In situ device for studying kinetics of ion-molecule reactions

Abstract

The present invention relates to the technical field of gas-phase reaction dynamics of sample ions and molecules, and in particular to an in-situ device for studying the dynamics of ion-molecule reactions, comprising: a main cavity assembly; an electrospray ion source assembly; an ion funnel assembly disposed in the main cavity assembly and connected to the electrospray ion source assembly; a guide assembly disposed in the main cavity assembly; a quadrupole mass analyzer disposed in the main cavity assembly; a linear ion trap disposed in the main cavity assembly, wherein gas-phase ions react with target gas in the linear ion trap; and a detector for acquiring and receiving signals. The device can perform structural analysis of sample components and ions generated therein, further react in the ion trap, introduce molecular dynamics into an electrospray mass spectrometer, and obtain information such as a clear reaction channel, reaction rate, and reaction efficiency. Liquid-phase sampling is implemented, thereby improving ion transmission efficiency and analytical performance, as well as multi-stage tandem analysis efficiency and sensitivity.

Description

Technical Field

[0001] The present invention relates to the technical field of sample ion molecule gas phase reaction related dynamics, and in particular to an in-situ device for studying ion molecule reaction dynamics. Background Art

[0002] A mass spectrometer is an advanced, high-end analytical instrument capable of molecular structure identification and quantitative analysis. It boasts powerful structural identification capabilities, high sensitivity, a wide analytical range, rapid analysis speed, and excellent compatibility with chromatographs. The primary hardware components of a mass spectrometer include a sample introduction system, an ion source, a mass analyzer, a detector, and a data analysis system. For example, the QExactive hybrid quadrupole-Orbitrap mass spectrometer comprises an ion source, a stacked ring ion guide (S-lens), a quadrupole mass filter, a curved linear trap (C-trap), a high-energy collisional dissociation (HCD) chamber, and an Orbitrap mass analyzer. However, these mass spectrometers primarily analyze sample composition and the structure of the ions produced. They are unable to analyze reactions between organic ligand-containing cluster molecules and stable gaseous small molecules and obtain clear kinetic information. They are relatively limited in functionality, complex in structure, expensive, and difficult to maintain. Summary of the Invention

[0003] The present invention provides an in-situ device for studying the kinetics of ion-molecule reactions, which is used to solve the problems in the prior art that the equipment cannot realize the reaction between cluster molecules containing organic ligands and stable gas small molecules and obtain clear kinetic-related information, and the structure is relatively complicated, the cost is relatively high, and it is difficult to maintain.

[0004] The present invention provides an in-situ device for studying ion-molecule reaction kinetics, comprising:

[0005] Main cavity assembly;

[0006] an electrospray ion source device, used to convert the sample solution into gas-phase ions;

[0007] An ion funnel device is provided on one side of the main cavity assembly, the ion funnel device is used to focus and transmit the gas phase ions, and one end of the ion funnel device is connected to the electrospray ion source device;

[0008] A guiding device, disposed in the main cavity assembly, for guiding the gas-phase ions;

[0009] A quadrupole mass analyzer is provided in the main cavity assembly, and the quadrupole mass analyzer has a first working state and a second working state. In the first working state, the quadrupole mass analyzer guides ions under the condition that only radio frequency exists; in the second working state, the quadrupole mass analyzer performs mass selection of single mass ion clusters under the condition that radio frequency and direct current voltage exist simultaneously;

[0010] A linear ion trap is provided in the main cavity assembly, wherein a target gas can be introduced into the linear ion trap, and gas-phase ions guided into the linear ion trap by the quadrupole mass analyzer can react with the target gas introduced into the linear ion trap;

[0011] Detector, used to collect and receive signals;

[0012] Wherein, the electrospray ion source device, the ion funnel device, the guide device, the quadrupole mass analyzer, the linear ion trap and the detector are arranged in sequence and connected.

[0013] According to an in-situ device for studying ion-molecule reaction kinetics provided by the present invention, the electrospray ion source device comprises:

[0014] a mounting assembly, the mounting assembly being mounted on one side of the ion funnel device, the mounting assembly extending into the ion funnel device at one end thereof facing the ion funnel device, and the mounting assembly being provided with a liquid inlet channel and a mounting channel;

[0015] a spray needle, the spray needle being arranged in the mounting channel and extending into the ion funnel device, the liquid inlet end of the spray needle being connected to the liquid inlet channel, and the spraying end of the spray needle being connected to the ion funnel device;

[0016] A sliding cover is slidably mounted on one end of the mounting assembly, and a partial area of ​​the sliding cover is located within the ion funnel device. The sliding cover cooperates with the area of ​​the mounting assembly corresponding to the spray needle. The sliding cover slides relative to the mounting assembly so that the spray needle can be extended or accommodated in the sliding cover.

[0017] According to an in-situ device for studying ion-molecule reaction kinetics provided by the present invention, the ion funnel device comprises:

[0018] An ion source cover, wherein the interior of the ion source cover is an atmospheric environment, an insertion channel is provided at one end of the ion source cover, the electrospray ion source device is connected to the ion source cover, and the ejection end of the electrospray ion source device extends into the ion source cover along the insertion channel;

[0019] a first vacuum chamber, one end of the first vacuum chamber being connected to the ion source cover, and the other end of the first vacuum chamber being connected to the main chamber assembly;

[0020] An injection structure comprising an injection capillary, an ion funnel, and a heating and fixing assembly for heating the injection capillary, the heating and fixing assembly being located within the ion source housing and connected to the first vacuum chamber, the injection capillary being passed through and mounted on the heating and fixing assembly, one end of the injection capillary extending into the first vacuum chamber, the ion funnel being mounted in the first vacuum chamber, and the ion funnel being in communication with the guide device;

[0021] Wherein, the center lines of the injection capillary and the ion funnel coincide with each other.

[0022] According to an in-situ device for studying ion-molecule reaction kinetics provided by the present invention, the heating and fixing component includes:

[0023] a fixing seat connected to the first vacuum chamber;

[0024] A heating base is fixedly arranged on one side of the fixing seat, and the heating base is provided with a first fixing sleeve and a second fixing sleeve;

[0025] A heating pressure ring is connected to the heating base, and a ceramic heating element is provided between the heating base and the heating pressure ring;

[0026] A cover body is connected to the heating and pressing ring, and the cover body is covered on the heating and pressing ring;

[0027] Among them, the end of the first fixed sleeve facing away from the heating base is located in the enclosed area of ​​the heating base, the ceramic heating element, the heating pressure ring and the cover body; the second fixed sleeve passes through the fixed seat and the first vacuum chamber in sequence, and extends into the interior of the first vacuum chamber.

[0028] According to an in-situ device for studying ion-molecule reaction dynamics provided by the present invention, a fixing plate is provided on one side wall of the first vacuum chamber facing the guiding device, and the ion funnel is connected to the fixing plate;

[0029] Two extension plates are provided on one end of the fixing base facing the first vacuum chamber, the two extension plates are spaced apart and arranged facing each other, and each extension plate extends into the first vacuum chamber and is connected to the fixing plate;

[0030] The second fixed sleeve, the injection capillary and the ion funnel are all located in an area enclosed by the fixing seat, the fixing plate and the two extension plates.

[0031] According to an in-situ device for studying the kinetics of ion-molecule reactions provided by the present invention, a first lens is provided on the fixed plate, and the first lens is mounted on one end of the first vacuum chamber facing the guiding device. A conical hole corresponding to the center line of the ion funnel is provided on the first lens, so that the ion funnel is connected to the guiding device through the conical hole of the first lens.

[0032] According to an in-situ device for studying ion-molecule reaction kinetics provided by the present invention, the guiding device comprises:

[0033] A second vacuum chamber connected to the main chamber assembly, wherein the second vacuum chamber is opened at one end facing the ion funnel device;

[0034] a fixed tube with openings at both ends, the fixed tube being located in the second vacuum chamber, one end of the fixed tube being connected to a side wall of the second vacuum chamber facing away from the ion funnel device;

[0035] a guide rod assembly located in the fixed cylinder, the guide rod assembly being provided with a guide channel, one end of the guide channel being connected to the outlet end of the transmission region of the ion funnel device, and the other end being connected to the quadrupole mass analyzer;

[0036] Wherein, the guide rod assembly is fixedly connected to the inner wall of the fixing cylinder through a fixing ring.

[0037] According to an in-situ device for studying ion-molecule reaction dynamics provided by the present invention, the guide rod assembly includes four guide rods, the four guide rods are spaced apart and arranged opposite to each other in pairs, so that the guide channel is formed in the middle of the area surrounded by the four guide rods;

[0038] The fixing ring is provided with a fixing channel for the four guide rods to pass through, and the side wall of the fixing channel is provided with four positioning grooves, which are arranged at intervals and around the center line of the fixing channel, and each guide rod is engaged with each positioning groove in sequence;

[0039] Wherein, the guide rod, the fixing ring and the fixing cylinder are connected via a connecting structure.

[0040] According to an in-situ device for studying ion-molecule reaction kinetics provided by the present invention, a second lens is provided on an end of the second vacuum chamber away from the ion funnel device, and a guide hole is formed in the second lens, and the guide hole is connected to the inlet end of the quadrupole mass analyzer;

[0041] The fixed cylinder is arranged around the second lens, and the guide channel of the guide rod assembly is connected to the quadrupole mass analyzer through the guide hole of the second lens.

[0042] According to an in-situ device for studying ion-molecule reaction dynamics provided by the present invention, the main cavity assembly is provided with a main chamber;

[0043] The guiding device, the quadrupole mass analyzer and the linear ion trap are all located in the main chamber, and the electrospray ion source device and the ion funnel device are both located outside the main chamber;

[0044] The electrospray ion source device is bolted to the ion funnel device. The ion funnel device, the guide device and the quadrupole mass analyzer are all bolted to the main cavity assembly. The guide device and the quadrupole mass analyzer are bolted together.

[0045] The present invention provides an in-situ device for studying ion-molecule reaction dynamics. The device comprises an electrospray ion source device, an ion funnel device, a guide device, a quadrupole mass analyzer, a linear ion trap and a detector, which are sequentially arranged and connected. During operation, a sample solution is introduced into the electrospray ion source device, and the sample solution is sprayed out from a spray needle to which voltage is applied to form very fine charged droplets. By continuously applying electricity, the solvent in the droplets gradually evaporates, the droplet volume decreases, the surface charge density increases, a strong electrostatic field is formed to ionize polar molecules, and finally ions are sputtered from the droplet surface to obtain gas-phase ions. The gas-phase ions are transmitted by the ion funnel device to the guide device, and under the guidance of the guide device, enter the quadrupole mass analyzer for mass selection of single-mass ion clusters. The gas-phase ions then enter the linear ion trap to react with a target gas, and are then detected by a time-of-flight mass spectrometer. Through the above structure, an electrospray ion source is provided to cooperate, so that the equipment research sensitivity is high and very low concentration substances can be detected, usually reaching the nanomolar level. Secondly, the reliability is good, and the electrospray ion source device is relatively simple to process the sample, without too many pre-processing steps, thereby reducing sample loss and analysis errors. In short, the present invention can realize the analysis of sample components and the structural analysis of ions generated therein, and can also realize the function of further reaction in the linear ion trap to obtain relevant molecular dynamics information; introduce molecular dynamics into the electrospray mass spectrometer to obtain clear reaction channels, reaction rates and reaction efficiency information; in addition, through the design of the electrospray ion source device, the ion funnel device and the guide device, not only can liquid phase sampling be realized, but also ion loss can be reduced, and the ion transmission efficiency can be improved, thereby improving the analysis performance, multi-stage series analysis efficiency and sensitivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] In order to more clearly illustrate the technical solutions in the present invention or the prior art, a brief introduction is given below to the drawings required for use in the embodiments or the description of the prior art. 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 any creative work.

[0047] Figure 1 Schematic diagram of the structure of the in-situ device for studying ion-molecule reaction kinetics provided by the present invention, in which the linear ion trap and detector are not shown;

[0048] Figure 2 yes Figure 1 Schematic cross-section diagram;

[0049] Figure 3 is a cross-sectional schematic diagram of the electrospray ion source device provided by the present invention;

[0050] Figure 4 is a cross-sectional schematic diagram of the ion funnel device provided by the present invention;

[0051] Figure 5 is an exploded schematic diagram of the ion funnel device provided by the present invention;

[0052] Figure 6 is an exploded schematic diagram of the internal structure of the ion funnel device provided by the present invention;

[0053] Figure 7 is an exploded schematic diagram of the guiding device provided by the present invention;

[0054] Figure 8 It is a cross-sectional schematic diagram of the guiding device provided by the present invention with the second vacuum cavity removed.

[0055] Reference numerals:

[0056] 10. Main cavity assembly; 11. Main cavity; 12. Main cavity body; 121. First communication channel; 122. Second communication channel; 123. Third communication channel; 124. Fourth communication channel; 125. Fifth communication channel; 126. Sixth communication channel; 127. First through hole; 13. Upper cover flange; 131. Second through hole; 132. Third through hole; 133. Fourth through hole; 134. Fifth through hole; 14. First flange; 15. Second flange

[0057] 20. Electrospray ion source device; 21. Mounting assembly; 211. Mounting base; 2111. Boss; 212. Mounting sleeve; 213. Connector body; 214. First inner core; 215. Second inner core; 216. Nut fixing member; 22. Spray needle; 23. Sliding cover;

[0058] 30. Ion funnel assembly; 31. Ion source cover; 311. Insertion channel; 32. First vacuum chamber; 321. Fixing plate; 3211. First lens; 33. Injection capillary; 34. Ion funnel; 35. Heating and fixing assembly; 351. Fixing seat; 3511. Extension plate; 352. Heating base; 3521. First fixing sleeve; 3522. Second fixing sleeve; 353. Heating pressure ring; 354. Ceramic heating element; 355. Cover; 356. Insulation pad; 36. Shielding box;

[0059] 40. Guiding device; 41. Second vacuum chamber; 42. Fixing cylinder; 421. Fixing hole; 422. Annular limit platform; 43. Guide rod assembly; 431. Guide channel; 432. Guide rod; 4321. Connecting screw hole; 4322. Positioning protrusion; 44. Fixing ring; 441. Fixing channel; 442. Positioning groove; 443. Positioning hole; 45. Second lens; 46. Insulating ring; 50. Quadrupole mass analyzer; 60. Bellows. DETAILED DESCRIPTION

[0060] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0061] The following combination Figures 1-8 The in-situ device for studying the kinetics of ion-molecule reactions of the present invention is described.

[0062] Reference Figure 1 and Figure 2According to the present invention, an in-situ device for studying the kinetics of ion-molecule reactions is provided, comprising: a main cavity assembly 10; an electrospray ion source assembly 20 for converting a sample solution into gas-phase ions; an ion funnel assembly 30, disposed on one side of the main cavity assembly 10, the ion funnel assembly 30 for focusing and transmitting gas-phase ions, one end of the ion funnel assembly 30 being connected to the electrospray ion source assembly 20; a guiding device 40, disposed on the main cavity assembly 10, the guiding device 40 for guiding gas-phase ions; a quadrupole mass analyzer 50, disposed on the main cavity assembly 10, the quadrupole mass analyzer 50 having a first working state and a second working state. In the first working state, in the presence of only radio frequency, the quadrupole mass analyzer 50 has a first working state and a second working state. Under the condition of, the quadrupole mass analyzer 50 guides ions; in the second working state, under the condition of simultaneous existence of radio frequency and DC voltage, the quadrupole mass analyzer 50 performs mass selection of single mass ion clusters; a linear ion trap is arranged in the main cavity assembly 10, and the target gas can be introduced into the linear ion trap. The gas-phase ions guided into the linear ion trap by the quadrupole mass analyzer 50 can react with the target gas introduced into the linear ion trap; a detector is used to detect the reacted substances in the linear ion trap; wherein, the electrospray ion source device 20, the ion funnel device 30, the guiding device 40, the quadrupole mass analyzer 50, the linear ion trap and the detector are arranged in sequence and connected.

[0063] The present invention provides an in-situ device for studying ion-molecule reaction dynamics. The device comprises an electrospray ion source device 20, an ion funnel device 30, a guide device 40, a quadrupole mass analyzer 50, a linear ion trap and a detector, which are arranged in sequence and connected. During operation, a sample solution is introduced into the electrospray ion source device 20, and the sample solution is sprayed out from a needle 22 to which voltage is applied to form very fine charged droplets. By continuously applying electricity, the solvent in the droplets gradually evaporates, the droplet volume decreases, the surface charge density increases, and a strong electrostatic field is formed to ionize polar molecules. Finally, ions are sputtered from the droplet surface to obtain gas-phase ions. The gas-phase ions are transmitted by the ion funnel device 30 to the guide device 40, and under the guidance of the guide device 40, enter the quadrupole mass analyzer 50 for mass selection of single-mass ion clusters. The gas-phase ions then enter the linear ion trap to react with the target gas, and are then detected by time-of-flight mass spectrometry. Through the above structure, an electrospray ion source is provided, so that the equipment has high research sensitivity and can detect substances at very low concentrations, usually reaching the nanomolar level. Secondly, it has good reliability. The electrospray ion source device 20 is relatively simple to process samples and does not require too many pre-processing steps, thereby reducing sample loss and analysis errors. In short, the present invention can realize the analysis of sample components and the structural analysis of ions generated therein, and can also realize the function of further reaction in the linear ion trap to obtain relevant molecular dynamics information; molecular dynamics is introduced into the electrospray mass spectrometer to obtain clear reaction channels, reaction rates and reaction efficiency information; in addition, through the design of the electrospray ion source device 20, the ion funnel device 30 and the guide device 40, not only can liquid phase sampling be realized, but ion loss can also be reduced, and the ion transmission efficiency is improved, thereby improving the analysis performance, multi-stage series analysis efficiency and sensitivity.

[0064] It should be noted that the above-mentioned detector is a time-of-flight mass spectrometer, and the ions then enter the linear ion trap to react with the target gas, and are then detected by the time-of-flight mass spectrometer, and the final signal is transmitted to the oscilloscope; in this embodiment, the in-situ device for studying the kinetics of ion-molecule reactions of the present invention transmits ions through gas pressure difference, potential difference and radio frequency.

[0065] It is understandable that, referring to Figure 1 and Figure 2In some embodiments of the present invention, the main cavity assembly 10 is provided with a main cavity 11; the guide device 40, the quadrupole mass analyzer 50 and the linear ion trap are all located in the main cavity 11, and the electrospray ion source device 20 and the ion funnel device 30 are both located outside the main cavity 11; the electrospray ion source device 20 is bolted to the ion funnel device 30, and the ion funnel device 30, the guide device 40 and the quadrupole mass analyzer 50 are all bolted to the main cavity assembly 10, and the guide device 40 and the quadrupole mass analyzer 50 are bolted together. With the above structure, the above arrangement allows easy maintenance and replacement of the external electrospray ion source device 20 and the ion funnel device 30 without opening the entire main chamber assembly 10. To disassemble or replace the electrospray ion source device 20 and the ion funnel device 30, it is only necessary to release the connection with the main chamber assembly 10, while the guide device 40, the quadrupole mass analyzer 50 and the linear ion trap can all be maintained inside the main chamber 11. In addition, with the above bolted connection, connection and separation can be achieved by tightening or loosening the bolts, which is very convenient for maintenance, replacement or adjustment without the need for destructive operations on other parts. The structure is simple to install, easy to disassemble and has a low cost.

[0066] Specifically, refer to Figure 1 and Figure 2In some embodiments of the present invention, the main cavity assembly 10 includes a main cavity body 12, an upper cover flange 13, a first flange 14 and a second flange 15. The main cavity 11 is formed inside the main cavity body 12. The upper end of the main cavity body 12 is provided with a first communicating channel 121, and the lower end of the main cavity body 12 is provided with a second communicating channel 122. The upper cover flange 13 is bolted to the upper end outer wall of the main cavity body 12 and covers the first communicating channel 121. The left end of the main cavity body 12 is provided with a third communicating channel 123, the right end of the main cavity body 12 is provided with a fourth communicating channel 124, the front side of the main cavity body 12 is provided with a fifth communicating channel 125, and the rear side of the main cavity body 12 is provided with a sixth communicating channel 126. The first flange 14 is bolted to the left end outer wall of the main cavity body 12 and is correspondingly connected to the third communicating channel. Channel 123, the second flange 15 is bolted to the outer wall of the right end of the main cavity body 12 and is correspondingly connected to the fourth connecting channel 124, wherein the ion funnel device 30 is bolted to the first flange 14, and the second flange 15 is used to bolt the time-of-flight mass spectrometer. The lower end of the main cavity body 12 is also provided with a first through hole 127 connected to the second connecting channel 122, and the upper cover flange 13 is provided with a second through hole 131, a third through hole 132, a fourth through hole 133 and a fifth through hole 134. The first through hole 127 is used to connect the ionization gauge, the second through hole 131 is used to cooperate with the guide device 40 and to connect the small molecule pump, the third through hole 132, the fourth through hole 133, the fifth through hole 134, the fifth connecting channel 125 and the sixth connecting channel 126 are all used for electrode terminals, and the second connecting channel 122 is used to connect the molecular pump. With the above structure, the main cavity assembly 10 is matched with the detachable main cavity body 12, the upper cover flange 13, the first flange 14 and the second flange 15. The structure is simple, easy to disassemble and maintain, and fixed by bolting, which further makes the connection more reliable and stable, and the installation and cost are low.

[0067] It is understandable that, referring to Figure 1 and Figure 2 In some embodiments of the present invention, the third connecting channel 123 and the fourth connecting channel 124 correspond to each other and their axes coincide with each other. The electrospray ion source device 20, the ion funnel device 30, the guide device 40, the quadrupole mass analyzer 50, the linear ion trap and the detector are all arranged in sequence from left to right along the axis direction of the third connecting channel 123 and the fourth connecting channel 124. Ions can pass through and be transmitted in sequence, which is beneficial to reduce ion loss and drift, improve the efficiency and stability of ion transmission, and effectively utilize space, and make the design of the entire in-situ device for studying the kinetics of ion-molecule reactions more compact.

[0068] Specifically, refer to Figure 1 and Figure 2In some embodiments of the present invention, the center lines of the electrospray ion source device 20, the ion funnel device 30, the guide device 40 and the quadrupole mass analyzer 50 coincide, which further makes the direction of ion movement consistent, which is beneficial to reduce ion loss and drift and improve ion transmission efficiency and stability.

[0069] Specifically, refer to Figure 1 and Figure 2 In some embodiments of the present invention, the electrospray ion source device 20 is bolted to the ion funnel device 30. The ion funnel device 30, the guide device 40, and the quadrupole mass analyzer 50 are all bolted to the main cavity assembly 10. The guide device 40 and the quadrupole mass analyzer 50 are bolted together. The bolted connection method described above allows connection and separation by tightening or loosening the bolts, making it very convenient for maintenance, replacement, or adjustment without requiring destructive operations on other parts. The structure is simple to install, easy to disassemble, and has a low cost.

[0070] It is understandable that, referring to Figure 1 、 Figure 2 and Figure 3 In some embodiments of the present invention, the electrospray ion source device 20 includes: a mounting component 21, the mounting component 21 is mounted on one side of the ion funnel device 30, the mounting component 21 extends into the ion funnel device 30 toward one end of the ion funnel device 30, and the mounting component 21 is provided with a liquid inlet channel and a mounting channel; a spray needle 22, the spray needle 22 is arranged in the mounting channel and extends into the ion funnel device 30, the liquid inlet end of the spray needle 22 is connected to the liquid inlet channel, and the spraying end of the spray needle 22 is connected to the ion funnel device 30; a sliding cover 23, which is slidably mounted on one end of the mounting component 21, and a partial area of ​​the sliding cover 23 is located in the ion funnel device 30, the sliding cover 23 cooperates with the area of ​​the mounting component 21 corresponding to the spray needle 22, and the sliding cover 23 slides relative to the mounting component 21 so that the spray needle 22 can be extended or accommodated in the sliding cover 23.

[0071] With the above structure, during installation, the mounting assembly 21 is bolted to one side of the ion funnel device 30, and a DC high voltage is applied to the spray needle 22. Driven by the high voltage electric field, the sample solution in the spray needle 22 forms very fine charged droplets. By continuously applying power, the solvent in the droplets gradually evaporates, the droplet volume becomes smaller, and the surface charge density increases, forming a strong electrostatic field to ionize the polar molecules. Finally, ions are sputtered from the droplet surface to obtain gas-phase ions, which are finally transmitted to the next device, namely the ion funnel device 30. The ionization process is gentle and will not destroy the original spatial structure of the sample solution. In addition, by providing a sliding cover 23, the sliding cover 23 protects, guards and stabilizes the spray needle 22, which is beneficial to improving the performance and working efficiency of the electrospray ion source device 20 and ensuring accurate and reliable mass spectrometry analysis results.

[0072] Specifically, refer to Figure 1 、 Figure 2 and Figure 3 In some embodiments of the present invention, the above-mentioned mounting assembly 21 includes a mounting base 211, a mounting sleeve 212, a joint body 213, a first inner core 214, a second inner core 215 and a nut fixing piece 216. The mounting base 211 is bolted to the ion funnel device 30, and the joint body 213 is inserted into the end of the mounting base 211 away from the ion funnel device 30, and the two are screwed together. The first inner core 214 is inserted into the end of the joint body 213 facing the mounting base 211, the second inner core 215 is passed through the nut fixing piece 216 and is inserted into the end of the joint body 213 away from the mounting base 211, the mounting sleeve 212 is sleeved on the mounting base 211 and the joint body 213, and the nut fixing piece 216 is screwed to the joint body 213 to limit The second inner core 215 is prevented from being separated from the connector body 213, and the nut fixing member 216 abuts against the end of the mounting sleeve 212 away from the mounting base 211 to limit the axial movement of the mounting sleeve 212. The second inner core 215 is provided with the aforementioned liquid inlet channel, the first inner core 214 is provided with a first channel, and the mounting base 211 is provided with a boss 2111 at the end facing the ion funnel device 30. The sliding cover 23 is slidably mounted on the boss 2111, and the sliding cover 23 and the boss 2111 are compressed and positioned by bolts to limit the movement of the sliding cover 23. The boss 2111 is inserted into the interior of the ion funnel device 30 and provided with a second channel. The first channel and the second channel communicate and cooperate to form the aforementioned mounting channel for mounting the spray needle 22. The above-mentioned structure is not only simple in structure, but also easy to disassemble and maintain, and has a low installation cost.

[0073] Specifically, refer to Figure 1 、 Figure 2 and Figure 3 In some embodiments of the present invention, the centerline of the spray needle 22 and the centerline of the entrance to the transmission region of the ion funnel device 30 coincide, providing a more accurate and efficient ion transmission path. The coincident centerlines ensure a straight-line transmission of ions from the spray needle 22 into the transmission region, reducing possible deflection or scattering, thereby improving ion transmission efficiency. This can also reduce ion loss during transmission and avoid unnecessary interference and influence on ions during transmission, thereby improving ion quality and accuracy and obtaining more reliable results in applications such as mass spectrometry. In some embodiments, the centerline of the spray needle 22 and the centerline of the entrance to the transmission region of the ion funnel device 30 may be offset, or their extensions may intersect, without limitation.

[0074] Specifically, in some embodiments of the present invention, a sample solution is sprayed from a needle 22 with a voltage of 0-5000 volts (high voltage electric field) to form very fine charged droplets. A DC high voltage is applied to the needle 22, so that the sample solution in the needle 22 forms a cone at the tip of the needle 22 under the drive of the high voltage electric field, called a Taylor cone, and continuously emits micron-sized charged droplets from the tip of the Taylor cone. The solvent in the droplets is accelerated to evaporate by an auxiliary gas, which reduces the surface area of ​​the droplets, increases the number of like charges gathered on the surface, increases the Coulomb force between the charges, and finally causes a Coulomb explosion, generating smaller charged droplets. The charged droplets further explode, and the cycle repeats, ultimately obtaining gas-phase ions that enter the transmission device for analysis and detection.

[0075] It is understandable that, referring to Figure 2 、 Figures 4 to 6 In some embodiments of the present invention, the ion funnel device 30 includes: an ion source cover 31, the interior of the ion source cover 31 is an atmospheric environment, one end of the ion source cover 31 is provided with an insertion channel 311, the electrospray ion source device 20 is connected to the ion source cover 31, and the ejection end of the electrospray ion source device 20 extends into the ion source cover 31 along the insertion channel 311; a first vacuum chamber 32, one end of the first vacuum chamber 32 is connected to the ion source cover 31, and the other end is connected to the main chamber component 10; an injection structure, the injection structure includes an injection capillary Tube 33, ion funnel 34 and heating and fixing assembly 35 for heating the injection capillary 33, the heating and fixing assembly 35 is located in the ion source cover 31, and the heating and fixing assembly 35 is connected to the first vacuum chamber 32, the injection capillary 33 is passed through and installed on the heating and fixing assembly 35, and one end of the injection capillary 33 extends into the first vacuum chamber 32, the ion funnel 34 is installed in the first vacuum chamber 32, and the ion funnel 34 is connected to the guide device 40; wherein, the center lines of the injection capillary 33 and the ion funnel 34 coincide.

[0076] With the above structure, the mounting assembly 21, i.e., the mounting base 211, is bolted to the ion source cover 31. The spray needle 22 guides droplets through the ion source cover 31 and into the sampling capillary 33 and ion funnel 34 for collection and transmission. The ion source cover 31, disposed between the sampling capillary 33 and the spray needle 22, satisfies the pressure gradient difference in the atmospheric environment. Simultaneously, the heating fixture 35 heats the sampling capillary 33, facilitating the complete conversion of droplets into gas-phase ions and their transmission. Furthermore, the ion funnel 34 plays an important role in collecting, focusing, purifying, and transmitting ions, thereby improving ion signal intensity, the analytical sensitivity, and resolution of the device, and thus providing accurate and reliable mass spectrometric data. Furthermore, the centerline alignment of the sampling capillary 33 and the ion funnel 34 helps optimize ion transmission efficiency, minimize signal loss, and enhance ion selectivity.

[0077] It should be noted that in some embodiments of the present invention, an insertion channel 311 is provided on the end of the ion source cover 31 facing the electrospray ion source device 20, which is installed in conjunction with the slide cover 23. When the mounting base is removed, the slide cover 23 can be separated from the insertion channel 311 without hindrance, and the disassembly and assembly are convenient; the ion funnel 34 includes a plurality of annular electrodes with the same outer diameter and coaxially arranged at equal intervals, and the inner diameters of the plurality of annular electrodes decrease from left to right; the ion funnel device 30 also includes a drive plate for controlling the working state of the ion funnel 34 and a shielding box 36 covered on the outside of the drive plate, and a coil and some interfaces are provided on the drive plate for applying DC voltage and radio frequency; a flange for connecting a mechanical pump is provided on the first vacuum chamber 32 to draw vacuum from the first vacuum chamber 32.

[0078] Specifically, refer to Figure 4 In some embodiments of the present invention, a gap is provided between the facing end surfaces of the injection capillary 33 and the ion funnel 34. This structure helps reduce the risk of sample contamination. Samples may contain impurities or contaminants. Providing a certain gap can reduce the likelihood of these impurities or contaminants entering the ion funnel 34, optimizing ion transmission and thus protecting the normal operation of the device.

[0079] Specifically, refer to Figures 4 to 6In some embodiments of the present invention, the heating and fixing assembly 35 includes: a fixing seat 351, which is connected to the first vacuum chamber 32; a heating base 352, which is fixedly arranged on one side of the fixing seat 351, and the heating base 352 is provided with a first fixing sleeve 3521 and a second fixing sleeve 3522; a heating pressure ring 353, which is connected to the heating base 352, and a ceramic heating element 354 is provided between the heating base 352 and the heating pressure ring 353; a cover 355, which is connected to the heating pressure ring 353, and the cover 355 is covered on the heating pressure ring 353; wherein, the end of the first fixing sleeve 3521 away from the heating base 352 is located in the enclosed area of ​​the heating base 352, the ceramic heating element 354, the heating pressure ring 353 and the cover 355; the second fixing sleeve 3522 passes through the fixing seat 351 and the first vacuum chamber 32 in sequence, and extends into the interior of the first vacuum chamber 32. With the above structure, the sampling capillary 33 is sequentially inserted with the cover 355, the heating pressure ring 353, the ceramic heating element 354, the heating base 352, the fixing seat 351 and the first vacuum chamber 32. The structure is compact, which can improve the installation stability of the sampling capillary 33. Moreover, through the ceramic heating element 354, the structure is simple, the volume and weight are small, and the sampling capillary 33 can be quickly responded to heating requirements and provide stable temperature control and fast and uniform heating.

[0080] It is understandable that a first sealing ring, a thermal insulation pad 356 and a second sealing ring are sequentially arranged between the fixing seat 351 and the heating base 352 , thereby improving the thermal insulation and sealing between the fixing seat 351 and the heating base 352 .

[0081] Specifically, refer to Figures 4 to 6 In some embodiments of the present invention, a fixing plate 321 is provided on the side wall of the first vacuum chamber 32 facing the guide device 40, and the ion funnel 34 is connected to the fixing plate 321; two extension plates 3511 are provided on the end of the fixing seat 351 facing the first vacuum chamber 32, and the two extension plates 3511 are spaced apart and arranged opposite to each other, and each extension plate 3511 extends into the first vacuum chamber 32 and is connected to the fixing plate 321; wherein, the second fixing sleeve 3522, the sampling capillary 33 and the ion funnel 34 are all located in the enclosed area of ​​the fixing seat 351, the fixing plate 321 and the two extension plates 3511, which is conducive to improving the position of the sampling capillary 33 and the ion funnel 34 to be fixed in a stable area, preventing them from moving or shaking, ensuring that the center lines of the sampling capillary 33 and the ion funnel 34 are aligned and coincident, and helping to ensure accurate sample injection and ion transmission accuracy.

[0082] Specifically, refer to Figures 4 to 6In some embodiments of the present invention, a first lens 3211 is provided on the fixing plate 321. The first lens 3211 is mounted on one end of the first vacuum chamber 32 facing the guide device 40. The first lens 3211 is provided with a tapered hole corresponding to the centerline of the ion funnel 34, so that the ion funnel 34 is connected to the guide device 40 through the tapered hole of the first lens 3211. Through the above-mentioned structure, a single lens plays a key role in ion focusing, ion separation, and ion deceleration, which can optimize the transmission and screening effects of the ion beam and improve the accuracy and reliability of the mass spectrometry analysis of the equipment. It can be understood that in this embodiment, the fixing plate 321 and the first lens 3211 are fixedly connected by bolting.

[0083] It is understandable that, referring to 1, Figure 2 、 Figure 7 and Figure 8 In some embodiments of the present invention, the guide device 40 includes: a second vacuum chamber 41 connected to the main chamber assembly 10, with one end of the second vacuum chamber 41 open toward the ion funnel assembly 30; a fixed tube 42 with both ends open, located within the second vacuum chamber 41, and one end of the fixed tube 42 connected to the side wall of the second vacuum chamber 41 facing away from the ion funnel assembly 30; a guide rod assembly 43 located within the fixed tube 42, the guide rod assembly 43 being provided with a guide channel 431, one end of the guide channel 431 being connected to the outlet end of the transmission region of the ion funnel assembly 30, and the other end being connected to the quadrupole mass analyzer 50; wherein the guide rod assembly 43 is fixedly connected to the inner wall of the fixed tube 42 via a fixing ring 44. It can be understood that in this embodiment, the second vacuum chamber 41 is fixedly connected to the first flange 14 of the main chamber assembly 10 by bolting.

[0084] By adopting the above structure and through the structural design of the above-mentioned guiding device 40, ions enter the second vacuum chamber 41 from the ion funnel 34, and are then transmitted to the quadrupole mass analyzer 50 through the guiding channel 431 in the guiding rod assembly 43 for analysis. The design of the guiding device 40 can ensure the smooth transmission of ions, reduce the loss and interference of ions during the transmission process, and improve the accuracy and sensitivity of the analysis.

[0085] Specifically, refer to Figure 7 and Figure 8In some embodiments of the present invention, the guide rod assembly 43 includes four guide rods 432, which are spaced apart and arranged in pairs opposite to each other, so as to form a guide channel 431 in the center of the area surrounded by the four guide rods 432; the guide rods 432 are provided with connecting holes, and the fixing ring 44 is provided with a fixing channel 441 for the four guide rods 432 to pass through. The sidewall of the fixing channel 441 is provided with four positioning grooves 442, which are spaced apart and arranged around the center line of the fixing channel 441, and each guide rod 432 is sequentially engaged with each positioning groove 442; wherein the guide rods 432, the fixing ring 44, and the fixing cylinder 42 are connected by a connecting structure. Through the above arrangement, the four guide rods 432 of the guide assembly are positioned to ensure that the position of the guide rods 432 in the fixing channel 441 is accurate and stable. Each guide rod 432 has a shape and size that matches the positioning groove 442, so that the guide rod 432 can be accurately inserted into the corresponding positioning groove 442. Through the snap-fit ​​and connection structure, the guide rod 432 can be fixed in the positioning groove 442 to ensure that its position will not shift or shake, which helps to maintain the overall stability of the guide rod assembly 43 and ensure that ions are accurately transmitted along the fixed channel 441 during transmission.

[0086] Specifically, refer to Figure 7 and Figure 8 In some embodiments of the present invention, the above-mentioned connecting structure is a connecting bolt, a connecting screw hole 4321 is provided on the guide rod 432, and each positioning groove 442 of the fixing ring 44 is provided with a positioning hole 443 that passes through the side wall of the fixing ring 44. The fixing cylinder 42 is provided with four fixing holes 421, and the connecting screw holes 4321, the positioning holes 443 and the fixing holes 421 correspond to each other one by one. The fixing holes 421, the positioning holes 443 and the connecting screw holes 4321 are sequentially penetrated by the connecting bolts, and the connecting bolts are screwed together with the guide rod 432 to fix the fixing ring 44 and the guide rod 432 to the fixing cylinder 42.

[0087] It should be noted that in some embodiments of the present invention, there are two of the above-mentioned fixing rings 44, and an annular limit platform 422 is provided on the end of the fixing cylinder 42 facing the quadrupole mass analyzer 50, and a positioning protrusion 4322 is provided on the side wall of each guide rod 432 facing away from the guide channel 431. The two fixing rings 44 are arranged at intervals in the fixing cylinder 42, and the two fixing rings 44 respectively abut against the two sides of the positioning protrusion 4322. One of the fixing rings 44 close to the quadrupole mass analyzer 50 abuts against the annular limit platform 422, thereby further limiting the relative position of the guide assembly and the fixing cylinder 42, with a compact structure and good stability.

[0088] Specifically, refer to Figure 7 and Figure 8In some embodiments of the present invention, a second lens 45 is provided on the end of the second vacuum chamber 41 facing away from the ion funnel device 30. The second lens 45 has a guide hole, which is connected to the entrance end of the quadrupole mass analyzer 50. The fixed cylinder 42 is arranged around the second lens 45, and the guide channel 431 formed by the four guide rods 432 of the guide rod assembly 43 is connected to the quadrupole mass analyzer 50 through the guide hole of the second lens 45. Through the above arrangement, the use of the second lens 45 is conducive to optimizing ion transmission, improving transmission efficiency and quality, and thus accurately positioning and focusing the ion beam. The fixed cylinder 42 can effectively reduce the impact of external vibration and mechanical interference on the second lens 45, thereby improving the stability and anti-interference capability of the system and facilitating accurate ion transmission.

[0089] It should be noted that, referring to Figure 7 and Figure 8 In some embodiments of the present invention, the second lens 45 is detachably mounted on the second vacuum chamber 41 by bolting via an insulating ring. A bellows 60 is connected to a side wall of the second vacuum chamber 41. The bellows 60 is correspondingly connected to the second through hole 131, and the two ends of the bellows 60 are respectively bolted to the second vacuum chamber 41 and the upper cover flange 13. This has a simple structure and is easy to disassemble and maintain.

[0090] 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 make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. An in-situ device for studying the kinetics of ion-molecule reactions, characterized in that: include: Main cavity assembly (10); an electrospray ion source device (20), for converting a sample solution into gas-phase ions; An ion funnel device (30) is provided on one side of the main cavity assembly (10), the ion funnel device (30) is used to focus and transmit the gas phase ions, and one end of the ion funnel device (30) is connected to the electrospray ion source device (20); A guiding device (40), provided in the main cavity assembly (10), for guiding the gas phase ions; A quadrupole mass analyzer (50) is provided in the main cavity assembly (10), and the quadrupole mass analyzer (50) has a first working state and a second working state. In the first working state, under the condition that only radio frequency exists, the quadrupole mass analyzer (50) guides ions; in the second working state, under the condition that radio frequency and direct current voltage exist at the same time, the quadrupole mass analyzer (50) selects single mass ion clusters; A linear ion trap is provided in the main cavity assembly (10), a target gas can be introduced into the linear ion trap, and gas-phase ions guided into the linear ion trap by the quadrupole mass analyzer (50) can react with the target gas introduced into the linear ion trap; Detector, used to collect and receive signals; Wherein, the electrospray ion source device (20), the ion funnel device (30), the guide device (40), the quadrupole mass analyzer (50), the linear ion trap and the detector are arranged in sequence and are connected; The ion funnel device (30) comprises: An ion source cover (31), wherein the interior of the ion source cover (31) is an atmospheric environment, an insertion channel (311) is provided at one end of the ion source cover (31), the electrospray ion source device (20) is connected to the ion source cover (31), and the ejection end of the electrospray ion source device (20) extends into the ion source cover (31) along the insertion channel (311); A first vacuum chamber (32), one end of the first vacuum chamber (32) being connected to the ion source cover (31), and the other end being connected to the main chamber assembly (10); An injection structure, the injection structure comprising an injection capillary (33), an ion funnel (34) and a heating and fixing assembly (35) for heating the injection capillary (33), the heating and fixing assembly (35) being located in the ion source cover (31), and the heating and fixing assembly (35) being connected to the first vacuum chamber (32), the injection capillary (33) being passed through and mounted on the heating and fixing assembly (35), and one end of the injection capillary (33) extending into the first vacuum chamber (32), the ion funnel (34) being mounted on the first vacuum chamber (32), and the ion funnel (34) being in communication with the guiding device (40); Wherein, the center lines of the injection capillary (33) and the ion funnel (34) coincide with each other; The guiding device (40) comprises: a second vacuum chamber (41) connected to the main chamber assembly (10), the second vacuum chamber (41) being arranged with an opening at one end facing the ion funnel device (30); a fixed cylinder (42) with openings at both ends, the fixed cylinder (42) being located in the second vacuum chamber (41), and one end of the fixed cylinder (42) being connected to a side wall of the second vacuum chamber (41) facing away from the ion funnel device (30); a guide rod assembly (43) located in the fixed cylinder (42), the guide rod assembly (43) being provided with a guide channel (431), one end of the guide channel (431) being connected to the outlet end of the transmission region of the ion funnel device (30), and the other end being connected to the quadrupole mass analyzer (50); The guide rod assembly (43) is fixedly connected to the inner wall of the fixed cylinder (42) via a fixing ring (44).

2. The in-situ device for studying ion-molecule reaction kinetics according to claim 1, characterized in that: The electrospray ion source device (20) comprises: a mounting assembly (21), the mounting assembly (21) being mounted on one side of the ion funnel device (30), one end of the mounting assembly (21) facing the ion funnel device (30) extending into the ion funnel device (30), and the mounting assembly (21) being provided with a liquid inlet channel and a mounting channel; A spray needle (22), the spray needle (22) being arranged in the installation channel and extending into the ion funnel device (30), the liquid inlet end of the spray needle (22) being connected to the liquid inlet channel, and the ejection end of the spray needle (22) being connected to the ion funnel device (30); A sliding cover (23) is slidably mounted on one end of the mounting assembly (21), and a partial area of ​​the sliding cover (23) is located in the ion funnel device (30). The sliding cover (23) cooperates with an area on the mounting assembly (21) corresponding to the spray needle (22). The sliding cover (23) slides relative to the mounting assembly (21) so that the spray needle (22) can be extended or accommodated in the sliding cover (23).

3. The in-situ device for studying ion-molecule reaction kinetics according to claim 1, characterized in that: The heating and fixing assembly (35) comprises: a fixing seat (351), the fixing seat (351) being connected to the first vacuum chamber (32); A heating base (352) is fixedly arranged on one side of the fixing seat (351), and the heating base (352) is provided with a first fixing sleeve (3521) and a second fixing sleeve (3522); A heating pressure ring (353) is connected to the heating base (352), and a ceramic heating element (354) is provided between the heating base (352) and the heating pressure ring (353); A cover body (355) is connected to the heating pressure ring (353), and the cover body (355) is provided to cover the heating pressure ring (353); The end of the first fixed sleeve (3521) facing away from the heating base (352) is located in the area enclosed by the heating base (352), the ceramic heating element (354), the heating pressure ring (353) and the cover (355); the second fixed sleeve (3522) passes through the fixed seat (351) and the first vacuum chamber (32) in sequence, and extends into the interior of the first vacuum chamber (32).

4. The in-situ device for studying ion-molecule reaction kinetics according to claim 3, characterized in that: A fixing plate (321) is provided on a side wall of one end of the first vacuum chamber (32) facing the guiding device (40), and the ion funnel (34) is connected to the fixing plate (321); Two extension plates (3511) are provided on one end of the fixing seat (351) facing the first vacuum cavity (32), the two extension plates (3511) are spaced apart and arranged facing each other, and each extension plate (3511) extends into the first vacuum cavity (32) and is connected to the fixing plate (321); The second fixed sleeve (3522), the injection capillary (33) and the ion funnel (34) are all located in an area enclosed by the fixed seat (351), the fixed plate (321) and the two extended plates (3511).

5. The in-situ device for studying ion-molecule reaction kinetics according to claim 4, characterized in that: A first lens (3211) is provided on the fixing plate (321). The first lens (3211) is mounted on one end of the first vacuum chamber (32) facing the guiding device (40). The first lens (3211) is provided with a conical hole corresponding to the center line of the ion funnel (34), so that the ion funnel (34) is connected to the guiding device (40) through the conical hole of the first lens (3211).

6. The in-situ device for studying ion-molecule reaction kinetics according to claim 1, characterized in that: The guide rod assembly (43) includes four guide rods (432), and the four guide rods (432) are spaced apart and arranged opposite to each other in pairs, so that the guide channel (431) is formed in the middle of the area surrounded by the four guide rods (432); The fixing ring (44) is provided with a fixing channel (441) for the four guide rods (432) to pass through, and the side wall of the fixing channel (441) is provided with four positioning grooves (442). The four positioning grooves (442) are spaced apart and arranged around the center line of the fixing channel (441), and each guide rod (432) is engaged with each positioning groove (442) in sequence. The guide rod (432), the fixing ring (44) and the fixing cylinder (42) are connected via a connecting structure.

7. The in-situ device for studying ion-molecule reaction kinetics according to claim 1 or 6, characterized in that: A second lens (45) is provided on one end of the second vacuum chamber (41) facing away from the ion funnel device (30), and the second lens (45) is provided with a guide hole, and the guide hole is connected to the inlet end of the quadrupole mass analyzer (50); The fixed cylinder (42) is arranged around the second lens (45), and the guide channel (431) of the guide rod assembly (43) is connected to the quadrupole mass analyzer (50) through the guide hole of the second lens (45).

8. The in-situ device for studying ion-molecule reaction kinetics according to claim 1, characterized in that: The main cavity assembly (10) is provided with a main cavity (11); The guiding device (40), the quadrupole mass analyzer (50) and the linear ion trap are all located in the main chamber (11), and the electrospray ion source device (20) and the ion funnel device (30) are both located outside the main chamber (11); The electrospray ion source device (20) is bolted to the ion funnel device (30), the ion funnel device (30), the guide device (40) and the quadrupole mass analyzer (50) are all bolted to the main cavity assembly (10), and the guide device (40) and the quadrupole mass analyzer (50) are bolted together.

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