CN113223918B - Multi-mode mass spectrometer and mass spectrometry method - Google Patents

Multi-mode mass spectrometer and mass spectrometry method Download PDF

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CN113223918B
CN113223918B CN202110352331.1A CN202110352331A CN113223918B CN 113223918 B CN113223918 B CN 113223918B CN 202110352331 A CN202110352331 A CN 202110352331A CN 113223918 B CN113223918 B CN 113223918B
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ion
ions
repulsion
mass analyzer
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CN113223918A (en
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于丙文
俞晓峰
李锐
徐岳
吴智威
韩双来
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Hangzhou Puyu Technology Development Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/0027—Methods for using particle spectrometers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/06—Electron- or ion-optical arrangements
    • H01J49/061—Ion deflecting means, e.g. ion gates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/06—Electron- or ion-optical arrangements
    • H01J49/062—Ion guides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/40—Time-of-flight spectrometers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons

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Abstract

The invention provides a multi-mode mass spectrometry device and a mass spectrometry method, wherein the multi-mode mass spectrometry device comprises an ion source, a vacuum interface and a multipole rod mass analyzer; an ion beam shaping module is arranged at the downstream of the ion outlet of the multipole rod mass analyzer; a TOF mass analyzer comprising a repulsion region, a flight region, and a first detector, the repulsion region disposed downstream of an ion exit of the ion beam shaping module; the second detector receives ions emitted by the non-working repulsion area; the controller is used for controlling whether the repulsion area works or not. The invention has the advantages of high sensitivity, high resolution and the like.

Description

Multi-mode mass spectrometer and mass spectrometry method
Technical Field
The present invention relates to mass spectrometry, and more particularly, to a multimode mass spectrometer and a mass spectrometry method.
Background
Quadrupole Mass Spectrometry (QMS) is the most common mass spectrometer instrument with outstanding quantitation capability, the vast majority of which are GC-MS. The device has the advantages of simple structure, low cost, simple maintenance, strong quantitative capability of SIM function and the like, is instrument equipment adopted in most detection standards, but also has the limitations of no cross-polar capability, insufficient qualitative capability, lower resolution, ion interference of isotopes and other m/z approximations, slow scanning speed, low upper limit of mass and the like.
Time-of-flight mass spectrometers (TOF) are the fastest mass spectrometers and are suitable for LC-MS applications. The method has high resolution capability, is beneficial to the difference between qualitative and m/z approximate ions, can well detect multi-charge ions generated by an ESI (electronic spray ionization) ion source, has high speed, is suitable for a rapid LC (ultra performance liquid chromatography) system (such as UPLC) with a high resolution full-scan spectrogram of 2-100 sheets per second, has high upper limit of quality (6000-10000 u), and has slightly insufficient quantitative capability compared with QMS (QMS). Quadrupole time-of-flight tandem mass spectrometers (QTOF) are mass spectrometers with QMS as the mass filter and TOFMS as the mass analyzer, which inherit the advantages and disadvantages of TOF.
Due to the respective characteristics of QMS and QTOF, different mass spectrometers are usually selected by chemical analysis workers for analysis in different application occasions, so that the purchase cost of the instrument and the inconvenience in practical operation are increased.
The toffrerk corporation adds a TOF module on the basis of a thermoelectric corporation iCAP Q quadrupole mass spectrometer, and when the TOF working mode is switched, the iCAP Q quadrupole mass analyzer and the detector are replaced by an elongated quadrupole wave trap and the TOF module is connected in series at the downstream of the elongated quadrupole wave trap. The disadvantages of this solution are:
the solution of towderk essentially remains two mass spectrometers, with long time consuming structure switching and the need for vacuum venting and evacuation of the mass spectrometers, multiple switching operations can quickly reduce the lifetime of the detector and introduce external environmental contamination into the mass spectrometer, reducing instrument performance.
2. The structural switching operation has high requirements on the professional skills of operators, and the use cost of the instrument is increased.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a multimode mass spectrometer device.
The purpose of the invention is realized by the following technical scheme:
a multimode mass spectrometry apparatus comprising an ion source, a vacuum interface, and a multipole rod mass analyzer; the multimode mass spectrometry apparatus further comprises:
an ion beam shaping module disposed downstream of the multipole rod mass analyzer ion outlet;
a TOF mass analyzer comprising a repulsion region, a flight region, and a first detector; the repulsion zone is disposed downstream of the ion outlet of the ion beam shaping module;
a second detector that receives ions emerging from the inoperative repulsion zone;
and the controller is used for controlling whether the repulsion area works or not.
The invention also aims to provide a multimode mass spectrometry method, and the aim of the invention is realized by the following technical scheme:
a method of multimodal mass spectrometry comprising:
in the first mode, the repulsion zone of the TOF mass analyzer does not work, and ions emitted by the ion source sequentially pass through the ion interface, the multipole rod mass analyzer, the ion beam shape module and the repulsion zone of the TOF mass analyzer and are then received by the second detector; the ion beam shape module improves the focusing effect of ions;
in the second mode, a repulsion area of the TOF mass analyzer works, and ions emitted by the ion source sequentially pass through the ion interface, the multipole rod mass analyzer, the ion beam shape module, the repulsion area of the TOF mass analyzer and the flight area and are then received by the first detector; the ion beam shape module shapes the ion beam so that the velocity dispersion and the space dispersion of the ions in the repulsion region become smaller.
Compared with the prior art, the invention has the beneficial effects that:
1. various working modes are selected, so that the working performance is improved;
the combination of the QMS and the QTOF mode can accelerate the experiment progress, for example, a QTOF can be used to obtain a full spectrogram under a certain scanning mode, the advantage of high TOF resolution is used for accurately determining the nature of the target ions, and then the QMS mode is used for accurately quantifying and monitoring the target ions according to actual needs;
under QTOF, the enhanced plate of daughter ion 'scan' can be realized: scanning voltage (RF + DC) is fixed by a multipole rod mass analyzer, certain mass ions (parent ions) are selected to enter a collision cell, fragment ions are generated by collision dissociation, and a right-angle acceleration flight time mass analyzer is used as a second mass analyzer to obtain a fragment ion spectrogram, namely a daughter ion spectrum; the time for obtaining the sub-ion spectrogram is reduced from the second level or dozens of milliseconds to the microsecond level, so that the scanning time is greatly reduced;
the combination of the quadrupole rod, the collision reaction pool and the mass analyzer can realize various scanning modes, and the combination of the QMS and the QTOF mode can accelerate the progress of the experiment;
the second detector is arranged off-axis, so that the influence of neutral particles is reduced;
2. the structure is simple, and the cost is low;
the system has two functions, the functions and the advantages of QMS and QTOF are realized on one mass spectrometer, and different working modes are switched under different scenes without structure change, so that the configuration and the structure of the device are simplified;
3. the volume is small;
the first annular flying area and the second annular flying area are used for the ions to fly spirally in the flying areas, so that the flying distance of the ions is greatly increased in a smaller space range, and the volume of the mass analyzer is correspondingly reduced;
4. the resolution is high;
the design of the first annular flying area and the second annular flying area compensates the dispersion effect of the ion orbit radius on the ion flight time, so that the flight distance is increased in a limited space, and the mass spectrum resolution is correspondingly improved;
the concept of a reflecting region is introduced into an ion flight orbit, the compensation of ion initial energy dispersion can be realized, the second-order spatial focusing of ions at a detector is realized through the adjustment of a reflecting electric field, and the mass spectrum resolution is further improved.
Drawings
The disclosure of the present invention will become more readily understood with reference to the accompanying drawings. As is readily understood by those skilled in the art: these drawings are only for illustrating the technical solutions of the present invention and are not intended to limit the scope of the present invention. In the figure:
FIG. 1 is a schematic structural view of a multimode mass spectrometry apparatus according to embodiment 1 of the invention;
fig. 2 is a schematic structural view of a TOF mass analyzer according to embodiment 2 of the present invention;
FIG. 3 is a schematic structural view of an annular flight zone according to embodiment 2 of the present invention;
fig. 4 is a schematic view of the structure of a TOF mass analyzer according to embodiment 3 of the invention;
FIG. 5 is a schematic structural view of an annular flight zone according to embodiment 3 of the present invention;
fig. 6 is a schematic structural view of a TOF mass analyzer according to embodiment 4 of the invention;
fig. 7 is a schematic structural view of an annular flight zone according to embodiment 4 of the present invention.
Detailed Description
Fig. 1-7 and the following description depict alternative embodiments of the invention to teach those skilled in the art how to make and use the invention. Some conventional aspects have been simplified or omitted for the purpose of explaining the technical solution of the present invention. Those skilled in the art will appreciate that variations or substitutions from these embodiments will be within the scope of the invention. Those skilled in the art will appreciate that the features described below can be combined in various ways to form multiple variations of the invention. Thus, the present invention is not limited to the following alternative embodiments, but is only limited by the claims and their equivalents.
Example 1:
fig. 1 schematically shows a simple structure of a multimode mass spectrometry apparatus according to an embodiment of the invention, which, as shown in fig. 1, comprises:
an ion source, a vacuum interface, and a multipole rod mass analyzer (e.g., a quadrupole rod mass analyzer); these devices are all prior art in the field;
an ion beam shaping module disposed downstream of the multipole mass analyzer ion outlet for enhancing the focusing effect of ions as needed to enhance sensitivity and for ion beam shaping such that the velocity dispersion and spatial dispersion of ions in the repulsion region become smaller to enhance resolution;
a TOF mass analyzer comprising a repulsion region, a flight region, and a first detector; the repulsion zone is disposed downstream of the ion outlet of the ion beam shaping module;
a second detector that receives ions emerging from the inoperative repulsion zone;
and the controller is used for controlling whether the repulsion area works or not.
To remove neutral particles, further, the multimode mass spectrometry apparatus further comprises:
an ion deflector for deflecting ions exiting the inoperative repeller region, the deflected ions entering the second detector.
In order to reduce the apparatus volume and improve the resolution, further, the TOF mass analyzer comprises:
a repulsion zone, a flight zone and a first detector; the flight zone comprises a first annular flight zone and a second annular flight zone, the first annular flight zone comprises a coaxial first electrode and a second electrode surrounding the first electrode, and the second annular flight zone comprises a coaxial third electrode and a fourth electrode surrounding the third electrode;
the second electrode has an ion inlet, the fourth electrode has an ion outlet, ions exiting the ion outlet are received by the detector; the axis of the first electrode is parallel to the axis of the third electrode, and the distance D between the first electrode and the third electrode satisfies r 11 +r 21 ＜D＜r 12 +r 22 ，r 11 Is the outer diameter of the first electrode, r 21 Is the outer diameter of the third electrode, r 21 Is the inner diameter of the second electrode, r 22 Is the inner diameter of the fourth electrode;
a power supply that applies a voltage to the electrodes in each annular flight zone.
In order to enable the ions to make uniform-speed circular motion around the first electrode in the flight zone, further, the kinetic energy E of the ions entering from the ion inlet satisfies the following conditions:
Figure GDA0003729539510000051
K∈[-0.3，0.3]，U 2 is the voltage on the second electrode, U 1 Is the voltage on the first electrode, z is the number of charges carried by the ion, and e is the amount of charges.
To increase ion kinetic energy, further, the TOF mass analyser further comprises:
an acceleration zone from which the outgoing ions pass through the ion inlet into a first annular flight zone.
To achieve second order spatial focusing of ions at the detector, further, the TOF mass analyser further comprises:
and the ions emitted from the first annular flying area enter the reflecting area, and the reflected ions enter the second annular flying area.
To obtain an accurate time of flight, further, the time of flight of the ions within the first and second annular flight zones
Figure GDA0003729539510000061
R 2 Is the orbital radius, θ, of ions in said second annular flight zone 1 Is the angle of orbit, θ, of the ions in the first annular flight zone 2 Is the angle of the ions' orbit within the second annular flight zone.
The multimode mass spectrometry method, namely the working method of the multimode mass spectrometry device according to the embodiment of the invention, comprises the following steps:
in the first mode, the repulsion zone of the TOF mass analyzer does not work, and ions emitted by the ion source sequentially pass through the ion interface, the multipole rod mass analyzer, the ion beam shape module and the repulsion zone of the TOF mass analyzer and are then received by the second detector; the ion beam shape module improves the focusing effect of ions;
in the second mode, a repulsion area of the TOF mass analyzer works, and ions emitted by the ion source sequentially pass through the ion interface, the multipole rod mass analyzer, the ion beam shape module, the repulsion area of the TOF mass analyzer and the flight area and are then received by the first detector; the ion beam shape module shapes the ion beam so that the velocity dispersion and the space dispersion of the ions in the repulsion region become smaller.
To remove neutral particles, further, in the first mode, ions exiting the repulsion region are deflected to enter a second detector.
To improve resolution, further, in the second mode, ions enter the first annular flight zone, travel helically around the first electrode within the second electrode;
the ions emitted from the first annular flying area enter the second annular flying area, and spirally travel around the third electrode in the fourth electrode;
the first electrode is coaxial with a second electrode surrounding the first electrode, and the third electrode is coaxial with a fourth electrode surrounding the third electrode; the axis of the first electrode is parallel to the axis of the third electrode, and the distance D between the first electrode and the third electrode satisfies r 11 +r 21 ＜D＜r 12 +r 22 ，r 11 Is the outer diameter of the first electrode, r 21 Is the outer diameter of the third electrode, r 21 Is the inner diameter of the second electrode, r 22 Is the inner diameter of the fourth electrode.
Example 2:
an application example of the multimode mass spectrometer and the mass spectrometry method according to embodiment 1 of the present invention.
In the present application example, as shown in fig. 1, the ion transport module is disposed between the ion interface and the quadrupole mass analyzer; the ion deflector is used for deflecting ions emitted from the non-working repulsion region, and the deflected ions enter the second detector arranged off-axis; the ion beam shape module comprises a direct current quadrupole and an Einzel single lens;
as shown in fig. 2, the TOF mass analyser comprises:
the repulsion area 11 consists of a repulsion plate and a grounding grid mesh, a high-voltage pulse signal is applied to the repulsion plate, ions enter the repulsion area 11 when no pulse signal exists, and the ions obtain kinetic energy and vertically fly into the acceleration area 21 after the pulse is applied;
an acceleration region 21 including an acceleration electric field, under the action of which kinetic energy of the entering ions is increased;
a flight zone 31, as shown in fig. 3, comprising a first annular flight zone comprising a coaxial first electrode 32 and a second electrode 33 surrounding the first electrode 32, and a second annular flight zone comprising a coaxial third electrode 34 and a fourth electrode 35 surrounding the third electrode 34; the first electrode 32 is the same as the third electrode 34, and the second electrode 33 is the same as the fourth electrode 35;
the second electrode 33 has a first ion inlet on the upper side and a first ion outlet on the lower side, the fourth electrode 35 has a second ion outlet on the lower side and a second ion inlet on the upper side, and ions emitted from the second ion outlet are received by the first detector 51; the axes of the first electrode 32 and the third electrode 34 are parallel and in the same horizontal plane, and the distance D between the axes satisfies r 11 +r 21 ＜D＜r 12 +r 22 ，r 11 Is the outer diameter of the first electrode 32, r 21 Is the outer diameter of the third electrode 34, r 21 Is the inner diameter, r, of the second electrode 33 22 Is the inner diameter of the fourth electrode 35;
a reflective region 41 having a double-field reflective structure, for reflecting ions emitted from the second electrode 33 into the fourth electrode 35;
a power supply for applying a voltage to the electrodes in each annular flight zone, U being applied to the first electrode 32 1 Applied to the second electrode 33 is U 2 The voltage applied to the third electrode 34 is U 3 The voltage applied to the fourth electrode 35 is U 4 Satisfy the following requirements
Figure GDA0003729539510000071
Such as U 3 ＝U 1 ，U 2 ＝U 4 The first electrode is the same as the third electrode, and the second electrode is the same as the fourth electrode.
The multimode mass spectrometry method, namely the working method of the multimode mass spectrometry device according to the embodiment of the invention, comprises the following steps:
in a first mode (QMS), under the action of the controller, the repulsion region of the TOF mass analyzer does not operate, ions exiting the ion source sequentially pass through the ion interface, the ion transport module, the multipole mass analyzer, the ion beam shaping module, and the repulsion region of the TOF mass analyzer, are then deflected by the ion deflector, and finally enter the second detector; the ion beam shape module can improve the focusing effect of ions by adjusting voltage parameters;
in a second mode (QTOF), under the action of the controller, a repulsion area of the TOF mass analyzer works, and ions emitted by the ion source sequentially pass through the ion interface, the multipole mass analyzer, the ion beam shape module, the repulsion area, the acceleration area and the flight area of the TOF mass analyzer and are then received by the first detector; the ion beam shape module shapes the ion beam so that the initial velocity dispersion and the initial space dispersion of the ions in the repulsion region are reduced;
the working method of the TOF mass analyzer is as follows:
applying a high-voltage pulse signal to a repulsion plate of the repulsion area 11, enabling ions to enter the repulsion area 11 when no pulse signal exists, and obtaining kinetic energy after applying a pulse to vertically fly into the acceleration area 21;
ions are accelerated in an acceleration zone 21 with kinetic energy increased to
Figure GDA0003729539510000081
K∈[-0.3，0.3]Z is the number of charges carried by the ions, e is the amount of charges, and the ions can spirally advance around the electrode in the flight zone as long as the kinetic energy of the ions meets the requirement;
the accelerated ions enter the first annular flight zone, pass through the first ion inlet, enter the second electrode 33, spirally advance anticlockwise around the first electrode 32, and make a turn around the first electrode by an angle theta 1 Ion trajectories are shown in phantom in FIG. 2;
the ions exiting from the first ion outlet of the first annular flight zone enter the reflection zone 41, and the ions are reflected into the second annular flight zone;
the ions enter the fourth electrode 35 through the second ion inlet and spiral counterclockwise around the third electrode 34 by an angle θ 2 ＝θ 1 Ion trajectories are shown in dashed lines in FIG. 2; the trajectory curved surface of the ions in the first annular flying area is tangent to the trajectory curved surface in the second annular flying area;
ions exiting the second ion outlet are received by the first detector 51 and second order of ions at the detector 51 position is achieved by adjusting the voltage of the reflective region 41Spatial focusing, time of flight of ions in flight zone
Figure GDA0003729539510000091
The mass spectrum working mode of the embodiment is as follows:
scanning mode Q1 quadrupole rod Mass analyzer mode of operation
MS1 scanning Quality selection Scan (RF + DC) QMS
Full spectrum of MS2 Ion transport (RF ONLY) QTOF
Single Ion Monitoring (SIM) Fixed mass (RF + DC) QMS
Example 3:
an application example of the multimode mass spectrometer and the mass spectrometry method according to embodiment 1 of the present invention is different from embodiment 2 in that:
1. the collision reaction pool is arranged between the quadrupole rod mass analyzer and the ion beam-shaped module;
2. as shown in fig. 4, the reflecting region is no longer provided, and the ions exiting from the second annular flight region enter the detector 51 through the additional field-free flight region 61;
3. as shown in fig. 5, the ions enter from the first ion inlet of the second electrode 33 and spirally proceed counterclockwise around the first electrode 32, then enter into the fourth electrode 35, spirally proceed clockwise around the third electrode 34, and finally exit from the ion outlet of the fourth electrode 35; the motion trail of the ions in the flight zone is shown in a dotted line part in the attached figure 5;
time of flight of ions in first and second annular flight zones
Figure GDA0003729539510000092
R 2 Is the orbital radius, θ, of ions in said second annular flight zone 1 Is the angle of orbit, θ, of the ions in the first annular flight zone 2 The detour angle of the ions in the second annular flight zone; when D theta 1 ＞＞R 2 (θ 2 -θ 1 ) In time, the ion orbit radius has little effect on the flight time and then on the resolution.
The mass spectrum working mode of the embodiment is as follows:
Figure GDA0003729539510000093
Figure GDA0003729539510000101
example 4:
an application example of the multimode mass spectrometer and the mass spectrometry method according to embodiment 1 of the present invention is different from embodiment 2 in that:
1. as shown in fig. 6, the reflection area is no longer provided, and the detector 51 is provided on the lower side of the flight area;
2. as shown in fig. 7, the ion outlet is provided on the lower side of the fourth electrode 35; ions enter from the ion inlet of the second electrode 33 and spiral around the first electrode 32 anticlockwise, then enter into the fourth electrode 35, spiral around the third electrode 34 clockwise, and finally exit from the ion outlet of the fourth electrode 35 into the detector 51; the motion trajectory of ions in the flight zone is shown in the dotted line of fig. 7;
time of flight of ions in first and second annular flight zones
Figure GDA0003729539510000102
R 2 Is the orbital radius, θ, of ions in said second annular flight zone 1 Is the angle of orbit, θ, of the ions in the first annular flight zone 2 The detour angle of the ions in the second annular flight zone; when D theta 1 ＞＞R 2 (θ 2 -θ 1 ) In time, the ion orbit radius has little effect on the flight time and then on the resolution.

Claims (9)

1. A multimode mass spectrometry apparatus comprising an ion source, a vacuum interface, and a multipole rod mass analyzer; characterized in that the multimode mass spectrometry apparatus further comprises:
an ion beam shaping module disposed downstream of the multipole rod mass analyzer ion outlet;
a TOF mass analyzer comprising a repulsion region, a flight region, and a first detector; the repulsion zone is disposed downstream of the ion outlet of the ion beam shaping module;
a second detector that receives ions emerging from the inoperative repulsion region;
the controller is used for controlling whether the repulsion area works or not;
the flight zone includes:
a first annular flight zone comprising a first electrode and a second electrode surrounding the first electrode, the first annular flight zone comprising a third electrode and a fourth electrode surrounding the third electrode; the second electrode has an ion inlet and the fourth electrode has an ion outlet; the axis of the first electrode is parallel to the axis of the third electrode, and the distance D between the first electrode and the third electrode satisfies r 11 +r 21 ＜D＜r 12 +r 22 ，r 11 Is the outer diameter of the first electrode, r 21 Is the outer diameter of the third electrode, r 21 Is the inner diameter of the second electrode, r 22 Is the inner diameter of the fourth electrode;
a power supply that applies a voltage to the electrodes in each annular flight zone.
2. The multimode mass spectrometry apparatus of claim 1, further comprising:
an ion deflector for deflecting ions exiting the inoperative repeller region, the deflected ions entering the second detector.
3. The multimode mass spectrometry apparatus of claim 1, further comprising:
an ion transport module disposed between the ion interface and a multipole mass analyzer;
a collision reaction cell disposed between the multipole mass analyzer and the ion beam shaping module.
4. The multimode mass spectrometry apparatus of claim 1, wherein the ion beam shaping module comprises a dc multipole and an Einzel singlet lens.
5. The multimode mass spectrometry apparatus of claim 1, wherein the kinetic energy E of ions entering from the ion inlet satisfies:
Figure FDA0003729539500000021
U 2 is the voltage on the second electrode, U 1 Is the voltage on the first electrode, z is the number of charges carried by the ion, and e is the amount of charges.
6. The method of claim 1Multimode mass spectrometry apparatus, characterized in that the time of flight of said ions in a first and a second annular flight zone
Figure FDA0003729539500000022
R 2 Is the orbital radius, θ, of ions in said second annular flight zone 1 Is the angle of orbit, θ, of the ions in the first annular flight zone 2 Is the angle of the ions' orbit within the second annular flight zone.
7. The multimode mass spectrometry method comprises the following steps:
in the first mode, the repulsion zone of the TOF mass analyzer does not work, and ions emitted by the ion source sequentially pass through the ion interface, the multipole rod mass analyzer, the ion beam shape module and the repulsion zone of the TOF mass analyzer and are then received by the second detector; the ion beam shape module improves the focusing effect of ions;
in the second mode, a repulsion area of the TOF mass analyzer works, and ions emitted by the ion source sequentially pass through the ion interface, the multipole rod mass analyzer, the ion beam shape module, the repulsion area of the TOF mass analyzer and the flight area and are then received by the first detector; the ion beam shape module shapes the ion beam so that the velocity dispersion and the space dispersion of the ions in the repulsion region become smaller.
8. The method of claim 7, wherein in the first mode, ions exiting the repulsion region are deflected to enter a second detector.
9. A method of multimodal mass spectrometry according to claim 7 wherein in the second mode, ions enter the first annular flight zone, travel within the second electrode, spiralling around the first electrode;
the ions emitted from the first annular flying area enter the second annular flying area and spirally travel around the third electrode in the fourth electrode;
the above-mentionedThe first electrode is coaxial with the second electrode surrounding the first electrode, and the third electrode is coaxial with the fourth electrode surrounding the third electrode; the axis of the first electrode is parallel to the axis of the third electrode, and the distance D between the first electrode and the third electrode satisfies r 11 +r 21 ＜D＜r 12 +r 22 ，r 11 Is the outer diameter of the first electrode, r 21 Is the outer diameter of the third electrode, r 21 Is the inner diameter of the second electrode, r 22 Is the inner diameter of the fourth electrode.
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