A high-inertance electrostatically dissipative collision cell device and mass spectrometer system thereof

Abstract

The application discloses a high-inert electrostatic dissipation type collision cell device and a mass spectrometer system thereof, comprising a collision cell device, one end of the collision cell device is connected with a first quadrupole mass analyzer, the other end of the collision cell device is connected with a third quadrupole mass analyzer, and a metal flange is assembled at the positions where the collision cell device is connected with the first quadrupole mass analyzer and the third quadrupole mass analyzer.The high-inert electrostatic dissipation type collision cell device and the mass spectrometer system thereof increase a gas path precise regulation and control module, the module can accurately adjust the gas inlet flow, pressure and gas inlet rate of the collision gas according to the type and ion property of the detected sample, cooperates with a gas flow guide structure in the gas chamber shell, realizes uniform distribution of the collision gas in the gas chamber, supports dynamic switching and precise proportioning of the collision gas at the same time, adapts to different collision dissociation requirements, and improves the universality and detection flexibility of the device.

Description

Technical Field

[0001] This invention relates to the field of analytical instrument technology, and in particular to a highly inert electrostatic dissipation collision cell device and its mass spectrometer system. Background Technology

[0002] Triple quadrupole mass spectrometers are the gold standard in the field of quantitative analysis and are widely used in food safety testing, environmental pollutant monitoring, pharmaceutical research and development and drug metabolism analysis, biological sample testing and other fields. The collision cell, as its core component, is the key site for ion collision-induced dissociation and directly determines the sensitivity, accuracy and stability of mass spectrometry detection.

[0003] In existing technologies, the collision cell outer shell of triple quadrupole mass spectrometers is generally made of metals such as stainless steel and molybdenum. This design reveals several inherent defects in practical applications, severely limiting the detection performance and efficiency of the mass spectrometer: First, even after passivation, the metal surface retains strong chemical activity, easily causing non-specific adsorption of analytes such as polar compounds, acid-base compounds, phosphorus- and sulfur-containing compounds, and peptides, resulting in significant ion loss during transport and a substantial reduction in detection sensitivity. Second, analytes adsorbed on the metal inner wall are difficult to completely remove, easily forming residues that are slowly released in subsequent blank or low-concentration sample analyses, producing a severe memory effect, leading to falsely high limits of quantitation and compromising the accuracy of quantification for low-concentration samples. Third, to mitigate the memory effect, operators need to frequently perform prolonged baking or strong acid / solvent cleaning of the collision cell, which is not only cumbersome but also... The problems include: excessive downtime, significantly reducing the efficiency of high-throughput analysis; contaminants or oxide layers on metal surfaces releasing ions under specific conditions such as plasma glow discharge, creating chemical background noise and reducing the signal-to-noise ratio; and the lack of precise control over the collision gas inlet method in traditional collision cells, resulting in uneven gas distribution within the chamber and inconsistent ion collision dissociation efficiency, further affecting the repeatability of detection results. To address these issues, researchers have attempted to modify the surface of the metal collision cell, but the modified layer has poor adhesion to the metal substrate and is prone to detachment during long-term use, and cannot simultaneously achieve the dual effects of high inertia and electrostatic dissipation. Attempts have also been made to use pure insulating dielectric materials to fabricate the collision cell shell, but the accumulation of static charge leads to distortion of the ion transport electric field, resulting in significant signal fluctuations. Therefore, we propose a high-inertia electrostatic dissipation collision cell device and its mass spectrometer system. Summary of the Invention

[0004] Technical Problem Solved: To address the shortcomings of existing technologies, this invention provides a high-inert electrostatic dissipation collision cell device and its mass spectrometer system. It adds a precise gas path control module, which can precisely adjust the inlet flow rate, pressure, and inlet speed of the collision gas according to the type and ionic properties of the sample being detected. Combined with the airflow guiding structure inside the gas chamber shell, this achieves uniform distribution of the collision gas within the chamber, solving the problems of inconsistent ion collision dissociation efficiency and poor repeatability of detection results caused by uneven local concentrations of the collision gas in existing devices. Simultaneously, the gas path control module supports dynamic switching and precise proportioning of the collision gas, adapting to the collision dissociation requirements of different types of analytes, significantly improving the versatility and detection flexibility of the device, and effectively solving the problems in the background technology.

[0005] Technical Solution: To achieve the above objectives, the technical solution adopted by this invention is as follows: A high-inertia electrostatic dissipation collision cell device, comprising a collision cell device, one end of which is connected to a single-stage quadrupole mass analyzer, and the other end of which is connected to a triple quadrupole mass analyzer. A metal flange is assembled at the connection points of the collision cell device to the single-stage and triple quadrupole mass analyzers. A collision gas inlet pipe is provided at the end of the metal flange connected to the single-stage quadrupole mass analyzer. A gas path control module is provided at the collision gas inlet pipe. A gas chamber shell is positioned on the outer side of the collision cell device. A multi-stage rod electrode assembly is provided inside the collision cell device. The multi-stage rod electrode assembly is connected to a radio frequency voltage generator. A high-vacuum sealing structure is provided between the collision cell device and the metal flange. An electrostatic dissipation layer, a metal substrate, and a high-resistivity coating are provided on the outer side of the gas chamber shell. The collision cell device has two structures.

[0006] As a preferred technical solution of this application, in the first structure, the collision cell device is an integral electrostatic dissipative quartz tube structure, including a single-stage quadrupole mass analyzer, a triple-stage quadrupole mass analyzer, a gas path control module, a radio frequency voltage generator, a gas chamber shell, a multi-stage rod electrode assembly, a metal flange, a collision gas inlet pipeline, a high-vacuum sealing structure, and an electrostatic dissipation layer. The gas chamber shell on the collision cell device is an integral doped quartz round tube. The metal flanges at both ends of the gas chamber shell are respectively connected to the single-stage quadrupole mass analyzer and the triple-stage quadrupole mass analyzer. The multi-stage rod electrode assembly inside the collision cell device is a molybdenum rod structure, which is fixed to the metal flange by a ceramic bracket.

[0007] As a preferred technical solution of this application, in the second structure, the collision cell device is a coated electrostatic dissipation structure, including a single-stage quadrupole mass analyzer, a triple-stage quadrupole mass analyzer, a gas path control module, a radio frequency voltage generator, a gas chamber shell, a multi-stage rod electrode assembly, a metal flange, a collision gas inlet pipeline, a high-vacuum sealing structure, an electrostatic dissipation layer, a metal substrate, and a high-resistivity coating. The gas chamber shell on the collision cell device is a coated structure. The metal substrate is made of stainless steel, and after the inner wall of the stainless steel is precisely cleaned and polished, a high-resistivity coating with a thickness of micrometers is uniformly deposited on the inner wall using a PVD process. The high-resistivity coating is electrically connected to the metal flange.

[0008] As a preferred technical solution of this application, in the third structure, the outer shell of the air chamber includes a quartz tube segment structure and a coated metal segment structure. A flange positioning mechanism is provided between the quartz tube segment structure and the coated metal segment structure. The flange positioning mechanism includes an inner sealing ring, a high-precision flange, bolts, an outer sealing ring, and nuts. The inner sealing ring is located inside the high-precision flange, and the outer sealing ring is located outside the high-precision flange. The bolts and nuts are located at both ends of the high-precision flange. The quartz tube segment structure and the coated metal segment structure are sealed and positioned by the flange positioning mechanism.

[0009] As a preferred technical solution of this application, an auxiliary air intake pipe is provided on the outside of the metal flange, and ion guide ring assemblies are positioned inside both the first-stage quadrupole mass analyzer and the third-stage quadrupole mass analyzer. A sealing ring is positioned on the outer ring of the ion guide ring assembly, an ion channel is positioned in the middle of the ion guide ring assembly, a channel groove is opened in the middle of the ion channel, a fin is positioned on the inner side of the ion channel, and guide ring bodies are positioned at both ends of the ion guide ring assembly, with fixing grooves opened on the guide ring bodies.

[0010] As a preferred technical solution of this application, the resistivity of the highly inert dielectric material with electrostatic dissipation characteristics in the collision pool device is 10. 8 Ω·cm to 10 12 Ω·cm, avoid 10 5 Good electrical conductivity range below Ω·cm.

[0011] As a preferred technical solution of this application, the two ends of the gas chamber shell are connected to the metal interfaces of the vacuum chambers of the first-stage quadrupole mass analyzer and the third-stage quadrupole mass analyzer through a high-vacuum sealing structure. The high-vacuum sealing structure is a mechanical compression seal, which uses a low-release O-ring and a metal C-ring to press between the end face of the gas chamber shell and the metal flange. The sealing structure ensures that the electrostatic dissipation layer and the high-resistance coating of the gas chamber shell are reliably electrically connected to the metal flange.

[0012] As a preferred technical solution of this application, the multi-stage rod electrode assembly is one of a hexapole, an octapole, or a bent quadrupole electrode assembly. The multi-stage rod electrode assembly is externally connected to a radio frequency voltage generator for applying a radio frequency field to confine the ion beam. The metal flange is integrated with a collision gas inlet pipe, and the outlet of the collision gas inlet pipe faces the inside of the gas chamber shell. The collision gas is one or a mixture of argon and nitrogen.

[0013] A high-inert electrostatic dissipation mass spectrometer system includes an ion source module, a mass analysis module, a dedicated module for a high-inert electrostatic dissipation collision cell, a vacuum module, a radio frequency high-voltage power supply module, and a signal detection and data processing module.

[0014] As a preferred technical solution of this application, the ion source module is compatible with electrospray ionization source, atmospheric pressure chemical ionization source, and matrix-assisted laser desorption / ionization source. The mass analysis module includes a single-stage quadrupole, a high-inert electrostatic dissipation collision cell device, and a triple-stage quadrupole. The dedicated supporting modules for the high-inert electrostatic dissipation collision cell include a gas path precision control module and an electrostatic dissipation and grounding module. The vacuum module consists of a mechanical pump, a molecular pump, a vacuum gauge tube, and vacuum pipelines. The radio frequency high-voltage power supply module provides stable radio frequency and DC power to the mass analysis module, using a high-precision digital power supply. The signal detection and data processing module consists of an industrial control computer, dedicated mass spectrometry analysis software, and a data storage unit.

[0015] Beneficial Effects: Compared with the prior art, the present invention provides a highly inert electrostatic dissipation collision cell device and its mass spectrometer system, which has the following beneficial effects: The highly inert electrostatic dissipation collision cell device and its mass spectrometer system significantly improve detection sensitivity and signal-to-noise ratio: The inner surface of the gas cell shell is made of a highly inert dielectric material with extremely low adsorption energy, which completely eliminates the non-specific adsorption loss of polar and active analytes. Target ions can pass through the collision cell efficiently, the signal intensity is increased by several times or even several orders of magnitude, and the signal-to-noise ratio is also greatly improved, meeting the needs of trace analysis.

[0016] Eliminating the memory effect and improving quantitative accuracy: The highly inert surface leaves no analyte adsorption residue. After high-concentration sample detection, subsequent blank detection can immediately recover to the baseline level, making the limit of quantitation more realistic and lower. This ensures accurate quantification over a wide dynamic range, making it particularly suitable for trace detection in fields with strict regulatory requirements such as food safety and environmental monitoring.

[0017] Stable ion transport and avoidance of electrostatic interference: By precisely controlling the resistivity of the dielectric material and reliably grounding it, the charging problem of pure insulating materials is solved, and the short-circuit interference and field distortion of the radio frequency field by good conductors are avoided. This ensures that the multi-stage rod electric field operates stably for a long time under a 0V reference background, eliminating the uncertainty of signal fluctuation and ion transport efficiency.

[0018] Improved collision-induced dissociation efficiency and guaranteed detection repeatability: The added gas path control module achieves uniform distribution of collision gas in the gas chamber, keeps the collision probability between ions and collision gas consistent, significantly improves collision-induced dissociation efficiency, and ensures repeatability and consistency of multiple detection results, reducing detection errors.

[0019] Significantly improves analytical throughput and reduces operating costs: This device eliminates the need for numerous blank and cleaning steps between high and low concentration sample detections, enabling a "test and go" detection mode that greatly shortens the single-sample analysis cycle. At the same time, the inert surface is corrosion-resistant and easy to clean, reducing the frequency of instrument maintenance and downtime caused by baking and cleaning, thus significantly reducing the total cost of ownership of the instrument.

[0020] Expanding the application scope of mass spectrometers: It solves the problem that traditional triple quadrupole mass spectrometers have extremely poor response or cannot detect highly adsorbed compounds such as free fatty acids, highly polar pesticides, acidic and basic groups in drug metabolism, and small molecule peptides, making routine and highly sensitive quantification of such compounds possible, and greatly expanding the application fields of mass spectrometers.

[0021] Reduce background interference and purify mass spectrometry signals: The dielectric shell can effectively isolate the plasma glow discharge in the collision cell, preventing it from interacting with metal components to generate unnecessary background ions. At the same time, it avoids the release of ions from contaminants and oxide layers on the metal surface, further purifying the mass spectrometry background and improving the accuracy of detection.

[0022] Flexible structure and strong versatility: The gas chamber shell is available in both integral and coated structures to adapt to different instrument modification and production needs; the gas path control module supports dynamic switching and precise ratio of collision gases, which can meet the collision dissociation requirements of different types of analytes. The versatility and adaptability of the device are greatly improved. The entire dissipative collision cell device and its mass spectrometer system have a simple structure, are easy to operate, and have better performance than traditional methods. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the overall structure of a high-inert electrostatic dissipation collision cell device and its mass spectrometer system according to the present invention.

[0024] Figure 2 This is a schematic diagram of the coating structure in the high inert electrostatic dissipation collision cell device and its mass spectrometer system of the present invention.

[0025] Figure 3 This is a schematic diagram of the split structure of a high-inert electrostatic dissipation collision cell device and its mass spectrometer system according to the present invention.

[0026] Figure 4This is a schematic diagram of the structure of the gas chamber shell in the high inert electrostatic dissipation collision cell device and its mass spectrometer system according to the present invention.

[0027] Figure 5 This is a magnified structural schematic diagram of point A in the high-inert electrostatic dissipation collision cell device and its mass spectrometer system of the present invention.

[0028] Figure 6 This is a magnified structural schematic diagram of point B in the high inert electrostatic dissipation collision cell device and its mass spectrometer system of the present invention.

[0029] Figure 7 This is a schematic diagram of the structure of the ion guiding ring assembly in the mass spectrometer system of a highly inert electrostatic dissipation collision cell device of the present invention.

[0030] In the diagram: 1. Single-stage quadrupole mass analyzer; 2. Collision cell device; 3. Three-stage quadrupole mass analyzer; 4. Gas path control module; 5. Radio frequency voltage generator; 6. Gas chamber shell; 7. Multistage rod electrode assembly; 8. Metal flange; 9. Collision gas inlet pipeline; 10. High vacuum sealing structure; 11. Static dissipation layer; 12. Metal substrate; 13. High-resistance coating; 14. Ion guide ring assembly; 15. Auxiliary inlet pipeline; 16. Quartz tube section structure; 17. Coated metal section structure; 18. Flange positioning mechanism; 19. Inner sealing ring; 20. High-precision flange; 21. Bolt; 22. Outer sealing ring; 23. Nut; 24. Sealing ring; 25. Ion channel; 26. Fin; 27. Channel groove; 28. Fixing groove; 29. ​​Guide ring body. Detailed Implementation

[0031] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0032] In the description of this invention, it should be noted that the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0033] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0034] like Figure 1-7 As shown, a high-inertia electrostatic dissipation collision cell device includes a collision cell device 2. One end of the collision cell device 2 is connected to a single-stage quadrupole mass analyzer 1, and the other end is connected to a triple quadrupole mass analyzer 3. A metal flange 8 is assembled at the connection between the collision cell device 2 and the single-stage quadrupole mass analyzer 1 and the triple quadrupole mass analyzer 3. A collision gas inlet pipe 9 is provided at the end of the metal flange 8 connected to the single-stage quadrupole mass analyzer 1. A gas path control module 4 is provided at the collision gas inlet pipe 9. A gas chamber shell 6 is positioned on the outside of the collision cell device 2. A multi-stage rod electrode assembly 7 is provided inside the collision cell device 2. The multi-stage rod electrode assembly 7 is connected to a radio frequency voltage generator 5. A high-vacuum sealing structure 10 is provided between the collision cell device 2 and the metal flange 8. An electrostatic dissipation layer 11, a metal substrate 12, and a high-resistivity coating 13 are provided on the outside of the gas chamber shell 6. The collision cell device 2 has two structures.

[0035] A new gas path precision control module has been added. This module can precisely adjust the inlet flow rate, pressure, and inlet speed of the collision gas according to the type and ionic properties of the sample being tested. In conjunction with the airflow guiding structure inside the gas chamber shell, it achieves uniform distribution of the collision gas within the gas chamber. This solves the problem of inconsistent ion collision dissociation efficiency and poor repeatability of detection results caused by uneven local concentration of collision gas in existing devices. At the same time, the gas path control module supports dynamic switching and precise ratio of collision gas, which can adapt to the collision dissociation requirements of different types of analytes, greatly improving the versatility and detection flexibility of the device.

[0036] In the first structure, the collision cell device 2 is an integral electrostatic dissipative quartz tube structure, including a single-stage quadrupole mass analyzer 1, a triple-stage quadrupole mass analyzer 3, a gas path control module 4, a radio frequency voltage generator 5, a gas chamber shell 6, a multi-stage rod electrode assembly 7, a metal flange 8, a collision gas inlet pipe 9, a high vacuum sealing structure 10, and an electrostatic dissipation layer 11. The gas chamber shell 6 on the collision cell device 2 is an integral doped quartz round tube. The metal flanges 8 at both ends of the gas chamber shell 6 are connected to the single-stage quadrupole mass analyzer 1 and the triple-stage quadrupole mass analyzer 3, respectively. The multi-stage rod electrode assembly 7 inside the collision cell device 2 is a molybdenum rod structure, which is fixed to the metal flange 8 by a ceramic bracket.

[0037] In the second structure, the collision cell device 2 is a coated electrostatic dissipation type structure, including a single-stage quadrupole mass analyzer 1, a three-stage quadrupole mass analyzer 3, a gas path control module 4, a radio frequency voltage generator 5, a gas chamber shell 6, a multi-stage rod electrode assembly 7, a metal flange 8, a collision gas inlet pipe 9, a high vacuum sealing structure 10, an electrostatic dissipation layer 11, a metal substrate 12, and a high-resistivity coating 13. The gas chamber shell 6 on the collision cell device 2 is a coated structure. The metal substrate 12 is made of stainless steel. After the stainless steel inner wall is precisely cleaned and polished, a high-resistivity coating 13 with a thickness of 3 micrometers is uniformly deposited on the inner wall using PVD process. The high-resistivity coating 13 is electrically connected to the metal flange 8.

[0038] In the third structure, the outer shell 6 of the air chamber includes a quartz tube segment structure 16 and a coated metal segment structure 17. A flange positioning mechanism 18 is provided between the quartz tube segment structure 16 and the coated metal segment structure 17. The flange positioning mechanism 18 includes an inner sealing ring 19, a high-precision flange 20, bolts 21, an outer sealing ring 22, and nuts 23. The inner sealing ring 19 is located inside the high-precision flange 20, and the outer sealing ring 22 is located outside the high-precision flange 20. Bolts 21 and nuts 23 are located at both ends of the high-precision flange 20. The quartz tube segment structure 16 and the coated metal segment structure 17 are sealed and positioned by the flange positioning mechanism 18.

[0039] An auxiliary air intake pipe 15 is provided on the outside of the metal flange 8. An ion guide ring assembly 14 is positioned inside both the first-stage quadrupole mass analyzer 1 and the third-stage quadrupole mass analyzer 3. A sealing ring 24 is positioned on the outer ring of the ion guide ring assembly 14. An ion channel 25 is positioned in the middle of the ion guide ring assembly 14. A channel groove 27 is opened in the middle of the ion channel 25. A fin 26 is positioned on the inner side of the ion channel 25. Guide ring bodies 29 are positioned at both ends of the ion guide ring assembly 14. A fixing groove 28 is opened on the guide ring body 29.

[0040] The resistivity of the highly inert dielectric material with electrostatic dissipation properties in collision pool device 2 is 10. 8 Ω·cm to 1012 Ω·cm, avoid 10 5 Good electrical conductivity range below Ω·cm.

[0041] The two ends of the gas chamber shell 6 are connected to the vacuum chamber metal interfaces of the first-stage quadrupole mass analyzer 1 and the third-stage quadrupole mass analyzer 3 through the high-vacuum sealing structure 10. The high-vacuum sealing structure 10 is a mechanical compression seal, which uses low-release O-rings and metal C-rings to press between the end face of the gas chamber shell 6 and the metal flange 8. The sealing structure ensures that the electrostatic dissipation layer 11 and the high-resistance coating 13 of the gas chamber shell 6 are reliably electrically connected to the metal flange 8.

[0042] The multi-stage rod electrode assembly 7 is one of a hexapole, octapole, or bent quadrupole electrode assembly. The multi-stage rod electrode assembly 7 is externally connected to a radio frequency voltage generator 5, which is used to apply a radio frequency field to confine the ion beam. The metal flange 8 is integrated with a collision gas inlet pipe 9. The outlet of the collision gas inlet pipe 9 faces the inside of the gas chamber shell 6. The collision gas is one or a mixture of argon and nitrogen.

[0043] A high-inert electrostatic dissipation mass spectrometer system includes an ion source module, a mass analysis module, a dedicated module for a high-inert electrostatic dissipation collision cell, a vacuum module, a radio frequency high-voltage power supply module, and a signal detection and data processing module.

[0044] The ion source module is compatible with electrospray ionization sources, atmospheric pressure chemical ionization sources, and matrix-assisted laser desorption / ionization sources. The mass analysis module includes a single-stage quadrupole, a high-inert electrostatic dissipation collision cell device, and a triple-stage quadrupole. The dedicated supporting modules for the high-inert electrostatic dissipation collision cell include a gas path precision control module and an electrostatic dissipation and grounding module. The vacuum module consists of a mechanical pump, a molecular pump, a vacuum gauge, and vacuum tubing. The RF high-voltage power supply module provides stable RF and DC power to the mass analysis module and adopts a high-precision digital power supply. The signal detection and data processing module consists of an industrial control computer, dedicated mass spectrometry analysis software, and a data storage unit.

[0045] The highly inert electrostatic dissipation mass spectrometry system uses a triple quadrupole tandem mass spectrometer as its core architecture. Addressing the limitations of traditional mass spectrometer collision cells, such as adsorption, memory effects, and electrostatic interference, it integrates a highly inert electrostatic dissipation collision cell as its core improved component. Combined with an ion source module, mass analysis module, vacuum module, gas path control module, RF / high-voltage power supply module, and signal detection and data processing module, it forms a complete, highly sensitive, and highly stable mass spectrometry analysis system. The system is suitable for trace / ultra-trace quantitative analysis in fields such as food safety, environmental monitoring, drug metabolism, biological sample detection, and chemical raw material analysis. It can efficiently detect highly adsorbed analytes that are difficult to detect with traditional mass spectrometers, such as polar compounds, acid-base compounds, phosphorus / sulfur-containing compounds, peptides, and free fatty acids.

[0046] Example 1: Integrated electrostatic dissipative quartz tube collision cell device and matching mass spectrometer system like Figure 1 As shown, a high-inertia electrostatic dissipation collision cell device and its mass spectrometer system include a collision cell device 2, a first-stage quadrupole mass analyzer 1 (Q1), a third-stage quadrupole mass analyzer 3 (Q3), a gas path control module 4, and a radio frequency voltage generator 5. The collision cell device 2 is disposed between Q1 and Q3.

[0047] The outer shell 6 of the gas chamber of the collision pool device 2 is an integral doped quartz round tube with an inner diameter of 20 mm and a length of 150 mm. The resistivity of the doped quartz is 10. 9 Ω·cm, possessing excellent electrostatic dissipation characteristics; the outer shell 6 of the gas chamber is provided with a front metal flange and a rear metal flange at both ends, which are connected to the metal interfaces of the vacuum chambers of Q1 and Q3 respectively. A Kalrez® O-ring is placed on each of the two polished end faces of the quartz tube, and the front and rear metal flanges are tightened by tie rod bolts to form a mechanical compression high vacuum sealing structure 10, while realizing a reliable electrical connection between the quartz tube and the metal flange. The quartz tube is grounded through the metal flange.

[0048] The multi-stage rod electrode assembly 7 inside the collision cell device 2 is an octagonal structure composed of 8 molybdenum rods. It is fixed to the front and rear metal flanges by ceramic brackets and is suspended and coaxial with the quartz tube without direct contact. The radio frequency voltage generator 5 is connected to the octagonal assembly to apply a radio frequency field to it, which confines the ions to transport along the central axis.

[0049] The front-end metal flange integrates an impact gas inlet pipe 9, and the gas path control module 4 is connected to the inlet pipe 9, which can precisely control the inlet flow rate and pressure of argon gas. In this embodiment, the gas path control module 4 introduces argon gas into the quartz tube at a flow rate of 5 mL / min to achieve uniform distribution of argon gas in the tube.

[0050] The working principle of this embodiment is as follows: Q1 screens pesticide residue ions in food samples to obtain target precursor ions; the gas path control module 4 precisely introduces argon gas into the quartz tube of the collision cell to form a uniform collision gas environment; the radio frequency voltage generator 5 applies a radio frequency field to the octupole assembly, confining the target precursor ions to the central axis of the quartz tube for transmission. The precursor ions collide with the argon gas to induce dissociation and generate daughter ions. The static charge generated by a small number of ions hitting the inner wall of the quartz tube is conducted to the ground potential through the bulk conductive layer of the quartz tube to avoid static electricity accumulation; the dissociated daughter ions are led out through the rear metal flange and enter Q3 for quality analysis and detection, realizing the accurate quantification of trace pesticide residues in food.

[0051] Example 2: Coated electrostatic dissipative collision cell device and matching mass spectrometer system like Figure 2 As shown, a high-inertia electrostatic dissipation collision cell device and its mass spectrometer system include a collision cell device 2, a first-stage quadrupole mass analyzer 1 (Q1), a third-stage quadrupole mass analyzer 3 (Q3), a gas path control module 4, and a radio frequency voltage generator 5. The collision cell device 2 is disposed between Q1 and Q3.

[0052] The outer shell 6 of the collision pool device 2 is a coated structure. The metal substrate 12 is made of stainless steel. After the stainless steel inner wall is precisely cleaned and polished, a layer of indium tin oxide (ITO) high-resistivity coating 13 with a thickness of 3 micrometers is uniformly deposited on the inner wall using PVD process. The resistivity of the coating is precisely controlled at 10 Ω·cm. 9 Ω·cm, possessing both high inertia and electrostatic dissipation characteristics; the two ends of the gas chamber shell 6 form a high vacuum sealing structure 10 with the metal flange 8 through metal C-type sealing rings, and the coating 13 is reliably electrically connected to the metal flange 8 to achieve grounding.

[0053] The multi-stage rod electrode assembly 7 inside the collision pool device 2 is a hexapole structure, which is fixed to the metal flange 8 by a ceramic bracket and is suspended and coaxial with the gas chamber shell 6; the radio frequency voltage generator 5 applies a radio frequency field to the hexapole assembly to constrain ion transport.

[0054] The collision gas inlet pipe 9 on the metal flange 8 is connected to the gas path control module 4. In this embodiment, for the detection of acidic group ions in drug metabolism analysis, the gas path control module 4 introduces argon-nitrogen mixed gas (argon:nitrogen = 7:3) into the gas chamber shell 6 at a flow rate of 8 mL / min to ensure ion collision dissociation efficiency.

[0055] The working principle of this embodiment is as follows: Q1 screens the target precursor ions in the drug metabolism sample. The gas path control module 4 accurately introduces the argon-nitrogen mixed gas into the coated collision cell to form a uniform collision environment. Under the action of the radio frequency field, the hexapole assembly constrains the target precursor ions to propagate along the central axis. The precursor ions collide with the mixed gas and induce dissociation to generate daughter ions. The static charge generated by the ions hitting the inner wall is conducted to the ground potential through the ITO coating. The daughter ions are led out through the metal flange 8 and enter Q3 for mass analysis to achieve high-sensitivity detection of drug metabolites.

[0056] Example 3:

[0057] Split-type gas chamber shell: The gas chamber shell is designed as a split structure with a front quartz tube section and a rear coated metal section. The front section is connected to a single-stage quadrupole, which uses the high inertia of the quartz tube to reduce the adsorption loss of the target ions during initial transport. The rear section is connected to a triple quadrupole, which uses the structural strength of the coated metal substrate to ensure the stable extraction of ions after collision dissociation. The two sections are connected by a flange to achieve high vacuum sealing and electrical conduction.

[0058] Layered gas path intake structure: Abandoning the original single intake pipeline, a layered structure of main intake path + auxiliary gas distribution path is set on the metal flange. The main intake path supplies gas along the ion transmission axis, and the auxiliary gas distribution path supplies gas through uniformly distributed holes in the circumference of the inner wall of the gas chamber shell, so as to achieve a three-dimensional uniform distribution of collision gas in the radial and axial directions and improve the collision dissociation efficiency.

[0059] Ion guiding ring assembly: Ceramic-insulated electrostatic dissipative ion guiding rings are added at the inlet and outlet of the gas chamber shell. By fine-tuning the radio frequency voltage, edge ions are constrained to travel along the axis, reducing ion escape loss and improving ion transmission efficiency; Ion channel fins: 36 radially distributed fins at equal intervals form a uniform electric field constraint area, guiding ions to travel along the central axis and reducing edge loss.

[0060] It should be noted that, in this document, relational terms such as first and second (number one, number two), etc., are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0061] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A high-inertia electrostatic dissipation collision cell device, comprising a collision cell device (2), characterized in that: One end of the collision pool device (2) is connected to a first-stage quadrupole mass analyzer (1), and the other end of the collision pool device (2) is connected to a third-stage quadrupole mass analyzer (3). A metal flange (8) is assembled at the connection point between the collision pool device (2) and the first-stage quadrupole mass analyzer (1) and the third-stage quadrupole mass analyzer (3). A collision gas inlet pipe (9) is provided at the middle of the metal flange (8) at the end connected to the first-stage quadrupole mass analyzer (1). A gas path control is provided at the collision gas inlet pipe (9). Module (4), the collision pool device (2) has a gas chamber shell (6) positioned on the outside, the collision pool device (2) has a multi-stage rod electrode assembly (7) inside, the multi-stage rod electrode assembly (7) is connected to a radio frequency voltage generator (5), a high vacuum sealing structure (10) is provided between the collision pool device (2) and the metal flange (8), and an electrostatic dissipation layer (11), a metal substrate (12) and a high resistance coating (13) are provided on the outside of the gas chamber shell (6). The collision pool device (2) has three structures.

2. The highly inert electrostatic dissipation collision pool device according to claim 1, characterized in that: In the first structure, the collision cell device (2) is an integral electrostatic dissipative quartz tube structure, including a first-stage quadrupole mass analyzer (1), a third-stage quadrupole mass analyzer (3), a gas path control module (4), a radio frequency voltage generator (5), a gas chamber shell (6), a multi-stage rod electrode assembly (7), a metal flange (8), a collision gas inlet pipeline (9), a high vacuum sealing structure (10), and an electrostatic dissipative layer (11). The gas chamber shell (6) on the collision cell device (2) is an integral doped quartz tube. The metal flanges (8) at both ends of the gas chamber shell (6) are connected to the first-stage quadrupole mass analyzer (1) and the third-stage quadrupole mass analyzer (3), respectively. The multi-stage rod electrode assembly (7) inside the collision cell device (2) is a molybdenum rod structure, which is fixed to the metal flange (8) by a ceramic bracket.

3. The highly inert electrostatic dissipation collision pool device according to claim 1, characterized in that: In the second structure, the collision pool device (2) is a coated electrostatic dissipation structure, including a single-stage quadrupole mass analyzer (1), a three-stage quadrupole mass analyzer (3), a gas path control module (4), a radio frequency voltage generator (5), a gas chamber shell (6), a multi-stage rod electrode assembly (7), a metal flange (8), a collision gas inlet pipe (9), a high vacuum sealing structure (10), an electrostatic dissipation layer (11), a metal substrate (12), and a high-resistance coating (13). The gas chamber shell (6) on the collision pool device (2) is a coated structure. The metal substrate (12) is made of stainless steel. After the stainless steel inner wall is precisely cleaned and polished, a high-resistance coating (13) with a thickness of 3 micrometers is uniformly deposited on the inner wall using PVD process. The high-resistance coating (13) is electrically connected to the metal flange (8).

4. The highly inert electrostatic dissipation collision pool device according to claim 1, characterized in that: In the third structure, the outer shell (6) of the air chamber includes a quartz tube section structure (16) and a coated metal section structure (17). A flange positioning mechanism (18) is provided between the quartz tube section structure (16) and the coated metal section structure (17). The flange positioning mechanism (18) includes an inner sealing ring (19), a high-precision flange (20), bolts (21), an outer sealing ring (22), and nuts (23). The inner sealing ring (19) is located inside the high-precision flange (20), and the outer sealing ring (22) is located outside the high-precision flange (20). The bolts (21) and nuts (23) are located at both ends of the high-precision flange (20). The quartz tube section structure (16) and the coated metal section structure (17) are sealed and positioned by the flange positioning mechanism (18).

5. The highly inert electrostatic dissipation collision pool device according to claim 1, characterized in that: An auxiliary air intake pipe (15) is provided on the outside of the metal flange (8). An ion guide ring assembly (14) is positioned inside both the first-stage quadrupole mass analyzer (1) and the third-stage quadrupole mass analyzer (3). A sealing ring (24) is positioned on the outer ring of the ion guide ring assembly (14). An ion channel (25) is positioned in the middle of the ion guide ring assembly (14). A channel groove (27) is opened in the middle of the ion channel (25). A fin (26) is positioned on the inner side of the ion channel (25). Guide ring bodies (29) are positioned at both ends of the ion guide ring assembly (14). A fixing groove (28) is opened on the guide ring body (29).

6. The highly inert electrostatic dissipation collision pool device according to claim 1, characterized in that: The resistivity of the highly inert dielectric material with electrostatic dissipation properties in the collision pool device (2) is 10. 8 Ω·cm to 10 12 Ω·cm.

7. The collision pool device with high inertia and electrostatic dissipation according to claim 1, characterized in that: The two ends of the gas chamber shell (6) are connected to the vacuum chamber metal interface of the first-stage quadrupole mass analyzer (1) and the third-stage quadrupole mass analyzer (3) through a high vacuum sealing structure (10). The high vacuum sealing structure (10) is a mechanical compression seal, which uses a low-release O-ring and a metal C-ring to press between the end face of the gas chamber shell (6) and the metal flange (8). The sealing structure ensures that the electrostatic dissipation layer (11) and the high-resistance coating layer (13) of the gas chamber shell (6) are reliably electrically connected to the metal flange (8).

8. The highly inert electrostatic dissipation collision pool device according to claim 1, characterized in that: The multi-stage rod electrode assembly (7) is one of a hexapole, an octapole, or a bent quadrupole electrode assembly. The multi-stage rod electrode assembly (7) is externally connected to a radio frequency voltage generator (5) for applying a radio frequency field to confine the ion beam. The metal flange (8) is integrated with a collision gas inlet pipe (9). The outlet of the collision gas inlet pipe (9) faces the inside of the gas chamber shell (6). The collision gas is one or a mixture of argon and nitrogen.

9. A highly inert electrostatic dissipation mass spectrometer system, characterized in that: It includes an ion source module, a mass analysis module, a dedicated module for a high-inert electrostatic dissipation collision cell, a vacuum module, a radio frequency high-voltage power supply module, and a signal detection and data processing module.

10. A highly inert electrostatic dissipative mass spectrometer system according to claim 9, characterized in that: The ion source module is compatible with electrospray ionization sources, atmospheric pressure chemical ionization sources, and matrix-assisted laser desorption / ionization sources. The mass analysis module includes a single-stage quadrupole, a high-inert electrostatic dissipation collision cell device, and a triple-stage quadrupole. The dedicated supporting modules for the high-inert electrostatic dissipation collision cell include a gas path precision control module and an electrostatic dissipation and grounding module. The vacuum module consists of a mechanical pump, a molecular pump, a vacuum gauge, and vacuum tubing. The RF high-voltage power supply module provides stable RF and DC power to the mass analysis module, using a high-precision digital power supply. The signal detection and data processing module consists of an industrial control computer, dedicated mass spectrometry analysis software, and a data storage unit.

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