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CN109887822B - Novel sleeve type ion migration tube - Google Patents

Novel sleeve type ion migration tube Download PDF

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CN109887822B
CN109887822B CN201711272311.3A CN201711272311A CN109887822B CN 109887822 B CN109887822 B CN 109887822B CN 201711272311 A CN201711272311 A CN 201711272311A CN 109887822 B CN109887822 B CN 109887822B
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sleeve
separation
detection
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CN109887822A (en
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王卫国
李海洋
陈红
黄卫
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

本发明公开了一种新型套筒式离子迁移管,具体讲一种套筒式高场非对称波形离子迁移管,它包括进样口、电离区、分离区、检测区等,沿轴向方向依次排列。分离区由两个及两个以上套筒电极构成;检测区由两个及两个以上套筒电极对构成。通过调控不同套筒电极的间距,可以同时实现多种化合物的同时测定;也可以获得同一种化合物在不同分离电压下的谱图信息,提高识别准确性。每本发明可以同时提供两个或两个以上的检测通道,实现两个或两个以上化合物的同时测定,缩短检测周期;使用单一的高场非对称性射频电压和直流补偿电源,不需要多个电源,结构简单、体积小,便于加工和产业化推广。

Figure 201711272311

The invention discloses a novel sleeve-type ion transfer tube, in particular a sleeve-type high-field asymmetric waveform ion transfer tube, which comprises a sample inlet, an ionization zone, a separation zone, a detection zone, etc. in order. The separation area consists of two or more sleeve electrodes; the detection area consists of two or more sleeve electrode pairs. By adjusting the distances of different sleeve electrodes, the simultaneous determination of multiple compounds can be achieved; the spectral information of the same compound under different separation voltages can also be obtained to improve the identification accuracy. Each invention can provide two or more detection channels at the same time, realize the simultaneous determination of two or more compounds, and shorten the detection period; using a single high-field asymmetric radio frequency voltage and DC compensation power supply, it does not need more It is a power supply with simple structure and small volume, which is convenient for processing and industrialization promotion.

Figure 201711272311

Description

Novel sleeve type ion migration tube
Technical Field
The invention relates to an atmospheric pressure separation analysis technology, in particular to a novel sleeve type ion transfer tube, which comprises an ionization region, a separation region, a detection region and the like which are sequentially arranged along the axial direction. The separation area is composed of a central electrode and two or more than two coaxial, parallel and non-coplanar sleeve electrodes; the detection area is composed of N coaxial cylindrical electrodes which are parallel and insulated with each other. Two or more detection electrode pairs. At least one of the separated electrodes of each pair faces towards the ground electrode, and at least one electrode faces towards the high-voltage asymmetric field electrode. Each pair of detection electrodes applies a positive bias voltage to one electrode and a negative bias voltage to one electrode. The invention can utilize the same asymmetric power supply, realize the simultaneous determination of two or more compounds by regulating and controlling the distance between two or more detection channels, and shorten the detection period; the single high-field asymmetric radio frequency voltage and direct current compensation power supply are used, a plurality of power supplies are not needed, the structure is simple, the size is small, and the processing and the industrialized popularization are facilitated.
Background
The high-field asymmetric waveform ion mobility tube is a mass analysis detection technology which is continuously developed based on the traditional ion mobility spectrometry technology, and the first public report is provided by Buryakov et al, Soviet Union in 1993. It is based on ions in high field (E/N)>40Td,1Td=10-17Vcm2) Low field (E/N)<2Td) to enable detection of different species.
The principle of asymmetric field ion mobility spectrometry is as follows: the mobility of the ions can be expressed as:
K=K0(1+α)
wherein K is the mobility of ions in a high field, K0The value of the mobility of the ions under low field is the rate of change of the mobility of the ions under high field relative to the mobility under low field, which may be positive or negative, and varies depending on the material α is equal to 0 under low field.
The carrier gas makes the matter ion pass through the drift region in the direction perpendicular to the electric field, the drift region applies the asymmetric field switched by radio frequency positive and negative, and the time average value of the voltage is zero in the whole radio frequency period. Thus, in the high and low field regions, the ions are both vertically displaced along the electric field at mobility K, but if the mobilities at the high and low fields are different, the ions will generally move away from their original positions in a direction perpendicular to the direction during a period, resulting in a net displacement. Over time, this displacement of the ions will cause them to strike the electrodes and be neutralized. In order to make the ions pass through the detection area smoothly, a direct current electric field can be superposed on the original electric field, and when the direct current electric field is properly added, the net displacement of the ions in the vertical direction is zero, so that the ions can be detected through the detection channel smoothly. By scanning the dc field, different ions can be detected.
The high-field asymmetric waveform ion mobility tube technology has the advantages of high detection sensitivity, simple equipment, small volume, portability, low detection cost and the like, and is more and more valued by people. At present, the method can be applied to a plurality of fields such as monitoring of explosives, drug inspection, detection of biochemical warfare agents and the like. At present, the high-field asymmetric waveform ion mobility tube reported in the literature and the patent comprises a flat plate structure (200910086487.9, 201310191739.0) and a cylindrical structure (200810229883.8). Previous flat panel structure devices only enabled the detection of ions of a single polarity (electrophilic or protonophilic). In order to increase the detection speed and reduce the analysis time, patent 200810229883.8 proposes a parallel-type and series-type combined high-field asymmetric waveform ion mobility tube, which is provided with two or more ground electrode sleeves; however, the concentration of the target compound is decreased by shunting the sample, resulting in a decrease in detection sensitivity. In addition, the array structure usually needs a plurality of high-field asymmetric radio frequency voltages and a direct current compensation power supply, which is not favorable for miniaturization and industrial popularization.
The invention provides a sleeve type high-field asymmetric waveform ion transfer tube, which is processed by integrated design and uses a single high-field asymmetric radio frequency voltage and a direct current compensation power supply to realize simultaneous determination of multiple compounds, reduce analysis time and realize high-flux analysis.
Disclosure of Invention
The invention aims to provide a multi-channel sleeve type high-field asymmetric waveform ion transfer tube, and the ion transfer separation and detection channel of the transfer tube adopts a structural integrated design, so that the simultaneous detection of two channels or multiple channels is realized, the false alarm rate is reduced, and the accuracy and the application range of the instrument detection are improved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the sleeve type ion migration tube comprises: the device comprises a cylindrical insulating sleeve with a closed left end and an open right end, wherein a sample inlet is arranged in the middle of the closed left end of the insulating sleeve, a central electrode is arranged in the middle of the insulating sleeve along the axis direction of the insulating sleeve, a cylindrical first separation electrode sleeve is sleeved outside the central electrode, a cylindrical second separation electrode sleeve is sleeved outside the first separation electrode sleeve, the central electrode, the first separation electrode sleeve and the second separation electrode sleeve are mutually spaced and coaxially arranged, an ion separation zone is formed by the central electrode, the first separation electrode sleeve and the second separation electrode sleeve, and an ionization source is arranged between the ion separation zone and the sample inlet; a second detection electrode pair formed by a pair of coaxially sleeved cylindrical electrodes and a first detection electrode pair formed by a pair of coaxially sleeved cylindrical electrodes sleeved outside the second detection electrode pair are arranged in the cylinder body close to the right opening end of the insulating sleeve along the axis direction of the cylinder body; the ion detection area is formed by the first detection electrode pair and the second detection electrode pair; be equipped with shielding electrode between ion separation district and ion detection district, shielding electrode includes that the middle part sets up in the middle part electrode along insulating sleeve axis direction, and the outside cover of middle part electrode is equipped with cylindric electrode, and the outside cover of electrode is equipped with cylindric two electrodes, and middle part electrode, two electrodes are mutual interval, coaxial setting.
The ion separation area of the ion migration tube is composed of a central electrode, a first separation electrode sleeve and a second separation electrode sleeve from inside to outside, the central electrode, the first separation electrode sleeve and the second separation electrode sleeve are coaxial, and the lengths of the central electrode, the first separation electrode sleeve and the second separation electrode sleeve are the same along the axial direction of the insulating sleeve; a first separation area is formed between the central electrode and the first separation electrode sleeve; a second separation area is formed between the first separation electrode sleeve and the second separation electrode sleeve; the lengths of the inner cylindrical detection electrode and the outer cylindrical detection electrode which form the first detection electrode pair and the second detection electrode pair are the same along the axial direction of the insulating sleeve; the detection electrode pair comprises a first detection electrode pair and a second detection electrode pair; each electrode pair is divided into an inner cylindrical detection electrode and an outer cylindrical detection electrode which are insulated from each other, and positive bias voltage and negative bias voltage are respectively applied to the inner detection electrode and the outer detection electrode and are respectively used for detecting positive ions and negative ions; the ionization source, the ion separation area and the ion detection area are all located inside the insulating sleeve.
The length of the middle electrode, the first electrode and the second electrode which form the shielding electrode along the axial direction of the insulating sleeve is the same.
The ion migration tube is characterized in that: the number n of the coaxially sleeved separation electrode sleeves is 2 or more than two;
when the number of the electrodes is 2, the voltages connected with the adjacent electrodes of the central electrode, the first separated electrode sleeve and the second separated electrode sleeve are different, and the voltages connected with the non-adjacent (spaced) electrodes are the same;
for example, the central electrode and the separated electrode sleeve are respectively connected with the ground wire (or a high-field asymmetric power supply and a supplementary direct-current power supply) through leads; the first split electrode sleeve is connected with a high-field asymmetric power supply and a supplementary direct current power supply (or a ground wire) through leads.
The distance between the central electrode and the first separation electrode sleeve of the ion migration tube is different from the distance between the first separation electrode sleeve and the second separation electrode sleeve; the spacing is between 0.1 and 10 mm.
The ion migration tube is characterized in that: the central or middle electrode is a cylindrical or cylindrical electrode, respectively.
The ionization source of the ion migration tube is a pair of parallel plate-shaped discharge electrodes, and the electrodes are parallel to the axial direction of the insulating sleeve (9).
The invention has the advantages that:
1. the integrally designed stepped high-field asymmetric waveform ion mobility tube is designed.
2. The multi-channel ion detector realizes multi-channel detection of positive and negative ions, can detect electrophilic substances and proton-philic substances simultaneously, not only enlarges the detection range, but also improves the detection efficiency.
3. The invention uses single high-field asymmetric radio frequency voltage and a direct current compensation power supply, has simple structure and convenient processing, and is easy for batch production;
the invention can realize two or more than two detection channels in one cavity, realize the simultaneous determination of various compounds, shorten the analysis period, improve the analysis efficiency and realize the rapid analysis of mass samples; in addition, the invention can apply different high-field asymmetric-wave radio-frequency high voltages on different electrode pairs aiming at the same compound, obtain a two-position spectrogram of the compensation voltage and the radio-frequency voltage in a short time and improve the identification accuracy. This novel asymmetric waveform ion mobility tube in high field can reduce the influence of parameters such as temperature, environment, float gas, is particularly useful for the environment of higher air humidity to the realization is to the high sensitivity and the high discernment accuracy of determinand.
Drawings
FIG. 1 is a schematic diagram of a sleeve-type high-field asymmetric waveform ion transfer tube;
Detailed Description
The schematic diagram of the sleeve type high-field asymmetric waveform ion transfer tube of the invention is shown in figure 1.
The sleeve type ion migration tube comprises: the device comprises a cylindrical insulating sleeve 9 with a closed left end and an open right end, wherein a sample inlet 8 is arranged in the middle of the closed left end of the insulating sleeve, a central electrode 4 is arranged in the middle of the insulating sleeve along the axis direction of the insulating sleeve, a cylindrical first separation electrode sleeve 3 is sleeved outside the central electrode, a cylindrical second separation electrode sleeve 2 is sleeved outside the first separation electrode sleeve, the central electrode 4, the first separation electrode sleeve 3 and the second separation electrode sleeve 2 are mutually spaced and coaxially arranged, an ion separation zone is formed by the central electrode, the first separation electrode sleeve and the second separation electrode sleeve 2, and an ionization source 1 is arranged between the ion separation zone and the sample inlet 8; a second detection electrode pair 7 formed by a pair of coaxially sleeved cylindrical electrodes and a first detection electrode pair 6 formed by a pair of coaxially sleeved cylindrical electrodes and sleeved outside the second detection electrode pair 7 are arranged in the cylinder body close to the right opening end of the insulating sleeve along the axis direction of the cylinder body; the ion detection area is formed by the first detection electrode pair and the second detection electrode pair; be equipped with shielding electrode between ion separation district and ion detection district, shielding electrode 5 includes that the middle part sets up in the middle part electrode along insulating sleeve axis direction, and the outside cover of middle part electrode is equipped with cylindric electrode, and the outside cover of electrode is equipped with cylindric two electrodes, and middle part electrode, two electrodes are mutual interval, coaxial setting.
The ion migration tube is characterized in that: the ion separation zone is composed of a central electrode, a first separation electrode sleeve and a second separation electrode sleeve from inside to outside, the central electrode, the first separation electrode sleeve and the second separation electrode sleeve are coaxial, and the lengths of the central electrode, the first separation electrode sleeve and the second separation electrode sleeve are the same along the axial direction of the insulating sleeve; a first separation area is formed between the central electrode and the first separation electrode sleeve (3); a second separation area is formed between the first separation electrode sleeve and the second separation electrode sleeve; the lengths of the inner cylindrical detection electrode and the outer cylindrical detection electrode which form the first detection electrode pair and the second detection electrode pair are the same along the axial direction of the insulating sleeve; the detection electrode pair comprises a first detection electrode pair and a second detection electrode pair; each electrode pair is divided into an inner cylindrical detection electrode and an outer cylindrical detection electrode which are insulated from each other, and positive bias voltage and negative bias voltage are respectively applied to the inner detection electrode and the outer detection electrode and are respectively used for detecting positive ions and negative ions; the ionization source, the ion separation area and the ion detection area are all located inside the insulating sleeve.
The length of the middle electrode, the first electrode and the second electrode which form the shielding electrode along the axial direction of the insulating sleeve is the same.
The ion migration tube is characterized in that: the number n of the coaxially sleeved separation electrode sleeves is 2 or more than two;
when the number of the electrodes is 2, the voltages connected with the adjacent electrodes of the central electrode, the first separated electrode sleeve and the second separated electrode sleeve are different, and the voltages connected with the non-adjacent (spaced) electrodes are the same;
for example, the central electrode and the separated electrode sleeve (3) are respectively connected with the ground wire (or a high-field asymmetric power supply and a supplementary direct-current power supply) through leads; the first separated electrode sleeve (3) is connected with a high-field asymmetric power supply and a supplementary direct current power supply (or a ground wire) through leads.
The spacing between the center electrode and the first split electrode sleeve is different from the spacing between the first split electrode sleeve and the second split electrode sleeve; the spacing is between 0.1 and 10 mm.
The central or middle electrode is a cylindrical or cylindrical electrode, respectively.
The ionization source is a pair of parallel plate-shaped discharge electrodes, and the electrodes are parallel to the axial direction of the insulating sleeve (9).
During measurement, a sample enters the ionization source 2 through the air inlet 8 under the carrying effect of carrier gas and is ionized; then enters a first separation area formed between the central electrode 4 and the first separation electrode sleeve 3; a second separation area is formed between the first separation electrode sleeve 3 and the second separation electrode sleeve 2; because the distance between the central electrode 4 and the first separation electrode sleeve 3 is different from the distance between the first separation electrode sleeve 3 and the second separation electrode sleeve 2, ions with different mobility changes are allowed to enter a detection area through the separation area 1, and the simultaneous separation of different compounds is realized; and finally, the ions enter a detection area, and positive and negative ions respectively reach a detection electrode pair 6 and a detection electrode pair 7 under the action of bias voltage to be detected.

Claims (5)

1.一种套筒式离子迁移管,包括:左端密闭右端开口的圆筒状绝缘套筒(9),于绝缘套筒(9)的左侧密闭端中部设有进样口(8),于绝缘套筒(9)中部沿其轴线方向设有中心电极(4),中心电极(4)外部套设有圆筒状第一分离电极套筒(3),第一分离电极套筒(3)外部套设有圆筒状第二分离电极套筒(2),中心电极(4)、第一分离电极套筒(3)、第二分离电极套筒(2)相互间隔、同轴设置,由中心电极(4)、第一分离电极套筒(3)、第二分离电极套筒(2)构成的离子分离区,于离子分离区与进样口(8)之间设有电离源(1);1. A sleeve-type ion transfer tube, comprising: a cylindrical insulating sleeve (9) with a closed left end and an open right end, and a sample inlet (8) in the middle of the left closed end of the insulating sleeve (9), A central electrode (4) is arranged in the middle of the insulating sleeve (9) along the axis direction thereof, and a cylindrical first separation electrode sleeve (3) is sleeved outside the central electrode (4). The first separation electrode sleeve (3) ) is sleeved with a cylindrical second separation electrode sleeve (2), the center electrode (4), the first separation electrode sleeve (3), and the second separation electrode sleeve (2) are spaced apart and coaxially arranged, The ion separation area consisting of the central electrode (4), the first separation electrode sleeve (3), and the second separation electrode sleeve (2) is provided with an ionization source ( 1); 于靠近绝缘套筒(9)右开口端的筒体内部沿其轴线方向设有由一对同轴套设的圆筒状电极构成的第二检测电极对(7),以及套设于第二检测电极对(7)外部的一对同轴套设的圆筒状电极构成的第一检测电极对(6);第一检测电极对(6)、第二检测电极对(7)与绝缘套筒(9)同轴设置,由第一检测电极对(6)、第二检测电极对(7)构成的离子检测区;A second detection electrode pair (7) consisting of a pair of coaxially sleeved cylindrical electrodes is arranged inside the cylinder near the right open end of the insulating sleeve (9) along its axis direction, and a second detection electrode pair (7) sleeved on the second detection electrode A first detection electrode pair (6) formed by a pair of coaxially sleeved cylindrical electrodes outside the electrode pair (7); the first detection electrode pair (6), the second detection electrode pair (7) and the insulating sleeve (9) coaxially arranged, an ion detection area composed of a first detection electrode pair (6) and a second detection electrode pair (7); 于离子分离区和离子检测区之间设有屏蔽电极(5),屏蔽电极(5)包括中部沿绝缘套筒(9)轴线方向设置的中部电极,中部电极外部套设有圆筒状一电极,一电极外部套设有圆筒状二电极,中部电极、一电极、二电极相互间隔、同轴设置;A shielding electrode (5) is arranged between the ion separation zone and the ion detection zone, the shielding electrode (5) comprises a middle electrode whose middle is arranged along the axis of the insulating sleeve (9), and a cylindrical electrode is sleeved outside the middle electrode , one electrode is sleeved with two cylindrical electrodes, and the middle electrode, one electrode and two electrodes are spaced apart from each other and arranged coaxially; 离子分离区由从内到外的中心电极(4)、第一分离电极套筒(3)、第二分离电极套筒(2)构成,中心电极(4)、第一分离电极套筒(3)、第二分离电极套筒(2)同轴,沿绝缘套筒(9)轴线方向长度相同;中心电极(4)和第一分离电极套筒(3)之间构成第一分离区;第一分离电极套筒(3)和第二分离电极套筒(2)之间构成第二分离区;The ion separation zone is composed of a center electrode (4), a first separation electrode sleeve (3), and a second separation electrode sleeve (2) from the inside to the outside, the center electrode (4), the first separation electrode sleeve (3) ), the second separation electrode sleeve (2) is coaxial, and has the same length along the axis of the insulating sleeve (9); a first separation area is formed between the central electrode (4) and the first separation electrode sleeve (3); A second separation area is formed between a separation electrode sleeve (3) and a second separation electrode sleeve (2); 构成第一检测电极对(6)和第二检测电极对(7)的内、外两个圆筒状检测电极沿绝缘套筒(9)轴线方向长度相同;The inner and outer two cylindrical detection electrodes constituting the first detection electrode pair (6) and the second detection electrode pair (7) have the same length along the axis of the insulating sleeve (9); 检测电极对包括第一检测电极对(6)和第二检测电极对(7);每个电极对分为彼此绝缘的内、外两个圆筒状检测电极,内外检测电极分别施加正、负偏置电压,分别用于正、负离子的检测;The detection electrode pair includes a first detection electrode pair (6) and a second detection electrode pair (7); each electrode pair is divided into inner and outer cylindrical detection electrodes insulated from each other, and the inner and outer detection electrodes are respectively applied with positive and negative Bias voltage, respectively used for positive and negative ion detection; 电离源、离子分离区、离子检测区均位于绝缘套筒(9)内部;The ionization source, the ion separation area, and the ion detection area are all located inside the insulating sleeve (9); 同轴套设的分离电极套筒数目n为两个以上;为2个时,中心电极(4)、第一分离电极套筒(3)、第二分离电极套筒(2)相邻的电极所连接的电压不同、而不相邻相间隔的电极所连接的电压相同;中心电极(4)通过导线与地线或高场非对称性电源和补充直流电源相连;第一分离电极套筒(3)通过导线与高场非对称性电源和补充直流电源或地线相连。The number n of the coaxially sleeved separation electrode sleeves is two or more; when it is 2, the electrodes adjacent to the center electrode (4), the first separation electrode sleeve (3), and the second separation electrode sleeve (2) The connected voltages are different, but the voltages connected to the electrodes that are not adjacent to each other are the same; the central electrode (4) is connected to the ground wire or the high-field asymmetric power supply and the supplementary DC power supply through a wire; the first separated electrode sleeve ( 3) Connect with high-field asymmetric power supply and supplementary DC power supply or ground wire through wires. 2.如权利要求 1 所述的离子迁移管,其特征在于:构成屏蔽电极(5)的中部电极、一电极、二电极沿绝缘套筒(9)轴线方向长度相同。2 . The ion transfer tube according to claim 1 , wherein the middle electrode, the first electrode and the second electrode constituting the shield electrode ( 5 ) have the same length along the axis of the insulating sleeve ( 9 ). 3 . 3.如权利要求 1 所述的离子迁移管,其特征在于:3. The ion transfer tube of claim 1, wherein: 中心电极(4)和第一分离电极套筒(3)之间的间距与第一分离电极套筒(3)和第二分离电极套筒(2)之间的间距不同;间距在0.1到10mm之间。The spacing between the center electrode (4) and the first split electrode sleeve (3) is different from the spacing between the first split electrode sleeve (3) and the second split electrode sleeve (2); the spacing is between 0.1 and 10mm between. 4.如权利要求 1 所述的离子迁移管,其特征在于:4. The ion transfer tube of claim 1, wherein: 中心电极(4)或中部电极分别为圆柱形或圆筒形电极。The center electrode (4) or the middle electrode is a cylindrical or cylindrical electrode, respectively. 5.如权利要求 1 所述的离子迁移管,其特征在于:5. The ion transfer tube of claim 1, wherein: 电离源(1)为一对平行设置的板状放电电极,该放电电极与绝缘套筒(9)轴线方向平行。The ionization source (1) is a pair of plate-shaped discharge electrodes arranged in parallel, and the discharge electrodes are parallel to the axial direction of the insulating sleeve (9).
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101752178A (en) * 2008-12-17 2010-06-23 中国科学院大连化学物理研究所 Cylindrical non-symmetric field ion migration tube
CN101752177A (en) * 2008-12-17 2010-06-23 中国科学院大连化学物理研究所 A Combined High-field Asymmetric Waveform Ion Transfer Tube
CN102414779A (en) * 2009-05-01 2012-04-11 萨莫芬尼根有限责任公司 Ion transfer tube and mass spectrometer system
CN102636555A (en) * 2011-12-19 2012-08-15 中国科学院合肥物质科学研究院 Miniature measurement and control system fit for high-field asymmetric waveform transference tube

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101752178A (en) * 2008-12-17 2010-06-23 中国科学院大连化学物理研究所 Cylindrical non-symmetric field ion migration tube
CN101752177A (en) * 2008-12-17 2010-06-23 中国科学院大连化学物理研究所 A Combined High-field Asymmetric Waveform Ion Transfer Tube
CN102414779A (en) * 2009-05-01 2012-04-11 萨莫芬尼根有限责任公司 Ion transfer tube and mass spectrometer system
CN102636555A (en) * 2011-12-19 2012-08-15 中国科学院合肥物质科学研究院 Miniature measurement and control system fit for high-field asymmetric waveform transference tube

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