CN104934289A - Ion trap quality analyzer and signal applying method thereof - Google Patents
Ion trap quality analyzer and signal applying method thereof Download PDFInfo
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- CN104934289A CN104934289A CN201510236905.3A CN201510236905A CN104934289A CN 104934289 A CN104934289 A CN 104934289A CN 201510236905 A CN201510236905 A CN 201510236905A CN 104934289 A CN104934289 A CN 104934289A
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Abstract
The invention discloses an ion trap quality analyzer and a signal applying method thereof; the ion trap quality analyzer comprises a center ring electrode, and end cap electrodes symmetrically arranged on two sides of the center ring electrode; the center of each end cap electrode is respectively provided with an ion inlet and an ion emission hole; the features are that the two end cap electrode are respectively formed by an inner ring electrode and an outer ring electrode electrically isolated; the ion inlet and the ion emission hole are respectively arranged on the corresponding inner ring electrode; the inner ring electrodes on two sides respectively serve as a resonance excitation signal coupling end; signal applying modes are listed as follow: the signal can be directly applied to the inner ring electrode or through a coupling mode. The signal is applied to the inner ring electrodes of the end cap electrodes, thus reducing influences against ion trap internal ion motions by an AC signal, improving ion emission accuracy and intensity, and improving whole performance of the ion trap.
Description
Technical field
The present invention relates to a kind of ion trap mass spectrometer correlative technology field, be specifically related to the applying method of a kind of ion strap mass analyzer and signal thereof.
Background technology
At Aero-Space of today, environmental sanitation, food security and field of scientific study, the effect that mass spectrometer plays just is becoming increasing.As a kind of Modern Analytical Instrument, mass spectrometer has higher detectivity, effectively can detect trace materials, is a kind of well qualitative and quantitative analysis instrument.
Mass analyzer is as mass spectrometric core component, and according to the difference of mass analyzer, mass spectrometer can be divided into magnetic mass spectrometer, Fourier Transform Ion Cyclotron Resonance Mass Spectrometry instrument, ion trap mass spectrometer, level Four bar mass spectrometer and time-of-flight mass spectrometer.Wherein, ion trap mass spectrometer can carry out multi-stage ms analysis better with its good ion storage ability, thus improves the global analysis performance of instrument.And its core ion strap mass analyzer (hereinafter referred to as ion trap) have compact size, structure simple, be easy to processing and to features such as operating air pressure requirement are looser.Therefore, ion trap becomes the first-selection of mass spectrometer miniaturization.
The model of traditional 3D ion trap is as shown in Fig. 1 (shaft section), it is made up of two identical hyperbolic endcap electrode 101,103 and hyperbolic annular electrodes 102, have in the central authorities of two endcap electrodes the aperture 104 and 105 that diameter is about 1mm, be respectively used to introducing and the outgoing of ion.In quality analysis process, ion is stored in the spheric region of central authorities.Radio frequency during real work applies mode and is divided into two kinds: one to be only on hyperbolic annular electrode 102, apply radio-frequency voltage RF; Two is apply radio-frequency voltage RF+ on hyperbolic annular electrode 102, and hyperbolic endcap electrode 101 and 103 all applies radio-frequency voltage RF-that is identical with RF+ amplitude, phase difference 180 °.Simultaneously in order to promote ion exit, improving mass resolution, adopting axial oscillations to excite emission mode.In mode one, two resonant excitation signal AC+ and AC-that are amplitude is identical, phase difference 180 ° are applied on hyperbolic endcap electrode 101 and 103 respectively, as shown in Figure 2.In mode two, two resonant excitation signal AC+ and AC-that are amplitude is identical, phase difference 180 ° are coupled on radio-frequency voltage RF-, then are applied on hyperbolic endcap electrode 101 and 103 respectively, as shown in Figure 3.
Propose a kind of ion trap structure of column type in US Patent No. 3065640A, its structure as shown in Figure 4.By two identical disk endcap electrodes 201 and 203, and the ring electrode 302 of a cylindrical tube shape forms, and the central authorities of disk endcap electrode 201 and 203 have aperture 204 and 205, for injection and the outgoing of ion.At that time, more using the storage device of this equipment as ion.After more than ten years, scientist starts to utilize this device as quadrupole ion trap to carry out quality analysis.Its voltage applying mode is similar to traditional 3D ion trap.
In these devices and working method, resonant excitation signal AC is applied on whole endcap electrode.But the volume of the ion cloud in ion trap is quite little, namely ion all by paracentral one very among a small circle in move.Introduce resonant excitation signal AC, be order about ion to resonate with it at axial direction, sharply increase amplitude, thus injection ion trap.But whole endcap electrode all applies AC signal, can have an impact to the motion in other directions of ion unavoidably, cause ionic bombardment ion trap to be buried in oblivion or different kinds of ions outgoing simultaneously, reduce signal strength signal intensity and resolution, cause the sacrifice of ion trap analytical performance.
Summary of the invention
The object of the invention is to provide the applying method of a kind of ion strap mass analyzer and signal thereof, by the improvement to structure and the mode of applying, improves accuracy and the intensity of ion exit, effectively promotes the mass resolution of ion trap, improve overall performance.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of ion strap mass analyzer, comprise a central rings electrode, with the endcap electrode being symmetrically placed in these central rings electrode both sides, ion introduction hole and ion ejection hole is respectively equipped with in the heart in endcap electrode described in each, endcap electrode described in both sides is made up of inner ring electrode and outer ring electrode respectively, electrical isolation is provided with between described inner ring electrode and outer ring electrode, described ion introduction hole and ion ejection hole lay respectively on corresponding inner ring electrode, and both sides inner ring electrode is respectively resonant excitation signal connection end, described outer ring electrode does not apply resonant excitation signal.
In technique scheme, described central rings electrode is hyperbolic ring electrode, and described endcap electrode is discrete type hyperbolic endcap electrode.
In technique scheme, described central rings electrode is hyperbolic ring electrode, and described endcap electrode is discrete type disk endcap electrode.
In technique scheme, described central rings electrode is cylinder ring electrode, and described endcap electrode is discrete type hyperbolic endcap electrode.
In technique scheme, described central rings electrode is cylinder ring electrode, and described endcap electrode is discrete type disk endcap electrode.
In technique scheme, the diameter of described ion introduction hole and ion ejection hole is 0.8 ㎜ ~ 1 ㎜.
In technique scheme, described electrical isolation is formed for embedding polyether-ether-ketone PEEK between described inner ring electrode and outer ring electrode.
To achieve the above object of the invention, the method and technology scheme that the present invention adopts is: a kind of signal application method of ion strap mass analyzer, comprises A or B two kinds of modes, as follows:
Mode A: apply radio-frequency voltage RF on central rings electrode, the inner ring electrode of endcap electrode applies resonant excitation signal AC, the outer ring electrode grounding of endcap electrode;
Or,
Mode B: apply radio-frequency voltage RF+ on central rings electrode, the outer ring electrode of endcap electrode applies the radio-frequency voltage RF-of, phase difference 180 ° equal with RF+ amplitude, and on the inner ring electrode of endcap electrode, applying has been coupled the radio-frequency voltage RF-of resonant excitation signal AC.
In technique scheme, described central rings electrode is the one in hyperbolic ring electrode or cylinder ring electrode, and described endcap electrode is the one in discrete type hyperbolic endcap electrode or discrete type disk endcap electrode.
In technique scheme, in described mode B, described " the radio-frequency voltage RF-of the resonant excitation that has been coupled signal AC " is by obtaining with centre tapped two-way transformer, the inner ring electrode of endcap electrode described in both sides is connected to the secondary coil two ends of two-way transformer respectively, the primary coil of described two-way transformer is connected with resonance excitation signal AC, and the outer ring electrode of described endcap electrode and radio-frequency voltage RF-are connected on the centre cap of described two-way transformer.
Due to the employing of technique scheme, the present invention has the following advantages compared to original technology: the endcap electrode of ion trap is designed to discrete type end cap, be made up of inner ring electrode and outer ring electrode, be provided with electrical isolation between the two, in quality analysis process, only resonant excitation signal AC is applied on inner ring electrode, outer ring electrode does not apply resonant excitation signal AC, thus be conducive to reducing the impact that AC signal moves on ion trap inner ion, improve accuracy and the intensity of ion exit, and then improve the mass resolution of ion trap, to improve the overall performance of ion trap.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described:
Fig. 1 is the structural representation of traditional 3D hyperbolic ion trap.
Fig. 2 is the mode one operating circuit schematic diagram of traditional 3D hyperbolic ion trap.
Fig. 3 is the mode two operating circuit schematic diagram of traditional 3D hyperbolic ion trap.
Fig. 4 is the structural representation of cylindrical ion trap in background technology.
Fig. 5 is the structural representation of the embodiment of the present invention one.
Fig. 6 is the operating circuit schematic diagram of the embodiment of the present invention one.
Fig. 7 is the operating circuit schematic diagram of the embodiment of the present invention two.
Fig. 8 is the structural representation of the embodiment of the present invention three.
Fig. 9 is the operating circuit schematic diagram of the embodiment of the present invention three.
Figure 10 is the operating circuit schematic diagram of the embodiment of the present invention four.
Figure 11 is the structural representation of the embodiment of the present invention five.
Figure 12 is the structural representation of the embodiment of the present invention six.
Embodiment
Embodiment one: with reference to shown in Fig. 5, a kind of ion strap mass analyzer, comprises a central hyperbolic ring electrode 302, a pair of identical discrete type hyperbolic endcap electrode.One of them endcap electrode is divided into inner ring electrode 311 and outer ring electrode 301, embeds polyether-ether-ketone PEEK and realize electrical isolation and spacing between described inner ring electrode 311 and outer ring electrode 301, with one heart and be centrally located on the straight line at symmetry axis place of ring electrode; Another endcap electrode of placement symmetrical with it is divided into inner ring electrode 313 and outer ring electrode 303 similarly.Have the aperture of diameter 1mm in the central authorities of inner ring electrode 311 and inner ring electrode 313, be respectively ion introduction hole 304 and ion ejection hole 305, ion is entered in ion trap by ion introduction hole 304.In quality analysis process, ion, under the effect of quadripolar electric field, according to the order of mass-to-charge ratio successively by described ion ejection hole 305, thus realizes quality analysis.
Shown in Figure 6,7 is the radio-frequency power supply of doubleway output, can export two-way amplitude identical, the radiofrequency signal that phase difference is 180 °, is designated as respectively " RF+ " and " RF-", and in the course of the work, the amplitude of radio-frequency power supply can scan.8 is resonant excitation modules A C, can produce two-way amplitude identical, and the simple alternating current ripple signal of phase difference 180 °, is designated as " AC+ " and " AC-" respectively.
The electric connecting mode of this discrete type endcap electrode ion trap is as shown in Figure 6: exported with any road of radio-frequency power supply 7 by central hyperbolic annular electrode 302 and be connected, outer ring electrode 301 and 303 ground connection respectively of discrete type hyperbolic endcap electrode, inner ring electrode 311 is connected with two-way AC+ with AC-of resonance excitation module respectively with 313.
This discrete type endcap electrode ion trap is when carrying out quality analysis, the amplitude of radio-frequency voltage will scan, storage ion is in an ion trap by under the effect of electric field, ion trap is penetrated by ion introduction hole 304 and ion ejection hole 305 successively according to the order of mass-to-charge ratio, and then be positioned at neighbouring ion detector and detect, finally realize quality analysis, obtain corresponding mass spectrogram.
Embodiment two: with reference to shown in Fig. 7, a kind of ion strap mass analyzer, the structure of its ion trap is identical with embodiment one, and difference is: the electric connecting mode applying resonant excitation signal.Be connected with a wherein road RF+ of radio-frequency power supply 7 by central hyperbolic ring electrode 302, the outer ring electrode 301 of discrete type hyperbolic endcap electrode is connected with another road RF-of radio-frequency power supply 7 with after 303 short circuits.In figure, 9 is with centre tapped two-way transformer, the sine wave signal that resonant excitation module 8 produces can be coupled in radiofrequency signal.Described two-way transformer has two inputs, two outputs and a centre tap, during work, input is connected with resonance excitation module 8, centre tap outputs signal RF-with a wherein road of radio-frequency power supply 7 and is connected, and two outputs are connected on the inner ring electrode 311 and 313 of ion trap end caps electrode.So in fact, on the inner ring electrode 311 and 313 of endcap electrode, be applied with radio frequency voltage signal RF-and resonant excitation signal AC simultaneously.
Embodiment three: with reference to shown in Fig. 8, a kind of discrete type endcap electrode ion trap, comprises a central cylindrical ring electrode 402, a pair of identical discrete type hyperbolic endcap electrode.Described discrete type hyperbolic endcap electrode is divided into inner ring electrode 411 and outer ring electrode 401, with one heart and be centrally located on the straight line at symmetry axis place of ring electrode; Symmetrical another endcap electrode placed is divided into inner ring electrode 413 and outer ring electrode 403 similarly with it, have ion introduction hole 404 and the ion ejection hole 405 of diameter 0.8mm in the central authorities of inner ring electrode 411 and 413, ion is entered in ion trap by ion introduction hole 404.In quality analysis process, ion, under the effect of quadripolar electric field, according to the order of mass-to-charge ratio successively by described said ion leadout hole 404, thus realizes quality analysis.
Shown in Figure 9,7 is the radio-frequency power supply of doubleway output, can export two-way amplitude identical, the radiofrequency signal that phase difference is 180 °, is designated as respectively " RF+ " and " RF-", and in the course of the work, the amplitude of radio-frequency power supply can scan.8 is resonant excitation modules A C, can produce two-way amplitude identical, and the simple alternating current ripple signal of phase difference 180 °, is designated as " AC+ " and " AC-" respectively.
Electric connecting mode is as shown in Figure 9: exported with any road of radio-frequency power supply 7 by central cylindrical ring electrode 402 and be connected, outer ring electrode 401 and 403 ground connection of endcap electrode, and inner ring electrode 411 is connected with two-way AC+ with AC-of resonance excitation module 8 respectively with 413.
When carrying out quality analysis, the amplitude of radio-frequency voltage will scan, storage ion is in an ion trap by under the effect of electric field, ion trap is penetrated by ion introduction hole 404 and ion ejection hole 405 successively according to the order of mass-to-charge ratio, and then be positioned at neighbouring ion detector and detect, finally realize quality analysis, obtain corresponding mass spectrogram.
Embodiment four: with reference to shown in Figure 10, a kind of ion strap mass analyzer, the structure of its ion trap is identical with embodiment three, and difference is: the electric connecting mode of ion trap.Be connected with a wherein road RF+ of radio-frequency power supply 7 by central cylindrical ring electrode 402, the outer ring electrode 401 of endcap electrode is connected with another road RF-of radio-frequency power supply 7 with after 403 short circuits.In figure, 10 is with centre tapped two-way transformer, the sine wave signal that resonant excitation module 8 produces can be coupled in radiofrequency signal.Described two-way transformer has two inputs, two outputs and a centre tap, during work, input is connected with resonance excitation module 8, centre tap outputs signal RF-with a wherein road of radio-frequency power supply and is connected, and two outputs are connected on the inner ring electrode 411 and 413 of ion trap end caps electrode.So in fact, on the inner ring electrode 411 and 413 of endcap electrode, be applied with radio frequency voltage signal RF-and resonant excitation signal simultaneously.
Embodiment five: with reference to shown in Figure 11, a kind of discrete type endcap electrode ion trap, comprises a central hyperbolic ring electrode 502, a pair of identical discrete type disk endcap electrode.One of them endcap electrode is divided into inner ring electrode 511 and outer ring electrode 501, with one heart and be centrally located on the straight line at symmetry axis place of ring electrode; Another endcap electrode of placement symmetrical with it is divided into inner ring electrode 513 and outer ring electrode 503 similarly.Ion introduction hole 504 and the ion ejection hole 505 of diameter 0.9mm is had in the central authorities of inner ring electrode 511 and 513, ion enters in ion trap by ion introduction hole 504, in quality analysis process, ion is under the effect of quadripolar electric field, pass through ion ejection hole 505 successively according to the order of mass-to-charge ratio, thus realize quality analysis.
In the present embodiment, electric connecting mode can be mode A: on central hyperbolic ring electrode 502, apply radio-frequency voltage RF, and the inner ring electrode 511 and 513 of endcap electrode applies resonant excitation signal AC, outer ring electrode 501 and 503 ground connection of endcap electrode;
Or,
Mode B: apply radio-frequency voltage RF+ on central hyperbolic ring electrode 502, at the radio-frequency voltage RF-of after-applied, the phase difference 180 ° equal with RF+ amplitude of outer ring electrode 501 and 503 short circuit of endcap electrode, the radio-frequency voltage RF-of the resonant excitation signal AC that the inner ring electrode 511 and 513 of endcap electrode applies be coupled.
Embodiment six: with reference to shown in Figure 12, a kind of discrete type endcap electrode ion trap, comprises a central cylindrical ring electrode 602, a pair of identical discrete type disk endcap electrode.One of them endcap electrode is divided into inner ring electrode 611 and outer ring electrode 601, with one heart and be centrally located on the straight line at symmetry axis place of ring electrode; Another endcap electrode of placement symmetrical with it is divided into inner ring electrode 613 and outer ring electrode 603 similarly.Ion introduction hole 604 and the ion ejection hole 605 of diameter 1mm is had in the central authorities of inner ring electrode 611 and 613, ion enters in ion trap by ion introduction hole 604, in quality analysis process, ion is under the effect of quadripolar electric field, pass through ion ejection hole 605 successively according to the order of mass-to-charge ratio, thus realize quality analysis.
Its electric connecting mode and embodiment five similar, difference is: in mode A, and radio-frequency voltage RF puts on central cylinder ring electrode 602, and the resonant excitation signal AC put on discrete type disk endcap electrode is constant; In mode B, radio-frequency voltage RF+ puts on central cylinder ring electrode 602, and other are identical with mode B in embodiment five.
Claims (10)
1. an ion strap mass analyzer, comprise a central rings electrode, with the endcap electrode being symmetrically placed in these central rings electrode both sides, ion introduction hole and ion ejection hole is respectively equipped with in the heart in endcap electrode described in each, it is characterized in that: endcap electrode described in both sides is made up of inner ring electrode and outer ring electrode respectively, electrical isolation is provided with between described inner ring electrode and outer ring electrode, described ion introduction hole and ion ejection hole lay respectively on corresponding inner ring electrode, and both sides inner ring electrode is respectively resonant excitation signal connection end, described outer ring electrode does not apply resonant excitation signal.
2. ion strap mass analyzer according to claim 1, is characterized in that: described central rings electrode is hyperbolic ring electrode, and described endcap electrode is discrete type hyperbolic endcap electrode.
3. ion strap mass analyzer according to claim 1, is characterized in that: described central rings electrode is hyperbolic ring electrode, and described endcap electrode is discrete type disk endcap electrode.
4. ion strap mass analyzer according to claim 1, is characterized in that: described central rings electrode is cylinder ring electrode, and described endcap electrode is discrete type hyperbolic endcap electrode.
5. ion strap mass analyzer according to claim 1, is characterized in that: described central rings electrode is cylinder ring electrode, and described endcap electrode is discrete type disk endcap electrode.
6. ion strap mass analyzer according to claim 1, is characterized in that: the diameter of described ion introduction hole and ion ejection hole is 0.8 ㎜ ~ 1 ㎜.
7. ion strap mass analyzer according to claim 1, is characterized in that: described electrical isolation is formed for embedding polyether-ether-ketone PEEK between described inner ring electrode and outer ring electrode.
8. to a signal application method for claim 1 intermediate ion trap mass analyzer, it is characterized in that: comprise A or B two kinds of modes, as follows:
Mode A: apply radio-frequency voltage RF on central rings electrode, the inner ring electrode of endcap electrode applies resonant excitation signal AC, the outer ring electrode grounding of endcap electrode;
Or,
Mode B: apply radio-frequency voltage RF+ on central rings electrode, the outer ring electrode of endcap electrode applies the radio-frequency voltage RF-of, phase difference 180 ° equal with RF+ amplitude, and on the inner ring electrode of endcap electrode, applying has been coupled the radio-frequency voltage RF-of resonant excitation signal AC.
9. the signal application method of ion strap mass analyzer according to claim 8, it is characterized in that: described central rings electrode is the one in hyperbolic ring electrode or cylinder ring electrode, described endcap electrode is the one in discrete type hyperbolic endcap electrode or discrete type disk endcap electrode.
10. the signal application method of ion strap mass analyzer according to claim 8, it is characterized in that: in described mode B, described " the radio-frequency voltage RF-of the resonant excitation that has been coupled signal AC " is by obtaining with centre tapped two-way transformer, the inner ring electrode of endcap electrode described in both sides is connected to the secondary coil two ends of two-way transformer respectively, the primary coil of described two-way transformer is connected with resonance excitation signal AC, and the outer ring electrode of described endcap electrode and radio-frequency voltage RF-are connected on the centre cap of described two-way transformer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109360782A (en) * | 2018-09-21 | 2019-02-19 | 上海卫星装备研究所 | Six electrode linear ion trap mass analyzers and radio frequency applying method |
| CN110277301A (en) * | 2019-06-28 | 2019-09-24 | 清华大学深圳研究生院 | A kind of air pressure inside ion trap unevenly distributed and its working method |
| CN112233963A (en) * | 2020-10-29 | 2021-01-15 | 上海裕达实业有限公司 | High collision energy alternating voltage ion dissociation device and mass spectrometry analysis method |
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| US20040149903A1 (en) * | 2003-01-31 | 2004-08-05 | Yang Wang | Ion trap mass spectrometry |
| CN101364519A (en) * | 2008-09-27 | 2009-02-11 | 复旦大学 | Circular ring ion trap and circular ring ion trap array |
| CN103779171A (en) * | 2014-01-21 | 2014-05-07 | 苏州大学 | Combined electrode type ion trap mass analyzer |
| CN104377109A (en) * | 2013-08-16 | 2015-02-25 | 中国人民解放军63975部队 | Linear ion trap mass analyzer |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040149903A1 (en) * | 2003-01-31 | 2004-08-05 | Yang Wang | Ion trap mass spectrometry |
| CN101364519A (en) * | 2008-09-27 | 2009-02-11 | 复旦大学 | Circular ring ion trap and circular ring ion trap array |
| CN104377109A (en) * | 2013-08-16 | 2015-02-25 | 中国人民解放军63975部队 | Linear ion trap mass analyzer |
| CN103779171A (en) * | 2014-01-21 | 2014-05-07 | 苏州大学 | Combined electrode type ion trap mass analyzer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109360782A (en) * | 2018-09-21 | 2019-02-19 | 上海卫星装备研究所 | Six electrode linear ion trap mass analyzers and radio frequency applying method |
| CN110277301A (en) * | 2019-06-28 | 2019-09-24 | 清华大学深圳研究生院 | A kind of air pressure inside ion trap unevenly distributed and its working method |
| CN112233963A (en) * | 2020-10-29 | 2021-01-15 | 上海裕达实业有限公司 | High collision energy alternating voltage ion dissociation device and mass spectrometry analysis method |
| CN112233963B (en) * | 2020-10-29 | 2023-12-05 | 上海裕达实业有限公司 | High-collision-energy alternating-voltage ion dissociation device and mass spectrometry method |
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