CN106324078A - Modified Hadamard multiplexing counter ion migration spectrum experimental apparatus - Google Patents
Modified Hadamard multiplexing counter ion migration spectrum experimental apparatus Download PDFInfo
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- CN106324078A CN106324078A CN201610817712.1A CN201610817712A CN106324078A CN 106324078 A CN106324078 A CN 106324078A CN 201610817712 A CN201610817712 A CN 201610817712A CN 106324078 A CN106324078 A CN 106324078A
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- counter ion
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- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/68—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 using electric discharge to ionise a gas
- G01N27/70—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 using electric discharge to ionise a gas and measuring current or voltage
Abstract
The invention relates to a modified Hadamard multiplexing counter ion migration spectrum experimental apparatus, comprising a migration pipe, a modified Hadamard multiplexing counter ion gating module and a data processing unit, wherein the migration pipe comprises an ionic source area, a curtain gas area, a reaction area, a migration area, a detection area and an ionic gate, the curtain gas area is used for blocking a sample from entering the ionic source area, the ionic gate is arranged between the reaction area and the migration area, and the modified Hadamard multiplexing counter ion gating module is composed of a linear feedback shifting register set, a secondary multiplexing encoder, and a reverse boost ionic gating module; first, the linear feedback shifting register set generates a pseudorandom gating digital sequence, the secondary multiplexing encoder modifies the initial pseudorandom sequence into a set of isolated quasi-pseudorandom sequence codes, the reverse boost ionic gating module is used to convert the digital sequence into reverse pulses to finish boosting, the boosted reverse gating pulse signals are connected to two ends of the ionic gate, and multiplex reverse on-off control of the ionic gate is achieved. The signal-noise ratio detecting performance of existing counter ion migration spectrum can be effectively improved.
Description
Technical field
The Hadamard multiplexing counter ion that the present invention relates to a kind of improvement migrates spectrum experimental device.
Background technology
In recent years, the most external or domestic, various sudden and violent probably activities are becoming increasingly rampant, and ion mobility spectrometry is quick as one
Trace explosive, gas detection equipment, increasingly get more and more people's extensive concerning, its technology have also been obtained swift and violent sending out
Exhibition.
Ion mobility spectrometry, compared with other anti-riot anti-terrorism detection instruments, has that equipment is simple, detection limit is low, detection speed is fast
Etc. advantage, thus it is particularly suitable for the compound such as poison, explosive is used for quickly detecting.Ion mobility spectrometry ultimate principle is to utilize not
Homo-ion have different migration velocities to distinguish test substance after the match in Weak Uniform Electromagnetic.Ion migration spectrum detection device initially goes out
Now the sixties in 20th century, it was mainly used in the military fields such as trace chemistry war agent at that time.At present, along with various suicide bombings
Deng being becoming increasingly rampant of terrorist activity, join the most in a large number in the safety check department in the places such as airport, railway station, subway station, customs port
For ionic migration spectrometer, to assist security staff to complete the quick detection of people and thing.
The working mechanism of corona discharge ionization mobility spectrometer: first in ionization source region, by electrion for air or nitrogen
The electric discharge reaction of formation thing ion such as gas or electronics, following reaction thing ion enters reaction zone under the traction of axial electric field；Instead
Answer district, reactant ion (also referred to as parent ion), with the sample gas molecule being passed through, a series of ion-molecule reaction occurs,
Sample molecule changes into product ion the most at last；Product ion or reactant ion continue to transport vertically under uniform electric field effect
Dynamic, reaction zone and migration area are separated by by ion gate, and ion gate is periodically beaten under ion gate sequencing contro
Open and close, when ion gate opens moment, the product ion or the reactant ion that are deposited on ion gate quickly enter migration
District, migration area has uniform and stable weak electric field, and it gives axial migration electric field action to product ion or reactant ion
Power so that it is carry out lateral drift, collides, due to different products with oncoming neutral fluxes gas molecule when drift
Thing ion has different electric charge, quality and collision cross sections, and therefore different ions is migrating electric field and the effect of impact force
Lower can form different migration rates, this results in different product ions and arrives detector with the different time, the most not
Same product ion is effectively separated.
For ion mobility spectrometry, signal to noise ratio and resolution always weigh the important technology index of its detection performance.
In order to improve the resolution of ion mobility spectrometry, Iranian proposes a kind of counter ion and migrates spectral technology, and this technology is on the biggest rule
On the basis of mould changes hardware configuration, effectively improve the resolution of ion mobility spectrometry, by the increase resolution of conventional method
About 60%.But, this technology still suffers from certain defect, i.e. detection signal-to-noise ratio is low, and this defect causes counter ion to migrate combining of spectrum
Close detection hydraulic performance decline, it is difficult to be widely popularized.
Therefore, while ensureing that counter ion migrates spectrum high-resolution, how improving its signal to noise ratio is urgently to solve at present
Problem certainly, this further genralrlization that counter ion is migrated spectrum is of great advantage.
Summary of the invention
The technology of the present invention solves problem: overcome existing counter ion to migrate the deficiency of spectrum poor signal to noise, it is provided that a kind of Hadamard
Multiplexing counter ion migrates spectrum experimental device, utilizes multiplexing technique effectively to solve conventional counter ion and migrates spectrum signal utilization
The low problem accounting for poor signal to noise of rate, effectively improves counter ion and migrates the detection performance of spectrum.
The technology of the present invention solution: the Hadamard multiplexing counter ion of a kind of improvement migrates spectrum experimental device, its bag
Include: migration tube, Hadamard multiplexing counter ion gating module, data processing unit three bulk are constituted.Migration tube mainly includes
Ionized region, Lian Qi district, reaction zone, ion gate, migration area and charge detection district are constituted.Described ionized region uses negative corona for plate
Formula discharge mode reaction of formation thing ion, the curtain gas being passed through in described Lian Qi district can intercept sample gas and enter described ionized region,
Described reaction zone is provided with gas sampling mouth and gas outlet, and described ion gate is connected with ion door control unit, described migration area by
The alternately placement of a series of beckets and polytetrafluoroethylene ring forms, and the concatenation formation of each becket is uniformly moved by even resistance
Move electric field；Described charge detection district detects ionic charge signal by faraday's plate, and signal accesses inspection stream amplifier.Institute
State Hadamard multiplexing counter ion gating module mainly by four module compositions, including pseudo-random sequence generator, isolation
Hadamard encoder, phase-reversal coding device and a few part of level switch module are constituted.First 2 are generated by n bit shift registern-1
Pseudo-random sequence, this pseudo-random sequence is transformed into a quasi-pseudo-random sequence by recycling secondary coding device, utilizes one reversely
This quasi-pseudo-random sequence is converted into reverse ion gate output signal and is connected with ion gate two ends by level switch module；Described
Data processing unit mainly realizes the multichannel stack spectral data collected are carried out inversion process, obtains the reverse ion of reduction
Migrate spectrum signal.
In one embodiment of the invention, described ionized region uses negative corona discharge pattern, utilizes negative high voltage module defeated
Going out high pressure to realize for board-like electric discharge to spray point, ionization source is by a negative high voltage module output-6000V to-14000V
High pressure, obtains reactant ion or electronics by spray point to air or nitrogen discharge.
In one embodiment of the invention, BN type ion gate, ion gate it are provided with between described reaction zone and migration area
It is connected with Hadamard multiplexing counter ion door control unit.
In one embodiment of the present of invention, migration area is uniformly composed in series by the valued resistor such as a group, carries for ion motion
For a uniform weak electric field.
In one embodiment of the invention, the Hadamard counter ion door control unit of described improvement is occurred by pseudo-random sequence
Device, modified model Hadamard encoder and counter ion gating module are constituted.Described pseudo-random sequence generator is carried out structure by FPGA software
Make, utilize the Verilog of FPGA first to construct one group of linear feedback shift register, and and then export corresponding pseudorandom sequence
Row；Described modified model Hadamard encoder carries out secondary coding and obtains one group of quasi-pseudo-random sequence pseudo-random sequence；Described instead
Ion gating module quasi-puppet Serial No. immediately (TTL low level signal) is converted into reversely gate pulse pulse signal (0～
The high level signal of 200V).
In one embodiment of the invention, described migration area uniformly migrates electric field and is obtained by dividing potential drop mode, migrates electric field
Field intensity is 200～about 400V/cm.
In one embodiment of the invention, described charge detection district is made up of metallic shield net and charge detection plate.
Further, described data processing unit utilizes the multichannel stack spectral that inversion process software based on VC will collect
Data carry out inversion process, obtain demultiplexing spectrum signal.
Further, described data processing unit utilizes USB interface to be connected with PC, host computer complete the initial of capture card
Change operation sum factually time read and interface display.
In one embodiment of the invention, described Hadamard counter ion migrates spectrum and is operated in room temperature, atmospheric pressure environment, need not
Temperature or humidity control apparatus are set.
Present invention advantage compared with prior art is: the Hadamard multiplexing counter ion of a kind of improvement of the present invention moves
Moving spectrum experimental device is the Hadamard multichannel multiplexing method of improvement to be applied to counter ion first migrate in spectral technology, and the method is also
It not simply with counter ion, Hadamard method to be migrated spectral technology to combine, but utilize the multiplexing coded method improved
Migrate spectral technology with counter ion to combine, both ensured that counter ion migrates the high-resolution characteristic of spectrum, can be effectively improved again instead from
Son migrates the signal to noise ratio of spectrum, it is provided that counter ion migrates the comprehensive detection performance of spectrum, and this invention is that counter ion migrates spectral technology
Further genralrlization provides a kind of effective solution.The Hadamard multiplexing counter ion of a kind of improvement of the present invention migrates spectrum
The detection signal-to-noise ratio that experimental provision obtains is 57 times that conventional counter ion migrates spectrum, and additionally the present invention can be additionally used in other class
As in pulse separation technique.
Accompanying drawing explanation
Fig. 1 is that the Hadamard multiplexing counter ion of a kind of improvement of the present invention migrates spectrum experimental device structure
Fig. 2 is that the modified model Hadamard multiplexing counter ion door control unit in the present invention controls sequential chart
Fig. 3 is that the present invention composes single material (CCl with other several migration4) testing result comparison diagram
Fig. 4 is that the present invention composes many product ion (CHCl with other several migration3) testing result comparison diagram
Wherein, 1-ionizes source region, 2-Lian Qi district, 3-reaction zone, 4-migration area, 5-detecting area, 6-corona discharge needle, 7-electricity
From gas outlet, district, 8-curtain gas air inlet, gas outlet, 9-reaction zone, 10-carrier gas air inlet, 11-ion gate, 12-modified model hada
Agate multiplexing counter ion door control unit, 13-uniformly migrates electric field, 14-metallic shield net, 15-charge detector, 16-signal
Amplifier, 17-data processing unit, 18-migration area air inlet.
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of the present invention is described in detail.
As it is shown in figure 1, the Hadamard multiplexing counter ion of a kind of improvement migrates spectrum experimental device, it includes ionizing source region
1, Lian Qi district 2, reaction zone 3, migration area 4, charge detection district 5, ion gate 11, Hadamard multiplexing counter ion door control unit 12
Form with data processing section 17.Described ionization source region use negative corona discharge pattern, utilize negative high voltage module output high pressure to
Corona discharge needle 6 completes for board-like electric discharge, reaction of formation thing ion；Described Lian Qi district utilizes the curtain gas 8 being blown into stop sample
Gas enters ionization source region 1；Described reaction zone is provided with sample air inlet 10 and gas outlet 9；Described ion gate 11 and Hadamard
Multiplexing counter ion door control unit 12 is connected；Described migration area 4 is handed over polytetrafluoroethylene ring by a series of stainless steel metal rings
Forming for placement, concatenate each becket by even resistance and then form uniformly migration electric field 13, in migration area, end moves
Move district's air inlet 18；The ion current signal detected is converted into voltage by faraday's plate 15 and believes by described charge detection district 5
Number, after signal amplifier 16 amplifies, access data processing unit 17.
In place of Hadamard multiplexing counter ion gating module is the main innovation of the present invention.As far back as 2010, in order to carry
Macroion migrates the resolution of spectrum, and foreign scholar proposes counter ion and migrates spectral technology, and this technology is hard in extensive change
On the premise of part structure, successfully the resolution of ion mobility spectrometry is improve about about 60%, but, the method still suffers from portion
Point defect, is exactly wherein that signal to noise ratio is low than more typical problem, has declined relative to the signal to noise ratio of traditional ion mobility spectrometry；
It is true that for the signal to noise ratio improving ion mobility spectrometry, just propose to apply Hadamard multiplexing technique as far back as 2006 people
In ion mobility spectrometry, compared with Fourier transformation method, it is fast that Hadamard multiplexing technique has simple in construction, decoding speed
Feature, thus be especially suitable for the detection performance for improving ion mobility spectrometry.Therefore, the letter of spectrum is migrated in order to make up counter ion
Making an uproar the low defect of ratio, the present invention proposes that Hadamard multiplexing technique is applied to counter ion and migrates in spectral technology, constructs one
Plant Hadamard multiplexing counter ion and migrate spectral apparatus.
The critical component of the present invention is the Hadamard multiplexing counter ion door control unit improved, and it constructs sequential such as Fig. 2
Shown in.Described Hadamard multiplexing counter ion gating module 12, by linear feedback shift register 19, generates initial pseudorandom
Sequence set, then by secondary multiplexing coding module 20, initial pseudorandom sequence is converted into one group of quasi-pseudo-random sequence, finally
(export, when Serial No. " 1 " is corresponding, electricity of closing the door through reverse boost module 21 output multi-channel multiplexing reverse ion gate pulse signals
Pressure 80～200V, sequence " 0 " corresponding output enabling voltage 0V, i.e. ion gate is opened), this and conventional ion mobility spectrometry forward arteries and veins
Punch die formula is different.The a width of 200 μ s of intermediate ion portal vein of the present invention.Finally, Hadamard counter ion gate pulse signals is received ion
Door 11 two ends realize the High-speed on-off control of ion gate.
The pseudo random sequence code selected in the embodiment of the present invention is 255 that 8 longest linear feedback shift registers generate
Rank sequence, often in group pseudo-random sequence, many one of the number of 1 number than 0；In order to obtain more preferable signal to noise ratio, keep simultaneously
Higher resolution, the present invention and non-immediate using this pseudo-random sequence as final counter ion gate input signal, but right
This sequence is improved, and i.e. uses the mode inserting isolation code element after pseudo-random sequence to obtain one group of quasi-pseudo-random sequence,
Finally again this sequence is applied on counter ion gating device, it is achieved the multiplexing of ion gate controls.
Fig. 3 show and uses distinct methods to contrast the testing result of CCl4: detection method have conventional counter ion migrate compose,
Hadamard counter ion migrates spectrum and the Hadamard counter ion improved migrates spectrum, and its testing result corresponds respectively to Fig. 3-a～c.Can
See, be directly applied to Hadamard method in counter ion migration spectrum signal to noise ratio to be improved about 4 times, but resolution have dropped about
50%；When the Hadamard counter ion of improvement utilizing the Hadamard method improved to obtain migrates spectrum, its signal to noise ratio than conventional anti-from
Son migrates spectral method and improves about 5 times, and resolution is about conventional counter ion and migrates the 92.5% of spectrum.
Fig. 4 show employing distinct methods to CHCl3Testing result contrast: detection method has counter ion to migrate
Spectrum, Hadamard counter ion migrate spectrum and the Hadamard counter ion improved migrates spectrum, and its testing result corresponds respectively to Fig. 4-a～c.
Signal to noise ratio can be improved about 6 times by visible directly Hadamard method being applied in counter ion migration spectrum, but resolution have dropped about
40%；When the Hadamard counter ion of improvement utilizing the Hadamard method improved to obtain migrates spectrum, its signal to noise ratio than conventional anti-from
Son migrates spectral method and improves about 7 times, and the resolution obtained is about conventional counter ion and migrates the 93% of spectrum, and letter is relatively substantially improved
For making an uproar than performance, the decline of resolution is negligible.
Test result indicate that, either mono-product species ion is detected or the detection to many product ions, utilize this
Bright method can be effectively improved counter ion and migrate the comprehensive detection performance of spectrum.
There is provided above example to be only used to describe the purpose of the present invention, and be not intended to limit the scope of the present invention.This
The scope of invention is defined by the following claims.Various equivalents made without departing from spirit and principles of the present invention and repairing
Change, all should contain within the scope of the present invention.
Claims (9)
1. the Hadamard multiplexing counter ion improved migrates a spectrum experimental device, and it includes ionizing source region 1, Lian Qi district 2, anti-
Answer district 3, migration area 4, charge detection district 5, ion gate 11, Hadamard multiplexing counter ion door control unit 12 and data processing division
Divide 17 compositions.Described ionization source region uses negative corona discharge pattern, utilizes negative high voltage module output high pressure complete to corona discharge needle 6
Become for board-like electric discharge, reaction of formation thing ion；Described Lian Qi district utilizes the curtain gas 8 being blown into stop sample gas to enter ionization
District；Described reaction zone is provided with sample air inlet 10 and gas outlet 9；Described ion gate 11 multiplexes counter ion door with Hadamard
Control unit 12 is connected；Described migration area 4 is formed with polytetrafluoroethylene ring alternately placement by a series of stainless steel metal ring, passes through
Even resistance concatenates each becket and then forms uniformly migration electric field 13, has migration area air inlet 18 at migration area end；Institute
State charge detection district 5 and the ion current signal detected is converted into voltage signal, through signal amplifier by faraday's plate 15
Data processing unit 17 is accessed after 16 amplifications.
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 1 migrates spectrum experimental device, its feature
It is: described migration area (4) are staggeredly placed by a series of beckets and polytetrafluoroethylene ring and form, by even resistance by each
Becket concatenation is formed and migrates electric field (13) uniformly.
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 1 migrates spectrum experimental device, its feature
It is: described ionization source region (1) utilizes negative high voltage module to apply negative high voltage to spray point, and uses for board-like discharge mode.
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 1 migrates spectrum experimental device, its feature
It is: described ionization source region (1) and described reaction zone (3) are intercepted by described Lian Qi district (2), and described Lian Qi district is used for completely cutting off sample
Molecule enters ionized region.
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 1 migrates spectrum experimental device, its feature
Be: the gate-width time range of the ion gate of described ion gate (11) is 100～250 μ s, migrate electric field strength be 200～
400V/cm。
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 1 migrates spectrum experimental device, its feature
Being, described charge detection district (5) includes a porous metals gauze screen (14) and faraday's plate (15), by faraday's plate (15)
Detection charge signal, and finally access data processing unit (17) through signal amplifier (16).
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 6 migrates spectrum experimental device, its feature
It is: described data processing unit (17) is to be realized by high speed USB data capture card, it entered by signal real-time detected
Row A/D high-speed transitions and automatically storage, sample frequency is 20k～50khz, and data acquisition uses continuous acquisition pattern, subchannel
Receive the data of sensor acquisition, it is not necessary to external A/D chip.
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 6 migrates spectrum experimental device, its feature
It is: the collection start-stop action of described data processing unit (17) is controlled by periodically pulsing synchronizing signal, this synchronizing signal
Cycle in the same size with one group of Hadamard counter ion gate sequence cycle, and be all controlled by FPGA ion gate software control.
The Hadamard multiplexing counter ion of a kind of improvement the most according to claim 1 migrates spectrum experimental device, its feature
It is: described Hadamard multiplexing counter ion gating module (12), by linear feedback shift register (19), generates initial pseudo-
Random sequence group, then by secondary multiplexing encoder (20), initial pseudorandom sequence is converted into one group of quasi-pseudo-random sequence,
It is connected with ion gate (11) two ends through reverse boost module (21) output multi-channel multiplexing reverse ion gate pulse signals after, real
The high-speed reverse multiplexing of existing ion gate controls.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107478710A (en) * | 2017-09-14 | 2017-12-15 | 安徽理工大学 | One kind eliminates Hadamard ion mobility spectrometry baseline drift distortion methods |
| CN108169321A (en) * | 2017-12-21 | 2018-06-15 | 中国科学院电子学研究所 | High pure nitrogen detection method and device |
| CN108776166A (en) * | 2018-05-29 | 2018-11-09 | 中国科学院合肥物质科学研究院 | A kind of spectrum modulation Hadamard transform ionic migration spectrometer |
| CN110289203A (en) * | 2019-06-03 | 2019-09-27 | 清华大学深圳研究生院 | A kind of corona discharge ionization source structure and ionic migration spectrometer |
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