Mass spectrum ionization source for high-throughput detection based on inert protection and use method

Abstract

The invention relates to a mass spectrum ionization source for high-flux detection based on inert protection and a use method, the mass spectrum ionization source comprises a closed inert gas protection ionization source, the sample introduction end of the closed inert gas protection ionization source is provided with an ionization source top sealing gate valve; the closed inert gas shielding ionization source is provided with a spatial position adjusting device, so that the detection end of the closed inert gas shielding ionization source can be connected with a mass spectrum detector in a detection state; the bottom of the closed inert gas protection ionization source is connected with an ionization source bottom end storage sample piece for storing the detected array probe assembly, and the closed inert gas protection ionization source has a sealed working state and an opened sample loading state for transferring a sample to be detected; a metal electrode for completing ionization of a sample to be detected is arranged at one end, close to the mass spectrum detector, of the closed inert gas shielding ionization source.

Description

Technical Field

[0001] The present invention relates to the technical field of electrospray ionization, and in particular to a mass spectrometry ionization source for high-throughput detection based on inert protection and a method for using the same. Background Art

[0002] Organic mass spectrometry is an analytical method widely used in the field of life science research. Electrospray ionization is a common ionization method for organic mass spectrometers. For mass spectrometry analysis, the core lies in the ionization source of ionization. Prior art, such as CN201410198671.3, non-contact DC induction electrospray ionization device and ionization method, adopts non-contact DC induction electrospray ionization device and ionization method. It includes an electrode, a high-voltage DC power supply and a nanoliter electrospray nozzle. The axis of the nanoliter electrospray nozzle and the long straight wire electrode are in the same straight line, and the nozzle is located between the electrode and the mass spectrometer injection port. The patent provides an ionization structure, in which the ionization of the compound is achieved by an external electric field, and the position movement of the sample is achieved by using a multi-dimensional adjustment structure. CN201610753809.0, a high-throughput nanoliter electrospray analysis system based on a micro-array and its application, discloses a high-throughput nanoliter electrospray mass spectrometry analysis device based on a micro-funnel-shaped sample carrier array and its application. The invention comprises: an electrospray device, a mass spectrometer, a funnel-shaped micro-sample carrier, and a bracket, wherein a funnel-shaped micro-sample carrier is arranged between the capillary tip of the electrospray and the injection port of the mass spectrometer, and the funnel-shaped micro-sample carrier is located on the bracket. The patent is characterized in that an array-type ionization source is used, and its advantage is that a variety of different samples can be detected at one time.

[0003] The prior art can realize the alignment of the ionization capillary with the mass spectrometer injection port, but lacks a closed cavity structure to protect the position of the injection probe. In addition, continuous ionization of the sample cannot be realized. Summary of the invention

[0004] According to the technical problems raised above, a mass spectrometry ionization source for high-throughput detection based on inert protection and a method for using the same are provided.

[0005] The technical means adopted by the present invention are as follows:

[0006] A mass spectrometry ionization source for high-throughput detection based on inert protection comprises a sealed inert gas protection ionization source, wherein the sampling end of the sealed inert gas protection ionization source is provided with an ionization source top sealing plug valve, the sealed inert gas protection ionization source is provided with a spatial position adjustment device, so that the detection end of the sealed inert gas protection ionization source can be connected to a mass spectrometry detector in a detection state, the bottom of the sealed inert gas protection ionization source is connected with an ionization source bottom storage sample piece for storing a detected array probe assembly, the sealed inert gas protection ionization source has a sealed working state and an open sample loading state for transferring a sample to be tested, in the sealed working state, the cavity of the sealed inert gas protection ionization source is in a protective gas atmosphere throughout the whole process, and a metal electrode for completing the ionization of the sample to be tested is provided at one end of the sealed inert gas protection ionization source close to the mass spectrometry detector.

[0007] Furthermore, the sealing gate valve at the top of the ionization source can be docked with the sealing gate valve of the transfer chamber of the micro-sample transfer device, thereby completing the transfer of the sample to be tested between the micro-sample transfer device and the closed inert gas protection ionization source.

[0008] Furthermore, the array probe assembly includes an array probe lower end support base, an array probe upper end fixed cover plate and an array probe fixing screw. The upper surface of the array probe lower end support base is uniformly provided with a plurality of grooves parallel to its width direction along its length direction, and each groove forms a linear array arranged at equal intervals. The groove of the array probe lower end support base is a complete groove capable of accommodating sampling and ionization detection probes, or a groove matching the array probe lower end support base is provided on the bottom surface of the array probe upper end fixed cover plate, and the bottom surface groove of the array probe upper end fixed cover plate and the groove of the array probe lower end support base form a complete groove capable of accommodating sampling and ionization detection probes; the spacing A screw hole is provided on the lower end support base of the array probe at a preset distance away from the preset groove, and a screw hole matching the screw hole of the lower end support base of the array probe is also provided on the upper end fixing cover plate of the array probe, and the upper end fixing cover plate of the array probe and the lower end support base of the array probe are detachably connected by the array probe fixing screws; a protruding step structure is provided at the bottom of the lower end support base of the array probe of the array probe assembly, and the array probe assembly is introduced into the sample adapter assembly to be tested based on the step structure, and the array probe assembly clamping device specifically includes a spring-type pressing piece of the adapter assembly provided at one end of the sample adapter assembly to be tested, and the array probe assembly is clamped by the spring-type pressing piece of the adapter assembly.

[0009] Furthermore, the micro-sample transfer device includes an array probe storage cavity, a transfer cavity sealing gate valve, an array probe assembly, a self-locking rotary sampling head and a self-locking rotary sampling head position adjustment mechanism. The array probe storage cavity is filled with a preset protective gas. The transfer cavity sealing gate valve is installed at the end of the array probe storage cavity. The other end of the array probe storage cavity is installed with the self-locking rotary sampling head position adjustment mechanism. The self-locking rotary sampling head is arranged inside the array probe storage cavity, and the distance of its output end relative to the transfer sealing gate valve can be adjusted by the self-locking rotary sampling head position adjustment mechanism. The output end of the self-locking rotary sampling head can be detachably connected to the array probe assembly. After the gate valve and the transfer sealing gate valve are docked, the array probe assembly is in an atmosphere of protective gas throughout the entire process.

[0010] Furthermore, the self-locking rotary sampling head position adjustment mechanism is a multi-layer nested structure, including a self-locking rotary sampling head storage cavity and a coarse position adjustment device, a linear telescopic fine adjustment component, the end of the array probe storage cavity is connected to one end of the self-locking rotary sampling head storage cavity, the linear telescopic fine adjustment component is installed at one end of the self-locking rotary sampling head storage cavity close to the array probe storage cavity, the self-locking rotary sampling head is connected to the output end of the magnetic internal connecting rod, the self-locking rotary sampling head storage cavity is specifically a magnetic support outer bracket, the coarse position adjustment device includes a magnetic external drive component, the magnetic external drive component is sleeved on the outer wall of the magnetic support outer bracket, the magnetic external drive component can slide linearly on the magnetic support outer bracket, and synchronously drive the linear sliding of the internal magnetic rod.

[0011] Furthermore, the spatial position adjustment device includes an upper flange, a lower flange, and an X-direction fine-tuning screw respectively arranged on the upper flange and a Y-direction fine-tuning screw arranged on the lower flange, the X-direction fine-tuning screw and the Y-direction fine-tuning screw are arranged vertically in space, the lower flange is installed on the upper plate of the closed inert gas shielded ionization source, and the upper flange and the lower flange are connected by a bellows.

[0012] Furthermore, the main body of the closed inert gas protection ionization source is a rectangular metal support, one side of which cooperates with the mass spectrometer detector, and a visible non-metallic lens is installed on the left side sealing panel of the ionization source and the right side sealing panel of the ionization source for sealing, and an ionization source positive side sealing panel is arranged on the side facing the ionization source injection port position, and a non-metallic transparent panel is installed on the ionization source positive side sealing panel.

[0013] Furthermore, two clamps are placed on both sides of the injection port of the mass spectrometer detector, both of which are used to place the locking shaft of the injection port of the ionization source mass spectrometer; after the mass spectrometer detector cavity is placed at a specific position of the injection port of the ionization source, the assembly of the two is completed by locking the shaft and the clamp, and a sealing device is provided at the locking position of the two;

[0014] A filling hole for inert gas and an extraction port for gas inside the cavity are arranged on the main body of the closed inert gas protection ionization source, and the extraction port is connected to a connection port of an exhaust pump.

[0015] Furthermore, the base of the metal electrode is movable in at least one-dimensional plane, the base is a non-metallic electrode support, the input end of the metal electrode is connected to the high-voltage input end of the external ionization source through an electrode connecting metal conductive member, the connecting wire connecting the metal electrode to the high-voltage input end of the ionization source is provided with a through-plate electrode at the connection with the main body sealing plate of the closed inert gas protection ionization source, the through-plate electrode is a through-plate metal electrode straight-through rod, and the through-plate metal electrode straight-through rod is connected to the sealing plate through the through-plate electrode radial sealing O-ring and the through-plate electrode axial sealing O-ring,

[0016] The device capable of completing movement in a one-dimensional plane specifically includes an electrode support connecting sliding member connected to the bottom of a non-metallic electrode support member, the electrode support connecting sliding member can move on a fixed slide rail arranged below it, the input end of the electrode support connecting sliding member is connected to a screw rotating head advancing member, the screw rotating head advancing member is provided with an identification device with scale markings, the screw rotating head advancing member is connected to the main sealing plate of a closed inert gas shielded ionization source through a screw head external support member, and a screw advancement radial sealing O-ring is provided at the sealing position.

[0017] The present invention also discloses a method for using the mass spectrometry ionization source for high-throughput detection based on inert protection, comprising the following steps:

[0018] The closed inert gas protection ionization source is set to an inert gas protection gas atmosphere in advance;

[0019] The array probe assembly storing the sample to be tested is placed on the micro-sample transfer device, and the bottom of the micro-sample transfer device is connected to the sealing plug valve at the top of the ionization source;

[0020] Open the plug valve of the micro-sample transfer device and the sealing plug valve at the top of the ionization source. Before and after the valves are opened, the insides of the two chambers are in an inert gas protection atmosphere;

[0021] The height of the array probe assembly is adjusted by the locking rotary sampling head position adjustment mechanism. At this time, the probe should be at the upper end of the mass spectrometer injection port. The two-dimensional adjustment member is used to ensure that the lowermost probe is at the center of the mass spectrometer injection port. The height is further lowered to ensure that the lowermost probe is coaxial with the mass spectrometer injection port.

[0022] The metal electrode is gradually moved forward by adjusting the screw to rotate the top advance member, and has a preset spatial distance with the lowest probe. At this time, the high-voltage switch is turned on to start the high-voltage input end of the high-voltage ionization source; then the probe is gradually moved closer to the mass spectrometer injection port, and the distance between the probe and the mass spectrometer injection port is gradually increased according to the strength of the generated ion flow, and the distance is maintained between 1-3mm. When the detection is completed, the voltage is turned off, and the metal electrode is moved back a distance away from the probe;

[0023] By adjusting the linear telescopic precision adjustment assembly, the probes are lowered one by one in sequence to complete the ionization of all subsequent probes. During this process, the metal electrode moves repeatedly and does not hinder the gradual descent of the array probe assembly in a non-ionized state.

[0024] After completing all sample inspections, the precision adjustment component is raised by rotating the linear telescopic component in the opposite direction, and the height is restored to the initial position, and then restored to the initial position by the magnetic external drive component.

[0025] Compared with the prior art, the present invention has the following advantages: by setting up a vacuum and inflation device, the present invention can achieve seamless switching of the protective gas atmosphere when the sample enters the device and the sample is in the patented process. After one gas replacement, more than dozens of samples can be detected. By realizing one gas replacement in the transfer chamber, multiple samples can be detected, thereby ensuring the detection accuracy and efficiency of the samples. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0027] Figure 1 The figure is a schematic diagram of the overall assembly of the mass spectrometry ionization source for high-throughput detection based on inert protection of the present invention.

[0028] Figure 2 This is a schematic diagram of the state in which the external plug-in valve ionization source and the micro-sample transfer chamber of the present invention are not connected.

[0029] Figure 3 It is an isometric view of the micro-sample transfer chamber of the present invention.

[0030] Figure 4 It is an isometric view of the structure of the closed inert gas protection ionization source of the present invention.

[0031] Figure 5 This is a macroscopic view of the sealed inert gas protection ionization source of the present invention assembled on a mass spectrometer detector.

[0032] Figure 6 This is an observation view of the sealed inert gas protection ionization source of the present invention assembled on the right side of the mass spectrometer detector.

[0033] Figure 7 This is an observation view of the closed inert gas protection ionization source of the present invention assembled on the left side of the mass spectrometer detector.

[0034] Figure 8 This is an enlarged view of the sealed inert gas protection ionization source of the present invention assembled on the left side of the mass spectrometer detector.

[0035] Fig. 9 Schematic diagram of the internal structure of the micro-sample transfer chamber of the present invention.

[0036] Fig.10 This is the explosion diagram of the closed inert gas protection ionization source of the present invention - observed from the right side.

[0037] Fig.11 This is the explosion diagram of the closed inert gas protection ionization source of the present invention - observed from the left side.

[0038] Fig.12 This is the exploded view of the closed inert gas protection ionization source of the present invention - isometric side.

[0039] Fig.13 This is an exploded view of the structure of the core cavity component of the ionization source of the present invention.

[0040] Fig.14 It is an exploded view of the structure of the ionization source contact position moving component of the present invention.

[0041] Fig.15 This is a front view of the sealed inert gas shielded ionization source of the present invention, wherein the sensing electrode is close to the probe position.

[0042] Fig.16 It is a front view of the sealed inert gas shielded ionization source of the present invention, wherein the sensing electrode is far away from the probe position.

[0043] Fig.17 The micro-sample transfer chamber of the present invention is placed in the initial position on the top of the ionization source - overall style diagram.

[0044] Fig.18 This is a partial enlarged view of the micro-sample transfer chamber of the present invention placed at the initial position on the top of the ionization source.

[0045] Fig.19 This is the initial position of the micro-sample transfer chamber of the present invention placed at the top of the ionization source - an enlarged view of the interior of the ionization source.

[0046] Fig. 20 This is the overall pattern diagram of the internal array probe assembly of the micro-sample transfer chamber of the present invention moving downward to the first probe at the mass spectrometer injection port.

[0047] Fig.21 This is a partial enlarged view of the internal array probe assembly of the micro-sample transfer chamber of the present invention moving downward to the first probe at the mass spectrometer injection port.

[0048] Fig. 22 This is an enlarged view of the interior of the ionization source where the array probe assembly inside the micro-sample transfer chamber of the present invention moves downward to the first probe at the mass spectrometer injection port.

[0049] Fig.23 This is an overall pattern diagram of the internal array probe assembly of the micro-sample transfer chamber of the present invention moving downward to the middle position.

[0050] Fig.24 This is a partial enlarged view of the array probe assembly inside the micro-sample transfer chamber of the present invention moving downward to the middle position.

[0051] Fig.25 This is an enlarged view of the interior of the ionization source when the array probe assembly inside the micro-sample transfer chamber of the present invention moves downward to the middle position.

[0052] Fig.26 This is an overall pattern diagram of the internal array probe assembly of the micro-sample transfer chamber of the present invention moving downward to the last probe at the mass spectrometer injection port.

[0053] Fig. 27 This is a partial enlarged view of the internal array probe assembly of the micro-sample transfer chamber of the present invention moving downward to the last probe at the mass spectrometer injection port.

[0054] Fig.28 This is an enlarged view of the interior of the array probe assembly in the micro-sample transfer chamber of the present invention, which moves downward to the last probe at the mass spectrometer injection port - the ionization source.

[0055] Fig.29 It is a schematic diagram of the structure of the array probe assembly of the present invention.

[0056] In the figure: 001: micro-sample transfer chamber; 002: closed inert gas protection ionization source; 003: ionization source top sealing plug valve; 004: closed two-dimensional XY direction adjustment device; 005: metal support; 006: ionization source bottom storage sample piece; 007: mass spectrometer detector; 008: mass spectrometer injection port; 101: array probe assembly; 103: linear telescopic precision adjustment assembly; 104: magnetic support link rod; 105: magnetic external drive assembly; 107: array probe storage chamber; 108: transfer chamber sealing plug valve; 109: self-locking rotary sampling head and connecting rod; 201: inert gas inlet; 202: vacuum pump connection port; 203: ionization source front sealing panel; 204: ionization source upper plate; 205: ionization source The rotating shaft is locked with the mass spectrometer injection port; 206: the ionization source contact electrode position moving component; 207: the sealing panel on the left side of the ionization source; 208: the sealing panel on the right side of the ionization source; 301: the metal electrode; 302: the non-metallic electrode support; 303: the electrode connection metal conductive part; 304: the electrode support connection sliding part; 305: the fixed slide rail; 306: the screw rotating head advancing part; 307: the external scale nut part; 308: the screw head external support part; 309: the screw advancing radial sealing O-ring; 401: the through-plate electrode sealing part; 402: the through-plate electrode axial sealing O-ring; 403: the through-plate metal electrode straight rod; 404: the through-plate electrode radial sealing O-ring; 405: the ionization source high voltage input end; 406: the through-plate electrode and the metal electrode connecting wire. DETAILED DESCRIPTION

[0057] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0058] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. The following description of at least one exemplary embodiment is actually only illustrative and is by no means intended to limit the present invention and its application or use. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0059] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is also intended to include the plural form. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, it indicates the presence of features, steps, operations, devices, components and / or combinations thereof.

[0060] Unless otherwise specifically stated, the relative arrangement of the parts and steps described in these embodiments, the numerical expressions and numerical values ​​do not limit the scope of the present invention. At the same time, it should be clear that, for ease of description, the sizes of the various parts shown in the drawings are not drawn according to the actual proportional relationship. The technology, methods and equipment known to ordinary technicians in the relevant field may not be discussed in detail, but in appropriate cases, the technology, methods and equipment should be regarded as part of the authorization specification. In all examples shown and discussed here, any specific value should be interpreted as merely exemplary, rather than as a limitation. Therefore, other examples of exemplary embodiments may have different values. It should be noted that similar numbers and letters represent similar items in the following drawings, so once an item is defined in one drawing, it does not need to be further discussed in subsequent drawings.

[0061] In the description of the present invention, it is necessary to understand that the directions or positional relationships indicated by directional words such as "front, back, up, down, left, right", "lateral, vertical, perpendicular, horizontal" and "top, bottom" are usually based on the directions or positional relationships shown in the drawings. They are only for the convenience of describing the present invention and simplifying the description. Unless otherwise specified, these directional words do not indicate or imply that the device or element referred to must have a specific direction or be constructed and operated in a specific direction. Therefore, they cannot be understood as limiting the scope of protection of the present invention: the directional words "inside and outside" refer to the inside and outside relative to the contours of each component itself.

[0062] For ease of description, spatially relative terms such as "above", "above", "on the upper surface of", "above", etc. may be used here to describe the spatial positional relationship between a device or feature and other devices or features as shown in the figure. It should be understood that spatially relative terms are intended to include different orientations of the device in use or operation in addition to the orientation described in the figure. For example, if the device in the accompanying drawings is inverted, the device described as "above other devices or structures" or "above other devices or structures" will be positioned as "below other devices or structures" or "below their position devices or structures". Thus, the exemplary term "above" can include both "above" and "below". The device can also be positioned in other different ways (rotated 90 degrees or in other orientations), and the spatially relative descriptions used here are interpreted accordingly.

[0063] In addition, it should be noted that the use of terms such as "first" and "second" to limit components is only for the convenience of distinguishing the corresponding components. If not otherwise stated, the above terms have no special meaning and therefore cannot be understood as limiting the scope of protection of the present invention.

[0064] like Figures 1 to 29 As shown, the embodiment of the present invention discloses a mass spectrometry ionization source for high-throughput detection based on inert protection, including a closed inert gas protection ionization source 002, the injection end of the closed inert gas protection ionization source 002 is provided with an ionization source top sealing plug valve 003, the closed inert gas protection ionization source 002 is provided with a spatial position adjustment device, so that in the detection state, the detection end of the closed inert gas protection ionization source 002 can be connected to the mass spectrometry detector 007, the closed inert gas protection ionization source 002 is connected to the mass spectrometry detector 007, and the closed inert gas protection ionization source 002 is connected to the mass spectrometry detector 007. The bottom of the ionization source 002 is connected to an ionization source bottom storage sample piece 006 for storing the detected array probe assembly 101. The sealed inert gas protection ionization source 002 has a sealed working state and an open loading state for transferring the sample to be tested. In the sealed working state, the cavity of the sealed inert gas protection ionization source 002 is in a protective gas atmosphere throughout the process. The sealed inert gas protection ionization source 002 is provided with a metal electrode 301 for completing the ionization of the sample to be tested at one end close to the mass spectrometer detector 007. The present invention can realize the ability of batch detection. During the sampling process, the ionization needles are lowered one by one from the top to realize one-time sampling without repeatedly replacing the chamber gas, thereby realizing high-throughput detection of samples.

[0065] Furthermore, the sealing gate valve 003 at the top of the ionization source can be docked with the sealing gate valve 108 of the transfer chamber of the micro-sample transfer device 001, thereby completing the transfer of the sample to be tested between the micro-sample transfer device 001 and the closed inert gas protection ionization source 002.

[0066] Further, the array probe assembly 101 includes an array probe lower end support base 503, an array probe upper end fixed cover plate 502 and an array probe fixing screw 501, the upper surface of the array probe lower end support base 503 is uniformly provided with a plurality of grooves parallel to its width direction along its length direction, and each groove forms a linear array arranged at equal intervals, the groove of the array probe lower end support base 503 is a complete groove capable of accommodating the sampling and ionization detection probe 504, or a groove matching the array probe lower end support base 503 is provided on the bottom surface of the array probe upper end fixed cover plate 502, and the bottom surface groove of the array probe upper end fixed cover plate 502 and the groove of the array probe lower end support base 503 form a complete groove capable of accommodating the sampling and ionization detection probe 504; Screw holes are provided on the array probe lower end support base 503 which is separated from the preset grooves by a preset distance. Screw holes matching the screw holes of the array probe lower end support base 503 are also provided on the array probe upper end fixed cover plate 502. The array probe upper end fixed cover plate 502 and the array probe lower end support base 503 are detachably connected by the array probe fixing screws 501. A protruding step structure is provided at the bottom of the array probe lower end support base 503 of the array probe assembly 101. Based on the step structure, the array probe assembly 101 is introduced into the sample adapter assembly to be tested. The array probe assembly 101 clamping device specifically includes a spring-type pressing piece of the adapter assembly provided at one end of the sample adapter assembly to be tested, and the array probe assembly 101 is clamped by the spring-type pressing piece of the adapter assembly.

[0067] Furthermore, the micro-sample transfer device 001 includes an array probe storage cavity 107, a transfer cavity sealing gate valve 108, an array probe assembly 101, a self-locking rotary sampling head 109 and a self-locking rotary sampling head position adjustment mechanism. The array probe storage cavity 107 is filled with a preset protective gas, the transfer cavity sealing gate valve 108 is installed at the end of the array probe storage cavity 107, and the other end of the array probe storage cavity 107 is installed with the self-locking rotary sampling head position adjustment mechanism. The self-locking rotary sampling head 109 is arranged inside the array probe storage cavity 107, and the distance of its output end relative to the transfer sealing gate valve can be adjusted by the self-locking rotary sampling head position adjustment mechanism. The output end of the self-locking rotary sampling head 109 can be detachably connected to the array probe assembly 101. After the gate valve and the transfer sealing gate valve are docked, the array probe assembly 101 is in an atmosphere of protective gas throughout the entire process.

[0068] Furthermore, the self-locking rotary sampling head position adjustment mechanism is a multi-layer nested structure, including a self-locking rotary sampling head storage cavity and a position coarse adjustment device, a linear telescopic fine adjustment component 103, the end of the array probe storage cavity 107 is connected to one end of the self-locking rotary sampling head storage cavity, the linear telescopic fine adjustment component 103 is installed at one end of the self-locking rotary sampling head storage cavity close to the array probe storage cavity 107, the self-locking rotary sampling head 109 is connected to the output end of the magnetic internal connecting rod 104, the self-locking rotary sampling head storage cavity is specifically a magnetic support outer bracket, the position coarse adjustment device includes a magnetic external drive component 105, the magnetic external drive component 105 is sleeved on the outer wall of the magnetic support outer bracket, the magnetic external drive component 105 can slide linearly on the magnetic support outer bracket, and synchronously drive the linear sliding of the internal magnetic rod.

[0069] Further, the spatial position adjustment device includes an upper flange, a lower flange and a closed two-dimensional XY direction adjustment device 004, the closed two-dimensional XY direction adjustment device includes an X-direction fine-tuning screw respectively arranged on the upper flange and a Y-direction fine-tuning screw arranged on the lower flange, the X-direction fine-tuning screw and the Y-direction fine-tuning screw are arranged in a spatial vertical manner, the lower flange is installed on the upper plate 204 of the closed inert gas protection ionization source, and the upper flange and the lower flange are connected by a bellows. Through the upper and lower flanges, the middle bellows is connected, and a small range adjustment in the XY plane is achieved, and the conditional distance setting can be within the range of ±10mm (the same adjustment range in the X direction and the Y direction). During the adjustment process, the upper flange drives the bellows to move a certain distance, and the main adjustment part does not touch the bellows to achieve interference of parts, and ensures the sealed connection between the upper and lower flanges and the bellows during use. Specifically, by moving the fine-tuning screw back and forth, the top flange is moved in the direction of one dimension.

[0070] The main body of the enclosed inert gas protection ionization source 002 is a rectangular metal support 005, one side of which cooperates with the mass spectrometer detector 007, the ionization source left sealing panel 207, and the ionization source right sealing panel 208 are equipped with a visible non-metallic lens for sealing, and the side facing the ionization source injection port position is provided with an ionization source positive side sealing panel 203, and the ionization source positive side sealing panel is equipped with a non-metallic transparent panel. In the connection process with the mass spectrum, the two adopt the O-ring seal at the mass spectrometer injection port position. When the ionization source top sealing plug valve 003 is closed, the sealing of the cavity can be achieved.

[0071] Two clamps are placed on both sides of the injection port of the mass spectrometer detector 007, both of which are used to place the locking shaft 205 of the ionization source mass spectrometer injection port; after the mass spectrometer detector 007 cavity is placed at a specific position of the injection port of the ionization source, the assembly of the two is completed by locking the shaft and the clamp, and a sealing device is provided at the locking position of the two; the locking shaft has two functions, namely positioning and locking cooperation. When the mass spectrometer cavity is placed at a specific position of the injection port of the ionization source, the shaft can be rotated to a certain angle, and when it is rotated to a specific clamping position, the ionization source core cavity is assembled to the injection port front end of the mass spectrometer cavity. At this time, after rotating a certain angle again, the injection port locking shaft can be reliably matched to the mass spectrum, ensuring that the entire closed inert gas protection ionization source will not fall. This design is easy to install and disassemble, but after each installation, the ionization source cavity must be gas circulated once.

[0072] During use of the ionization source, the sealing of the core cavity needs to be ensured. For this purpose, an inert gas inlet 201 and an extraction port for the gas inside the cavity are provided on the main body of the closed inert gas protection ionization source 002, and the extraction port is connected to the vacuum pump connection port 202.

[0073] The base of the metal electrode 301 is movable in at least one-dimensional plane, and the base is a non-metallic electrode support 302. The input end of the metal electrode 301 is connected to the external ionization source high-voltage input end 405 through the electrode connecting metal conductive member 303. The connecting wire 406 connecting the metal electrode 301 to the ionization source high-voltage input end 405 is provided with a through-plate electrode at the connection with the main sealing plate of the closed inert gas protection ionization source 002. The through-plate electrode includes a through-plate metal electrode straight-through rod 403. The through-plate metal electrode straight-through rod 403 is connected to the sealing plate through a through-plate electrode seal 401, a through-plate electrode radial sealing O-ring 404 and a through-plate electrode axial sealing O-ring 402, which can complete the one-dimensional The device for moving in a plane, i.e., the ionization source contact electrode position moving assembly 206 specifically includes an electrode support connecting sliding member 304 connected to the bottom of the non-metallic electrode support 302, and the electrode support connecting sliding member 304 can move on a fixed slide rail 305 arranged thereunder, and the input end of the electrode support connecting sliding member 304 is connected to a screw rotating head advancing member 306, and the screw rotating head advancing member 306 is provided with an identification device 307 with scale markings, and the screw rotating head advancing member 306 is connected to the main sealing plate of the closed inert gas protection ionization source 002 through a screw head external support member 308, and a screw advancement radial sealing O-ring 309 is provided at the sealing position.

[0074] The present invention also discloses a method for using the mass spectrometry ionization source for high-throughput detection based on inert protection, comprising the following steps:

[0075] The inside of the sealed inert gas protection ionization source 002 is set to an inert gas protection gas atmosphere in advance;

[0076] Place the array probe assembly 101 storing the sample to be tested on the micro-sample transfer device 001, and dock the bottom of the micro-sample transfer device 001 with the sealing gate valve 003 at the top of the ionization source;

[0077] The micro-sample transfer chamber is used to cooperate with the ionization source. After the cooperation is completed, the plug valve of the micro-sample transfer device 001 and the sealing plug valve 003 at the top of the ionization source are opened. At this time, before and after the valve is opened, the inside of the two chambers are in an inert gas protection gas atmosphere;

[0078] The telescopic magnetic rod of the micro-sample transfer chamber can be used to roughly adjust the height of the array probe. The height of the array probe assembly 101 is adjusted by the locking rotary sampling head position adjustment mechanism. At this time, the probe should be at the upper end of the mass spectrometer injection port 008. The two-dimensional adjustment member is used to ensure that the lowermost probe is at the center of the mass spectrometer injection port 008. The height is further lowered to ensure that the lowermost probe is coaxial with the mass spectrometer injection port 008. Specifically, during use, the probe is aligned with the center of the mass spectrometer injection port. During adjustment, the probe is kept between 1-3 mm and the mass spectrometer injection port, and is moved closer to or farther away from the mass spectrometer according to the needs of detection.

[0079] By adjusting the screw to rotate the head advancing member 306, the metal electrode 301 is gradually moved forward and has a preset spatial distance with the lowermost probe. At this time, the high-voltage switch is turned on to start the high-voltage input terminal 405 of the high-voltage ionization source; then the probe is gradually moved closer to the mass spectrometer injection port 008, and the distance between the probe and the mass spectrometer injection port 008 is gradually increased according to the strength of the generated ion flow, and the distance is maintained between 1-3 mm. When the detection is completed, the voltage is turned off, and the metal electrode 301 is moved back a distance away from the probe;

[0080] By adjusting the linear telescopic precision adjustment component 103, the probes are lowered one by one in sequence to complete the ionization of all subsequent probes. During this process, the metal electrode 301 repeatedly moves and does not hinder the gradual descent of the array probe component 101 in a non-ionized state.

[0081] After all sample tests are completed, the linear telescopic precision adjustment component 103 is raised by reverse rotation, and the height is restored to the initial position, and then restored to the initial position by the magnetic external drive component 105.

[0082] During the ionization process, the induction ionization method is adopted, and the metal electrode is brought close to the injection port of the ionization needle, and an AC voltage is applied to the metal electrode.

[0083] The specific process of the gas circulation mentioned above is: when the entire ionization source core cavity assembly is installed in the mass spectrometry system, the gas inside the ionization source core cavity needs to be replaced. When just installed, the inside of the cavity is air, which contains a large amount of water vapor and oxygen, so it is necessary to replace the gas inside the cavity. An inert gas inlet and a vacuum pump connection port are respectively provided in the core cavity. First, the inside of the ionization source is evacuated to a negative pressure using the vacuum port, and an external pressure gauge is used for observation (not shown in the figure). When the pressure in the cavity is below 100pa, an inert gas is filled, wherein the inert gas can be nitrogen. Observe the change in pressure, wherein the pressure in the cavity can be 100kPa one atmosphere, complete the above cycle once, and then go through two cycles, a total of 3 cycles, it can be determined that the gas in the chamber is an ionization injection cavity with an inert gas atmosphere. At this time, the subsequent ionization source detection meets the conditions.

[0084] It should be noted that the solutions contained in the array probes may be of the same concentration or different concentrations, and may be compounds of the same type or different types.

[0085] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A mass spectrometry ionization source for high-throughput detection based on inert protection, characterized in that: The invention comprises a sealed inert gas protection ionization source (002), wherein the injection end of the sealed inert gas protection ionization source (002) is provided with an ionization source top sealing plug valve (003), the sealed inert gas protection ionization source (002) is provided with a spatial position adjustment device, so that the detection end of the sealed inert gas protection ionization source (002) can be connected to a mass spectrometer detector (007) in a detection state, and the bottom of the sealed inert gas protection ionization source (002) is connected with a detection array. The probe assembly (101) stores a sample piece (006) at the bottom of the ionization source. The sealed inert gas protection ionization source (002) has a sealed working state and an open sample loading state for transferring the sample to be tested. In the sealed working state, the cavity of the sealed inert gas protection ionization source (002) is in a protective gas atmosphere throughout the entire process. The sealed inert gas protection ionization source (002) is provided with a metal electrode (301) for completing the ionization of the sample to be tested at one end close to the mass spectrometer detector (007).

2. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: The sealing plug valve (003) at the top of the ionization source can be docked with the sealing plug valve (108) of the transfer chamber of the micro-sample transfer device (001), thereby completing the transfer of the sample to be tested between the micro-sample transfer device (001) and the closed inert gas protection ionization source (002).

3. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: The array probe assembly (101) comprises an array probe lower end support base (503), an array probe upper end fixed cover plate (502) and an array probe fixing screw (501); the upper surface of the array probe lower end support base (503) is uniformly provided with a plurality of grooves parallel to its width direction along its length direction, and each groove forms a linear array arranged at equal intervals; the groove of the array probe lower end support base (503) is a complete groove capable of accommodating a sampling and ionization detection probe (504) or a groove matching the array probe lower end support base (503) is provided on the bottom surface of the array probe upper end fixed cover plate (502); the bottom surface groove of the array probe upper end fixed cover plate (502) and the groove of the array probe lower end support base (503) form a complete groove capable of accommodating a sampling and ionization detection probe (504); A screw hole is provided on the array probe lower end support base (503) separated from the preset groove by a preset distance, and a screw hole matching the screw hole of the array probe lower end support base (503) is also provided on the array probe upper end fixed cover plate (502), and the array probe upper end fixed cover plate (502) and the array probe lower end support base (503) are detachably connected by the array probe fixing screw (501); a protruding step structure is provided at the bottom of the array probe lower end support base (503) of the array probe assembly (101), and the array probe assembly (101) is introduced into the sample adapter assembly to be tested based on the step structure, and the array probe assembly (101) clamping device specifically includes a transfer assembly spring-type pressing piece provided at one end of the sample adapter assembly to be tested, and the array probe assembly (101) is clamped by the transfer assembly spring-type pressing piece.

4. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: The micro-sample transfer device (001) comprises an array probe storage cavity (107), a transfer cavity sealing gate valve (108), an array probe assembly (101), a self-locking rotary sampling head (109) and a self-locking rotary sampling head position adjustment mechanism, wherein the array probe storage cavity (107) is filled with a preset protective gas, the transfer cavity sealing gate valve (108) is installed at the end of the array probe storage cavity (107), and the other end of the array probe storage cavity (107) is installed with the A self-locking rotary sampling head position adjustment mechanism, wherein the self-locking rotary sampling head (109) is arranged inside the array probe storage cavity (107), and the distance of its output end relative to the transfer sealing gate valve can be adjusted by the self-locking rotary sampling head position adjustment mechanism, the output end of the self-locking rotary sampling head (109) can be detachably connected to the array probe assembly (101), and after the gate valve and the transfer sealing gate valve are docked, the array probe assembly (101) is formed in an atmosphere of protective gas throughout the process.

5. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: The self-locking rotary sampling head position adjustment mechanism is a multi-layer nested structure, including a self-locking rotary sampling head storage cavity and a position coarse adjustment device, and a linear telescopic precision adjustment component (103). The end of the array probe storage cavity (107) is connected to one end of the self-locking rotary sampling head storage cavity. The linear telescopic precision adjustment component (103) is installed at one end of the self-locking rotary sampling head storage cavity close to the array probe storage cavity (107). The self-locking rotary sampling head (109) is connected to the output end of the magnetic internal connecting rod (104). The self-locking rotary sampling head storage cavity is specifically a magnetic support outer bracket. The position coarse adjustment device includes a magnetic external drive component (105). The magnetic external drive component (105) is sleeved on the outer wall of the magnetic support outer bracket. The magnetic external drive component (105) can slide linearly on the magnetic support outer bracket to synchronously drive the linear sliding of the internal magnetic rod.

6. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: The spatial position adjustment device comprises an upper flange, a lower flange and a sealed two-dimensional XY direction adjustment device (004), wherein the sealed two-dimensional XY direction adjustment device comprises an X-direction fine-tuning screw rod respectively arranged on the upper flange and a Y-direction fine-tuning screw rod arranged on the lower flange, wherein the X-direction fine-tuning screw rod and the Y-direction fine-tuning screw rod are arranged vertically in space, and the lower flange is mounted on an upper plate (204) of a sealed inert gas shielded ionization source (002), and the upper flange and the lower flange are connected via a bellows.

7. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: The main body of the sealed inert gas protection ionization source (002) is a rectangular metal support (005), one side of which cooperates with the mass spectrometer detector (007), and a visible non-metallic lens is installed on the left side sealing panel (207) of the ionization source and the right side sealing panel (208) of the ionization source for sealing, and an ionization source positive side sealing panel (203) is arranged on the side facing the ionization source injection port, and a non-metallic transparent panel is installed on the ionization source positive side sealing panel.

8. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: Two clamps are placed on both sides of the injection port of the mass spectrometer detector (007), both of which are used to place the locking shaft (205) of the injection port of the ionization source mass spectrometer; after the cavity of the mass spectrometer detector (007) is placed at a specific position of the injection port of the ionization source, the two are assembled by locking the shaft and the clamp, and a sealing device is provided at the locking position of the two; The main body of the sealed inert gas protection ionization source (002) is provided with an inert gas inlet (201) and an outlet for extracting gas inside the cavity, and the outlet is connected to an exhaust pump connection port (202).

9. The mass spectrometry ionization source for high-throughput detection based on inert protection according to claim 1, characterized in that: The base of the metal electrode (301) is movable in at least one-dimensional plane, and the base is a non-metallic electrode support (302). The input end of the metal electrode (301) is connected to an external ionization source high voltage input end (405) through an electrode connection metal conductive member (303). A connecting wire (106) connecting the metal electrode (301) and the ionization source high voltage input end (405) is provided at a connection with a main body sealing plate of a closed inert gas protection ionization source (002). The through-plate electrode includes a through-plate metal electrode straight-through rod (403). The through-plate metal electrode straight-through rod (403) is connected to the sealing plate through a through-plate electrode seal (401), a through-plate electrode radial sealing O-ring (404), and a through-plate electrode axial sealing O-ring (402). The device capable of completing movement in a one-dimensional plane, i.e., an ionization source contact electrode position moving component (206), specifically comprises an electrode support connecting sliding member (304) connected below a non-metallic electrode support member (302), wherein the electrode support connecting sliding member (304) is capable of moving on a fixed slide rail (305) arranged below the electrode support connecting sliding member (304), an input end of the electrode support connecting sliding member (304) is connected to a screw rotating head advancing member (306), an identification device (307) with scale markings is arranged on the screw rotating head advancing member (306), the screw rotating head advancing member (306) is connected to a main body sealing plate of a closed inert gas protection ionization source (002) through a screw head external support member (308), and a screw advancing radial sealing O-ring (309) is arranged at the sealing position.

10. A method for using a mass spectrometry ionization source for high-throughput detection based on the inert protection according to any one of claims 1 to 9, characterized in that: The steps include: The interior of the sealed inert gas protection ionization source (002) is set to an inert gas protection gas atmosphere in advance; Placing the array probe assembly (101) storing the sample to be tested on the micro-sample transfer device (001), and docking the bottom of the micro-sample transfer device (001) with the sealing plug valve (003) at the top of the ionization source; The micro-sample transfer chamber is used to cooperate with the ionization source. After the cooperation is completed, the plug valve of the micro-sample transfer device (001) and the sealing plug valve (003) at the top of the ionization source are opened. At this time, before and after the valve is opened, the inside of the two chambers are in a gas atmosphere protected by an inert gas; The height of the array probe assembly (101) is adjusted by a locking rotary sampling head position adjustment mechanism. At this time, the probe should be located at the upper end of the mass spectrometer injection port (008). The lowermost probe is ensured to be located at the center of the mass spectrometer injection port (008) by a two-dimensional adjustment member. The height is further lowered to ensure that the lowermost probe is coaxial with the mass spectrometer injection port (008). The metal electrode (301) is gradually moved forward by adjusting the screw to rotate the top advancing member (306) and to have a preset spatial distance with the probe at the bottom. At this time, the high-voltage switch is turned on to start the high-voltage input end (405) of the high-voltage ionization source; then, the probe is gradually moved closer to the mass spectrometer injection port (008), and the distance between the probe and the mass spectrometer injection port (008) is gradually increased according to the strength of the generated ion flow, and the distance is maintained between 1 and 3 mm. When the detection is completed, the voltage is turned off, and the metal electrode (301) is moved back a certain distance away from the probe; By adjusting the linear telescopic precision adjustment component (103), the probes are lowered one by one in sequence to complete the ionization of all subsequent probes. During this process, the metal electrode (301) repeatedly moves and does not hinder the gradual descent of the array probe component (101) in a non-ionized state; After all samples are tested, the linear telescopic precision adjustment component (103) is raised by reverse rotation, and the height is restored to the initial position, and then restored to the initial position by the magnetic external drive component (105).

Images