CN113345791B - Multi-switching pulse voltage waveform for ion mobility spectrometry - Google Patents

Multi-switching pulse voltage waveform for ion mobility spectrometry Download PDF

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CN113345791B
CN113345791B CN202110747914.4A CN202110747914A CN113345791B CN 113345791 B CN113345791 B CN 113345791B CN 202110747914 A CN202110747914 A CN 202110747914A CN 113345791 B CN113345791 B CN 113345791B
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ion gate
group
metal electrodes
gate
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CN113345791A (en
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仓怀文
王卫国
李海洋
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Dalian Institute of Chemical Physics of CAS
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/06Electron- or ion-optical arrangements
    • H01J49/061Ion deflecting means, e.g. ion gates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/0027Methods for using particle spectrometers
    • H01J49/0031Step by step routines describing the use of the apparatus
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00Energy generation of nuclear origin
    • Y02E30/10Nuclear fusion reactors

Abstract

The invention discloses a multi-switching pulse voltage waveform for ion mobility spectrometry, which divides the working state of a BN ion gate into: a door opening state, a door closing state and a plurality of switching states. The multiple switching states are that the voltages of the first metal electrode and the second metal electrode are switched for multiple times after the ion gate is in the closed state and the switching time is delayed, so that the ion concentration distribution of the rear edge of the ion gate cut ion groups is continuously corrected, a clear space area, a diffusion area and a compression area are continuously switched after the ion gate is closed, the clear space area, the diffusion area and the compression area which are formed by the traditional pulse voltage waveform after the ion gate is closed are thoroughly changed, the ion loss caused by the clear space area can be reduced as much as possible, the ions in the diffusion area are compressed for multiple times, the ion distribution of the rear edge of the ion groups is adjusted, the ion density is improved, the injection efficiency and the resolution of the ion gate are greatly improved, more ions with small mobility are injected into the migration area, and the mobility discrimination effect of the BN type ion gate is weakened.

Description

Multi-switching pulse voltage waveform for ion mobility spectrometry
Technical Field
The invention belongs to the field of ion mobility spectrometry, and particularly relates to a multi-switching pulse voltage waveform applied to a BN ion gate.
Background
The BN ion gate has the characteristics of strong universality, no requirement on an ionization source, wide applicability to all migration tubes, small gate closing potential difference, simple control circuit and the like, and is widely used in commercial ion migration spectrums. However, the disadvantage is also remarkable, since the applied closing voltage forms a closing electric field perpendicular to the ion migration direction, the electric field penetrates the reaction region and the migration region to cause electric field distortion near the ion gate, and the higher the closing voltage is, the more serious the electric field distortion is. The distortion of the electric field causes ion group deformation and mobility discrimination, which affects the ion mobility spectrometry performance.
BN ion gates are typically constructed from two sets of mutually parallel, insulated metal electrodes, typically very thin wires, arranged in a plane at intervals in sequence. The chopping of ions is accomplished by applying a switching voltage waveform to the ion gate electrode by the pulse generator, so that the chopping behavior of the ion gate to the ion stream is determined by the voltage waveform applied to the ion gate and directly related to the ion mobility spectrometry performance. In the patent CN110310882a and CN110534395A, it is proposed that when the ion gate is closed, the gate closing voltages of two groups of electrodes on the ion gate are simultaneously raised, so that a high electric field region is formed behind the ion gate, the ions are further compressed, and the mobility spectrometry performance is improved. Specifically, CN110310882a is an ion compression effect when the ion gate is closed, which is enhanced by increasing the electric potential of both metal electrodes of the ion gate with the closing voltage unchanged. After a period of time, the voltage of the two metal electrodes of the ion gate is returned to the normal voltage level. Increasing the potential of the ion gate electrode can cause serious distortion of the migration electric field, which is unfavorable for the performance of ion mobility spectrometry. In order to reduce the discrimination effect of the ion gate, the patent CN110534395A increases the ion injection amount by reducing the voltage of the low-voltage electrode before the opening of the ion gate, and the voltage waveform after the closing is the same as that of the patent CN110310882 a. The voltage waveform has complex time sequence, the potential of the ion gate electrode is continuously lifted, the complexity of the ion gate control circuit is increased, and particularly, the control circuit is more complex under positive and negative working modes.
The invention provides a new ion gate regulation and control mode, which is called as a multi-time switching pulse waveform, the ion loss caused by a clear-cut zone can be reduced as much as possible by applying the voltage waveform, ions in a diffusion zone and a compression zone are compressed for multiple times, the concentration distribution of the rear edge of an ion group is changed densely, and the sensitivity and the resolution are greatly improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the voltage waveform applied to the BN type ion gate, which greatly improves the ion mobility spectrometry performance, greatly improves the sensitivity and the resolution and weakens the discrimination effect of the resolution.
The technical scheme of the invention is as follows:
in one aspect, the present invention provides a multi-switching pulse voltage waveform for an ion mobility spectrometry, where an ion gate of the ion mobility spectrometry is a BN-type ion gate, and the BN-type ion gate includes two sets of parallel, insulated first and second sets of metal electrodes sequentially arranged on a plane at intervals, where the multi-switching pulse voltage waveform can be applied to the first and second sets of metal electrodes, respectively, and the working states of the ion gate are controlled periodically through the following three states:
door open state: in a first preset time interval (t 1< t 2), a first high voltage (HV 1) is applied to the first group of metal electrodes, a first high voltage is also applied to the second group of metal electrodes, the ion gate is in an open state, and ion clusters can penetrate the ion gate.
Door closing state: and in a second preset time interval (t 2 is less than t 3), applying a first high voltage to the first group of metal electrodes, applying a second high voltage (HV 2) to the second group of metal electrodes, wherein the voltage applied to the second group of metal electrodes is higher than the voltage applied to the first group of metal electrodes, and the ion door is in a door closing state.
Multiple switching states: and in a third preset time interval (t 3 is less than t 4), applying a second high voltage on the first group of metal electrodes, applying a first high voltage on the second group of metal electrodes, and switching the voltages on the first group of metal electrodes and the second group of metal electrodes for the first time, wherein the ion gate is in a first switching state.
And in a fourth preset time interval (t 4 is less than t 5), applying a first high voltage on the first group of metal electrodes, applying a second high voltage on the second group of metal electrodes, and switching the ion gate in a second switching state for the second time by using voltages on the first group of metal electrodes and the second group of metal electrodes.
The number of times of the ion gate switching state and the switching delay time after the ion gate is closed are set according to the needs, and in order to realize more accurate chopping of the ion gate, the concentration distribution of the trailing edge of the ion gate is corrected, and the number of times of switching is preferably an even number of times greater than or equal to 2.
The ion mobility spectrometry method comprises the steps of completing one switching cycle of an ion mobility spectrometry from a door opening state to a plurality of switching states, wherein a first preset time interval is the door opening time of the ion door, and the time after a second preset time interval is the door closing time of the ion door.
The first preset time interval is the opening time of the ion gate, so that the ions can pass through the ion gate smoothly, and the time interval between the second preset time interval and the third preset time interval is the switching delay time of the ion gate, and the time length is set according to the requirement, and is usually set to be 1-100 us. The fourth preset time interval, which is maintained until the next ion gate opening, is typically set between 1-50 ms.
The first high voltage is a reference voltage of the position of the ion gate; the second high pressure value is greater than or equal to the second high pressure value in the conventional manner, preferably the second high pressure value is greater than the second high pressure value in the conventional manner, and the difference between the second high pressure value and the first high pressure value is generally 10v-600v with reference to the first high pressure.
The second high voltage and the first high voltage are the absolute value of the voltage.
On the other hand, the invention protects the BN type ion gate controlled by adopting the multi-switching pulse voltage waveform.
In yet another aspect, the invention provides ion mobility spectrometry employing the ion gate described above.
Advantageous effects
The invention discloses a multi-switching pulse voltage waveform, which divides the working state of an ion gate into: a door opening state, a door closing state and a plurality of switching states. The multiple switching state is that the voltage of the first metal electrode and the voltage of the second metal electrode are switched for multiple times after the ion gate is in the switching delay time of the closing state, so that the ion concentration distribution of the rear edge of the ion gate cut ion groups is continuously corrected, a clear space area, a diffusion area and a compression area (three areas) are formed after the ion gate is closed, the clear space area, the diffusion area and the compression area which are formed by the traditional pulse voltage waveform after the ion gate is closed are continuously switched, the ion loss caused by the clear space area can be reduced as much as possible, the ions in the diffusion area are compressed for multiple times, the ion distribution of the rear edge of the ion groups is regulated, the ion density is improved, the injection efficiency of the ion gate is improved, more ions with small mobility are injected into the migration area, and the mobility discrimination effect of the BN type ion gate is weakened. In the continuous switching process of the voltages of the two metal electrodes of the ion gate, the electric field of the ion gate is also changed continuously, so that the repeated compression (at least three times) of ions is realized, and the resolution is improved.
The ion gate regulation and control method realizes the change of the ion gate electric field by utilizing the multiple switching pulse waveforms, achieves the aim of influencing the ion movement of the rear edge of the ion group after the gate is closed, reduces the ion loss by controlling the periodic change of the electrode voltage of the BN ion gate along with time in four stages, compresses the ions for multiple times, trims the concentration distribution of the rear edge of the ion group and improves the ion mobility spectrometry performance.
The voltage waveform adopted by the invention does not change the total vertical electric field intensity of the ion gate after the voltage exchange of the ion gate electrode, does not increase the torsion degree of the migration electric field, and is beneficial to the performance of ion migration spectrum.
Drawings
Fig. 1 is a timing diagram of a conventional voltage waveform applied to a BN ion gate.
Fig. 2 is a timing diagram of a multi-switching pulse voltage waveform for ion mobility spectrometry according to the present invention.
Fig. 3 shows ion mobility spectrometry using a conventional voltage waveform for detecting a sample.
FIG. 4 shows ion mobility spectrometry of a sample using the voltage waveform of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. It should be emphasized that the following description is merely exemplary in nature and is in no way intended to limit the scope of the invention or its applications.
Fig. 1 shows two general operating states of a conventional BN ion gate: a door open state and a door closed state. In the open state (t 1 is less than t 2), the potentials of the two groups of metal electrodes of the ion gate are the same, and the movement of ions is not prevented. In the closing state (t 2 is less than t 3), one closing voltage is superposed on one group of metal electrodes, or opposite closing voltages are superposed on two groups of metal electrodes, so that potential difference is generated between the two groups of metal electrodes, a closing electric field perpendicular to the ion migration direction is formed between the adjacent electrodes, ions reaching the ion gate are neutralized, and the ions cannot pass through the ion gate.
As shown in fig. 2, the ion gate of the ion mobility spectrometry is a BN-type ion gate, the BN-type ion gate includes two sets of parallel and insulated first and second sets of metal electrodes grid1 and grid1 sequentially arranged on a plane at intervals, and the multiple switching pulse voltage waveforms can be applied to the first and second sets of metal electrodes grid1 and grid1 respectively, so that the working state of the ion gate is periodically controlled to pass through the following four stages.
And in a first preset time interval (t 1 is less than t 2), applying a first high voltage HV1 to the first group of metal electrodes grid1, and applying a first high voltage HV1 to the second group of metal electrodes grid1, wherein the ion gate is in an open state, and ion clusters can penetrate the ion gate to realize ion implantation.
And in a second preset time interval (t 2 is less than t 3), applying a first high voltage HV1 to the first group of metal electrodes grid1, applying a second high voltage HV2 to the second group of metal electrodes grid1, and applying a voltage higher than that applied to the first group of metal electrodes grid1 to the second group of metal electrodes grid1, wherein the ion gate is in a closing state, and ion implantation is completed to realize the first compression of ion clusters.
And in a third preset time interval (t 3 is less than t 4), applying a second high voltage HV2 to the first group of metal electrodes grid1, applying a first high voltage HV1 to the second group of metal electrodes grid1, switching the voltages on the first group of metal electrodes grid1 and the second group of metal electrodes grid1 for the first time, reestablishing a new three regions, and performing a second compression of experimental ion clusters.
And in a fourth preset time interval (t 4 is less than t 5), applying a first high voltage HV1 to the first group of metal electrodes grid1, applying a second high voltage HV2 to the second group of metal electrodes grid1, switching the ion gate in a second switching state, switching the voltages on the first group of metal electrodes grid1 and the second group of metal electrodes grid1 for the second time, reestablishing a new three region, and performing third compression of experimental ion clusters.
The time intervals of the second preset time interval and the third preset time interval are ion gate switching delay time, and the time length is set according to the needs.
The number of times of the ion gate switching state and the switching delay time after the ion gate is closed are set according to the requirement, preferably the number of times of switching is more than or equal to 2 even number of times, and one compression of ions and adjustment of ion mass distribution are realized after one switching.
In this embodiment, the time from the first preset time interval to the fourth preset time interval is a primary switching period of the ion mobility spectrometry, the first preset time interval is an ion gate opening time, and the time after the second preset time interval is an ion gate closing time.
The first high voltage HV1 is a reference voltage at the position of the ion gate, preferably a certain appropriate potential between the migration zone and the reaction zone on the migration tube, so as to realize effective ion implantation.
The second high voltage HV2 and the first high voltage HV1 are absolute values of voltages. The waveform of the present invention is applicable to both positive and negative high voltage modes of ion mobility spectrometry.
Under the control of traditional voltage pulse, the obtained ion group trailing edge drags along a long tail. The ion beam trailing edge obtained by chopping the multi-time switching pulse voltage waveform is continuously adjusted and optimized under the action of the multi-time pulse switching electric field, so that the trailing phenomenon of the ion beam trailing edge is weakened, the purposes of improving ion implantation efficiency and multi-time compression are realized, and the ion mobility spectrometry performance is greatly improved. In the ion implantation process of the ion gate, the movement speed of ions with small mobility is slow, the ions run on the rear part of the ion group, and more ion groups can be implanted into the migration tube along the rear edge of the ion group by adopting a plurality of switching pulse voltage waveforms, so that the voltage waveforms can weaken the mobility discrimination effect of the BN type ion gate.
Example 1
In one embodiment, the pulse voltage waveform is switched multiple times, the migration electric field is set to 400V/cm, the opening time of the ion gate is set to 100us, the ion gate switching period is set to 20.1ms, the reference voltage at the ion gate is 1600V, the closing voltage is set to 250V, namely, hv1=1600v, hv2=1850v, and the method is used for measuring a DMMP sample with the concentration of 10ppb, and comprises the following steps:
firstly, t1=0us < t2=100us, the BN gate is in a door opening state, ion groups are injected, and the voltages of a first metal electrode grid1 and a second metal electrode grid2 are set to be HV1;
secondly, t2=100 us < t < t3=130 us, the BN door is in a door closing state, the ion group is cut off, the voltage of the first metal electrode grid1 is set to be the reference voltage HV1 of the migration tube, and the voltage of the second metal electrode grid2 is set to be HV2;
thirdly, t3=130 us < t < t4=160 us, the BN gate is in a first switching state, the voltage of the ion gate electrode is switched to repel and compress ion groups, the voltage of the first metal electrode grid1 is set to be the reference voltage HV2 of the migration tube, and the voltage of the second metal electrode grid2 is set to be HV1;
fourthly, t4=160 us < t < t5=20100 us, the BN gate is in a second switching state, the ion gate electrode voltage is switched again, the ion groups are repelled and compressed again, the first metal electrode grid1 voltage is set to be the reference voltage HV1 of the migration tube, and the second metal electrode grid2 voltage is set to be HV2; and then continuously cycling back to the first step opening state to prepare for the next ion implantation.
Comparative example 1
Setting a migration electric field of 400V/cm, an opening time of an ion gate of 100us, an ion gate switching period of 20.1ms, a reference voltage of 1600V at the ion gate, and a closing voltage of 250V, namely HV 1=1600V, HV2=1850V, and adopting a traditional voltage waveform to actually measure a DMMP sample with the concentration of 10ppb, wherein the method comprises the following steps:
the first step, t < t1=0us, the BN gate is in a closed state, the migration tube is in a preparation state for injecting ion groups, the voltage of the first metal electrode grid1 is set as the reference voltage HV1 of the migration tube, and the voltage of the second metal electrode grid2 is set as HV2;
secondly, t1=0us < t2=100us, the BN gate is in a door opening state, ion groups are injected, and the voltages of the first metal electrode grid1 and the second metal electrode grid2 are set to be HV1;
thirdly, t2=100 us < t < t3=20100 us, the BN door is in a door closing state, the ion group is cut off, the voltage of the first metal electrode grid1 is set to be the reference voltage HV1 of the migration tube, and the voltage of the second metal electrode grid2 is set to be HV2;
the three steps are continuously circulated, so that the periodic injection of ions into the ion transfer tube can be realized. However, the ion clusters chopped by the voltage waveform are affected by the low-voltage metal electrode goaf and the diffusion region and are distributed in a wave shape, so that the resolution and sensitivity of ions are limited, and the ion mobility spectrometry performance is not facilitated.
To demonstrate the effect of applying the multiple switching pulse voltage waveforms, fig. 3 and 4 are graphs of ion mobility patterns obtained for detecting DMMP samples, in comparison with conventional voltage waveforms. It can be seen that all signals of the voltage waveform are enhanced by applying the switching pulses a plurality of times. Wherein the signal intensities of RIP, DMMP monomer and DMMP dimer are respectively increased by 106%, 133% and 200%, and the resolutions thereof are respectively increased by 20%, 12% and 11%. The smaller the mobility, the larger the ion enhancement rate, and the adoption of the multi-switching pulse voltage waveform not only improves the detection sensitivity and resolution, but also weakens the mobility discrimination of the BN ion gate.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention.

Claims (6)

1. The utility model provides a many times switch pulse voltage waveform for ion mobility spectrometry, ion gate of ion mobility spectrometry be BN type ion gate, BN type ion gate is including two sets of mutual parallel, insulating first group metal electrode and the second group metal electrode of interval arrangement in proper order on a plane, its characterized in that: the multi-switching pulse voltage waveforms can be respectively applied to the first group of metal electrodes and the second group of metal electrodes, and the working state of the ion gate is periodically controlled to sequentially pass through the following three states:
door open state: applying a first high voltage to the first group of metal electrodes and a first high voltage to the second group of metal electrodes within a first preset time interval, namely t1< t < t2, wherein the ion gate is in an open state, and an ion group can penetrate through the ion gate;
door closing state: applying a first high voltage to the first group of metal electrodes and a second high voltage to the second group of metal electrodes within a second preset time interval, namely t2< t < t3, wherein the voltage applied to the second group of metal electrodes is higher than the voltage applied to the first group of metal electrodes, and the ion gate is in a door closing state;
multiple switching states: applying a second high voltage to the first group of metal electrodes and applying a first high voltage to the second group of metal electrodes within a third preset time interval, namely t3< t < t4, wherein the ion gate is in a first switching state, and voltages on the first group of metal electrodes and the second group of metal electrodes are switched for the first time;
applying a first high voltage to the first group of metal electrodes and a second high voltage to the second group of metal electrodes within a fourth preset time interval, namely t4< t < t5, wherein the ion gate is in a second switching state, and voltages on the first group of metal electrodes and the second group of metal electrodes are switched for the second time;
in order to realize more accurate chopping of the ion gate, the concentration distribution of the trailing edge of the ion gate is corrected, and the number of times of switching states of the ion gate after the ion gate is closed is more than or equal to an even number of times of 2 times;
the second high voltage and the first high voltage are the absolute value of the voltage;
the waveform is suitable for either a positive high-pressure mode or a negative high-pressure mode of the ion mobility spectrometry.
2. The multi-switching pulse voltage waveform of claim 1, wherein: the ion mobility spectrometry method comprises the steps of completing one switching cycle of an ion mobility spectrometry from a door opening state to a plurality of switching states, wherein a first preset time interval is the door opening time of the ion door, and the time after a second preset time interval is the door closing time of the ion door.
3. The multi-switching pulse voltage waveform of claim 1, wherein: the first preset time interval is the opening time of the ion gate, so that the ions can pass through the ion gate smoothly and the ion gate is arranged between 1 and 500 us; the time intervals of the second preset time interval and the third preset time interval are ion gate switching delay time and are set between 1 us and 100 us; and a fourth preset time interval is kept until the next time the ion gate is opened, and is set between 1ms and 50 ms.
4. The multi-switching pulse voltage waveform of claim 1, wherein: the first high voltage is a reference voltage of the position of the ion gate; the difference between the second high pressure value and the first high pressure value is 10v-600v with reference to the first high pressure.
5. A BN-type ion gate controlled by the multi-switching pulse voltage waveform of any one of claims 1 to 4.
6. An ion mobility spectrometry employing the BN-type ion gate of claim 5.
CN202110747914.4A 2021-07-01 2021-07-01 Multi-switching pulse voltage waveform for ion mobility spectrometry Active CN113345791B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109659219A (en) * 2017-10-12 2019-04-19 中国科学院大连化学物理研究所 A kind of the ion door gear and control method of no ion discrimination
CN110310882A (en) * 2019-07-03 2019-10-08 清华大学深圳研究生院 The ion door control method of BN discrimination effects in a kind of improvement ion mobility spectrometry
CN111199865A (en) * 2018-11-20 2020-05-26 中国科学院大连化学物理研究所 Two-stage compression ion gate and control method
CN112331550A (en) * 2020-11-17 2021-02-05 辽宁警察学院 Ion gate for ion mobility spectrometer and control method thereof
CN112490108A (en) * 2020-11-24 2021-03-12 中国科学院大连化学物理研究所 Ion gate control method for automatically enriching ions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10309929B2 (en) * 2006-02-14 2019-06-04 Excellims Corporation Practical ion mobility spectrometer apparatus and methods for chemical and/or biological detection

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109659219A (en) * 2017-10-12 2019-04-19 中国科学院大连化学物理研究所 A kind of the ion door gear and control method of no ion discrimination
CN111199865A (en) * 2018-11-20 2020-05-26 中国科学院大连化学物理研究所 Two-stage compression ion gate and control method
CN110310882A (en) * 2019-07-03 2019-10-08 清华大学深圳研究生院 The ion door control method of BN discrimination effects in a kind of improvement ion mobility spectrometry
CN112331550A (en) * 2020-11-17 2021-02-05 辽宁警察学院 Ion gate for ion mobility spectrometer and control method thereof
CN112490108A (en) * 2020-11-24 2021-03-12 中国科学院大连化学物理研究所 Ion gate control method for automatically enriching ions

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