass analyzer array is to be operated under synchronous mode or asynchronous mode, described side
Method include with in sampling process signal change and to described difference ion mobility spectrometry analyzer array and/or described mass spectral analysis
The mode of operation of device array switches over.
18. methods according to claim 15, it is characterised in that comprise use level Four bar array or ion trap array conduct
Described mass analyzer array.
19. methods according to claim 15, it is characterised in that when using a described ion detector, described side
Method includes that the mode using Time share scanning to evict from detects the ion information of each passage.
20. methods according to claim 15, it is characterised in that also comprise use one and be positioned at difference ion mobility spectrometry and divide
Ion current detector at each feeder connection of parser array, is monitored the ion introduction volume of each passage, and obtained is each logical
After the intensity normalization of the described ion stream in road, it is used for calibrating the object ion intensity finally recorded in each passage.
21. methods according to claim 15, it is characterised in that comprise one radiation being positioned in described ion source of use
Property ion source, and by use that described isotopic ion source produces by described ion analyzer each passage respectively certain is specific
Ion carries out periodic detection, after the ionic strength normalization that final each passage is obtained on described ion detector, for school
The object ion intensity finally recorded in accurate each passage.
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| CN103824750A (en) * | 2014-02-17 | 2014-05-28 | 同济大学 | Array triple-quadrupole mass spectrum system |
| GB2534331B (en) * | 2014-06-02 | 2017-06-21 | Thermo Fisher Scient (Bremen) Gmbh | Improved imaging mass spectrometry method and device |
| CN104992894B (en) * | 2015-05-05 | 2017-09-29 | 中国计量科学研究院 | Networking mass analysis method and device |
| US9607817B1 (en) * | 2015-09-11 | 2017-03-28 | Thermo Finnigan Llc | Systems and methods for ion separation |
| WO2017158534A1 (en) * | 2016-03-15 | 2017-09-21 | Dh Technologies Development Pte. Ltd. | Systems and methods for multi-channel differential mobility spectrometry |
| CN107271575B (en) * | 2016-04-08 | 2020-01-14 | 株式会社岛津制作所 | Method and device for parallel analysis of ion mobility spectrometry and mass spectrometry |
| CN106384705B (en) * | 2016-08-29 | 2019-02-19 | 山东省分析测试中心 | A kind of high-throughput Nanoliter electrospray analysis system and its application based on miniature array |
| CN109813798B (en) * | 2017-11-21 | 2021-10-29 | 中国科学院大连化学物理研究所 | Method for continuously monitoring hazardous chemical substances on line or rapidly identifying leaked substances |
| US10663428B2 (en) | 2018-06-29 | 2020-05-26 | Thermo Finnigan Llc | Systems and methods for ion separation using IMS-MS with multiple ion exits |
| CN114527187A (en) * | 2020-11-02 | 2022-05-24 | 岛津分析技术研发（上海）有限公司 | Ion analysis apparatus and method |
| CN112382554A (en) * | 2020-11-12 | 2021-02-19 | 上海裕达实业有限公司 | Device and method for adjusting high-order field in linear ion trap in real time |
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