Ion manipulation device and mass spectrometer

Abstract

The application discloses an ion manipulation device and a mass spectrometer, and belongs to the technical field of mass spectrometers. The ion manipulation device has a guiding mode, a deflection mode and a pulsed release mode. In the guiding mode, the ion manipulation device continuously transmits ions generated by an ion source to a first mass analyzer through a first electric field configuration. In the deflection mode, the ion manipulation device first enriches the ions generated by the ion source through a second electric field configuration, and then transmits the enriched ions to a second mass analyzer through a third electric field configuration. In the pulsed release mode, the ion manipulation device first enriches the ions generated by the ion source through a fourth electric field configuration, and then synchronously transmits the enriched ions to the first mass analyzer through a fifth electric field configuration. The ion manipulation device can be used as a general ion router, and can change the transmission direction and mode of the ions through electrical control, realize the high integration of multiple functions, and significantly simplify the instrument structure and reduce the cost.

Description

Technical Field

[0001] This invention relates to the field of mass spectrometry, and more specifically, to an ion manipulation device and a mass spectrometer. Background Technology

[0002] In mass spectrometry, ion guiding devices are used to efficiently transport ions from the front-end region to the subsequent mass analyzer. Common ion guiding devices, such as linear quadrupoles, can achieve radial focusing and axial transport and have a simple structure, but their function is highly limited, only able to perform linear transport tasks.

[0003] While complex ion traps (such as 3D ion traps or linear ion traps) have the ability to store ions in three dimensions and selectively excite them, their closed ring or end cap electrode structure inherently restricts the direction of ion entry and exit, making it difficult to flexibly change the ion transport path. This significantly limits their application flexibility and efficiency.

[0004] Therefore, there is an urgent need for a compact, versatile, and flexible ion guiding device to meet the requirements for dynamic control of ion pathways in complex mass spectrometry analysis. Summary of the Invention

[0005] The present invention aims to at least partially solve one of the aforementioned technical problems in the prior art. To this end, the present invention proposes an ion manipulation device that achieves a high degree of integration of multiple functions, significantly simplifies the instrument structure, and reduces costs.

[0006] The present invention also proposes a mass spectrometer having the above-mentioned ion manipulation device.

[0007] According to an embodiment of the present invention, the ion manipulation device is adapted to be connected to an ion source, a first mass analyzer, and a second mass analyzer, respectively. The ion manipulation device has a guiding mode, a deflection mode, and a pulse release mode. When the ion manipulation device switches to the guiding mode, it continuously transmits ions generated by the ion source to the first mass analyzer through a first electric field configuration. When the ion manipulation device switches to the deflection mode, it first enriches the ions generated by the ion source through a second electric field configuration, and then transmits the enriched ions to the second mass analyzer through a third electric field configuration. When the ion manipulation device switches to the pulse release mode, it first enriches the ions generated by the ion source through a fourth electric field configuration, and then synchronously transmits the enriched ions to the first mass analyzer through a fifth electric field configuration.

[0008] According to the ion manipulation device of the present invention, the ion manipulation device can be used as a general ion router. It can change the transmission direction and transmission mode of ions through electrical control. The guidance mode can realize efficient and low-loss direct transmission of ions, the deflection mode can realize the deflection extraction of ions, and the pulse release mode can improve the utilization rate and sensitivity of high-resolution mass spectrometry ions. The ion manipulation device can realize the high integration of multiple functions, significantly simplify the instrument structure and reduce costs.

[0009] According to some embodiments of the present invention, the first mass analyzer is a Fourier transform mass spectrometry analysis cell, and the second mass analyzer is a time-of-flight analyzer.

[0010] According to some embodiments of the present invention, the ion manipulation device includes: a manipulation assembly comprising a first lens, a first multistage rod, and a second lens, wherein the first lens is disposed between the ion source and the first multistage rod, and the second lens is disposed between the first multistage rod and the first mass analyzer, the first multistage rod having a slit facing the second mass analyzer; a pulse emission assembly disposed between the second lens and the first mass analyzer, the pulse emission assembly comprising a second multistage rod, an accelerating electrode, and a third lens, wherein the third lens is disposed between the second multistage rod and the first mass analyzer, and the accelerating electrode is sleeved on the outside of the second multistage rod; the first electric field configuration includes: the voltages of the first lens, the second lens, and the third lens decreasing sequentially, and the accelerating electrode not being energized. The first and second multi-stage rods are in RF-only guiding mode; the second electric field configuration includes: the voltages of the first and second lenses are equal, the voltage of the third lens is greater than the voltage of the second lens, the accelerating electrode is not energized, and the first and second multi-stage rods are in RF-only guiding mode; the third electric field configuration includes: adding a DC voltage to the first multi-stage rod on the side away from the slit based on the second electric field configuration; the fourth electric field configuration includes: the voltage of the second lens is less than the voltages of the first and third lenses, the accelerating electrode is not energized, and the first and second multi-stage rods are in RF-only guiding mode; the fifth electric field configuration includes: adding a DC voltage to the accelerating electrode based on the fourth electric field configuration.

[0011] According to some embodiments of the present invention, the accelerating electrode is sleeved on the side of the second multistage rod near the second lens, and when the fifth electric field is configured, the accelerating electrode forms a potential gradient field with decreasing potential from the enriched ions to the third lens (23).

[0012] According to some embodiments of the present invention, the inner diameter of the accelerating electrode gradually increases in the direction from the second lens to the third lens.

[0013] According to some embodiments of the present invention, the control component further includes: an enrichment electrode, the enrichment electrode being mounted on the first multi-stage rod and corresponding to the position of the slit; the second electric field configuration further includes: the voltage of the enrichment electrode being less than the voltage of the first lens.

[0014] According to some embodiments of the present invention, the enrichment electrode corresponds to the center position of the slit along its length.

[0015] According to some embodiments of the present invention, the ion manipulation device further includes: a pre-focusing component disposed between the ion source and the manipulation component, the pre-focusing component including: a fourth lens and a third multi-stage rod, the third multi-stage rod being disposed between the fourth lens and the first lens; the first electric field configuration further includes: the voltage of the fourth lens being greater than the voltage of the first lens; the second electric field configuration and the third electric field configuration further include: the voltage of the fourth lens being equal to the voltage of the third lens; the fourth electric field configuration and the fifth electric field configuration further include: the voltage of the fourth lens being greater than the voltage of the first lens.

[0016] According to some embodiments of the present invention, the ion manipulation device further includes a radial lens assembly disposed between the slit and the second mass analyzer, the radial lens assembly including at least two fifth lenses with staggered die holes.

[0017] According to some embodiments of the present invention, the ion manipulation device further includes: a housing having a communicating mounting cavity and an inflation port, wherein the pre-focusing assembly, the manipulation assembly, the pulse emission assembly and the radial lens assembly are all disposed within the mounting cavity, and the inflation port is used to fill the mounting cavity with buffer gas.

[0018] According to another embodiment of the present invention, a mass spectrometer includes an ion source, a first mass analyzer, a second mass analyzer, and the aforementioned ion manipulation device, wherein the ion manipulation device is connected to the ion source, the first mass analyzer, and the second mass analyzer, respectively.

[0019] According to the embodiments of the present invention, the ion manipulation device of the mass spectrometer can be used as a universal ion router. It can change the transmission direction and transmission mode of ions through electrical control. The guidance mode can realize efficient and low-loss direct transmission of ions, the deflection mode can realize the deflection extraction of ions, and the pulse release mode can improve the utilization rate and sensitivity of high-resolution mass spectrometry ions. The ion manipulation device can realize the high integration of multiple functions, which significantly simplifies the instrument structure and reduces costs.

[0020] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0021] Figure 1 This is a schematic diagram of the structure of a mass spectrometer according to an embodiment of the present invention;

[0022] Figure 2 This is a schematic diagram of the structure of an ion manipulation device according to an embodiment of the present invention;

[0023] Figure 3 This is a schematic diagram of the ion transport path in the guided mode of the ion manipulation device according to an embodiment of the present invention.

[0024] Figure 4 This is a schematic diagram of the ion transport path when the ion manipulation device according to an embodiment of the present invention is configured in the second electric field of the deflection mode;

[0025] Figure 5 This is a schematic diagram of the ion transport path when the ion manipulation device according to an embodiment of the present invention is configured in the third electric field of the deflection mode.

[0026] Figure 6 This is a schematic diagram of the ion transport path in the fourth electric field configuration of the ion manipulation device according to an embodiment of the present invention in the pulse release mode.

[0027] Figure 7 This is a schematic diagram of the ion transport path in the fifth electric field configuration of the ion manipulation device according to an embodiment of the present invention in the pulse release mode.

[0028] Figure label:

[0029] Control component 1; First lens 11; First multi-stage rod 12; Second lens 13; Enrichment electrode 14;

[0030] Pulse discharge assembly 2; second multi-stage rod 21; accelerating electrode 22; third lens 23;

[0031] Prefocusing component 3; fourth lens 31; third multistage rod 32;

[0032] Radial lens assembly 4; Fifth lens 41;

[0033] 5. Outer shell; 51. Mounting cavity; 52. Inflation port;

[0034] Ion manipulation device 10;

[0035] Ion source 20; First mass analyzer 30; Second mass analyzer 40;

[0036] Vacuum interface 50; First ion guiding device 60; Quadrupole mass filter 70; Collision cell 80; Second ion guiding device 90;

[0037] Mass spectrometer 100. Detailed Implementation

[0038] Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0039] In the description of this invention, it should be understood that the terms "length", "upper", "lower", "left", "right", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0040] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of this invention, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0041] In this invention, unless otherwise explicitly specified and limited, the terms "installation," "connection," "linking," and "fixing," etc., should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral part; they can refer to a mechanical connection, an electrical connection, or a connection that allows communication between them; they can refer to a direct connection or an indirect connection through an intermediate medium; they can refer to the internal communication of two components or the interaction between two components. Those skilled in the art can understand the specific meaning of the above terms in this invention according to the specific circumstances.

[0042] The ion manipulation device 10 and the mass spectrometer 100 according to embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

[0043] Reference Figure 1 As shown, according to a first aspect embodiment of the present invention, the ion manipulation device 10 is adapted to be connected to the ion source 20, the first mass analyzer 30, and the second mass analyzer 40, respectively. The ion manipulation device 10 has a guiding mode, a deflection mode, and a pulse release mode.

[0044] The ion manipulation device 10 can be used in the mass spectrometer 100. The ion source 20 and the first mass analyzer 30 can be arranged on both sides of the ion manipulation device 10 along the axis, and the second mass analyzer 40 can be arranged on one side of the ion manipulation device 10 in the radial direction. The ion manipulation device 10 can change the direction of ion transport by changing the electric field configuration. That is, the ions generated by the ion source 20 can enter the first mass analyzer 30 or the second mass analyzer 40 through the ion manipulation device 10. The first mass analyzer 30 and the second mass analyzer 40 can separate or distinguish the ions according to their mass-to-charge ratio and detect them in sequence, thereby obtaining a mass spectrum reflecting the ion type and abundance.

[0045] The first mass analyzer 30 and the second mass analyzer 40 can be Fourier transform mass spectrometry (FT-MSCELL), time-of-flight analyzer (TOF analyzer), electrostatic analyzer, etc. In this embodiment of the invention, the first mass analyzer 30 is a Fourier transform mass spectrometry cell and the second mass analyzer 40 is a time-of-flight analyzer as an example. The Fourier transform mass spectrometry cell can weigh and analyze ions, and the time-of-flight analyzer has the advantage of rapid scanning and can be used for real-time monitoring, high-throughput screening, or rapid data acquisition when coupled with liquid chromatography.

[0046] Reference Figures 1-3 As shown, when the ion manipulation device 10 switches to the guidance mode, the ion manipulation device 10 continuously transmits the ions generated by the ion source 20 to the first mass analyzer 30 through the first electric field configuration.

[0047] In this mode, the guidance mode can be used for high-resolution analysis of the first mass analyzer 30. The ion manipulation device 10 guides the ions to be transported non-destructively and continuously to the downstream first mass analyzer 30 through the configuration of the first electric field. In this mode, the ion manipulation device 10 can realize the axial guidance of the ions. The mass spectrometer 100 is functionally equivalent to a high-performance Fourier transform mass spectrometer and can perform routine high-resolution and accurate mass analysis.

[0048] Reference Figure 1 , Figure 4 and Figure 5 As shown, when the ion manipulation device 10 switches to deflection mode, the ion manipulation device 10 first enriches the ions generated by the ion source 20 through the second electric field configuration, and then transmits the enriched ions to the second mass analyzer 40 through the third electric field configuration.

[0049] The deflection mode can be used for high-speed detection by the second mass analyzer 40. The ion manipulation device 10 deflects the ion beam through the second electric field configuration and the third electric field configuration, for example, by 90 degrees. The ion beam is deflected from axial transmission by the ion manipulation device 10 to radial transmission. In this mode, the mass spectrometer 100 can take advantage of the rapid scanning of the second mass analyzer 40 and can be used for real-time monitoring, high-throughput screening or rapid data acquisition when coupled with liquid chromatography.

[0050] Reference Figure 1 , Figure 6 and Figure 7 As shown, when the ion manipulation device 10 switches to the pulse release mode, the ion manipulation device 10 first enriches the ions generated by the ion source 20 through the fourth electric field configuration, and then synchronously transmits the enriched ions to the first mass analyzer 30 through the fifth electric field configuration.

[0051] The pulse release mode can be used for enhanced resolution analysis of the first mass analyzer 30. The ion manipulation device 10 first enriches the ions generated by the ion source 20 through the fourth electric field configuration. The ion manipulation device 10 can act as an ion enricher, trapping ions of different mass-to-charge ratios from upstream within it for a period of time and cooling and focusing them. Then, at a precisely controlled moment, all the ions are combined into a compact ion pulse through the fifth electric field configuration and synchronously ejected and injected into the downstream first mass analyzer 30. Thus, through this "enrichment first, then pulse" mechanism, the time difference of ions of different mass-to-charge ratios entering the first mass analyzer 30 is greatly reduced, so that all ions start to gyrate in the first mass analyzer 30 almost simultaneously, thereby obtaining a coherent signal with synchronized start time. This overcomes the signal attenuation caused by the traditional continuous injection method and improves the resolution, especially the actual resolution and resolution capability in the mass number range (e.g., greater than 2000 AMU).

[0052] According to the ion manipulation device 10 of the present invention, the ion manipulation device 10 can be used as a general ion router. It can change the transmission direction and transmission mode of ions through electrical control. The guidance mode can realize efficient and low-loss direct transmission of ions, the deflection mode can realize the deflection extraction of ions, and the pulse release mode can improve the utilization rate and sensitivity of high-resolution mass spectrometry ions. The ion manipulation device 10 can realize the high integration of multiple functions, significantly simplify the instrument structure and reduce costs.

[0053] In some embodiments of the present invention, reference is made to... Figure 1 and Figure 2As shown, the ion manipulation device 10 includes a manipulation component 1 and a pulse emission component 2. The manipulation component 1 includes a first lens 11, a first multi-stage rod 12, and a second lens 13. The first lens 11 is disposed between the ion source 20 and the first multi-stage rod 12, and the second lens 13 is disposed between the first multi-stage rod 12 and the first mass analyzer 30. The first multi-stage rod 12 has a slit facing the second mass analyzer 40. The pulse emission component 2 is disposed between the second lens 13 and the first mass analyzer 30. The pulse emission component 2 includes a second multi-stage rod 21, an accelerating electrode 22, and a third lens 23. The third lens 23 is disposed between the second multi-stage rod 21 and the first mass analyzer 30, and the accelerating electrode 22 is sleeved on the outside of the second multi-stage rod 21.

[0054] Among them, the first lens 11, the second lens 13 and the third lens 23 are all aperture lenses. The aperture lens structure includes three coaxial electrodes, and each electrode has a small circular hole in the center that allows the ion beam to pass through. The aperture lens can be used for focusing, accelerating, decelerating, blocking and conducting.

[0055] Both the first multi-stage rod 12 and the second multi-stage rod 21 include multiple parallel electrode rods. For example, the first multi-stage rod 12 and the second multi-stage rod 21 can be a quadrupole, a hexapod, or an octupole. In this embodiment of the invention, a quadrupole is used as an example. The quadrupole includes four electrode rods that are parallel to each other and symmetrically arranged around a central axis. When ions pass through the central axis of the quadrupole, the quadrupole can perform mass filtering and transport of the ions.

[0056] The first multistage rod 12 has a slit facing the second mass analyzer 40. For example, the electrode rod at the lower part of the first multistage rod 12 has a slit, allowing ions inside the first multistage rod 12 to enter the second mass analyzer 40 through the slit. It is understood that when ions pass through the first multistage rod 12, they have two selectable paths: one path connects the first lens 11 and the second lens 13, enabling axial ion transport; the other path connects the first lens 11 and the second mass analyzer 40 outside the slit, enabling radial deflection ion transport.

[0057] The accelerating electrode 22 is sleeved on the outside of the second multistage rod 21. The accelerating electrode 22 can be a metal electrode. The electric field generated by the accelerating electrode 22 after being energized can cause the ions in the second multistage rod 21 to be subjected to a force pointing towards the third lens 23, thereby increasing the ion velocity and enabling the enriched ions to be ejected in a pulse manner, ensuring that ions of all mass numbers enter the first mass analyzer 30 of the next stage almost simultaneously.

[0058] Reference Figures 1-3As shown, the first electric field configuration includes: the voltages of the first lens 11, the second lens 13 and the third lens 23 decrease sequentially, the accelerating electrode 22 is not energized, and the first multi-stage rod 12 and the second multi-stage rod 21 are in RF-only guiding mode.

[0059] In the first electric field configuration, the ion manipulation device 10 is in the guiding mode. The voltage of the first lens 11 is greater than the voltage of the second lens 13, and the voltage of the second lens 13 is greater than the voltage of the third lens 23. That is, the voltages of the first lens 11, the second lens 13, and the third lens 23 decrease sequentially from the ion source 20 to the first mass analyzer 30, so that the ions passing through the ion manipulation device 10 are subjected to a force pointing towards the first mass analyzer 30 in the electric field. At the same time, the accelerating electrode 22 is not working, and the first multi-stage rod 12 and the second multi-stage rod 21 are in the RF-only guiding mode. That is, the first multi-stage rod 12 and the second multi-stage rod 21 are only set with RF (radio frequency) voltage and DC (direct current) voltage of 0, and are in a fully open state. At this time, the ion manipulation device 10 plays an axial full-pass guiding role for ions. The ion path is: ion source 20 → first lens 11 → first multi-stage rod 12 → second lens 13 → second multi-stage rod 21 → third lens 23 → first mass analyzer 30. This mode can realize efficient and low-loss direct transmission of ions.

[0060] Reference Figure 4 As shown, the second electric field configuration includes: the voltages of the first lens 11 and the second lens 13 are equal, the voltage of the third lens 23 is greater than the voltage of the second lens 13, the accelerating electrode 22 is not energized, and the first multi-stage rod 12 and the second multi-stage rod 21 are in RF-only guiding mode.

[0061] In the second electric field configuration, the ion manipulation device 10 is in a deflection mode enrichment state. The voltages of the first lens 11 and the second lens 13 are equal, and the voltage of the third lens 23 is greater than the voltage of the second lens 13. This causes the ions to be subjected to a force pointing towards the first multi-stage rod 12 in the electric field, thus enriching the ions within the first multi-stage rod 12. The accelerating electrode 22 does not work, and the first multi-stage rod 12 and the second multi-stage rod 21 are in RF-only guiding mode. At this time, the ion manipulation device 10 plays the role of enriching and trapping ions within the first multi-stage rod 12.

[0062] Reference Figure 1 and Figure 5 As shown, the third electric field configuration includes adding a DC voltage to the first multi-stage rod 12 on the side of the stage rod facing away from the slit, based on the second electric field configuration.

[0063] In the third electric field configuration, the ion manipulation device 10 is in the radial extraction state of the deflection mode. The voltages of the first lens 11 and the second lens 13 are equal, the voltage of the third lens 23 is greater than the voltage of the second lens 13, the accelerating electrode 22 is not working, the second multi-stage rod 21 is in the RF-only guiding mode, and while the first multi-stage rod 12 is set with RF (radio frequency) voltage, the DC voltage of the rod on the side of the first multi-stage rod 12 away from the slit is also increased. For example, a slit is opened on the lower rod of the first multi-stage rod 12, which significantly increases the DC voltage of the upper rod of the first multi-stage rod 12. A strong electric field pointing towards the slit of the lower rod can be formed in the first multi-stage rod 12, so that the ions enriched in the first multi-stage rod 12 are forced to be ejected from the micro slit of the lower rod under the action of the strong electric field, realizing a 90-degree deflection from the axial to the radial direction, so that the enriched ions are transmitted to the second mass analyzer 40 through the slit. This mode realizes ion extraction orthogonal to the axial path.

[0064] Reference Figure 6 As shown, the fourth electric field configuration includes: the voltage of the second lens 13 is less than the voltage of the first lens 11 and the voltage of the third lens 23, the accelerating electrode 22 is not energized, and the first multi-stage rod 12 and the second multi-stage rod 21 are in RF-only guiding mode.

[0065] In the fourth electric field configuration, the ion manipulation device 10 is in the enrichment state of pulse release mode. The voltage of the second lens 13 is less than the voltage of the first lens 11 and the voltage of the third lens 23, so that the ions are enriched and trapped near the second lens 13 under the action of the electric field. The accelerating electrode 22 does not work, and the first multi-stage rod 12 and the second multi-stage rod 21 are in RF-only guiding mode. At this time, under such a trapping barrier, the ion manipulation device 10 plays the role of enriching and trapping ions at the second lens 13. After the ions are constrained near the second lens 13, the time Tmax for the maximum mass number to reach this position can be calculated, and the duration of the fourth electric field configuration can be slightly greater than Tmax to ensure that all ions of all mass numbers have reached this position.

[0066] Reference Figure 1 and Figure 7 As shown, the fifth electric field configuration includes adding a DC voltage to the accelerating electrode 22 based on the fourth electric field configuration.

[0067] In the fifth electric field configuration, the ion manipulation device 10 is in the pulse acceleration ejection state of pulse release mode. The voltage of the second lens 13 is less than the voltage of the first lens 11 and the voltage of the third lens 23. The first multistage rod 12 and the second multistage rod 21 are in RF-only guidance mode. The accelerating electrode 22 is energized and the DC voltage is significantly increased, thereby accelerating the enriched ion clusters through the second multistage rod 21 and the third lens 23 and ejecting them to the first mass analyzer 30. The ion clusters are pulsed out according to their arrival time, realizing enrichment first and then pulse discharge, which greatly improves the ion utilization rate and sensitivity of high-resolution mass spectrometry.

[0068] In some embodiments of the present invention, reference is made to... Figure 2 As shown, the accelerating electrode 22 is sleeved on the side of the second multistage rod 21 near the second lens 13. When the fifth electric field is configured, the accelerating electrode 22 forms a driving electric field with decreasing potential from the enriched ions to the third lens 23. That is, in the length direction of the second multistage rod 21, the length of the accelerating electrode 22 can be less than the length of the second multistage rod 21. The accelerating electrode 22 can be sleeved on the left side of the second multistage rod 21, rather than the right side. When a direct current is applied to the accelerating electrode 22, a driving electric field can be formed on the left side of the second multistage rod 21 to drive the ions enriched at the second lens 13 to move synchronously towards the third lens 23.

[0069] It is understandable that the starting point of the driving electric field can be located at the location of the enriched ions, that is, in the region close to the second lens 13. From the second lens 13 to the third lens 23, the potential of the driving electric field decreases to form an axial electric field gradient, which acts like an inclined slide, guiding the enriched ions to accelerate towards the direction of the third lens 23.

[0070] It should be noted that, in this embodiment of the invention, the voltage of the accelerating electrode 22 is suddenly increased to actively push the enriched ions toward the third lens 23, rather than decreasing the voltage of the third lens 23 to passively release the enriched ions. The reason for this is that, in this embodiment of the invention, a "ion pulse" that is highly compact in time and highly concentrated in space is created to meet the stringent injection requirements of the subsequent first mass analyzer 30.

[0071] The problem with the approach of "reducing the voltage of the third lens 23 to passively release the enriched ions" is that, due to the lack of a strong external accelerating electric field, the ions fly out very slowly. More importantly, ions of different masses have different speeds; lighter ions fly faster, and heavier ions fly slower. As a result, ion clusters that were originally clustered together will disperse as they fly to the next analyzer.

[0072] Furthermore, the accelerating electrode 22 and the second multistage rod 21 are electrically isolated and have no electrical contact. The second multistage rod 21 is mainly responsible for the radial confinement of ions, and a high-frequency radio frequency voltage and a small amount of DC voltage are applied to it. The accelerating electrode 22 is mainly responsible for the axial propulsion of ions, and a momentary high-voltage DC pulse is applied to it. If the accelerating electrode 22 and the second multistage rod 21 are in electrical contact, the high-voltage pulse of the accelerating electrode 22 will momentarily cross-current into the radio frequency power supply of the second multistage rod 21. This will not only fail to form the required independent accelerating electric field, but will also directly burn out the precision high-frequency radio frequency power supply. Optionally, the accelerating electrode 22 and the second multistage rod 21 are separated by a vacuum or an insulating ceramic component.

[0073] Furthermore, although the presence of the second multistage rod 21 may partially shield the driving electric field generated by the accelerating electrode 22, the acceleration of ions can still be achieved by utilizing the penetration effect of the electric field. That is to say, the second multistage rod 21 consists of multiple parallel metal rods, which are not completely closed tubes but have physical gaps between them. Although the metal rods themselves have the shielding effect of a Faraday cage, once the accelerating electrode 22, which surrounds the second multistage rod 21, is subjected to high voltage, its strong electrostatic field will penetrate through the gaps between the multiple metal rods to the central axis of the second multistage rod 21. The enriched ions are located at the center of the second multistage rod 21. Although the electric field strength felt at the center is weaker than the actual voltage on the surface of the accelerating electrode 22, as long as the voltage on the accelerating electrode 22 is high enough, the electric field penetrating to the center is still strong enough to exert a huge thrust on the ions on the central axis.

[0074] In some embodiments of the present invention, reference is made to... Figure 2 As shown, in the direction from the second lens 13 to the third lens 23, the inner diameter of the accelerating electrode 22 gradually increases, that is, the distance between the accelerating electrode 22 and the second multi-stage rod 21 gradually increases. The direction from the second lens 13 to the third lens 23 can be... Figure 2In the left-right direction, the accelerating electrode 22 can be a cylindrical structure, and the right end of the inner wall can be trumpet-shaped. The cross-sectional shape of the accelerating electrode 22 can be a trapezoidal structure. The left side of the accelerating electrode 22 is attached to the second multi-stage rod 21, and the right side of the accelerating electrode 22 is separated from the second multi-stage rod 21. The distance between the accelerating electrode 22 and the second multi-stage rod 21 gradually increases from left to right. After the accelerating electrode 22 is supplied with DC current, the accelerating electrode 22 can form an electric field gradient with a strong left and weak right in the second multi-stage rod 21. During the process of the enriched ions transporting from left to right, the ions that run to the right will enter the region with a relatively lower voltage (lower potential, less attraction to positive ions), and the acceleration force will be slightly reduced. The ions that run slightly to the left are still in the region with a relatively higher voltage, and the acceleration force will be slightly increased. The ion clusters are not only not stretched during the acceleration process, but become more compact to form a more compact ion pulse. As a result, when injected into the analysis cell of the first mass analyzer 30, a coherent signal with a highly synchronized start time is obtained, which significantly improves the resolution.

[0075] It should be noted that the accelerating electrode 22 has a trapezoidal cross-sectional shape, meaning that the distance between the accelerating electrode 22 and the central axis of the second multi-stage rod 21 is uneven, with one end closer and the other farther away, exhibiting geometric asymmetry. Consequently, the electric field penetration is stronger and the potential is higher at the closer end (left), while the electric field penetration is weaker and the potential is lower at the farther end. When a pulsed high voltage is applied to the accelerating electrode 22, a potential gradient immediately forms along the central axis, sloping from the left end to the right, like a slide. This causes the force on the ions to point towards the third lens 23. It is precisely this trapezoidal structure that ensures the formed potential slide slopes downwards towards the exit third lens 23, thereby forcing all ions to accelerate uniformly towards the third lens 23.

[0076] In addition, at the moment the pulse is released, two main factors prevent ions from flowing backward into the upstream second lens 13. The first factor is the unidirectional thrust created by the accelerating electrode 22: the field penetration generated by the accelerating electrode 22 is not an explosive outward push, but rather forms an extremely strong unidirectional axial driving electric field, pointing directly at the third lens 23. Under the action of this strong electric field, ions will only rush towards the third lens 23 along the "potential slide" and will not flow backward.

[0077] The second factor is the potential barrier of the upstream second lens 13: during the enrichment stage, ions are trapped between the second lens 13 and the third lens 23. A certain DC voltage (usually a positive voltage for positive ions) is constantly applied to the perforated lens of the second lens 13, forming a "potential wall". When a pulsed high voltage is applied to the second lens 13, even if a very small number of ions try to move back due to space charge repulsion, the inherent potential wall on the second lens 13 will block them. At the same time, the voltage penetration is strongest at the end of the accelerating electrode 22 closest to the second lens 13, which is equivalent to instantly building a potential barrier higher than the second lens 13 itself near the second lens 13, directly "squeezing" the ions out towards the third lens 23.

[0078] In some embodiments of the present invention, reference is made to... Figure 2 and Figure 4 As shown, the control component 1 further includes: an enrichment electrode 14, which is mounted on the first multi-stage rod 12 and corresponds to the position of the slit. The second electric field configuration further includes: the voltage of the enrichment electrode 14 is less than the voltage of the first lens 11.

[0079] Specifically, the enrichment electrode 14 can be a central grid electrode. When the first electric field, third electric field, fourth electric field, and fifth electric field are configured, the enrichment electrode 14 can operate without being powered on. When the second electric field is configured, the enrichment electrode 14 is powered on and the voltage is less than the voltage of the first lens 11, that is, the potential of the enrichment electrode 14 is the lowest. The ions enriched by the first multi-stage rod 12 can be more concentrated at the position corresponding to the enrichment electrode 14. This allows the length of the first multi-stage rod 12 and the slit to be reduced in the length direction, thereby achieving miniaturization of the first multi-stage rod 12 and reducing its cost and space occupation.

[0080] In some embodiments of the present invention, reference is made to... Figure 2 and Figure 4 As shown, the enrichment electrode 14 corresponds to the center position along the length direction of the slit, which is the length direction of the slit. Figure 2 In the left-right direction, the enrichment electrode 14 is centered in the length direction of the slit, which can further focus ions in the middle position of the slit. That is, the projected area of ​​the enriched ion clusters in the lower rod of the first multi-stage rod 12 is smaller, so as to reduce ion transmission loss and improve the ion throughput at the slit.

[0081] In some embodiments of the present invention, reference is made to... Figure 1 and Figure 2 As shown, the ion manipulation device 10 further includes a pre-focusing component 3, which is disposed between the ion source 20 and the manipulation component 1. The pre-focusing component 3 includes a fourth lens 31 and a third multi-stage rod 32, which is disposed between the fourth lens 31 and the first lens 11.

[0082] The fourth lens 31 can be a perforated lens, and the third multi-stage rod 32 can be a quadruple rod. Ions generated by the ion source 20 can pass through the fourth lens 31 and the third multi-stage rod 32 of the pre-focusing assembly 3 in sequence before entering the control assembly 1. The pre-focusing assembly 3 can be used to perform preliminary redirection and beam shaping of the incident ions.

[0083] The first electric field configuration also includes: the voltage of the fourth lens 31 is greater than the voltage of the first lens 11, so that ions move from the fourth lens 31 to the first lens 11 through the third multi-stage rod 32 under the action of the electric field.

[0084] The second and third electric field configurations also include: the voltage of the fourth lens 31 is equal to the voltage of the third lens 23, so that ions move from the fourth lens 31 to the first lens 11 through the third multi-stage rod 32 under the action of the electric field. At the same time, the fourth lens 31 and the third lens 23, which have equal and relatively high voltages, can form a trapping barrier on the left and right sides of the ion manipulation device 10 to better enrich ions.

[0085] The fourth and fifth electric field configurations also include: the voltage of the fourth lens 31 is greater than the voltage of the first lens 11, so that ions move from the fourth lens 31 to the first lens 11 through the third multi-stage rod 32 under the action of the electric field.

[0086] In some embodiments of the present invention, reference is made to... Figure 1 , Figure 2 and 5 As shown, the ion manipulation device 10 also includes a radial lens assembly 4, which is disposed between the slit and the second mass analyzer 40. The radial lens assembly 4 includes at least two fifth lenses 41 with staggered die holes.

[0087] Specifically, in deflection mode, the ions enriched in the first multi-stage rod 12 enter the second mass analyzer 40 sequentially through the slit and the radial lens assembly 4. The fifth lens 41 can be a perforated lens, and the perforations of at least two fifth lenses 41 are staggered. Since neutral particles are not affected by the electric field force, the staggered perforations of the fifth lenses 41 can exclude neutral particles, leaving only charged target ions to enter the radial second mass analyzer 40.

[0088] In some embodiments of the present invention, reference is made to... Figure 2As shown, the stage bar of the third multistage bar 32 can be tilted at a certain angle to the incident direction of the main ion beam to initially redirect the incident ions. The stage bar of the third multistage bar 32 can be a short electrode bar to reduce its space occupation and cost. The second multistage bar 21 and the third multistage bar 32 are arranged symmetrically on both sides of the axial direction of the first multistage bar 12, that is, the stage bar of the second multistage bar 21 is a short electrode bar with the tilt direction opposite to that of the third multistage bar 32. In addition, the stage bar of the first multistage bar 12 can be a non-standard electrode bar that smoothly transitions between the third multistage bar 32 and the second multistage bar 21 to ensure lossless and smooth ion transmission.

[0089] In some embodiments of the present invention, reference is made to... Figure 2 As shown, the ion manipulation device 10 also includes: a housing 5, which has a connected mounting cavity 51 and an inflation port 52. The pre-focusing assembly 3, the manipulation assembly 1, the pulse emission assembly 2, and the radial lens assembly 4 are all disposed within the mounting cavity 51. The inflation port 52 is used to fill the mounting cavity 51 with buffer gas, which can be helium or nitrogen. The buffer gas frequently collides with the moving ions, causing the kinetic energy of the ions to dissipate rapidly (i.e., cool down). During the ion enrichment stage in deflection mode and pulse release mode, the gas valve at the inflation port 52 is opened, and buffer gas is filled into the mounting cavity 51 through the inflation port 52. The buffer gas can effectively confine the ions to the center of the potential well formed by the radio frequency electric field, making their spatial and kinetic energy distribution more concentrated, thereby improving the efficiency and stability of ion enrichment.

[0090] The ion manipulation device 10 according to an embodiment of the present invention can be an irregular structure to achieve ion bending guidance (C-GUIDE). It can serve as a core router. Through its unique mechanical structure and electric field configuration, combined with buffer gas collision cooling technology, it achieves efficient cooling and focusing of ions. Thus, it integrates the three functions of direct ion guidance, radial deflection and axial enrichment and release into one, realizing intelligent and dynamic switching of ion flow between the first mass analyzer 30 and the second mass analyzer 40. It not only builds a powerful hybrid platform, but also fundamentally optimizes the ion implantation process of the first mass analyzer 30 and improves its resolution.

[0091] In guided mode, the ion path is as follows: Figure 3 As shown by the middle arrow, the voltages of the fourth lens 31, the first lens 11, the second lens 13, and the third lens 23 decrease sequentially. The accelerating electrode 22, the enriching electrode 14, and the fifth lens 41 are not energized. The first multistage rod 12, the second multistage rod 21, and the third multistage rod 32 are all in RF-only guidance mode. The ion path is: ion source 20 → fourth lens 31 → third multistage rod 32 → first lens 11 → first multistage rod 12 → second lens 13 → second multistage rod 21 → third lens 23 → first mass analyzer 30.

[0092] In deflection mode, the ion path is as follows: Figure 4 and Figure 5 As indicated by the middle arrow, firstly, the first multistage rod 12, the second multistage rod 21, and the third multistage rod 32 are all in RF-only guidance mode. The accelerating electrode 22 and the fifth lens 41 are not energized. The voltage of the first lens 11 is equal to the voltage of the second lens 13, the voltage of the third lens 23 is equal to the voltage of the fourth lens 31, and the voltage of the first lens 11 is less than the voltage of the third lens 23. The voltage of the enrichment electrode 14 is less than the voltage of the first lens 11. That is, in the left-right direction, the lens voltage is lower closer to the enrichment electrode 14 and higher further away from the enrichment electrode 14, in order to form a trapping barrier. The ion path is: ion source 20 → fourth lens 31 → third multistage rod 32 → first lens 11 → first multistage rod 12 (enrichment). Then, the DC current on the upper rod of the first multistage rod 12 is significantly increased, and the fifth lens 41 is energized. The ion path is: slit of the first multistage rod 12 → multiple fifth lenses 41 → second mass analyzer 40.

[0093] In pulsed release mode, the ion pathway is as follows: Figure 6 and Figure 7 As indicated by the middle arrow, firstly, the accelerating electrode 22, enriching electrode 14, and fifth lens 41 are not energized. The first multistage rod 12, second multistage rod 21, and third multistage rod 32 are all in RF-only guidance mode. The voltages of the fourth lens 31, first lens 11, and second lens 13 decrease sequentially, while the voltage of the third lens 23 is greater than that of the second lens 13. That is, in the left-right direction, the lens voltage is lower closer to the second lens 13 and higher further away from the second lens 13, thus forming a trapping barrier. The ion path is: ion source 20 → fourth lens 31 → third multistage rod 32 → first lens 11 → first multistage rod 12 → second lens 13 (enrichment). Then, the accelerating electrode 22 is energized and the DC voltage is increased. The ion path is: second lens 13 → second multistage rod 21 → third lens 23 → first mass analyzer 30.

[0094] The ion manipulation device 10 according to an embodiment of the present invention can guide ions using a non-standard quadrupole and employ a multi-dimensional ion manipulation method, achieving a breakthrough compared to existing technologies. The ion manipulation device 10 integrates a pre-focusing component 3, a manipulation component 1, a pulse emission component 2, and a radial lens component 4, achieving a high degree of integration of axial guidance, radial deflection, and axial enrichment-pulse release functions through purely electrical control, significantly simplifying the instrument structure and reducing costs. High-quality ion pulses are provided in pulse release mode. This device can serve as a universal ion router, supporting the construction of compact and efficient multi-stage mass spectrometry systems, providing a core hardware platform for advanced methods such as high-throughput data-independent acquisition, and representing an important development direction for mass spectrometry technology.

[0095] Reference Figure 1 As shown, the mass spectrometer 100 according to a second aspect embodiment of the present invention includes: an ion source 20, a first mass analyzer 30, a second mass analyzer 40, and an ion manipulation device 10 as described above. The ion manipulation device 10 is connected to the ion source 20, the first mass analyzer 30, and the second mass analyzer 40, respectively.

[0096] According to the embodiment of the present invention, the mass spectrometer 100 has an ion manipulation device 10 that can be used as a universal ion router. It can change the transmission direction and transmission mode of ions through electrical control. The guidance mode can realize efficient and low-loss direct transmission of ions, the deflection mode can realize the deflection extraction of ions, and the pulse release mode can improve the utilization rate and sensitivity of high-resolution mass spectrometry ions. The ion manipulation device 10 can realize the high integration of multiple functions, which significantly simplifies the instrument structure and reduces costs.

[0097] Reference Figure 1 and Figure 2 As shown, the mass spectrometer 100 also includes: a vacuum interface 50, a first ion guide device 60 (L_GUIDE), a quadrupole mass filter 70, a collision cell 80, and a second ion guide device 90. The ion source 20, vacuum interface 50, first ion guide device 60, quadrupole mass filter 70, collision cell 80, and the pre-focusing assembly 3 of the ion manipulation device 10 are connected in sequence. The second ion guide device 90 is connected between the first mass analyzer 30 and the pulse exhaust assembly 2 of the ion manipulation device 10. The ion manipulation device 10 is manufactured with three ports, which are respectively coupled to the outlet of the collision cell 80, the inlet of the first mass analyzer 30, and the inlet of the second mass analyzer 40 to realize the mixed mass spectrometry function.

[0098] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. In addition, those skilled in the art can combine and integrate the different embodiments or examples described in this specification.

[0099] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. An ion manipulation device, characterized in that, The ion manipulation device is adapted to be connected to the ion source (20), the first mass analyzer (30), and the second mass analyzer (40), respectively. The ion manipulation device has a guiding mode, a deflection mode, and a pulse release mode. When the ion manipulation device switches to the guidance mode, the ion manipulation device continuously transmits the ions generated by the ion source (20) to the first mass analyzer (30) through the first electric field configuration; When the ion manipulation device switches to the deflection mode, the ion manipulation device first enriches the ions generated by the ion source (20) through the second electric field configuration, and then transmits the enriched ions to the second mass analyzer (40) through the third electric field configuration. When the ion manipulation device switches to pulse release mode, the ion manipulation device first enriches the ions generated by the ion source (20) through the fourth electric field configuration, and then transmits the enriched ions to the first mass analyzer (30) through the fifth electric field configuration.

2. The ion manipulation device according to claim 1, characterized in that, The first mass analyzer (30) is a Fourier transform mass spectrometry analysis cell, and the second mass analyzer (40) is a time-of-flight analyzer.

3. The ion manipulation device according to claim 1, characterized in that, The ion manipulation device includes: The control assembly (1) includes a first lens (11), a first multi-stage rod (12), and a second lens (13). The first lens (11) is disposed between the ion source (20) and the first multi-stage rod (12), and the second lens (13) is disposed between the first multi-stage rod (12) and the first mass analyzer (30). The first multi-stage rod (12) has a slit facing the second mass analyzer (40). A pulse discharge assembly (2) is disposed between the second lens (13) and the first mass analyzer (30). The pulse discharge assembly (2) includes a second multi-stage rod (21), an acceleration electrode (22) and a third lens (23). The third lens (23) is disposed between the second multi-stage rod (21) and the first mass analyzer (30). The acceleration electrode (22) is sleeved on the outside of the second multi-stage rod (21). The first electric field configuration includes: the voltages of the first lens (11), the second lens (13) and the third lens (23) decrease sequentially, the accelerating electrode (22) is not energized, and the first multi-stage rod (12) and the second multi-stage rod (21) are in RF-only guiding mode; The second electric field configuration includes: the voltages of the first lens (11) and the second lens (13) are equal, the voltage of the third lens (23) is greater than the voltage of the second lens (13), the accelerating electrode (22) is not energized, and the first multistage rod (12) and the second multistage rod (21) are in RF-only guiding mode; The third electric field configuration includes: adding a DC voltage to the first multi-stage rod (12) on the side of the slit that is away from the second electric field configuration; The fourth electric field configuration includes: the voltage of the second lens (13) is less than the voltage of the first lens (11) and the voltage of the third lens (23), the accelerating electrode (22) is not energized, and the first multistage rod (12) and the second multistage rod (21) are in RF-only guiding mode; The fifth electric field configuration includes adding a DC voltage to the accelerating electrode (22) based on the fourth electric field configuration.

4. The ion manipulation device according to claim 3, characterized in that, The accelerating electrode (22) is sleeved on the side of the second multi-stage rod (21) near the second lens (13), and when the fifth electric field is configured, the accelerating electrode (22) forms a driving electric field with a potential decreasing from the direction of the enriched ions to the third lens (23).

5. The ion manipulation device according to claim 4, characterized in that, The inner diameter of the accelerating electrode (22) gradually increases in the direction from the second lens (13) to the third lens (23).

6. The ion manipulation device according to claim 3, characterized in that, The control component (1) further includes: an enrichment electrode (14), which is mounted on the first multi-stage rod (12) and corresponds to the position of the slit; The second electric field configuration further includes: the voltage of the enrichment electrode (14) is less than the voltage of the first lens (11).

7. The ion manipulation device according to claim 6, characterized in that, The enrichment electrode (14) corresponds to the center position of the slit length direction.

8. The ion manipulation device according to any one of claims 3-7, characterized in that, The ion manipulation device further includes a pre-focusing component (3), which is disposed between the ion source (20) and the manipulation component (1). The pre-focusing component (3) includes a fourth lens (31) and a third multi-stage rod (32), which is disposed between the fourth lens (31) and the first lens (11). The first electric field configuration further includes: the voltage of the fourth lens (31) is greater than the voltage of the first lens (11); The second electric field configuration and the third electric field configuration further include: the voltage of the fourth lens (31) is equal to the voltage of the third lens (23); The fourth electric field configuration and the fifth electric field configuration further include: the voltage of the fourth lens (31) is greater than the voltage of the first lens (11).

9. The ion manipulation device according to claim 8, characterized in that, The ion manipulation device further includes a radial lens assembly (4), which is disposed between the slit and the second mass analyzer (40), and the radial lens assembly (4) includes at least two fifth lenses (41) with staggered die holes.

10. The ion manipulation device according to claim 9, characterized in that, The ion manipulation device further includes: a housing (5) having a communicating mounting cavity (51) and an inflation port (52), wherein the pre-focusing assembly (3), the manipulation assembly (1), the pulse discharge assembly (2) and the radial lens assembly (4) are all disposed in the mounting cavity (51), and the inflation port (52) is used to fill the mounting cavity (51) with buffer gas.

11. A mass spectrometer, characterized in that, include: The ion source (20), the first mass analyzer (30), the second mass analyzer (40), and the ion manipulation device according to any one of claims 1-10, wherein the ion manipulation device is connected to the ion source (20), the first mass analyzer (30), and the second mass analyzer (40), respectively.

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