Ion generating device, mass spectrometer, and ion generating method

Abstract

To provide an ion generator which can further improve the efficiency of disassociation of the ion generator at a relatively low cost and secondarily disassociate a sample particle by using a laser beam.SOLUTION: The ion generator includes: a desorption device for desorbing a sample particle in a predetermined region; a light source for emitting a light beam and causing the light beam to focus in a predetermined region to ionize, fragmentate, or atomize the sample particle in the predetermined region; and a reflection focusing device for reflecting the light beam having been emitted from the light source and having passed through the predetermined region and causing the light beam to focus in the predetermined region, thereby repeating ionization, fragmentation, or atomization of the sample particle in the predetermined region at least once. The ion generator generates one focus in the predetermined region accordingly every time the light beam is reflected at the surface of the reflection focusing device.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to the field of mass spectrometry, and more particularly to an ion generating device, a mass spectrometry device, and an ion generating method. [Background technology]

[0002] In some conventional material analysis instruments, when analyzing a material, it is necessary to first ionize, fragment or atomize the sample particles of the material, and then detect the sample particles from which the sample molecules are dissociated to identify the elemental composition or molecular information of the material. Accordingly, an ion generating device is an important component of such material analysis instruments.

[0003] The following findings were obtained through research. Samples after primary dissociation often contain a large amount of particles that are not completely dissociated. This greatly limits the dissociation efficiency of the ion generator and also limits the sensitivity of the analytical instrument, so that ion generators in the prior art generally perform multiple dissociations on sample particles. Taking matrix-assisted laser desorption / ionization (MALDI) as an example, the paper "Mass spectrometry imaging with laser-induced postionization" published by Soltwisch et al. in 2015 discloses a MALDI-TOF (time of flight) mass spectrometer, which uses a tunable laser light source in the range of 260-280 nm to post-ionize the particle plume obtained by primary ionization, and the mass spectrometer can improve the ion yield of some lipids and small molecular substances by about three orders of magnitude. The post-ionization technology is now also called MALDI-2 technology.

[0004] However, the ionization efficiency of post-ionization techniques such as MALDI-2 needs to be further improved.

[0005] Patent Document 1 discloses a MALDI-IM (ion mobility)-TOF mass spectrometer that improves ionization efficiency by using a pair of reflecting mirrors arranged opposite to each other. However, in this technical solution, in order to position the focal point of the reflecting mirrors in the area where the particle plume is located, multiple reflections are required for the laser light to be focused once on the particle plume, which leads to a significant decrease in the ionization efficiency of the post-ionization. In addition, since the laser energy is attenuated with each reflection and the post-ionization effect is positively correlated with the laser energy, further increase in the laser energy is required to ensure the ionization effect after reflection. In addition, the reflected but unfocused light beam is deviated from the focus, so the size and position of the primary ionization device must be changed to match the deviated light beam, which makes the optical path inside the device more complicated and difficult to handle.

[0006] Patent Document 2 proposes an apparatus and method for use in particle mass analysis, and specifically discloses an ion generating device that utilizes the principle of an optical resonator to repeatedly reflect laser light in a resonator up to the vicinity of sample particles, thereby ionizing the sample particles multiple times. However, the dissociation efficiency of laser desorption ionization is affected not only by the time and space of action of the laser light and the sample, but also by the intensity of the laser light, and the resonator in Patent Document 2 requires the laser light to be reflected multiple times by a combination of a semi-transparent reflecting mirror and a total reflecting mirror, and the laser light passes through the semi-transparent reflecting mirror before entering the resonator, resulting in a significant loss of laser power. Generally, the reflectance R of the concave mirror in the resonator is greater than 99.99%, and the laser light is incident from the center of the first concave mirror and reflected by 10 -4 Since only a certain amount of power can enter the resonator, it is necessary to provide an incident laser beam with a higher energy in order for the incident laser beam to reach an intensity sufficient to dissociate the sample. However, increasing the laser energy leads to an increase in the volume and cost of the ion generator.

[0007] Therefore, an improved solution is needed to solve the above problems of conventional ion generating devices. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] US8558168B2 [Patent Document 2] CN101592628A Summary of the Invention [Problem to be solved by the invention]

[0009] In view of the above problems of the prior art, the technical solution of the present invention provides an ion generating device that can further improve the dissociation (ie, ionization, fragmentation or atomization) efficiency of the ion generating device at a relatively low cost. [Means for solving the problem]

[0010] The present invention provides an ion generating device including a desorption device that desorbs sample particles into a predetermined region, a light source that emits a light beam and focuses the light beam on the predetermined region, thereby ionizing, fragmenting or atomizing the sample particles in the predetermined region, and a reflective focusing device that reflects the light beam emitted from the light source and passing through the predetermined region and focuses it on the predetermined region, thereby repeating the ionization, fragmentation or atomization of the sample particles in the predetermined region at least once, and each time the light beam is reflected off the surface of the reflective focusing device, focusing onto the predetermined region occurs correspondingly once. Effect of the Invention

[0011] According to this technical solution, a reflective focusing device is provided, and the light beam that has been focused on a predetermined area and passed through it is reflected back to the predetermined area and refocused, thereby realizing repeated dissociation of the sample particles, effectively improving the dissociation efficiency of the sample particles and avoiding the complication of the device due to the deviation of the light beam. In addition, since focusing occurs once for each reflection, the number of times the laser light is focused on the predetermined area is increased, reducing the energy loss caused by each focusing, and further improving the dissociation efficiency of the sample particles.

[0012] As an optional technical solution, the reflective focusing device includes a first concave mirror, the first concave mirror and the light source are disposed opposite each other across the predetermined area, and the spherical center of the first concave mirror is located within the predetermined area.

[0013] According to this technical solution, a concave mirror is installed in addition to the light source to realize the re-reflection and focusing of the focused light beam, and the spherical center position of the first concave mirror is set within a predetermined area, so that the focused light beam can be focused again in a predetermined area, thereby increasing the number of times that the sample particles are repeatedly dissociated by the light beam, thereby improving the dissociation efficiency and simplifying the device.

[0014] As an optional technical solution, the reflective focusing device further includes a second concave mirror, the first concave mirror and the second concave mirror are installed opposite each other across the predetermined area, and the spherical center of the second concave mirror is located within the predetermined area.

[0015] According to this technical proposal, a first concave mirror and a second concave mirror are installed opposite each other with a predetermined area between them, and their spherical centers are both installed within the predetermined area, so that a light beam focused from a light source on a predetermined area can be reflected between the first and second concave mirrors, and each time the light beam is reflected, it is focused to the predetermined area again, so that the light beam can be focused each time and the focused light beam can overlap with a sample particle within the predetermined area, thereby further improving the dissociation efficiency of the ion generating device.

[0016] As an optional technical solution, the light beam is repeatedly reflected and focused on the predetermined area multiple times between the first concave mirror and the second concave mirror.

[0017] According to this technical solution, for example, the reflective surfaces of the first concave mirror and the second concave mirror can be made into arc surfaces extending around a common spherical center, or the first concave mirror and the second concave mirror can be made into a multiple concave mirror assembly with the same spherical center, so that the light beam can be repeatedly reflected and focused between the first concave mirror and the second concave mirror multiple times, thereby further improving the dissociation efficiency.

[0018] As an alternative technical solution, the light beam is incident along the edge of the second concave mirror to the surface of the first concave mirror.

[0019] According to this technical solution, the light beam is incident on the edge of the second concave mirror, which can further increase the number of convergent reflections of the light beam, and can reduce the energy loss when the light beam is incident on the resonator compared to the conventional technology in which the light beam is incident on the resonator via a semi-transparent reflector.

[0020] As an alternative technical solution, the second concave mirror has a through hole, and the light beam passes through the through hole and is incident on the surface of the first concave mirror.

[0021] According to this technical proposal, when a light beam incident from the through hole of the second concave mirror is reflected between the first concave mirror and the second concave mirror, whose two spherical centers are the same or close to each other, the light beam can be reflected back and forth between the reflective surfaces of the first concave mirror and the second concave mirror a certain number of times, and energy consumption when the light beam is incident can be reduced.

[0022] As an alternative technical solution, the light source includes a convex lens, and the focal point of the convex lens is located within the predetermined area.

[0023] According to this technical solution, a parallel light beam emitted from a light source is focused within a predetermined area through a convex lens, and the focused high-energy photons interact with a particle plume within the predetermined area, causing the particles in the particle plume to dissociate.

[0024] As an alternative technical solution, the convex lens is coaxial with the optical axis of the first concave mirror.

[0025] According to this technical solution, the convex lens and the first concave mirror arranged coaxially can ensure that the reflected light beam is accurately focused on a predetermined area, and can simplify the device structure.

[0026] In alternative techniques, the sample particles are ions, neutral particles or a combination of both.

[0027] As an optional technical solution, the desorption device is one or a combination of a laser desorption device, a thermal desorption device, and an ultrasonic desorption device.

[0028] As an alternative technical solution, the desorption apparatus is a matrix-assisted laser desorption apparatus, and the predetermined region is a region through which a particle plume of the matrix-assisted laser desorption apparatus passes and adjacent to a sample electrode plate of the matrix-assisted laser desorption apparatus.

[0029] As an alternative technical solution, the light beam loses less than 10% of its energy each time it interacts with the reflective focusing device.

[0030] According to this technical proposal, for example, by adopting a total reflection concave mirror as a reflecting focusing device, the energy loss that occurs each time the light beam is reflected and focused can be reduced, and the light beam retains high energy even after multiple reflections, allowing the sample particles to be dissociated.

[0031] The present invention further provides another ion generation device comprising: a matrix-assisted laser desorption apparatus having a sample electrode plate; a laser light source; a convex lens installed coaxially with the laser light source and having a focal point located within a predetermined region adjacent to the sample electrode plate through which a particle plume of the matrix-assisted laser desorption apparatus passes; and a first concave mirror installed opposite the laser light source across the predetermined region and having a spherical center located within the predetermined region.

[0032] According to this technical solution, the laser light source of the matrix-assisted laser desorption device emits laser light to the sample on the sample electrode plate, performs a first dissociation on the sample, generates a particle plume after the sample has undergone the first dissociation, and after the particle plume disperses to a predetermined area near the sample electrode plate, the light beam emitted from the light source is focused and irradiated by the convex lens to generate a second dissociation of the particle plume in the predetermined area, and the focused light beam is incident on the surface of the first concave mirror, and is reflected and focused again into the predetermined area to perform a third dissociation on the particle plume in the predetermined area.

[0033] The ion generating device can tertiary dissociate the sample particles with a simple device setting, and can effectively improve the dissociation degree of the sample particles in time and space when the light beam and the sample particles act. Since the light beam emitted from the light source of the ion generating device according to the present invention is focused on a predetermined area, and the reflected light beam is focused on a predetermined area again, when the energy of the light beam is the same, the dissociation degree of the sample particles can be effectively improved and the dissociation efficiency of the ion generating device can be increased.

[0034] As an optional technical solution, the ion generating device further includes a second concave mirror, the second concave mirror and the first concave mirror are installed opposite each other across the specified area, and the spherical center of the second concave mirror is located within the specified area.

[0035] As an optional technical solution, the matrix-assisted laser desorption apparatus further includes a group of reflecting mirrors for changing the deflection angle of the light beam emitted by the laser light source.

[0036] According to this technical proposal, the group of reflecting mirrors can control the position of the light spot on the sample electrode plate by the desorption laser by changing the deflection angle of the light beam, so as to desorb sample particles in multiple predetermined areas near the sample electrode plate, and the position of the light spot can also be controlled to move along the flow direction of the sample plume, which facilitates scanning the sample particles in the predetermined areas more quickly and with less inertia, and eliminates the need to move the sample electrode plate.

[0037] The present invention further provides a mass spectrometer including an ion generating device combining any one or more of the above technical solutions.

[0038] The present invention relates to Desorbing sample particles into a predetermined area; projecting a light beam and focusing the light beam at the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; The method includes a step of repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once by reflecting the light beam that has passed through the predetermined area and focusing the light beam on the predetermined area, and the focusing on the predetermined area occurs once for each reflection of the light beam. A method for generating ions is also provided. [Brief description of the drawings]

[0039] [Figure 1] 1 is a block diagram of an ion generating device according to an embodiment of the present invention. [Diagram 2] 1 is a structural schematic diagram of an ion generating device according to an embodiment of the present invention. [Diagram 3] 6 is a structural schematic diagram of an ion generating device according to another embodiment of the present invention. FIG. [Figure 4] FIG. 4 is a structural schematic diagram of an ion generating device according to another embodiment of the present invention. [Diagram 5] 2 is a flowchart of an ion generation method according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0040] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the following embodiments, and various embodiments can be adopted within the scope of the technical concept of the present invention.

[0041] [term] Unless otherwise specified, the "overlap time of the light beam and the sample particle" means the total overlap time of the light beam and the sample particle. For example, if the overlap time of the first reflected light beam and the sample particle plume when passing through the predetermined region 4 is 0.05 s, and the overlap time of the second reflected light beam and the sample particle plume when passing through the predetermined region 4 is 0.05 s, the "overlap time of the light beam and the sample particle" in the two reflections is 0.05+0.05=0.1 s. The "space where the light beam and the sample particle overlap" means the spatial volume where the light beam and the sample particle overlap. For example, the overlap volume of the first reflected light beam and the predetermined region 4 is n1, the overlap volume of the second reflected light beam and the predetermined region 4 is n2, the space n is the union of n1 and n2, and if the concentration of the sample particle in the predetermined region 4 is c, the overlap volume of the light beam and the sample particle in the two reflections is n*c. "Dissociation" does not specifically refer to the ionization of sample particles, but refers to the process of ionizing, fragmenting, or atomizing sample particles, and the corresponding "degree of dissociation" refers to the proportion of sample particles that are ionized, fragmented, or atomized; the higher the proportion, the higher the degree of dissociation of the sample.

[0042] The present embodiment provides an ion generating device, and Fig. 1 is a block diagram of the ion generating device according to the embodiment of the present invention. As shown in Fig. 1, the ion generating device according to the present invention includes a desorption device 2, a light source 1 and a reflective focusing device 3.

[0043] In this embodiment, by providing a reflection focusing device 3, the light beam that has been focused on and passed through a predetermined region 4 is reflected back to the predetermined region 4 and refocused, thereby repeatedly dissociating the sample particles, and the dissociation efficiency for the sample particles can be effectively improved. In addition, focusing occurs once for each reflection (one reflection and one focusing will be described as an example in this embodiment), and the number of times the laser light is focused on the predetermined region 4 increases by one. Compared to a configuration in which one focusing corresponds to multiple reflections, energy loss due to focusing is reduced, and the dissociation efficiency for the sample particles can be further improved.

[0044] Specifically, in this embodiment, the desorption device 2 desorbs a sample of a substance to be analyzed, and the desorption device 2 may be one or a combination of a laser desorption device, a thermal desorption device, and an ultrasonic desorption device, and is not limited thereto. A particle plume consisting of atoms, neutral particles, ions, or ion fragments generated by sample desorption dissipates in a predetermined region 4. The predetermined region 4 is usually located near the sample, but the particle plume may be guided to a relatively distant predetermined region 4 by another guide device.

[0045] The light beam emitted from the light source 1 contains high-energy photons, such as UV laser light, that can dissociate sample particles, and the light source 1 emits the light beam and focuses the light beam within a predetermined area 4, so that a first dissociation can be performed on the particle plume within the predetermined area 4.

[0046] The reflective focusing device 3 receives the first focused light beam, reflectively focuses the first focused light beam again into a predetermined area 4, and performs a second dissociation on the particle plume within the predetermined area 4.

[0047] In this embodiment, a simple device setting can be used to dissociate the sample particles at least twice, i.e., the focused light beam overlaps with the sample particles and irradiates them at least twice. By increasing the number of irradiations, the time and space for the light beam to overlap with the sample particles can be increased, and the degree of dissociation of the sample particles can be effectively improved. In addition, the ion generator in this embodiment focuses the light beam emitted from the light source 1 on a predetermined area 4, and the reflected light beam is focused on the predetermined area 4 again, thereby improving the density of high-energy photons in the predetermined area 4, improving the degree of dissociation of the sample particles, and improving the dissociation efficiency of the ion generator.

[0048] Fig. 2 is a structural schematic diagram of an ion generating device according to an embodiment of the present invention. The structure shown in Fig. 2 is a more specific preferred structure of an ion generating device according to the present invention. Hereinafter, the ion generating device according to this embodiment will be described in more detail with reference to the drawings.

[0049] 1 and 2, the desorption apparatus 2 in this embodiment may be a matrix-assisted laser desorption apparatus 20, and the predetermined region 4 is a region through which a particle plume of the matrix-assisted laser desorption apparatus 20 passes and adjacent to a sample electrode plate 22 of the matrix-assisted laser desorption apparatus 20. Specifically, the matrix-assisted laser desorption apparatus 20 includes a laser light source 21 and a sample electrode plate 22, a mixed material of a matrix and a sample is placed on the sample electrode plate 22, and the laser light source 21 emits a laser to the sample electrode plate 22. Preferably, the laser emitted by the laser light source 21 is a UV laser.

[0050] In this embodiment, compared to other desorption devices, the matrix-assisted laser desorption device 20 can transmit laser energy to a sample via a matrix, thereby protecting the sample, particularly a biopolymer sample that is difficult to vaporize or is heat-sensitive, and the energy of the laser light is transmitted to the sample via the matrix to dissociate the sample.

[0051] However, because the dissociation process of the matrix-assisted laser desorption apparatus 20 is relatively mild, the particle plume generated by the first dissociation contains a large amount of neutral particles that are not completely dissociated, and these particle plumes usually escape from the sample electrode plate 22 of the matrix-assisted laser desorption apparatus 20 in a direction away from the laser light source 21 of the matrix-assisted laser desorption apparatus 20. Therefore, by providing the predetermined region 4 in a region adjacent to the sample electrode plate 22 (for example, in a structure in which the laser light source 21 is below the sample electrode plate 22 as illustrated in FIG. 2 , the predetermined region 4 is provided near the upper part of the sample electrode plate 22), most of the scattered particle plume is located in the predetermined region 4, the sample particle concentration in the predetermined region 4 is increased, and the space in which the light beam overlaps with the sample particles during secondary dissociation is increased, thereby improving the dissociation efficiency of the ion generator.

[0052] In a preferred embodiment, the matrix-assisted laser desorption apparatus 20 further includes a group of reflecting mirrors (not shown) for changing the deflection angle of the desorption laser light beam. The group of reflecting mirrors may be provided between the laser light source 21 and the sample electrode plate 22 and may be composed of at least two or more reflecting mirrors. Specifically, the laser light beam emitted from the laser light source 21 is reflected by a plurality of reflecting mirrors to form a light spot on the sample electrode plate 22, and at least one of the reflecting mirrors can move or rotate a reflecting surface to control the laser light path so that the reflected light spot can move on the sample electrode plate 22. That is, scanning of sample particles in a predetermined region 4 above the sample electrode plate 22 can be realized without moving the sample electrode plate 22.

[0053] The light source 1 emits a light beam and focuses it on a predetermined region 4, thereby ionizing, fragmenting, or atomizing the sample particles in the predetermined region 4. Specifically, the light source 1 includes a light beam generator 11 and a convex lens 12 installed between the light beam generator 11 and the predetermined region 4, the focal point of the convex lens 12 is located in the predetermined region 4, the parallel light beam emitted from the light beam generator 11 is focused in the predetermined region 4 via the convex lens 12, and the focused high-energy photons overlap with the particle plume in the predetermined region 4, causing the particles in the particle plume to dissociate. Note that the energy of the light beam emitted by the light beam generator 11 here can be adjusted according to the needs of dissociation. For example, when ionizing the sample particles, the light beam may be a UV laser, but when fragmenting the sample particles, the emitted light beam may be adjusted to be a light beam with a higher energy, as necessary.

[0054] The reflective focusing device 3 reflects the light beam emitted from the light source 1 and passing through the predetermined area 4 and focuses it on the predetermined area 4, thereby repeating ionization, fragmentation or atomization of the sample particles in the predetermined area 4 at least once, and the focusing on the predetermined area 4 occurs once each time the light beam is reflected on the surface of the reflective focusing device 3. Specifically, the reflective focusing device 3 may be a concave mirror, and it is preferable that the reflective focusing device 3 is a concave mirror with high reflectivity, since it can reduce the energy loss when the light beam is reflected. For example, if a concave mirror with reflectivity R>99.99% is selected, the energy loss when the light beam interacts with the reflective focusing device 3 is less than 10%, so that the light beam has high energy even after being reflected multiple times, and can dissociate the sample particles.

[0055] 2 illustrates an example in which the reflective focusing device 3 is a first concave mirror 31. As shown in FIG. 2, the first concave mirror 31 and the light source 1 are placed opposite each other with a predetermined area 4 in between, and the spherical center of the first concave mirror 31 is located within the predetermined area 4. By placing the first concave mirror 32 on the other side of the light source 1, it becomes possible to re-reflect and focus the light beam after it has been focused once. In addition, by placing the spherical center position of the first concave mirror 31 within the predetermined area 4, the light beam that has been focused once can be focused again on the predetermined area, improving the overlap time and space between the light beam and the sample particles and increasing the energy of the light beam.

[0056] In particular, the first concave mirror 31 and the light source 1 are placed opposite each other with a predetermined area 4 in between, and the first concave mirror 31 is coaxial with the optical axis of the concave mirror of the light source 1. The convex lens and the first concave mirror arranged coaxially allow the reflected light beam to be accurately refocused on the predetermined area, simplifying the device structure.

[0057] 3 is a structural schematic diagram of a reflective focusing device 3 of an ion generating device according to another embodiment of the present invention. The difference between the ion generating device in FIG. 3 and FIG. 2 is that the reflective focusing device 3 in FIG. 3 includes a first concave mirror 31 and a second concave mirror 32, the first concave mirror 31 and the second concave mirror 32 are installed opposite each other across a predetermined region 4, and the spherical center of the second concave mirror 32 is located within the predetermined region 4. The first concave mirror 31 and the second concave mirror 32 are installed opposite each other across a predetermined region 4, and both spherical centers are installed within the predetermined region 4. As a result, the light beam focused on the predetermined region 4 by the light source 1 is reflected between the first concave mirror 31 and the second concave mirror 32, and the light beam can be focused on the predetermined region 4 again each time it is reflected. As a result, the light beam is focused and reinforced each time, and the focused and reinforced light beam overlaps with the sample particles in the predetermined region 4, and the dissociation efficiency of the ion generating device can be further improved.

[0058] In particular, the light beam emitted from the light source 1 is incident on the surface of the first concave mirror 31 along the edge of the second concave mirror 32, and according to the optical characteristics of the light beam, when the light beam incident from outside the concave mirror is reflected between two concave mirrors with the same or close spherical center, if the reflecting surface of the concave mirror does not change, the larger the incident angle (the angle between the light beam and the optical axis of the concave mirror), the fewer the number of reflections, so it is possible to maximize the number of focused reflections of the light beam by making the light beam incident through the edge of the second concave mirror 32. Also, compared to the conventional technology in which the light beam is incident on the resonator through a semi-transparent reflecting mirror, it is possible to reduce the energy loss when the light beam is incident.

[0059] 4 is a structural schematic diagram of a reflective focusing device 3 according to another embodiment of the present invention. As shown in FIG. 4, the second concave mirror 32 has a through hole 321, and the light beam is incident on the surface of the first concave mirror 31 through the through hole 321.

[0060] In this embodiment, when the light beam incident from the through hole 321 of the second concave mirror 32 is reflected between the first concave mirror 31 and the second concave mirror 32, whose two spherical centers are the same or close to each other, the light beam is not immediately emitted outside the range of the first concave mirror 31 or the second concave mirror 32, but can be reflected back and forth a certain number of times between the reflecting surfaces of the first concave mirror 31 or the second concave mirror 32, thereby maximizing the time and space during which the light beam overlaps with the sample particles. In addition, compared to the conventional incidence method in which the light beam passes through a semi-transmissive reflecting mirror, the energy consumption during incidence of the light beam can be reduced by having the light beam enter from the through hole 321.

[0061] In another embodiment of the present invention, the reflecting surfaces of the first concave mirror 31 and the second concave mirror 32 in FIG. 3 or FIG. 4 may be arcuate surfaces extending around a common spherical center. In another embodiment of the present invention, the first concave mirror 31 and the second concave mirror 32 may be a plurality of concave mirror assemblies having the same spherical center, and the spherical centers of the plurality of concave mirror assemblies may all be configured to be located in the predetermined region 4, thereby increasing the number of reflections of the light beam between the first or second concave mirror 32 and improving the time and space in which the light beam and the sample ions overlap. Based on this, when the area of ​​the reflecting surfaces of the first concave mirror 31 and the second concave mirror 32 is approximately equal to the area of ​​a sphere having the predetermined region 4 as its center, the light beam can be brought into contact with the reflecting surface at any position within the sphere and reflected, maximizing the number of times the light beam overlaps with the sample particles, i.e., increasing the time and space in which the light beam overlaps with the sample particles.

[0062] 5 is a flow chart of an ion generating method according to an embodiment of the present invention. The dissociation process of the ion generating device will be described below with reference to FIGS.

[0063] First, the matrix-assisted laser desorption apparatus 20 of the ion generator executes step S1 of desorbing sample particles into a predetermined region 4. Specifically, the laser source 21 of the matrix-assisted laser desorption apparatus 20 emits laser light to the sample on the sample electrode plate, and a first dissociation is performed on the sample. The sample undergoes the first dissociation to generate a particle plume, and the particle plume disperses into the predetermined region 4 near the sample electrode plate 22.

[0064] Then, the light source 1 of the ion generator executes step S2 of emitting a light beam and focusing it on the predetermined region 4 to ionize, fragment or atomize the sample particles in the predetermined region 4. Specifically, the light beam generator 11 of the light source 1 emits a parallel light beam, which passes through a concave mirror and is focused in the predetermined region 4, overlapping with the sample particles in the predetermined region 4 and dissociating (ionizing, fragmenting or atomizing) the sample particles.

[0065] Finally, step S3 is performed in which the light beam passing through the predetermined area is reflected and focused on the predetermined area 4, thereby repeating ionization, fragmentation or atomization of the sample particles in the predetermined area 4 at least once, and focusing on the predetermined area 4 occurs once each time the light beam is reflected on the surface of the reflective focusing device 3. Specifically, the focused light beam is incident on the surface of a concave mirror and is reflected and focused again into the predetermined area 4 to dissociate the particle plume in the predetermined area 4.

[0066] In this embodiment, the sample particles can be dissociated three times with a simple device design, and the degree of dissociation of the sample particles can be effectively improved by adjusting the time and space in which the light beam overlaps with the sample particles. Since the light beam emitted from the light source 1 of the ion generator according to this embodiment is focused on a predetermined region 4, and the reflected light beam is focused on the predetermined region 4 again, when the energy of the light beam is the same, the energy of the high-energy photons irradiated on the sample particles in the predetermined region 4 can be effectively increased, improving the degree of dissociation of the sample particles and thus improving the dissociation efficiency of the ion generator.

[0067] In addition, since the dissociation of sample particles by the matrix-assisted laser desorption apparatus 20 is relatively mild and the particle plume generated by the first dissociation contains a large amount of neutral particles, the ratio of effective particles in the particle plume can be effectively increased by performing secondary dissociation on the particle plume dissociated by the matrix-assisted laser desorption apparatus 20, thereby improving the dissociation efficiency of the entire ion generating apparatus. Note that the matrix-assisted laser desorption apparatus 20 is often applied to substances that are difficult to vaporize or are sensitive to heat, such as biological samples, and such substances are difficult to vaporize and generate particles, so that the degree of dissociation is quite high. Therefore, the ion generating apparatus according to this embodiment first performs the first dissociation on the sample by the mild matrix-assisted laser desorption apparatus 20, and then performs secondary dissociation on the particle plume generated by the first dissociation, thereby generating sample particles without vaporizing the sample, and by improving the degree of dissociation of the sample by multiple dissociations of the sample particles, it becomes easier to perform composition analysis on such substances by a material analyzing apparatus.

[0068] Depending on the actual application scene, the substance detection device to which the ion generating device of the present invention is applied may include or replace various mass analyzers, ion mobility spectrometers, chromatographs, spectrometers, and electrochemical analyzers.

[0069] In another embodiment of the present invention, there is further provided a mass spectrometer including an ion generator according to any of the above embodiments, and capable of analyzing ions, ion fragments, or atoms obtained by dissociation of the ion generator.

[0070] Although the technical solutions of the present invention have been described above with reference to the drawings, it is obvious to those skilled in the art that the protection scope of the present invention is not limited to these specific embodiments. On the premise that it does not deviate from the principle of the present invention, those skilled in the art may make equivalent modifications or replacements to the technical features, and all of the technical solutions after such modifications or replacements fall within the protection scope of the present invention. [Explanation of symbols]

[0071] 1-light source; 11-light beam generator; 12-convex lens; 2-desorption device; 20-matrix assisted laser desorption device; 21-laser light source; 22-sample electrode plate; 3-reflective focusing device; 31-first concave mirror; 32-second concave mirror; 321-through hole; 4-predetermined area

Claims

1. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; an ion generating device characterized in that focusing onto the specified area occurs once each time the light beam is reflected off the surface of the first concave mirror, and focusing onto the specified area occurs once each time the light beam is reflected off the surface of the second concave mirror.

2. 2. The ion generating device according to claim 1, wherein the light beam is reflected and focused onto the predetermined area multiple times between the first concave mirror and the second concave mirror.

3. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light beam is reflected and focused multiple times between the first concave mirror and the second concave mirror onto the predetermined area; An ion generating device, wherein the light beam is incident along an edge of the second concave mirror to a surface of the first concave mirror.

4. 3. The ion generating device according to claim 2, wherein the second concave mirror has a through hole, and the light beam passes through the through hole and reaches the surface of the first concave mirror.

5. 2. The ion generating device according to claim 1, wherein the light source includes a convex lens, and a focal point of the convex lens is located within the predetermined area.

6. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; The ion generating device, wherein the light source includes a convex lens, and a focal point of the convex lens is located within the predetermined area.

7. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light beam is reflected and focused multiple times between the first concave mirror and the second concave mirror onto the predetermined area; The ion generating device, wherein the light source includes a convex lens, and a focal point of the convex lens is located within the predetermined area.

8. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light beam is reflected and focused multiple times between the first concave mirror and the second concave mirror onto the predetermined area; the light beam is incident along an edge of the second concave mirror to a surface of the first concave mirror; The ion generating device, wherein the light source includes a convex lens, and a focal point of the convex lens is located within the predetermined area.

9. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light beam is reflected and focused multiple times between the first concave mirror and the second concave mirror onto the predetermined area; the light beam is incident along an edge of the second concave mirror to a surface of the first concave mirror; the second concave mirror has a through hole, the light beam passes through the through hole and reaches a surface of the first concave mirror; The ion generating device, wherein the light source includes a convex lens, and a focal point of the convex lens is located within the predetermined area.

10. 6. The ion generating device according to claim 5, wherein the convex lens is coaxial with the optical axis of the first concave mirror.

11. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light source includes a convex lens, the focal point of the convex lens being located within the predetermined area; The ion generating device, wherein the convex lens is coaxial with the optical axis of the first concave mirror.

12. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light beam is reflected and focused multiple times between the first concave mirror and the second concave mirror onto the predetermined area; the light source includes a convex lens, the focal point of the convex lens being located within the predetermined area; The ion generating device, wherein the convex lens is coaxial with the optical axis of the first concave mirror.

13. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light beam is reflected and focused multiple times between the first concave mirror and the second concave mirror onto the predetermined area; the light beam is incident along an edge of the second concave mirror to a surface of the first concave mirror; the light source includes a convex lens, the focal point of the convex lens being located within the predetermined area; The ion generating device, wherein the convex lens is coaxial with the optical axis of the first concave mirror.

14. A desorption device for desorbing sample particles into a predetermined area; a light source for emitting a light beam and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a reflecting and focusing device that reflects and focuses the light beam emitted from the light source and passing through the predetermined area onto the predetermined area, thereby repeating ionization, fragmentation, or atomization of the sample particles in the predetermined area at least once; the reflective focusing device includes a first concave mirror and a second concave mirror; the first concave mirror and the light source are disposed opposite to each other across the predetermined area, and a spherical center of the first concave mirror is located within the predetermined area; the first concave mirror and the second concave mirror are disposed opposite to each other with the predetermined area interposed therebetween, and a spherical center of the second concave mirror is located within the predetermined area; focusing onto the predetermined area occurs correspondingly once each time the light beam reflects off a surface of the reflective focusing device; the light beam is reflected and focused multiple times between the first concave mirror and the second concave mirror onto the predetermined area; the light beam is incident along an edge of the second concave mirror to a surface of the first concave mirror; the second concave mirror has a through hole, the light beam passes through the through hole and reaches a surface of the first concave mirror; the light source includes a convex lens, the focal point of the convex lens being located within the predetermined area; The ion generating device, wherein the convex lens is coaxial with the optical axis of the first concave mirror.

15. 2. The ion generating device according to claim 1, wherein the sample particles are ions, neutral particles or a combination of both.

16. 2. The ion generating apparatus according to claim 1, wherein the desorption device is one or a combination of a laser desorption device, a thermal desorption device, and an ultrasonic desorption device.

17. 17. The ion generating apparatus according to claim 16, wherein the desorption apparatus is a matrix-assisted laser desorption apparatus, and the predetermined region is a region through which a particle plume of the matrix-assisted laser desorption apparatus passes and adjacent to a sample electrode plate of the matrix-assisted laser desorption apparatus.

18. 2. The ion generating device of claim 1, wherein the light beam loses less than 10% of its energy each time it interacts with the reflective focusing device.

19. a matrix-assisted laser desorption apparatus having a sample electrode plate; A laser light source; a convex lens disposed coaxially with the laser light source and having a focal point located within a predetermined area adjacent to the sample electrode plate and through which the particle plume of the matrix-assisted laser desorption apparatus passes; a first concave mirror disposed opposite the laser light source across the predetermined area, the first concave mirror having a spherical center located within the predetermined area; an ion generating device comprising: a second concave mirror disposed opposite the first concave mirror with the specified area interposed therebetween, the second concave mirror having a spherical center located within the specified area.

20. The ion generating apparatus according to claim 19, wherein the matrix-assisted laser desorption apparatus further includes a group of reflecting mirrors for changing a deflection angle of the light beam emitted by the laser light source.

21. A mass spectrometer comprising the ion generating device according to any one of claims 1 to 20.

22. Desorbing sample particles into a predetermined area; emitting a light beam from a light source and focusing the light beam on the predetermined area to ionize, fragment or atomize the sample particles in the predetermined area; a step of repeating ionization, fragmentation or atomization of the sample particles in the predetermined area at least once by using a first concave mirror that is installed opposite the light source across the predetermined area and a second concave mirror that is installed opposite the first concave mirror across the predetermined area and has a spherical center located within the predetermined area, reflecting the light beam that has passed through the predetermined area and focusing it on the predetermined area, wherein focusing on the predetermined area occurs once correspondingly each time the light beam is reflected off the surface of the first concave mirror, and focusing on the predetermined area occurs once correspondingly each time the light beam is reflected off the surface of the second concave mirror.

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