CN101777483A - Method and device for improving 3D ion trap detection efficiency - Google Patents

Method and device for improving 3D ion trap detection efficiency Download PDF

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Publication number
CN101777483A
CN101777483A CN200910156631A CN200910156631A CN101777483A CN 101777483 A CN101777483 A CN 101777483A CN 200910156631 A CN200910156631 A CN 200910156631A CN 200910156631 A CN200910156631 A CN 200910156631A CN 101777483 A CN101777483 A CN 101777483A
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Prior art keywords
electrode
ion
ion trap
electron lens
outgoing
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CN200910156631A
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CN101777483B (en
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李晓旭
吴文明
郑毅
刘立鹏
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Focused Photonics Hangzhou Inc
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Focused Photonics Hangzhou Inc
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Abstract

The invention relates to a method for improving 3D ion trap detection efficiency, which is as follows in detail: at the ionization stage, the electrons pass through a first electron lens and enter the 3D ion trap; at the mass analysis stage, no electron passes through the first electron lens; and the 3D ion trap emits ions, wherein the ions emitted in one direction deflect under the action of the first electron lens and then are detected, and the ions emitted in the other direction are also detected. The invention further discloses a device for realizing the method. The device has the advantages of high detection efficiency, high ionization efficiency and simple structure.

Description

A kind of method and apparatus that improves the 3D ion trap detection efficiency
Technical field
The present invention relates to the 3D ion trap, particularly a kind of method and apparatus that improves the 3D ion trap detection efficiency.
Background technology
Mass spectrometry is to realize a kind of method to the sample qualitative and quantitative analysis by the analysis to the sample ions mass-to-charge ratio.Mass spectrometric basic composition all comprises ion source, mass analyzer, detector and vacuum system.Ionogenic effect is with sample ionization to be analyzed, obtains having the ion of sample message.
As shown in Figure 1, a kind of internal electrical that generally adopts from the 3D ion trap, comprise the electron source 209, electron lens 208,3D ion trap, the detector 204 that set gradually, companies such as Varian, Thermo all use said structure.
Above-mentioned ion trap is in analytic process, and ion can be from the direction outgoing of two endcap electrodes, and can only detect an outgoing ion on the direction.As seen, the detection efficiency of ion is the highest in theory can only to arrive 50%, and this made the matter worse with regard to not strong 3D ion trap originally beyond doubt to the ion storage ability.
At present, most of producers all fail to address the above problem.Have only the solution that has proposed " triple resonant " in the product of Varian, be specially:
Catch dipole field TFD (Trapping Field Dipole) by on endcap electrode, applying one, make the field misalignment geometric center of ion trap; Applying on endcap electrode simultaneously provides the ion parametric oscillation to assist the alternation quadrupole field, and the alternation dipole field that the vibration of ion side frequency is provided, nonlinear resonance in conjunction with hexapole field, make ion be more prone to from the distance a closer endcap electrode on outgoing, thereby improved ion detection efficient.But triple resonant still exists with some shortcomings, as:
1, during triple resonant excites, part ion outgoing is in the opposite direction arranged still.
2, when the energy of resonant excitation signal strengthened, the ion populations of outgoing in the opposite direction can increase, thereby reduced ion detection efficient.And when the energy of excitation signal was big more, the detection efficiency of ion was low more.
3, for making the physical centre that catches the field depart from geometric center, need on termination electrode, apply RF and produce TFD, simultaneously also need to apply RF on the ring electrode, promptly use two-way RF mode (and RF need be coupled with AC), increased the complexity of circuit and the complexity of control greatly by coil.And because the close detector of endcap electrode, the loading of RF brings radio frequency interference easily, influences signal quality.
4, need to add extra auxiliary dipole field and level Four field in the triple resonant, because the introducing of these multipole fields has increased nonlinear effect, the poor controllability of system, the skew that also may bring mass number.
Summary of the invention
In order to solve above-mentioned deficiency of the prior art, the invention provides a kind of method and apparatus of the 3D of raising ion trap detection efficiency, the detection efficiency of existing 3D ion trap is doubled, the theoretical value of detection efficiency can reach 100%; Also improved simultaneously the Ionization Efficiency of sample.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method that improves the 3D ion trap detection efficiency, characteristics are:
In the ionization stage:
Electronics passes through electron lens, and enters described 3D ion trap;
In mass analysis stage:
There is not electronics to pass through described electron lens;
3D ion trap outgoing ion: wherein the ion of outgoing is in the effect deflect of electron lens on the direction, and detected afterwards, the ion of outgoing is also detected on the other direction.
As preferably, described electron lens comprises first electrode and second electrode that is oppositely arranged, and second electrode is provided with is convenient to the hole that ion or electronics pass.
Further, in the ionization stage, it is identical with voltage on second electrode to be added in first electrode, and in mass analysis stage, the voltage that is added on first electrode is higher than second electrode.
Further, in mass analysis stage, described electron lens has stopped passing of electronics.
As preferably, described first electrode and second electrode are halfpipes.
The invention allows for a kind of like this device of the 3D of raising ion trap detection efficiency, specifically comprise:
Be arranged on first side of 3D ion trap, be used to detect first detector of 3D ion trap from the ion of this side outgoing;
Be arranged on the electron lens of 3D ion trap second side, be convenient to electronics across and into described 3D ion trap;
Be arranged on second detector of described electron lens sidepiece, be used to detect from second side outgoing of 3D ion trap and the ion after electron lens deflection.
As preferably, described electron lens comprises first electrode and second electrode that is oppositely arranged, and second electrode is provided with the hole that cooperates with described second detector.
Further, described first electrode is provided with the hole, also is provided with the dynode that cooperates with this hole.
Further, described hole is provided with mesh electrode.
As preferably, described first electrode and second electrode are halfpipes.
Compared with prior art, the present invention has following beneficial effect:
1, ion detection efficient height.
Be provided with cathode lens, make the outgoing ion of 3D ion trap all be detected, theoretic ion detection efficient can reach 100%.
Be not subjected to the influence of resonant excitation signal, no matter under which kind of situation, detection efficiency all is the twice of existing 3D ion trap.
2, sample ions efficient height.
The cathode lens that is provided with is used for focused electron on the one hand, improves the Ionization Efficiency of sample, is used for the ion of deflection from the outgoing of 3D ion trap on the other hand, so that be detected; Be used to control whether passing through of electronics on the one hand again, play the effect of electronic gate.
Description of drawings
Fig. 1 is the structural representation of 3D ion trap in the prior art;
Fig. 2 is the structural representation of device among the embodiment 1;
Fig. 3 is the structural representation of cathode lens among the present invention;
Fig. 4 is the structural representation of device among the embodiment 2;
Fig. 5 is the structural representation of device among the embodiment 3;
Fig. 6 is the structural representation of device among the embodiment 4.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further details.
Embodiment 1:
As shown in Figure 2, a kind of device that improves the 3D ion trap detection efficiency is applied in the mass spectrometer, and described mass spectrometer comprises electron source 209, second electron lens 208, cathode lens, 3D ion trap and first detector 204 that sets gradually.
Described 3D ion trap comprises hyperboloid ring electrode 201, hyperboloid endcap electrode 202,203.First detector 204 is arranged on a side of endcap electrode 202.
As shown in Figure 3, described cathode lens comprises that semi-tubular first electrode 206 and second electrode, 207, the first electrodes 206 and second electrode 207 are oppositely arranged, and the electricity isolation, so that load different voltage.Described second electrode 207 is provided with hole 211, and the position relative with this hole 211 is provided with second detector 205.Hole 211 usefulness mesh electrodes cover, and the electric field error so that the compensation perforate causes focuses on the electronics that passes through better, and mesh electrode allows ion to pass through simultaneously.
Described cathode lens plays the effect of focused electron in the ionization stage, plays the effect of deflect ions in mass analysis stage, is detected by second detector 205 so that the ion after the deflection passes described hole 211.
Present embodiment has also disclosed a kind of method of the 3D of raising ion trap detection efficiency, is applied in the mass spectral analysis, and characteristics are:
In the ionization stage:
High pressure on first detector 204 and second detector 205 is closed, and detector is in off position;
Apply positive voltage or suitable negative voltage on second electron lens 208, (second electron lens 208 conducts) electronic gate is opened at this moment; The electronics that electron source 209 produces can pass through second electron lens 208.
Apply identical voltage on first electrode 206 and second electrode 207, this moment, first electrode 206 and second electrode 207 were combined, and were equivalent to electron focusing lens;
Electron source 209 emitting electrons enter the 3D ion trap, the neutral sample in the ionization 3D ion trap after electronics process second electron lens 208 and cathode lens focus on;
In mass analysis stage:
Apply high pressure on first detector 204 and second detector 205, detector enters detected state;
Apply negative voltage (this voltage should be lower than the direct current biasing on the electron source 209) on the second electron lens 208, (second electron lens 208 conducts) electronic gate is closed at this moment, and electronics can not pass through second electron lens 208;
On first electrode 206, apply positive voltage, then apply negative voltage or ground connection on second electrode 207,3D ion trap outgoing ion from the both direction: a part of ion is from endcap electrode 203 outgoing, effect of electric field deflect in first electrode 206 and 207 formation of second electrode, pass the aperture 211 on second electrode 207, thereby detected by second detector 205; Another part ion is detected by first detector 204 from endcap electrode 202 outgoing.
Therefore the ion of outgoing can both be detected from the 3D ion trap both direction, has improved the detection efficiency of ion significantly, and detection efficiency can reach 100% in theory.Cathode lens has further focused on electronics, has improved the Ionization Efficiency of sample.
Embodiment 2:
As shown in Figure 3, Figure 4, a kind of device that improves the 3D ion trap detection efficiency, as different from Example 1: between the cathode lens and second detector, ion focusing set of lenses 301 is set, is used to reduce dispersing of ion, further improve the detection efficiency of ion.
Present embodiment has also disclosed a kind of method of the 3D of raising ion trap detection efficiency, and as different from Example 1: ion enters ion focusing set of lenses 301 after penetrating from cathode lens, is detected by second detector afterwards.The ion focusing set of lenses can design different lens numbers as required, and the voltage on it can reach best ion focusing effect according to actual conditions optimization.
Embodiment 3:
As shown in Figure 5, a kind of device that improves the 3D ion trap detection efficiency, as different from Example 1:
1, above first detector, is provided with the first high energy dynode 401.
2, be provided with hole 212 on first electrode 206, the position relative with this hole 212 is provided with the second high energy dynode 402.Hole 212 usefulness mesh electrodes cover, and the electric field error so that the compensation perforate causes focuses on the electronics that passes through better, and mesh electrode allows ion to pass through simultaneously.
Present embodiment has also disclosed a kind of method of the 3D of raising ion trap detection efficiency, as different from Example 1:
In mass analysis stage:
Apply negative voltage on first electrode 206, and apply positive voltage on second electrode 207.
The 3D ion trap is from both direction outgoing ion, enters the first high energy dynode 401 from the ion of endcap electrode 202 outgoing, detected by first detector from the electronics of these dynode 401 outgoing; Under the electric field action of ion through first electrode 206 and 207 formation of second electrode of endcap electrode 203 outgoing, to enter the second high energy dynode 402 through via hole 212, after the electronics of these dynode 402 outgoing passes cathode lens, be detected by second detector.
Owing to be provided with two high energy dynodes, further improved ion detection efficient.
Embodiment 4:
As Fig. 3, shown in Figure 6, a kind of device that improves the 3D ion trap detection efficiency, as different from Example 1:
1, second electron lens 208 no longer is set.
2, the length of first electrode 206, second electrode 207 is greater than the 211 close endcap electrodes 203 of the hole on embodiment 1, the second electrode 207.
Present embodiment has also disclosed a kind of method of the 3D of raising ion trap detection efficiency, is applied in the mass spectral analysis, and characteristics are:
In the ionization stage:
High pressure on first detector 204 and second detector 205 is closed, and detector is in off position;
Apply identical positive voltage or suitable negative voltage on first electrode 206 and second electrode 207, cathode lens is opened as electronic gate;
Electron source 209 emitting electrons, electronics enter the 3D ion trap, the neutral sample in the ionization 3D ion trap after focusing on through cathode lens;
In mass analysis stage:
Apply high pressure on first detector 204 and second detector 205, detector enters detected state;
Apply positive voltage on first electrode 206, then apply negative voltage or ground connection on second electrode 207, at this moment, cathode lens is closed as electronic gate, has stopped passing of (electron source 209 produces) electronics; Simultaneously, 3D ion trap outgoing ion from the both direction: a part of ion is from endcap electrode 203 outgoing, in the electric field action deflect of first electrode 206 and 207 formation of second electrode, pass the aperture 211 on second electrode 207, thereby detected by second detector 205; Another part ion is detected by first detector 204 from endcap electrode 202 outgoing.
Therefore the ion of outgoing can both be detected from the 3D ion trap both direction, has improved the detection efficiency of ion significantly, and detection efficiency can reach 100% in theory.Cathode lens has focused on the electronics of electron source outgoing, has improved the Ionization Efficiency of sample.
Above-mentioned execution mode should not be construed as limiting the scope of the invention.Key of the present invention is: first side in the 3D ion trap is provided with first detector, second side is provided with cathode lens, cathode lens is used to control that electronics passes, ion deflecting, second detector is arranged on the sidepiece of cathode lens, is used to detect the ion after cathode lens deflection from the second side outgoing of 3D ion trap.Under the situation that does not break away from spirit of the present invention, any type of change that the present invention is made all should fall within protection scope of the present invention.

Claims (10)

1. method that improves the 3D ion trap detection efficiency is characterized in that:
In the ionization stage:
Electronics passes through electron lens, and enters described 3D ion trap;
In mass analysis stage:
There is not electronics to pass through described electron lens;
3D ion trap outgoing ion: wherein on the direction ion of outgoing in the effect deflect of electron lens, detected afterwards; The ion of outgoing is also detected on the other direction.
2. method according to claim 1 is characterized in that: described electron lens comprises first electrode and second electrode that is oppositely arranged, and second electrode is provided with is convenient to the hole that ion or electronics pass.
3. method according to claim 2 is characterized in that: in the ionization stage, it is identical with voltage on second electrode to be added in first electrode; In mass analysis stage, the voltage that is added on first electrode is higher than second electrode.
4. method according to claim 2 is characterized in that: in mass analysis stage, cathode lens has stopped passing of electronics.
5. according to claim 2 or 3 or 4 described methods, it is characterized in that: described first electrode and second electrode are halfpipes.
6. device that improves the 3D ion trap detection efficiency, it is characterized in that: described device comprises:
Be arranged on first side of 3D ion trap, be used to detect first detector of 3D ion trap from the ion of this side outgoing;
Be arranged on the electron lens of 3D ion trap second side, be convenient to electronics across and into described 3D ion trap;
Be arranged on second detector of described electron lens sidepiece, be used to detect from second side outgoing of 3D ion trap and the ion after electron lens deflection.
7. device according to claim 6 is characterized in that: described electron lens comprises first electrode and second electrode that is oppositely arranged, and second electrode is provided with the hole that cooperates with described second detector.
8. device according to claim 7 is characterized in that: described first electrode is provided with the hole, also is provided with the dynode that cooperates with this hole.
9. according to claim 7 or 8 described devices, it is characterized in that: described hole is provided with mesh electrode.
10. according to claim 7 or 8 described devices, it is characterized in that: described first electrode and second electrode are halfpipes.
CN2009101566311A 2009-12-29 2009-12-29 Method and device for improving 3D ion trap detection efficiency Expired - Fee Related CN101777483B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103247512A (en) * 2012-02-07 2013-08-14 上海华质生物技术有限公司 Pulse type light ionization device
CN104335323A (en) * 2013-01-31 2015-02-04 北京理工大学 Ion trap-based apparatus and method for analyzing and detecting bipolar ion
CN105632864A (en) * 2016-01-07 2016-06-01 中国计量科学研究院 Composite detector and quadrupole mass spectroscope with same
CN109065437A (en) * 2018-08-03 2018-12-21 北京理工大学 A kind of the ion resonance excitation operating method and device of quadripolar electric field joint dipole electric field

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103247512A (en) * 2012-02-07 2013-08-14 上海华质生物技术有限公司 Pulse type light ionization device
CN104335323A (en) * 2013-01-31 2015-02-04 北京理工大学 Ion trap-based apparatus and method for analyzing and detecting bipolar ion
US9368336B2 (en) 2013-01-31 2016-06-14 Beijing Institute Of Technology Ion trap-based apparatus and method for analyzing and detecting bipolar ions
CN104335323B (en) * 2013-01-31 2017-02-15 北京理工大学 Ion trap-based apparatus and method for analyzing and detecting bipolar ion
CN105632864A (en) * 2016-01-07 2016-06-01 中国计量科学研究院 Composite detector and quadrupole mass spectroscope with same
CN109065437A (en) * 2018-08-03 2018-12-21 北京理工大学 A kind of the ion resonance excitation operating method and device of quadripolar electric field joint dipole electric field

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