CN106783506B - It is a kind of to utilize dipulse, the ionic migration spectrometer and detection method of the voltage-controlled ion gate processed of Asymmetric Electric - Google Patents

It is a kind of to utilize dipulse, the ionic migration spectrometer and detection method of the voltage-controlled ion gate processed of Asymmetric Electric Download PDF

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CN106783506B
CN106783506B CN201611121527.5A CN201611121527A CN106783506B CN 106783506 B CN106783506 B CN 106783506B CN 201611121527 A CN201611121527 A CN 201611121527A CN 106783506 B CN106783506 B CN 106783506B
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voltage
ion
ion gate
plain conductor
electric field
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CN106783506A (en
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黄超群
夏磊
沈成银
江海河
储焰南
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Hefei Institutes of Physical Science of CAS
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Hefei Institutes of Physical Science of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/06Electron- or ion-optical arrangements
    • H01J49/067Ion lenses, apertures, skimmers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62Investigating 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
    • G01N27/622Ion mobility spectrometry
    • G01N27/624Differential mobility spectrometry [DMS]; Field asymmetric-waveform ion mobility spectrometry [FAIMS]

Abstract

Dipulse, the ionic migration spectrometer and detection method of the voltage-controlled ion gate processed of Asymmetric Electric, including Bradbury Nielson types ion gates (3), divider resistance (4), dual-pulse power supply (5) and an ion signal detector (6) being made of the plain conductor A (1), the conducting wire B (2) that are generally aligned in the same plane and are parallel to each other are utilized the present invention relates to a kind of.Using dipulse, the on and off of the voltage-controlled ion gate processed of Asymmetric Electric, the influence being distributed by the asymmetric voltage on dual-pulse power supply control and ion gate to migration tube internal electric field, realizes sensitivity and the resolution ratio for improving ion mobility spectrometry at the same time.

Description

It is a kind of using dipulse, the voltage-controlled ion gate processed of Asymmetric Electric ionic migration spectrometer and Detection method
Technical field
The invention belongs to analytical instrument and detection field, and in particular to one kind using dipulse, Asymmetric Electric it is voltage-controlled make from The ionic migration spectrometer and detection method of cervical orifice of uterus.
Background technology
The sensitivity of ion mobility spectrometry and resolution ratio are to weigh the core parameter of its performance.Sensitivity is weighed with peak area, The number of ions detected is more, and area is bigger, and sensitivity is better.And (t refers to transit time to resolution ratio R=t/ Δs t, and Δ t is migration The halfwidth of spectral peak), peak is narrower, and resolution ratio is higher.But resolution ratio and sensitivity mutually restrict, resolution ratio is improved often To sacrifice sensitivity as cost, vice versa.Ion gate is one of core component of ion mobility spectrometry instrument, utilizes Asymmetric Electric The switch of voltage-controlled ion gate processed, can change the electric field distribution in migration tube, so as to improve the sensitivity or resolution of ion mobility spectrometry Rate.
In ion mobility spectrometry, generally use pulse, symmetrical voltage control Bradbury-Nielson type ion gates, its Control mode is as shown in Figure 1:Ion gate is made of two groups of parallel metal wires A, B apart from one another by arrangement, R1And R2It is partial pressure electricity Resistance, V0It is the voltage of plane residing for ion gate, Vd、tdIt is the impulse amplitude and width of ion gate shutdown voltage respectively, ion gate is opened Pass is controlled by pulse voltage symmetry.When ion gate is closed, due to R1=R2, the voltage on A, B conducting wire is V respectively0+Vd/2With V0-Vd/2, there are potential difference Vd.At this time, as shown in Fig. 1 (b), ion gate will form shutdown electric field in migration tube cross-sectional direction, Ion gets to that conducting wire A, B are upper can not to pass through ion gate.It is V when applying amplitude on ion gatedPulse voltage when, conducting wire A, B When current potential is equal, ion gate is opened, and ion passes through migration area.It can be seen that from Fig. 1 (b), (c), in this pulse pair Claim under voltage mode control, no matter the electric field in closing or opening, migration tube axis is all close to uniform for ion gate Electric field, shutdown voltage is on the electric field in migration tube substantially without influence.
And pulse, asymmetric voltage mode control are used, that is, work as R1≠R2, i.e. R1> R2Or R1< R2When, ion Inhomogeneous field occurs afterwards in front of the door, so as to influence distribution and the motion state of ion, improve ion mobility spectrometry resolution ratio or Sensitivity.
(1) R is worked as1> R2, as shown in Fig. 2, considering a kind of extreme case:That is R2Disconnect, adjust R1, make the voltage on conducting wire A For V0+Vd, the voltage on conducting wire B is V0, that is, VA> VB, VA-VB=Vd, shutdown voltage VdIt is from conducting wire A (1) to produce one To the shutdown electric field of conducting wire B (2).It can be seen that from the analog result of Fig. 2 (b), when ion gate is closed, shutdown voltage VdIt can disturb and move The uniformity of pipe internal electric field is moved, causes the electric field of near zone before ion gate to die down, and the electric field after ion gate is by dying down by force.By The electric field of near zone dies down before ion gate, and the ion populations for causing to assemble here are reduced.After ion gate is opened, injection The amount of ions of migration area is accordingly reduced, and the sensitivity of ion mobility spectrometry declines.Ion gate enters closed mode again after opening, this When migration area electric field present by the trend that dies down by force, cause the electric field strength into the ion beam left side of migration area to be always more than the right Electric field strength, therefore ion beam migrate when, always compressed, spectral peak is narrowed, resolution ratio enhancing.Using this pulse, The mode of the voltage-controlled ion gate processed of Asymmetric Electric, is compared, sensitivity with the ion mobility spectrometry of pulse, symmetrical voltage control ion gate Reduce but resolution ratio improves.
(2) R is worked as1< R2, as shown in figure 3, considering a kind of extreme case, i.e. R1Disconnect, adjust R2, make the voltage on conducting wire B For V0+Vd, the voltage on conducting wire A is V0, that is, VA< VB.Under this pulse, asymmetric voltage mode control, such as Fig. 3 Shown, when ion gate is closed, the electric field of near zone becomes strong before ion gate, makes to be gathered in the ion populations before ion gate and increases, After ion gate is opened, more polyion will inject migration area;And the electric field after ion gate changes from weak to strong, ion bag can be pulled, make from Attached bag broadens.Using this control model, compared with the ion mobility spectrometry of pulse, symmetrical voltage control ion gate, resolution ratio Reduce but sensitivity improves.
To sum up analysis is understood, when ion gate processed voltage-controlled using pulse, Asymmetric Electric, Ion transfer can only be respectively increased The sensitivity of spectrum or resolution ratio, and them can not be improved at the same time.
The content of the invention
The technical problem to be solved in the present invention is:Overcome pulse, asymmetric voltage control method can only be respectively increased from The sensitivity of sub- migration spectrum or the deficiency of resolution ratio, there is provided a kind of to utilize dipulse, the ion of the voltage-controlled ion gate processed of Asymmetric Electric Mobility spectrometer and detection method.Using dipulse, the on and off of the voltage-controlled ion gate processed of Asymmetric Electric, controlled by dual-pulse power supply The influence being distributed with the asymmetric voltage on ion gate to migration tube internal electric field, realizes the sensitivity for improving ion mobility spectrometry at the same time And resolution ratio.
The technology of the present invention solution:
It is a kind of to utilize dipulse, the ionic migration spectrometer of the voltage-controlled ion gate processed of Asymmetric Electric, including Bradbury- Nielson types ion gate, divider resistance, dual-pulse power supply and ion signal detector, wherein, the Bradbury- The plain conductor A and plain conductor B that Nielson types ion gate is generally aligned in the same plane and is parallel to each other by one group are formed, dipulse Power supply is connected by divider resistance with plain conductor A, or dual-pulse power supply is connected by divider resistance with plain conductor B, from Subsignal detector is used to detect ion signal.
It is a kind of using dipulse, the ionic migration spectrometer detection method of the voltage-controlled ion gate processed of Asymmetric Electric, using above-mentioned Ionic migration spectrometer, the voltage of migration tube intermediate ion door present position is V0, when dual-pulse power supply and plain conductor A pass through partial pressure During resistance R connections, by selecting suitable divider resistance R, make the voltage V on plain conductor AA=V0+Vd, VdFor ion gate Shutdown voltage, and the voltage V on plain conductor BB=V0, shutdown voltage VdOne is produced from plain conductor A to plain conductor B's Shutdown electric field, ion gate are closed.In this asymmetric voltage (VA> VB) under control model, when ion gate is closed, before ion gate Electric field die down, and the electric field in migration area before more polyion is gathered ion gate, is improved ion and moved by weak change, to make by force The sensitivity of spectrum is moved, the electric field that must just allow before ion gate becomes strong, at this time, by dual-pulse power supply, produces first pulse electricity Press Vc, VcThe polarity and shutdown voltage V of pulsedPolar orientation is on the contrary, voltage V on plain conductor AA=V0+Vd-Vc, and metal Voltage V on conducting wire BB=V0, work as VB-VA=Vc-Vd≥VdWhen, ion gate is still within closed mode, but shutdown direction of an electric field Become from plain conductor B to plain conductor A, this reverse asymmetric electric field can make the electric field increasing of near zone before ion gate By force, more polyion is gathered near ion gate, just there are more ions to enter migration area after ion gate is opened, so as to reach Put forward highly sensitive target;And then, second pulse voltage V is applied to plain conductor Ad, make VA=VB=V0, plain conductor A, plain conductor B equipotentials, ion gate are opened, are gathered in the ion before ion gate and are injected into migration area, and then ion gate recovers To initial closed state, i.e.,:VA=V0+Vd, VB=V0, due to VA> VB, ion gate shutdown voltage produced in migration area by Weak electric field compression ion beam is arrived by force, makes its narrowed width, realization puies forward high-resolution target, and ion beam is finally by ion signal Detector is collected and detects.Ion mobility spectrometry can be improved at the same time using this dipulse, asymmetric voltage control method Sensitivity and resolution ratio.
The voltage of migration tube intermediate ion door present position is V0, when dual-pulse power supply and plain conductor B pass through divider resistance R When being connected, the voltage V of plain conductor AA=V0.By selecting suitable divider resistance R, the voltage V of plain conductor B can be madeB=V0 +Vd, shutdown voltage VdOne is produced to be closed for the shutdown electric field from plain conductor B to plain conductor A, ion gate.This non- Symmetrical voltage (VA< VB) under control model, when ion gate is closed, the electric field of near zone becomes strong before ion gate, more ions Before being gathered in ion gate, after ion gate is opened, more ions will enter migration area, and highly sensitive effect is put forward so as to reach; And the change that grows from weak to strong is presented in the electric field in migration area, at this time, first arteries and veins is applied on plain conductor B by dual-pulse power supply Rush voltage Vd, make VA=VB=V0, plain conductor A, plain conductor B equipotentials, ion gate unlatching, a fairly large number of ion implanting Migration area;And then dual-pulse power supply produces second pulse voltage Vc, make VA=V0+Vc, and VB=V0+VdRemain unchanged, when VA-VB=Vc-Vd≥VdWhen, shutdown direction of an electric field is changed into from plain conductor A to plain conductor B, in this asymmetric voltage (VA> VB) under control model, when ion gate is closed, in migration area generation make ion beamwidth by compressing ion beam to weak electric field by force Degree narrows, so as to improve the resolution ratio of ion mobility spectrometry, ion beam is finally collected and detected by ion signal detector, utilizes this Kind dipulse, asymmetric voltage control method can also improve sensitivity and the resolution ratio of ion mobility spectrometry at the same time.
When dual-pulse power supply is connected with the plain conductor A of ion gate by divider resistance R, VA> VBWhen, dual-pulse power supply production First raw pulse voltage VcMore than twice Vd, make VA< VB, the electric-field enhancing of near zone before ion gate, more polyion Gather near ion gate, realize the target for improving Ion transfer spectral sensitivity.
When dual-pulse power supply is connected with the plain conductor B of ion gate by divider resistance R, VA< VBWhen, dual-pulse power supply production Second raw pulse voltage VcMore than twice Vd, make VA> VB, produce in migration area by arriving weak electric field by force, compression ion beam, Realize the target for improving Ion transfer spectral resolution.
The present invention compared with prior art the advantages of be:
(1) present invention passes through dual-pulse power supply point using dipulse, the ion gate of the voltage-controlled ion mobility spectrometry processed of Asymmetric Electric It is not connected with Bradbury-Nielson type ion gates one group of plain conductor therein, dual-pulse power supply produces continuous two pulses Signal, for improving sensitivity and the resolution ratio of ion mobility spectrometry at the same time, efficiently solves Ion transfer spectral sensitivity and resolution The contradiction that rate mutually restricts.
(2) present invention passes through dual-pulse power supply control using dipulse, the ion gate of the voltage-controlled ion mobility spectrometry processed of Asymmetric Electric The influence that asymmetric voltage in system and ion gate is distributed migration tube internal electric field, can overcome the voltage-controlled system of pulse, Asymmetric Electric The sensitivity of ion mobility spectrometry or the deficiency of resolution ratio can only be respectively increased in method, realize and improve the sensitive of ion mobility spectrometry at the same time Degree and resolution ratio.
Brief description of the drawings
Fig. 1 (a) is tradition Bradbury-Nielson types pulse, symmetrical voltage controls ion gate schematic diagram and migration tube Interior electric field distribution schematic diagram, (b) close schematic diagram for ion gate, and (c) opens schematic diagram for ion gate;
Fig. 2 (a) is pulse, the voltage-controlled ion gate processed of Asymmetric Electric, works as R1> R2, VA>VBWhen migration tube in electric field distribution Schematic diagram, (b) close schematic diagram for ion gate, and (c) opens schematic diagram for ion gate;
Fig. 3 is to work as R1< R2, VA<VB, the electric field distribution schematic diagram in migration tube when ion gate is closed;
Structure diagram when Fig. 4 is the present invention voltage-controlled using dipulse, Asymmetric Electric ion gate processed, wherein, (I) is Dual-pulse power supply and conducting wire A connection diagrams, (II) are dual-pulse power supply and conducting wire B connection diagrams.
Embodiment
Below in conjunction with the accompanying drawings and embodiment further illustrates the present invention.
As shown in figure 4, the present invention be it is a kind of using dipulse, the voltage-controlled ion gate processed of Asymmetric Electric ionic migration spectrometer and Method, and traditional ionic migration spectrometer difference lies in:Its in dual-pulse power supply and Bradbury-Nielson type ion gates In one group of plain conductor A1 or B2 be connected, ion gate is in asymmetric voltage mode control.
As shown in Fig. 4 (I), when dual-pulse power supply is connected with ion gate conducting wire A1 by divider resistance R4, pass through selection The numerical value 3 of suitable divider resistance R, makes the voltage V of plain conductor A1A=V0+Vd, VdFor the shutdown voltage of ion gate, and metal The voltage V of conducting wire B2B=V0, shutdown voltage VdOne is produced to be closed for the shutdown electric field from conducting wire A1 to conducting wire B2, ion gate Close.In this asymmetric voltage (VA> VB) under control model, when ion gate is closed, the electric field before ion gate dies down, and migration area Interior electric field is by by force to weak change.Make before more polyion gathers ion gate, improve the sensitivity of ion mobility spectrometry, it is just necessary The electric field allowed before ion gate becomes strong.At this time, by dual-pulse power supply, first pulse voltage V is producedc, VcThe polarity of pulse and pass Gate voltage VdPolar orientation is opposite.V at this timeA=V0+Vd-Vc, VB=V0.Work as VB-VA=Vc-Vd≥VdWhen, ion gate is still within Closed mode, but the direction of an electric field closed the door becomes from conducting wire B2 to conducting wire A1, and this reverse asymmetric electric field can make ion gate The electric-field enhancing of preceding near zone, more polyion is gathered near ion gate, just has more ions after ion gate is opened Into migration area, highly sensitive target is put forward so as to reach.And then, second pulse voltage V is applied to conducting wire Ad, conducting wire A1, B2 equipotential, ion gate are opened, are gathered in the ion before ion gate and are injected into migration area.Then ion gate returns to initially Closed mode, i.e.,:VA=V0+Vd, VB=V0.Due to VAMore than VB, ion gate shutdown voltage produced in migration area by by force to Weak electric field compression ion beam, reaches and puies forward high-resolution target.Ion beam is finally collected and detected by ion signal detector. Sensitivity and the resolution ratio of ion mobility spectrometry can be improved at the same time using this dipulse, asymmetric voltage control method.
As shown in Fig. 4 (II), when dual-pulse power supply is connected with ion gate conducting wire B2 by divider resistance R, plain conductor The voltage V of A1A=V0, by selecting suitable divider resistance value R, the voltage V of plain conductor B2 can be madeB=V0+Vd, shutdown voltage VdOne is produced to be closed for the shutdown electric field from conducting wire B2 to conducting wire A1, ion gate.In this asymmetric voltage (VA< VB) control Under molding formula, when ion gate is closed, the electric field of near zone becomes strong before ion gate, before more ions are gathered in ion gate, from After cervical orifice of uterus is opened, more ions will enter migration area, and highly sensitive effect is put forward so as to reach;And the electric field in migration area is in Now grow from weak to strong change.At this time, first pulse voltage V is applied on conducting wire B2 by dual-pulse power supplyd, make VA=VB=V0, Conducting wire A1, B2 equipotential, ion gate are opened, a fairly large number of ion implanting migration area;And then dual-pulse power supply produces second A pulse voltage Vc, make VA=V0+Vc, and VB=V0+VdRemain unchanged, work as VA-VB=Vc-Vd≥VdWhen, shutdown direction of an electric field becomes For from conducting wire A1 to conducting wire B2, in this asymmetric voltage (VA> VB) under control model, when ion gate is closed, production in migration area Life improves the resolution ratio of ion mobility spectrometry by compressing ion beam to weak electric field by force.Ion beam is finally detected by ion signal Device is collected and detection.The sensitive of ion mobility spectrometry can also be improved at the same time using this dipulse, asymmetric voltage control method Degree and resolution ratio.
Description of the invention does not elaborate and partly belongs to techniques well known.

Claims (4)

  1. A kind of 1. ionic migration spectrometer detection method using the voltage-controlled ion gate processed of dipulse Asymmetric Electric, it is characterised in that:Move The voltage for moving pipe intermediate ion door present position is V0, when dual-pulse power supply is connected with plain conductor A (1) by divider resistance R, By selecting suitable divider resistance R, make the voltage V on plain conductor A (1)A=V0+Vd, VdFor the shutdown voltage of ion gate, And the voltage V on plain conductor B (2)B=V0, shutdown voltage VdOne is produced from plain conductor A (1) to plain conductor B (2) Shutdown electric field, ion gate are closed, in this asymmetric voltage, that is, VA> VBUnder control model, when ion gate is closed, before ion gate Electric field die down, and the electric field in migration area is by by force to weak change;At this time, by dual-pulse power supply, first pulse electricity is produced Press Vc, VcThe polarity and shutdown voltage V of pulsedPolar orientation is on the contrary, voltage V on plain conductor A (1)A=V0+Vd-Vc, and it is golden Belong to the voltage V on conducting wire B (2)B=V0, work as VB-VA=Vc-Vd≥VdWhen, ion gate is still within closed mode, but shutdown electric field Direction becomes from plain conductor B (2) to plain conductor A (1), and then, applies second pulse voltage to plain conductor A (1) Vd, make VA=VB=V0, plain conductor A (1), plain conductor B (2) equipotential, ion gate open, be gathered in before ion gate from Son is injected into migration area, and then ion gate returns to initial closed state, i.e.,:VA=V0+Vd, VB=V0, due to VA> VB, ion Door shutdown voltage produced in migration area by arriving weak electric field compression ion beam by force, make its narrowed width, the final quilt of ion beam Ion signal detector is collected and detects.
  2. 2. the ionic migration spectrometer detection side according to claim 1 using the voltage-controlled ion gate processed of dipulse Asymmetric Electric Method, it is characterised in that:Substitute, the voltage of migration tube intermediate ion door present position is V0, when dual-pulse power supply and plain conductor B (2) when being connected by divider resistance R, the voltage V of plain conductor A (1)A=V0, can by selecting suitable divider resistance R (4) Make the voltage V of plain conductor B (2)B=V0+Vd, shutdown voltage VdIt is from plain conductor B (2) to plain conductor A (1) to produce one Shutdown electric field, ion gate is closed;In this asymmetric voltage, that is, VA< VBUnder control model, when ion gate is closed, ion gate The electric field of preceding near zone becomes strong, and before more ions are gathered in ion gate, after ion gate is opened, more ions, which will enter, to be moved Area is moved, and the change that grows from weak to strong is presented in the electric field in migration area;At this time, applied by dual-pulse power supply on plain conductor B (2) First pulse voltage Vd, make VA=VB=V0, plain conductor A (1), plain conductor B (2) equipotential, ion gate unlatching, ion Inject migration area;And then dual-pulse power supply produces second pulse voltage Vc, make VA=V0+Vc, and VB=V0+VdKeep not Become, work as VA-VB=Vc-Vd≥VdWhen, shutdown direction of an electric field is changed into from plain conductor A (1) to plain conductor B (2), this non-right Claim voltage, that is, VA> VBUnder control model, when ion gate is closed, produced in migration area by compressing ion beam to weak electric field by force, Ion beam width is set to narrow, ion beam is finally collected and detected by ion signal detector.
  3. 3. the ionic migration spectrometer detection side according to claim 1 using the voltage-controlled ion gate processed of dipulse Asymmetric Electric Method, it is characterised in that:When dual-pulse power supply is connected with the plain conductor A (1) of ion gate by divider resistance R, VA> VBWhen, it is double First pulse voltage V that the pulse power producescMore than twice Vd, make VA< VB, the electric-field enhancing of near zone before ion gate, More polyion is gathered near ion gate.
  4. 4. the ionic migration spectrometer detection side according to claim 2 using the voltage-controlled ion gate processed of dipulse Asymmetric Electric Method, it is characterised in that:When dual-pulse power supply is connected with the plain conductor B (2) of ion gate by divider resistance R, VA< VBWhen, it is double Second pulse voltage V that the pulse power producescMore than twice Vd, make VA> VB, produce in migration area by by force to weak electric field, Compress ion beam.
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CN110491765B (en) * 2018-11-25 2020-06-19 中国科学院大连化学物理研究所 Control method of ion gate in ion mobility spectrometry
CN110176382B (en) * 2019-06-04 2021-01-29 清华大学深圳研究生院 Ion mobility spectrometer and ion gate opening and closing control method thereof
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CN110534395B (en) * 2019-08-27 2022-03-11 清华大学深圳研究生院 Ion gate control method for ion mobility spectrometer
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