CN102290318A - Proton transfer reaction device with multipole rod - Google Patents

Proton transfer reaction device with multipole rod Download PDF

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CN102290318A
CN102290318A CN2011101837541A CN201110183754A CN102290318A CN 102290318 A CN102290318 A CN 102290318A CN 2011101837541 A CN2011101837541 A CN 2011101837541A CN 201110183754 A CN201110183754 A CN 201110183754A CN 102290318 A CN102290318 A CN 102290318A
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proton
segmentation
drift tube
transfer reactions
bar
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CN102290318B (en
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程平
陈应
董俊国
黄正旭
傅忠
周振
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KUNSHAN HEXIN ZHIPU TECHNOLOGY CO LTD
University of Shanghai for Science and Technology
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KUNSHAN HEXIN ZHIPU TECHNOLOGY CO LTD
University of Shanghai for Science and Technology
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Abstract

The invention discloses a proton transfer reaction device with a multipole rod. The device comprises a drift tube for the proton transfer reaction of a proton supplier and analyte. The front end of the drift tube is provided with a proton supplier inlet and a carrier gas introduction channel for introducing sample molecules and a carrier gas, and the rear end of the drift tube is provided with a carrier gas outlet channel and an analyte ion outlet. The sectionalized multipole rod is arranged in the drift tube and connected with a controllable boosted radio frequency power supply. By the device, the cross section of an ion beam is controlled by controlling the amplitude of a boosted radio frequency voltage loaded on the sectionalized multipole rod, so the cross section for the proton transfer reaction at the front end is enlarged and then maximal proton transfer reaction is realized; the cross section of the ion beam at the rear end is reduced, so an ion transport rate is improved, pollution of neutral molecules to a spectrum analyzer is avoided and the flexibility of the analyzer is improved.

Description

A kind of multipole bar Proton-Transfer Reactions device
Technical field
The present invention relates to the ion transfer field, especially a kind of multipole bar Proton-Transfer Reactions device.
Background technology
Mass spectrum is to analysis of the molecular structure one of the most accurate method, can be used to unknown material is carried out qualitative analysis and known component in the mixture is carried out detection by quantitative.Ion source is the key component of mass spectrometer.The most frequently used ion source is EI(electron ionization) source, it adopts high-power electron beam bombardment sample, thereby makes sample generation ionization produce electronics and molecular ion.Principle is as follows:
Figure 2011101837541100002DEST_PATH_IMAGE001
M +Can continue fracture and carry out molecular rearrangement, produce multiple fragment ion.The ionizing efficiency height in EI source, good reproducibility, and existing complete spectrum storehouse are present most popular ion sources.But the fragment peak that the EI source produces is more, and is very difficult for the spectrum unscrambling that mixes unknown material.In order to address this problem, produced a series of soft ionization (soft ionization) method.
(chemical ionization CI) is exactly the mode of a kind of typical soft ionization of developing on the basis of EI to chemi-ionization.It is by introducing a kind of reacting gas (normally methane etc.), make electronics at first bombard reacting gas and produce relevant reactant gas molecules ion, and then with sample molecule generation ion molecule reaction, general quasi-molecular ion so the mass spectrogram that produces sample molecule is simple, can determine the molecular weight of sample fast and is widely used.The proton translocation ion source is exactly a kind of of CI source, can be used to combine with mass spectrometer formed present the most frequently used proton translocation mass spectrometer (PTRMS) apparatus that is used for the volatile organic matter (VOCs) in real-time, the online detection atmosphere.The Proton-Transfer Reactions ion source be by initial reaction ion and sample molecule generation Proton-Transfer Reactions (proton transfer reaction) thus principle make proton on the testing molecule band, carry out check and analysis by mass analyzer then.The initial reaction ion is generally by carrying out discharge generation hydrogen ion (H3O to steam and Air mixing gas +), and with it as reactive ion, then in drift tube with testing sample molecule generation Proton-Transfer Reactions, make the sample molecule ionization.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of Proton-Transfer Reactions device based on multipole bar is provided.Described device can be controlled the size in Proton-Transfer Reactions cross section, and can regulate the ion beam of reaction, makes ion focusing, and stops that to a certain extent neutral molecule enters in the follow-up mass spectrometer.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
A kind of multipole bar Proton-Transfer Reactions device, comprise that one supplies proton donor and analyte to carry out the drift tube of Proton-Transfer Reactions, the front end of described drift tube is provided with the proton donor inlet and introduces passage for the carrier gas that sample molecule, carrier gas are introduced, the rear end of described drift tube is provided with carrier gas extraction channel and analyte ions outlet, be provided with the multipole bar of segmentation in the described drift tube, the multipole bar of described segmentation is connected with the controlled radio-frequency power supply that boosts.
Further, the multipole bar of described segmentation is segmentation quadrupole rod, segmentation sextupole bar or segmentation ends of the earth bar; Described drift tube carries out the vacuum chamber of Proton-Transfer Reactions and ion adjusting for sealing.
Be further used as preferred embodiment, the voltage magnitude of the described radio-frequency power supply that boosts is variable, and amplitude is-10KV ~ 10KV.
Further, described proton donor is water and hydrogen ion; Described carrier gas is nitrogen, air, rare gas or other permanent gas.
Be further used as of the present invention this and advance, described drift tube also is provided with the heater that makes the multipole bar constant temperature of segmentation.
The invention has the beneficial effects as follows: the present invention is by the amplitude of the boost radio-frequency voltage of control loaded on the multipole bar of segmentation, can be good at controlling the cross section of ion beam, make at the cross section of front end Proton-Transfer Reactions big, realize maximum Proton-Transfer Reactions, reduce the cross section of ion beam in the rear end, realize ion focusing and neutral molecule are stopped, improve ion transmission efficiency, avoided the pollution of neutral molecule, the sensitivity that has improved instrument to mass spectrometer; Heater is installed in the present invention additional on drift tube, strengthened the warm-up movement of surface molecular and the activity of ion, reduces the loss in the ion transfer process.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described further:
Fig. 1 is a segmentation quadrupole rod Proton-Transfer Reactions plot structure schematic diagram;
Fig. 2 is a segmentation quadrupole rod Proton-Transfer Reactions district ion transfer design sketch;
Fig. 3 is a segmentation quadrupole rod structure chart;
Fig. 4 is a segmentation quadrupole rod axial side view;
Fig. 5 is a segmentation quadrupole rod front view;
Fig. 6 is a segmentation quadrupole rod axial, cross-sectional view;
Fig. 7 is a segmentation quadrupole rod proton translocation ion source device schematic three dimensional views;
Fig. 8 is the profile of segmentation quadrupole rod proton translocation ion source device.
Description of symbols:
1 proton donor inlet
Passage is introduced in 2 carrier gas
3 drift tubes
4 carrier gas extraction channels
The outlet of 5 analyte ions
The positive plate of 6 hollow-cathode tubes
The minus plate of 7 hollow-cathode tubes
8 regulate electrode
9 first dividing plates
10 vacuum chambers
11 mass spectrometer interface blocks
12 second partitions.
Embodiment
With reference to Fig. 1, a kind of multipole bar Proton-Transfer Reactions device, comprise that one supplies proton donor and analyte to carry out the drift tube 3 of Proton-Transfer Reactions, the front end of described drift tube 3 is provided with proton donor inlet 1 and introduces passage 2 for the carrier gas of sample molecule and carrier gas introducing, the rear end of described drift tube 3 is provided with carrier gas extraction channel 4 and analyte ions outlet 5, described drift tube 3 carries out the vacuum chamber of Proton-Transfer Reactions and ion adjusting for sealing, be provided with the segmentation quadrupole rod in the described drift tube 3, described segmentation quadrupole rod is connected with the controlled radio-frequency power supply that boosts.
Described segmentation quadrupole rod is as the electric field carrier in control Proton-Transfer Reactions cross section, be added with the radio-frequency power supply that boosts above, the described radio-frequency power supply that boosts is on the high-voltage radio-frequency basis, this high-voltage radio-frequency is carried out conversion be divided into a plurality of high-voltage radio-frequency sources of boosting, and on basis, a plurality of high-voltage radio-frequencies source, add the pressure drop of gradient direct current, finally realized high-voltage radio-frequency, boost radio frequency and direct current gradient.The radio-frequency power supply that boosts both had been used to control ion beam cross section and had finally realized focusing of ion beam, provided the gradient direct voltage to promote ion transfer simultaneously again, avoided the generation of cluster ion.
Described drift tube 3 is a vacuum chamber, in order to the zone that ionic reaction and ion adjusting are carried out in sealing, avoids being disturbed by the material in the atmosphere, and has realized mass spectral differential vacuum.
The voltage magnitude of the described radio-frequency power supply that boosts is variable, and amplitude is-10KV ~ 10KV.The amplitude of described radio-frequency voltage is big more, the cross section of ion beam is more little, therefore, need carry out radio frequency on the segmentation quadrupole rod boosts, the ion beam cross section that needs in leading portion Proton-Transfer Reactions district is very big, be convenient to the generation of proton translocation, just need dwindle the ion cross section behind the Proton-Transfer Reactions, the ion beam of focusing is convenient to the analysis of ion introducing and mass spectrometer.
Described proton donor is water and hydrogen ion; Described carrier gas is nitrogen, air, rare gas or other permanent gas, and airborne analyte (VOCs etc.) is followed carrier gas to introduce passage 2 from carrier gas and entered drift tube 3.
Fig. 2 has provided the design sketch of segmentation quadrupole rod Proton-Transfer Reactions ion transfer, and the cross section of described ion beam from left to right diminishes gradually, and the analysis of follow-up mass spectrometer is convenient in final focusing.
With reference to Fig. 3, the segmentation quadrupole rod is axle with the insulator at first with the quadrupole rod segmentation again, makes the way of realization of segmentation quadrupole rod with annulus.
Fig. 4 is the axial side view of segmentation quadrupole rod;
Fig. 5 is the front schematic view of segmentation quadrupole rod;
Fig. 6 is the axial, cross-sectional view of segmentation quadrupole rod;
With reference to Fig. 7-Fig. 8, comprise steam the discharge positive plate 6 of hollow-cathode tube of ionization and the minus plate 7 of hollow-cathode tube, be connected with the adjusting electrode 8 of scalable control thereafter, the electric field that produces is regulated the steam relevant ions, be provided with first dividing plate 9 between described adjusting electrode 8 and the Proton-Transfer Reactions district, be connected with vacuum chamber 10 behind first dividing plate 9, be provided with drift tube 3 in the described vacuum chamber 10, described drift tube 3 front ends are provided with for atmospheric carrier air and the carrier gas that the analyte (VOCs etc.) that is included in is wherein introduced and introduce passage 2, be provided with the multistage tetrode of segmentation in the drift tube 3, the rear portion of drift tube 3 is provided with the second partition 12 that Proton-Transfer Reactions ion source and mass spectrometer are separated, described second partition is connected with mass spectrometer interface block 11, the analyte ions outlet 5 of described drift tube 3 rear ends runs through second partition 12 and mass spectrometer interface block 11, gives mass spectrometer with the ion transfer behind the Proton-Transfer Reactions.
Be further used as improvement, described drift tube 3 also is provided with the heater that makes the multipole bar constant temperature of segmentation, is rebounded under the warm-up movement of surface molecular in ion and bar collision back, reduces the loss of ion.
Concrete parameter of the present invention is as follows:
Radio-frequency voltage: 1Hz~3GHz ,-10KV~10kV, square wave, sine wave and other periodic waveforms;
Operating pressure: 10 -4Pa~10kPa(negative pressure of vacuum);
Carrier gas: permanent gas such as nitrogen, air, rare gas;
The segmentation multipole bar of radio frequency that boosts comprises quadrupole rod, the sextupole bar, and ends of the earth bars etc. can be simple metal, are the electrodes that has plated metal also.
The present invention mainly is to be the improvement of drift tube part to the Proton-Transfer Reactions district, provides the Proton-Transfer Reactions chamber by the multipole bar of segmentation for the proton translocation ion source device.The multipole bar of segmentation can provide the electric field of the drift tube of similar typical Proton-Transfer Reactions, and the multipole bar of segmentation can be by controlling the sectional area of ion beam to the control of radio-frequency voltage, thereby the cross section at the leading portion Proton-Transfer Reactions is big, realize maximum Proton-Transfer Reactions, reduce the cross section of ion beam in the rear end, realization stops ion focusing and neutral molecule, improve ion transmission efficiency, avoided the pollution of neutral molecule, improved the sensitivity of instrument and prolonged life-span of detector mass spectrometer.
More than be that preferable enforcement of the present invention is specified, but the invention is not limited to described embodiment, those of ordinary skill in the art make all equivalent variations or replacement also can doing under the prerequisite of spirit of the present invention, the distortion that these are equal to or replace all is included in the application's claim institute restricted portion.

Claims (7)

1. multipole bar Proton-Transfer Reactions device, comprise that one supplies proton donor and analyte to carry out the drift tube (3) of Proton-Transfer Reactions, the front end of described drift tube (3) is provided with proton donor inlet (1) and introduces passage (2) for the carrier gas that sample molecule, carrier gas are introduced, the rear end of described drift tube (3) is provided with carrier gas extraction channel (4) and analyte ions outlet (5), it is characterized in that: be provided with the multipole bar of segmentation in the described drift tube (3), the multipole bar of described segmentation is connected with the controlled radio-frequency power supply that boosts.
2. a kind of multipole bar Proton-Transfer Reactions device according to claim 1 is characterized in that: the multipole bar of described segmentation is segmentation quadrupole rod, segmentation sextupole bar or segmentation ends of the earth bar.
3. a kind of multipole bar Proton-Transfer Reactions device according to claim 1 is characterized in that: described drift tube (3) carries out the vacuum chamber of Proton-Transfer Reactions and ion adjusting for sealing.
4. a kind of multipole bar Proton-Transfer Reactions device according to claim 1, it is characterized in that: the voltage magnitude of the described radio-frequency power supply that boosts is variable, and amplitude is-10KV ~ 10KV.
5. a kind of multipole bar Proton-Transfer Reactions device according to claim 1, it is characterized in that: described proton donor is water and hydrogen ion.
6. a kind of multipole bar Proton-Transfer Reactions device according to claim 1, it is characterized in that: described carrier gas is nitrogen, air, rare gas or other permanent gas.
7. a kind of multipole bar Proton-Transfer Reactions device according to claim 1, it is characterized in that: described drift tube (3) also is provided with the heater that makes the multipole bar constant temperature of segmentation.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
CN104183454A (en) * 2014-08-26 2014-12-03 昆山禾信质谱技术有限公司 Proton transfer reaction mass spectrum ion transmission device
CN105428200A (en) * 2015-12-30 2016-03-23 广州禾信分析仪器有限公司 Drift time ion migration spectral device
CN108091544A (en) * 2016-11-21 2018-05-29 中国科学院大连化学物理研究所 A kind of mass spectrum chemical ionization source based on differential mobility spectrum ion screening
CN108447762A (en) * 2018-05-15 2018-08-24 中国科学技术大学 A kind of Proton transfer reaction mass spectrometry instrument and its detection method
CN111640646A (en) * 2020-06-15 2020-09-08 成都艾立本科技有限公司 High-sensitivity proton transfer time-of-flight mass spectrometer and method for measuring ion time-of-flight by using same
CN113327837A (en) * 2021-02-08 2021-08-31 四川大学 Molecular ion reaction tank and proton transfer reaction mass spectrometer

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US20030089847A1 (en) * 2000-03-14 2003-05-15 Roger Guevremont Tandem high field asymmetric waveform ion mobility spectrometry ( faims)/ion mobility spectrometry
CN101401187A (en) * 2006-03-10 2009-04-01 瓦里安半导体设备公司 Technique for monitoring and controlling a plasma process
CN102103970A (en) * 2011-01-18 2011-06-22 四川大学 Microwave plasma generator and proton transfer mass spectrometer
CN202167454U (en) * 2011-07-01 2012-03-14 上海大学 Multi-pole proton transfer reaction device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030089847A1 (en) * 2000-03-14 2003-05-15 Roger Guevremont Tandem high field asymmetric waveform ion mobility spectrometry ( faims)/ion mobility spectrometry
US20020134933A1 (en) * 2001-03-20 2002-09-26 Ion Track Instruments Llc Enhancements to ion mobility spectrometers
CN101401187A (en) * 2006-03-10 2009-04-01 瓦里安半导体设备公司 Technique for monitoring and controlling a plasma process
CN102103970A (en) * 2011-01-18 2011-06-22 四川大学 Microwave plasma generator and proton transfer mass spectrometer
CN202167454U (en) * 2011-07-01 2012-03-14 上海大学 Multi-pole proton transfer reaction device

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104183454A (en) * 2014-08-26 2014-12-03 昆山禾信质谱技术有限公司 Proton transfer reaction mass spectrum ion transmission device
CN104183454B (en) * 2014-08-26 2017-02-15 昆山禾信质谱技术有限公司 Proton transfer reaction mass spectrum ion transmission device
CN105428200A (en) * 2015-12-30 2016-03-23 广州禾信分析仪器有限公司 Drift time ion migration spectral device
CN108091544A (en) * 2016-11-21 2018-05-29 中国科学院大连化学物理研究所 A kind of mass spectrum chemical ionization source based on differential mobility spectrum ion screening
CN108091544B (en) * 2016-11-21 2019-09-06 中国科学院大连化学物理研究所 A kind of mass spectrum chemical ionization source based on differential mobility spectrum ion screening
CN108447762A (en) * 2018-05-15 2018-08-24 中国科学技术大学 A kind of Proton transfer reaction mass spectrometry instrument and its detection method
CN108447762B (en) * 2018-05-15 2024-05-17 中国科学技术大学 Proton transfer reaction mass spectrometer and detection method thereof
CN111640646A (en) * 2020-06-15 2020-09-08 成都艾立本科技有限公司 High-sensitivity proton transfer time-of-flight mass spectrometer and method for measuring ion time-of-flight by using same
CN113327837A (en) * 2021-02-08 2021-08-31 四川大学 Molecular ion reaction tank and proton transfer reaction mass spectrometer

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