A mass spectrometry ionization source for high throughput detection based on inertial protection and methods of use

Abstract

The application relates to a mass spectrum ionization source based on high-throughput detection of inert protection and a use method, comprising a closed inert gas protection ionization source, the sampling end of the closed inert gas protection ionization source is provided with an ionization source top-end sealing plug-in valve, the closed inert gas protection ionization source is provided with a spatial position adjusting device, so that in a detection state, the detection end of the closed inert gas protection ionization source can be connected with a mass spectrum detector, the bottom of the closed inert gas protection ionization source is connected with an ionization source bottom-end storage sample piece for storing a detected array probe assembly, 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, and the closed inert gas protection ionization source is provided with a metal electrode close to the mass spectrum detector end for completing ionization of the sample to be detected.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrospray ionization, in particular, especially relates to a mass spectrometry ionization source based on inert protection high-throughput detection and use method. BACKGROUND

[0002] Organic mass spectrometry is an analysis method widely used in the field of life science research, and electrospray ionization is a common ionization method for organic mass spectrometry instrument. For mass spectrometry analysis, the ionization source is the core. The prior art, such as CN201410198671.3, non-contact direct current induction electrospray ionization device and ionization method, adopts a non-contact direct current induction electrospray ionization device and ionization method. It includes an electrode, a high-voltage direct current power supply and a nanoliter electrospray nozzle. The axis of the nanoliter electrospray nozzle and the long straight wire electrode is on the same straight line, and the nozzle is located between the electrode and the mass spectrometry inlet. The patent provides an ionization structure, in which the ionization of the compound is realized by an external electric field, and the position movement of the sample is realized by a multi-dimensional adjustment structure. CN201610753809.0, a high-throughput nanoliter electrospray analysis system based on a microarray 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. It includes: an electrospray device, a mass spectrometer, a funnel-shaped micro sample carrier, a bracket, characterized in that a funnel-shaped micro sample carrier is arranged between the tip of the electrospray capillary and the inlet of the mass spectrometer, and the funnel-shaped micro sample carrier is located on the bracket. The feature of the patent is to use an array type ionization source, and its advantage is to detect multiple different samples at a time.

[0003] The prior art can realize the alignment of the ionization capillary to the mass spectrometry inlet, but lacks the protection of the position of the sample probe by a sealed cavity structure, and also cannot realize the continuous ionization of the sample. SUMMARY

[0004] According to the above technical problems, a mass spectrometry ionization source based on inert protection high-throughput detection and use method is provided.

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

[0006] The application discloses a high-throughput detection mass spectrometry ionization source based on inert protection, which comprises a closed inert gas protection ionization source, the sampling end of the closed inert gas protection ionization source is provided with an ionization source top end sealing plug-in valve, the closed inert gas protection ionization source is provided with a spatial position adjusting device, so that the detection end of the closed inert gas protection ionization source can be connected with a mass spectrometry 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 a detected array probe assembly, 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, in the sealed working state, the cavity of the closed inert gas protection ionization source is in a protective gas atmosphere all the way, and the closed inert gas protection ionization source is provided with a metal electrode near the end close to the mass spectrometry detector for completing ionization of the sample to be detected.

[0007] Further, the ionization source top end sealing plug-in valve can be docked with a transfer cavity sealing plug-in valve of a micro sample transfer device, so as to complete the transfer of the sample to be detected between the micro sample transfer device and the closed inert gas protection ionization source.

[0008] Further, the array probe assembly comprises an array probe lower end support base, an array probe upper end fixed cover plate and array probe fixed screws, the upper surface of the array probe lower end support base is uniformly provided with a plurality of grooves parallel to the width direction along the length direction, the grooves form a linear array with equal intervals, the grooves of the array probe lower end support base are complete grooves capable of accommodating sampling and ionization detection probes or the bottom surface of the array probe upper end fixed cover plate is provided with grooves matched with the grooves of the array probe lower end support base, the grooves of the bottom surface of the array probe upper end fixed cover plate and the grooves of the array probe lower end support base form complete grooves capable of accommodating sampling and ionization detection probes, screw holes are arranged on the array probe lower end support base at a preset distance from the grooves, screw holes matched with the screw holes of the array probe lower end support base are also arranged on the array probe upper end fixed cover plate, and the array probe upper end fixed cover plate and the array probe lower end support base are detachably connected through the array probe fixed screws, the bottom of the array probe lower end support base of the array probe assembly is provided with a protruding step structure, the array probe assembly is introduced into a sample to be detected adapter assembly based on the step structure, and the array probe assembly clamping device specifically comprises a adapter spring type pressing piece arranged at one end of the sample to be detected adapter assembly and used for clamping the array probe assembly.

[0009] Further, the micro sample transfer device comprises an array probe storage cavity, a transfer cavity sealing plug-in valve, an array probe assembly, a self-locking rotary sampling head and a self-locking rotary sampling head position adjusting mechanism, the array probe storage cavity is filled with a preset protective gas, the transfer cavity sealing plug-in valve is installed at the end of the array probe storage cavity, the other end of the array probe storage cavity is provided with the self-locking rotary sampling head position adjusting mechanism, the self-locking rotary sampling head is arranged in the array probe storage cavity and can adjust the distance between the output end thereof and the transfer sealing plug-in valve through the self-locking rotary sampling head position adjusting mechanism, the output end of the self-locking rotary sampling head can be detachably connected with the array probe assembly, and the plug-in valve and the transfer sealing plug-in valve are butted to form an atmosphere in which the array probe assembly is in the protective gas all the time.

[0010] Further, the self-locking rotary sampling head position adjusting mechanism is a multi-layer nested structure comprising a self-locking rotary sampling head storage cavity and a position coarse adjusting device and a linear telescopic precision adjusting assembly, the end of the array probe storage cavity is connected with one end of the self-locking rotary sampling head storage cavity, the linear telescopic precision adjusting assembly is installed at the 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 with the output end of the magnetic internal connecting rod, and the self-locking rotary sampling head storage cavity is a magnetic support outer side bracket, the position coarse adjusting device comprises a magnetic external driving assembly, the magnetic external driving assembly is sleeved on the outer wall of the magnetic support outer side bracket and can linearly slide on the magnetic support outer side bracket to synchronously drive the linear sliding of the internal magnetic rod.

[0011] Further, the spatial position adjusting device comprises an upper flange, a lower flange, an X-direction fine adjustment screw arranged on the upper flange and a Y-direction fine adjustment screw arranged on the lower flange, the X-direction fine adjustment screw and the Y-direction fine adjustment screw are arranged in a spatial vertical manner, the lower flange is installed on the upper plate of the closed inert gas protection ionization source, and the upper flange and the lower flange are connected through a corrugated pipe.

[0012] Further, the main body of the closed inert gas protection ionization source is a rectangular metal support, one side of which is matched with a mass spectrum detector, the left sealing panel of the ionization source is sealed with a visible non-metal lens arranged on the right sealing panel of the ionization source, the ionization source positive side sealing panel is arranged on the side opposite to the ionization source sample inlet position, and a non-metal transparent panel is arranged on the ionization source positive side sealing panel.

[0013] Further, two clamps are respectively arranged on both sides of the sample inlet of the mass spectrometer detector, and are used for placing the locking shafts of the ion source mass spectrometer sample inlet; after the mass spectrometer detector cavity is placed at a specific position of the sample inlet of the ion source, the assembly of the two is completed through the locking shafts and the clamps, and a sealing device is arranged at the locking position.

[0014] The main body of the closed inert gas protection ion source is provided with a filling hole for inert gas and an outlet for the gas in the cavity, and the outlet is connected with a gas pump connection port.

[0015] Further, the base of the metal electrode is movable in at least one dimension, the base is a non-metal electrode support, the input end of the metal electrode is connected with the high-voltage input end of the ion source through an electrode connecting metal conductor, the connecting wire of the metal electrode connected with the high-voltage input end of the ion source is provided with a through-plate electrode at the connection with the main body sealing plate of the closed inert gas protection ion source, the through-plate electrode is a through-plate metal electrode straight rod, and the through-plate metal electrode straight rod is connected with the main body sealing plate through a through-plate electrode radial sealing O-ring and a through-plate electrode axial sealing O-ring.

[0016] The device capable of moving in one dimension includes an electrode support connecting sliding member connected below the non-metal electrode support, the electrode support connecting sliding member is movable on a fixed sliding rail arranged below the electrode support connecting sliding member, the input end of the electrode support connecting sliding member is connected with a screw rod rotating top head advancing member, the screw rod rotating top head advancing member is provided with an identification device with a scale mark, the screw rod rotating top head advancing member is connected with the main body sealing plate of the closed inert gas protection ion source through a screw rod top head external support, and a screw rod advancing radial sealing O-ring is arranged at the sealing position.

[0017] The application further discloses a use method of the mass spectrometer ion source based on the high-throughput detection under inert protection, and the method comprises the following steps:

[0018] The internal part of the closed inert gas protection ion source is set as an inert gas protection gas atmosphere in advance;

[0019] The array probe assembly storing the sample to be detected is placed on the micro sample transfer device, and the bottom of the micro sample transfer device is abutted with the top end sealing plug-in valve of the ion source;

[0020] The plug-in valve of the micro sample transfer device and the top end sealing plug-in valve of the ion source are opened, and at this time, the gas atmosphere in the two cavities is under inert gas protection before and after the valve is opened;

[0021] The height of the array probe assembly is adjusted by a lock type rotary sampling head position adjusting mechanism, at this time the probe should be at the upper end of the mass spectrometer inlet, the two-dimensional adjusting member is used to ensure that the lowermost probe is at the center position of the mass spectrometer inlet, and the height is continuously lowered to ensure that the lowermost probe is coaxial with the mass spectrometer inlet;

[0022] The metal electrode is gradually moved forward by adjusting the screw rod rotary top head advancing member, and has a preset spatial distance with the lowermost probe, at this time the high voltage switch is opened to start the high voltage input end of the high voltage ionization source; then the probe position is gradually moved close to the mass spectrometer inlet, according to the strength of the ion flow generated, the distance between the probe and the mass spectrometer inlet is gradually increased, and the distance is maintained between 1-3mm, when the detection is completed, the voltage is closed, and the metal electrode is retreated by a distance away from the probe;

[0023] The linear telescopic precision adjusting assembly is adjusted to sequentially lower the probes, and the ionization of all subsequent probes is completed, in this process, the metal electrode repeatedly advances, and does not hinder the gradual lowering of the array probe assembly in a non-ionization state;

[0024] After all the sample detection is completed, the height is restored to the initial position by reversely rotating the linear telescopic precision adjusting assembly, and then the initial position is restored by the magnetic external driving assembly.

[0025] Compared with the prior art, the present application has the following advantages: the present application is provided with a gas extraction and charging device, so that the sample realizes seamless protection gas atmosphere switching when entering the device and the sample detection process, after one gas replacement, more than dozens of samples can be detected, the transfer cavity realizes one gas replacement, and multiple samples can be detected, so that the sample detection precision and detection efficiency are ensured. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or the prior art description will be briefly introduced. Obviously, the drawings in the following description are some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0027] Figure 1 It is a schematic diagram of the overall assembly of the mass spectrometry ionization source based on the high-throughput detection of the present application.

[0028] Figure 2 It is a schematic diagram of the external plug-in valve ionization source and the micro sample transfer cavity of the present application in the disconnected state.

[0029] Figure 3 It is an isometric view of the micro sample transfer cavity of the present application.

[0030] Figure 4 Isometric view of the enclosed inert gas protected ionization source of the present invention.

[0031] Figure 5 Macro view of the enclosed inert gas protected ionization source of the present invention fitted to a mass spectrometer detector.

[0032] Figure 6 Right side view of the enclosed inert gas protected ionization source of the present invention fitted to a mass spectrometer detector.

[0033] Figure 7 Left side view of the enclosed inert gas protected ionization source of the present invention fitted to a mass spectrometer detector.

[0034] Figure 8 Close up left side view of the enclosed inert gas protected ionization source of the present invention fitted to a mass spectrometer detector.

[0035] Figure 9 Schematic view of the internal structure of the micro sample transfer chamber of the present invention.

[0036] Figure 10 Exploded view of the enclosed inert gas protected ionization source of the present invention - right side view.

[0037] Figure 11 Exploded view of the enclosed inert gas protected ionization source of the present invention - left side view.

[0038] Figure 12 Exploded view of the enclosed inert gas protected ionization source of the present invention - isometric view.

[0039] Figure 13 Exploded view of the ionization source core chamber assembly of the present invention.

[0040] Figure 14 Exploded view of the ionization source contact position shifting assembly of the present invention.

[0041] Figure 15 Front view of the enclosed inert gas protected ionization source of the present invention with the induction electrode close to the probe position.

[0042] Figure 16 Front view of the enclosed inert gas protected ionization source of the present invention with the induction electrode far from the probe position.

[0043] Figure 17 Micro sample transfer chamber placed in the initial position on top of the ionization source of the present invention - overall style view.

[0044] Figure 18 Micro sample transfer chamber placed in the initial position on top of the ionization source of the present invention - close up view.

[0045] Figure 19 Initial position of the micro-sample transfer chamber at the top of the ionization source - overall view of the ionization source interior.

[0046] Figure 20 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the first probe at the mass spectrometer inlet - overall view.

[0047] Figure 21 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the first probe at the mass spectrometer inlet - close-up view.

[0048] Figure 22 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the first probe at the mass spectrometer inlet - close-up view of the ionization source interior.

[0049] Figure 23 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the middle position - overall view.

[0050] Figure 24 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the middle position - close-up view.

[0051] Figure 25 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the middle position - close-up view of the ionization source interior.

[0052] Figure 26 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the last probe at the mass spectrometer inlet - overall view.

[0053] Figure 27 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the last probe at the mass spectrometer inlet - close-up view.

[0054] Figure 28 Downward movement of the array probe assembly inside the micro-sample transfer chamber to the last probe at the mass spectrometer inlet - close-up view of the ionization source interior.

[0055] Figure 29 Schematic diagram of the array probe assembly structure.

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

[0057] It should be noted that the embodiments and features of the embodiments in the present application can be combined with each other without conflict. The technical solutions in the embodiments of the present application will be described in detail below with reference to the drawings and in combination with the embodiments.

[0058] In order to make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the drawings of the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. The description of the at least one exemplary embodiment is actually only illustrative, but not as any limitation on the present application and its application or use. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0059] It is to be understood that the terms so far as the grammar used herein is concerned are to be interpreted in their dictionary meanings and should not be construed to open down the scope of the present application based on the usage as per se. It is also to be understood that the terminology and description used herein is only by way of explanation of the illustrative embodiments and should not be construed to limit the scope of the present application.

[0060] The relative arrangement of parts and steps, numerical expressions, and numerical values set forth in the examples are not intended to limit the scope of the present application unless otherwise specifically stated. It is also to be understood that the drawings are not necessarily drawn to scale of the actual proportions of the various parts and components shown therein. Techniques, methods, and apparatus known to those of ordinary skill are not discussed in detail because such techniques, methods, and apparatus are considered to be part of the art. All examples shown and discussed herein are intended to be exemplary and non-limiting. Therefore, other examples of the illustrative embodiments can have different values. It is noted that like numbers and letters on the figures identify like parts throughout the disclosure, thus, once an item is defined in one figure, it is not necessary to discuss it further in connection with other figures where it is not explicitly defined.

[0061] In the description of the present application, it is to be understood that the orientation or positional relationships indicated by terms such as "front", "back", "upper", "lower", "left", "right", "horizontal", "vertical", "top", "bottom", and the like are based on the orientation or positional relationships shown in the drawings, and are merely intended to facilitate the description of the present application and simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation or be constructed and operated in a particular orientation, and therefore should not be construed as limiting the scope of protection of the present application. The orientation terms "inner", "outer" refer to the inner and outer relative to the outline of the components themselves.

[0062] For the purposes of this description, spatially relative terms such as "above", "below", "up", "down", "between", "within", "left", "right", "front", "back", "upper", "lower", "horizontal", "vertical", "above", "below", "up", "down", "top", "bottom", "side", "end", etc., are intended to describe the orientation of one device or feature relative to another device or feature as illustrated in the figures. The spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientations depicted in the figures. The devices can be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly. For example, if a device in the figures is inverted, then a description of a device or feature as "above" another device or feature is meant to encompass both an orientation with the device above the other device or feature and an orientation with the device below the other device or feature. Likewise, descriptions of devices as "below" another device or feature are meant to encompass both orientations. The devices can be oriented in any direction and the spatially relative descriptors used herein interpreted accordingly.

[0063] In addition, it should be noted that the use of "first", "second", etc. words to define parts, only for the convenience of the corresponding parts, as there is no declaration, the above words have no special meaning, therefore can not be understood as the limitation of the scope of protection of the present application.

[0064] As Figures 1-29 As shown in the figure, the embodiment of the present application discloses a mass spectrometry ionization source based on high-throughput detection of inert protection, comprising airtight inert gas protection ionization source 002, the sampling end of the airtight inert gas protection ionization source 002 is provided with ionization source top end sealing plug valve 003, the airtight inert gas protection ionization source 002 is provided with spatial position adjusting device, so that the detection end of the airtight inert gas protection ionization source 002 can be connected with the mass spectrometry detector 007 in the detection state, the bottom of the airtight inert gas protection ionization source 002 is connected with ionization source bottom end storage sample piece 006 for storing the detected array probe assembly 101, the airtight inert gas protection ionization source 002 has airtight working state and open sample loading state for transferring the sample to be detected, in the airtight working state, the whole cavity of the airtight inert gas protection ionization source 002 is in the atmosphere of protective gas, the airtight inert gas protection ionization source 002 is provided with metal electrode 301 near one end of the mass spectrometry detector 007 for completing the ionization of the sample to be detected. The present application can realize the batch detection capability, in the sampling process, the ionization spray needle is placed one by one from the top, one-time sampling is realized, the cavity gas does not need to be repeatedly replaced, and high-throughput detection of the sample is realized.

[0065] Further, the ionization source top end sealing plug valve 003 can be docked with the transfer cavity sealing plug valve 108 of the micro sample transfer device 001, and then the transfer of the sample to be detected between the micro sample transfer device 001 and the airtight inert gas protection ionization source 002 is completed.

[0066] Further, 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 fixed screw 501. The upper surface of the array probe lower end support base 503 is uniformly provided with a plurality of grooves parallel to the width direction along the length direction, and each groove forms a linear array with equal spacing. The grooves of the array probe lower end support base 503 are complete grooves capable of accommodating sampling and ionization detection probes 504 or grooves provided on the bottom surface of the array probe upper end fixed cover plate 502 to match the grooves of the array probe lower end support base 503. The grooves on the bottom surface of the array probe upper end fixed cover plate 502 and the grooves of the array probe lower end support base 503 form complete grooves capable of accommodating sampling and ionization detection probes 504. Screw holes are provided on the array probe lower end support base 503 at a predetermined distance from the grooves, and 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 fixed screw 501. The bottom of the array probe lower end support base 503 of the array probe assembly 101 is provided with a protruding step structure. Based on the step structure, the array probe assembly 101 is introduced into the sample adapter assembly to be tested, and the array probe assembly 101 clamping device specifically comprises a spring type pressing piece provided at one end of the sample adapter assembly to be tested. The array probe assembly 101 is clamped by the spring type pressing piece of the sample adapter assembly.

[0067] Further, the micro sample transfer device 001 comprises an array probe storage cavity 107, a transfer cavity sealing plug-in valve 108, an array probe assembly 101, a self-locking rotary sampling head 109 and a self-locking rotary sampling head position adjusting mechanism. The array probe storage cavity 107 is filled with a predetermined protective gas. The transfer cavity sealing plug-in valve 108 is installed at the end of the array probe storage cavity 107. The other end of the array probe storage cavity 107 is provided with the self-locking rotary sampling head position adjusting mechanism. The self-locking rotary sampling head 109 is arranged inside the array probe storage cavity 107 and can adjust the distance between its output end and the transfer sealing plug-in valve through the self-locking rotary sampling head position adjusting mechanism. The output end of the self-locking rotary sampling head 109 can be detachably connected with the array probe assembly 101. After the plug-in valve and the transfer sealing plug-in valve are connected, the array probe assembly 101 is in the atmosphere of the protective gas all the time.

[0068] Further, the self-locking rotary sampling head position adjusting mechanism is a multi-layer nested structure, comprising a self-locking rotary sampling head storage cavity and a position coarse adjusting device, a linear telescopic precision adjusting assembly 103, the end of the array probe storage cavity 107 is connected with one end of the self-locking rotary sampling head storage cavity, the linear telescopic precision adjusting assembly 103 is installed at the 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 with the output end of the magnetic internal connecting rod 104, the self-locking rotary sampling head storage cavity is specifically a magnetic support outer side bracket, the position coarse adjusting device comprises a magnetic external driving assembly 105, the magnetic external driving assembly 105 is sleeved on the outer wall of the magnetic support outer side bracket, and the magnetic external driving assembly 105 can linearly slide on the magnetic support outer side bracket to synchronously drive the linear sliding of the internal magnetic rod.

[0069] Further, the spatial position adjusting device comprises an upper flange, a lower flange and a closed two-dimensional XY direction adjusting device 004, the closed two-dimensional XY direction adjusting device comprises an X direction fine adjustment screw rod arranged on the upper flange and a Y direction fine adjustment screw rod arranged on the lower flange, the X direction fine adjustment screw rod and the Y direction fine adjustment screw rod 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 through a bellows. Through the upper and lower flanges, the bellows in the middle is connected, and small-range adjustment in the XY plane is realized. The condition distance setting can be in 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, the main adjusting part does not touch the bellows, the interference of the part is realized, and the sealed connection of the upper and lower flanges with the bellows is ensured in the use process. Specifically, the flange at the top is moved in the direction of one dimension by moving the fine adjustment screw rod forward and backward.

[0070] The main body of the closed inert gas protection ionization source 002 is a rectangular metal support 005, one side of which is matched with the mass spectrometer detector 007, the left side sealing panel 207 of the ionization source is sealed with the visible non-metal lens installed on the right side sealing panel 208 of the ionization source, the ionization source positive side sealing panel 203 arranged opposite to the sample inlet position of the ionization source is provided with a non-metal transparent panel. In the connection process with the mass spectrometer, the two are sealed by O-ring at the sample inlet position of the mass spectrometer. When the top sealing plug valve 003 of the ionization source is closed, the cavity can be sealed.

[0071] Two clamps are respectively arranged on both sides of the sample inlet of the mass spectrometer detector 007, and are used for placing the locking shaft 205 of the ion source mass spectrometer sample inlet; after the mass spectrometer cavity is placed in a specific position of the sample inlet of the ion source, the assembly of the two is completed through the locking shaft and the clamp, and a sealing device is arranged 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 in a specific position of the sample inlet of the ion source, the shaft can be rotated by a certain angle, and when it is rotated to a specific clamping position, the ion source core cavity is assembled to the front end of the sample inlet of the mass spectrometer cavity. At this time, after rotating by a certain angle, the sample inlet locking shaft can be firmly matched to the mass spectrometer, so as to ensure that the whole sealed inert gas protection ion source will not fall off. The design is convenient to install and disassemble, but after each installation, the ion source cavity needs to be circulated once.

[0072] During use, the core cavity of the ion source needs to be sealed, therefore, the main body of the sealed inert gas protection ion source 002 is provided with an inert gas inlet 201 and a cavity internal gas outlet, and the outlet is connected with the gas pump connection port 202.

[0073] The base of the metal electrode 301 can move in at least one-dimensional plane, the base is a non-metal electrode support 302, the input end of the metal electrode 301 is connected with the external ion source high-voltage input end 405 through the electrode connection metal conductor 303, the connecting wire 406 connected with the ion source high-voltage input end 405 of the metal electrode 301 is provided with a through-plate electrode at the connection position of the main body sealing plate of the sealed inert gas protection ion source 002, the through-plate electrode includes a through-plate metal electrode straight rod 403, the through-plate metal electrode straight rod 403 is connected with the sealing plate through a through-plate electrode sealing piece 401, a through-plate electrode radial sealing O-ring 404 and a through-plate electrode axial sealing O-ring 402, and can complete the movement in the one-dimensional plane, that is, the ion source electric contact position moving assembly 206 specifically includes an electrode support connection sliding piece 304 connected below the non-metal electrode support 302, the electrode support connection sliding piece 304 can move on the fixed sliding rail 305 arranged below, the input end of the electrode support connection sliding piece 304 is connected with a screw rod rotating top head advancing piece 306, the screw rod rotating top head advancing piece 306 is provided with a marking device 307 with a scale mark, the screw rod rotating top head advancing piece 306 is connected with the main body sealing plate of the sealed inert gas protection ion source 002 through a screw rod top head external support 308, and a screw rod advancing radial sealing O-ring 309 is arranged at the sealing position.

[0074] The application also discloses a use method of the above-mentioned inert protection based high-throughput detection mass spectrometer ion source, which comprises the following steps:

[0075] The interior 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 connect the bottom of the micro-sample transfer device 001 to the sealing plug 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 gate valve of the micro-sample transfer device 001 and the gate valve 003 at the top of the ionization source are opened. At this time, before and after the valves are opened, the inside of the two chambers are in an inert gas protection atmosphere;

[0078] The telescopic magnetic rod of the micro-sample transfer chamber allows for coarse height adjustment of the array probe. The height of the array probe assembly 101 is adjusted using the locking rotary sampling head position adjustment mechanism. The probes should now be positioned above the mass spectrometer inlet 008. A two-dimensional adjustment member ensures that the bottommost probe is centered within the mass spectrometer inlet 008. Further lowering ensures that the bottommost probe is coaxial with the inlet. Specifically, during use, the probes are aligned with the center of the mass spectrometer inlet. During adjustment, the probes are kept between 1 and 3 mm from the inlet, moving closer to or further away from the mass spectrometer as needed for detection.

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

[0080] By adjusting the linear telescopic precision adjustment assembly 103, the probes are lowered one by one 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 assembly 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, induction ionization is used. 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 gas circulation process is as follows: when the ion source core cavity assembly is installed into the mass spectrometry system, the gas in the ion source core cavity needs to be replaced. When the ion source core cavity is just installed, the cavity is filled with air containing a large amount of water vapor and oxygen, and thus the gas in the cavity needs to be replaced. The ion source core cavity is provided with an inert gas inlet and a gas pump connection port. First, the ion source is pumped to a negative pressure by using the gas pump, and the pressure is observed by using an external pressure gauge. When the pressure in the cavity is less than 100 Pa, the cavity is filled with inert gas, which can be nitrogen. The change of the pressure is observed. The pressure in the cavity can be 100 kPa, that is, one atmosphere. The above process is one cycle. After two cycles, that is, three cycles, the gas in the cavity is determined to be an inert gas atmosphere ionization sampling cavity. Subsequent ion source detection meets the requirements.

[0084] It should be noted that the solutions in the array probe can be of the same concentration or different, and can be the same type or different type of compounds.

[0085] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not limited thereto. Although the present application has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical solutions described in the above embodiments can still be modified, or some or all of the technical features can be replaced by equivalent ones. The modification or replacement does not change the essence of the corresponding technical solution, which is within the scope of the technical solutions of the embodiments of the present application.

Claims

1. A mass spectrometry ionization source for high-throughput detection based on inert protection, characterized in that: The invention comprises a closed inert gas protection ionization source (002), wherein the injection end of the closed inert gas protection ionization source (002) is provided with an ionization source top sealing plug-in valve (003), the closed inert gas protection ionization source (002) is provided with a spatial position adjustment device, so that the detection end of the closed inert gas protection ionization source (002) can be connected to a mass spectrometer detector (007) in a detection state, and the bottom of the closed 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 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 ionization source top sealing plug valve (003) can be docked with the transfer chamber sealing plug valve (108) 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); 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 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), 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 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 (502), and the array probe upper end fixed cover (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 adapter 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 adapter assembly spring-type pressing piece; The micro-sample transfer device (001) comprises an array probe storage cavity (107), a transfer cavity sealing plug 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 plug 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 plug 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 plug valve and the transfer sealing plug valve are docked, the array probe assembly (101) is formed to be in a protective gas atmosphere throughout the entire process; The self-locking rotary sampling head position adjustment mechanism is a multi-layer nested structure, including a self-locking rotary sampling head storage chamber, a position coarse adjustment device, and a linear telescopic fine adjustment component (103). The end of the array probe storage chamber (107) is connected to one end of the self-locking rotary sampling head storage chamber. The linear telescopic fine adjustment component (103) is installed at one end of the self-locking rotary sampling head storage chamber close to the array probe storage chamber (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 chamber 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.

2. 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 respectively arranged on the upper flange and a Y-direction fine-tuning screw arranged on the lower flange, wherein the X-direction fine-tuning screw and the Y-direction fine-tuning screw are arranged in a spatial vertical manner, 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.

3. 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. An ionization source positive side sealing panel (203) is provided 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.

4. 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 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 two are assembled by locking the shaft and the clamp, and a sealing device is provided at the locking position of the two; An inert gas inlet (201) and an outlet for extracting gas from the cavity are provided on the main body of the sealed inert gas protection ionization source (002), and the outlet is connected to a gas extraction pump connection port (202).

5. 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 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) and the ionization source high-voltage input end (405) is provided with a through-plate electrode at the connection with the main body sealing plate of the closed inert gas protection ionization source (002). The through-plate electrode includes a through-plate metal electrode straight rod (403). The through-plate metal electrode straight 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 assembly (206), specifically comprises an electrode support connecting sliding member (304) connected to the bottom of 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) provided thereunder, an input end of the electrode support connecting sliding member (304) is connected to a screw rotating head advancing member (306), and an identification device (307) with a scale mark is provided on the screw rotating head advancing member (306), and the screw rotating head advancing member (306) is connected to a main body sealing plate of a closed inert gas shielded ionization source (002) through a screw head external support member (308), and a screw advancing radial sealing O-ring (309) is provided at the sealing position.

6. A method for using a mass spectrometry ionization source for high-throughput detection based on the inert protection of claim 5, characterized in that: The steps include: The interior of the sealed inert gas protection ionization source (002) is set in advance to an inert gas protection gas atmosphere; The array probe assembly (101) storing the sample to be tested is placed on the micro-sample transfer device (001), and the bottom of the micro-sample transfer device (001) is docked 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 valves are opened, the insides 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 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). The metal electrode (301) is gradually moved forward by adjusting the screw to rotate the head advancement member (306) and to have a preset spatial distance with the lowermost probe. 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 positioned 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 simultaneously moved back a 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 the sample tests are completed, the linear telescopic precision adjustment component (103) is raised by the 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).

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