Mass spectrometry preparation device

Abstract

The application relates to a mass spectrum preparation device, which comprises a cavity, a pulse thermal desorption module, a sample injection module, an ionization module and a mass spectrum interface. The ionization module is arranged in the cavity. The sample injection module comprises a sample target for receiving a sample. The sample target is arranged in the action area of the pulse thermal desorption module. The pulse thermal desorption module is used for thermal desorption of the sample in the sample target to generate sample molecules. The output port of the sample injection module is communicated with the cavity, and the sample molecules are introduced into the ionization module. The ionization module is used for ionization of the sample molecules to generate sample ions. The mass spectrum interface is used for communication between the cavity and a mass spectrometer, and introduction of the sample ions into the mass spectrometer. Rapid sample injection can be realized, ionization efficiency is improved, positive and negative ion detection of the sample can be realized, sensitivity and analysis speed are effectively improved, the device is easy to realize automation, convenient for on-site and real-time online analysis, can meet the requirements of rapid and efficient analysis of various samples, and is reliable in use.

Description

Technical Field

[0001] This application relates to the field of mass spectrometry analysis technology, and in particular to a mass spectrometry preparation apparatus. Background Technology

[0002] Mass spectrometry is a highly sensitive and fast analytical method that has been widely used in various fields. With the rapid development of modern science and technology, various fields have placed higher demands on mass spectrometry analysis, especially on the rapid detection of complex samples.

[0003] In recent years, direct ionization mass spectrometry (DIMS) has emerged as a technique capable of directly analyzing most compounds without sample pretreatment. Examples include desorption electrospray ionization (DESI), low-temperature plasma (LTP), dielectric barrier discharge ionization (DBDI), direct analysis in real time (DART), and paper spray ionization (PSI). These methods offer advantages such as real-time processing, high throughput, and ease of use, making them increasingly important for the rapid analysis of complex samples. However, these methods suffer from inconvenient sample introduction procedures and poor ionization effects on non-volatile and highly viscous substances, leading to unreliable and inaccurate subsequent mass spectrometry results. Summary of the Invention

[0004] Therefore, it is necessary to provide a mass spectrometry preparation device to address the unreliability of traditional direct ionization mass spectrometry methods.

[0005] A mass spectrometry preparation device includes a cavity, a pulsed thermal desorption module, a sample introduction module, an ionization module, and a mass spectrometry interface. The ionization module is disposed within the cavity. The sample introduction module includes a sample target for receiving samples, which is disposed within the effective region of the pulsed thermal desorption module. The pulsed thermal desorption module is used to thermally desorb the sample in the sample target to generate sample molecules. The output port of the sample introduction module is connected to the cavity to introduce the sample molecules into the ionization module. The ionization module is used to ionize the sample molecules to generate sample ions. The mass spectrometry interface is used to connect the cavity and the mass spectrometer and introduce the sample ions into the mass spectrometer.

[0006] The aforementioned mass spectrometry preparation device includes a cavity, a pulsed thermal desorption module, a sample introduction module, an ionization module, and a mass spectrometry interface. The ionization module is disposed within the cavity. The sample introduction module includes a sample target for receiving samples, which is disposed within the effective area of ​​the pulsed thermal desorption module. The pulsed thermal desorption module is used to thermally desorb the sample in the sample target to generate sample molecules. The output port of the sample introduction module is connected to the cavity to introduce the sample molecules into the ionization module. The ionization module is used to ionize the sample molecules to generate sample ions. The mass spectrometry interface is used to connect the cavity and the mass spectrometer and introduce the sample ions into the mass spectrometer. The sample introduction module receives the sample through the sample target, and the pulse thermal desorption module can rapidly desorb the sample into a gaseous state, generating sample molecules. The output port of the sample introduction module is connected to the cavity, introducing the sample molecules into the ionization module. The ionization module is located in the cavity and is used to ionize the sample molecules. The generated sample ions enter the mass spectrometer for analysis and detection through the mass spectrometry interface. This device can achieve rapid sample introduction, improve ionization efficiency, and also realize the detection of positive and negative ions of the sample, effectively improving sensitivity and analysis speed. Moreover, this device is easy to automate, convenient for on-site and real-time online analysis, and can meet the needs of rapid and efficient analysis of various samples. It is reliable in use.

[0007] In one embodiment, the cavity includes a metal cavity, an insulating cavity, an exhaust port, and a vacuum pump. The ionization module is disposed in the metal cavity, the output port of the sample injection module is connected to the metal cavity, the mass spectrometry interface is used to introduce the sample ions into the mass spectrometer, the insulating cavity is connected to the mass spectrometry interface and is provided with the exhaust port, and the exhaust port is connected to the vacuum pump.

[0008] In one embodiment, the mass spectrometry preparation apparatus further includes a heater and a temperature sensor disposed within the cavity.

[0009] In one embodiment, the pulsed thermal desorption module includes a laser, a laser driving power supply, and a focusing lens. The laser driving power supply is connected to the laser, the focusing lens is used to focus the laser, and the sample target is disposed in the effective area of ​​the focusing lens.

[0010] In one embodiment, the sample introduction module further includes a sealing gasket, an ion transmission tube, and an auxiliary gas heating line. The sealing gasket is disposed on the sample target and has a through hole. The ion transmission tube is connected to the sample target through the through hole and is connected to the auxiliary gas heating line. The auxiliary gas heating line is used to connect to an auxiliary gas. The end of the ion transmission tube away from the sealing gasket is connected to the cavity.

[0011] In one embodiment, the auxiliary gas heating pipeline includes a gas pipe, a flow controller, a gas temperature sensor, a heating pipe, and a heat insulation sleeve. The heating pipe, the gas pipe, and the heat insulation sleeve are nested together. The flow controller and the gas temperature sensor are both located on the gas pipe. The heat insulation sleeve is used to keep the auxiliary gas warm and provide insulation.

[0012] In one embodiment, the ionization module includes a discharge element, an adjustment base, a focusing electrode, and a heating pad disposed within the cavity. The discharge element is connected to the adjustment base, the focusing electrode is disposed at the outlet position of the discharge element, and the heating pad is disposed on the focusing electrode for heating the focusing electrode.

[0013] In one embodiment, the discharge element is a corona discharge needle or a plasma generation module.

[0014] In one embodiment, the mass spectrometry interface includes a sample injection element, an insulating pad, and an interface base. The sample injection element is disposed on the interface base via the insulating pad, and the sample injection element is used to connect the cavity and the mass spectrometer.

[0015] In one embodiment, the mass spectrometry preparation apparatus further includes a control device, wherein both the ionization module and the sample introduction module are connected to the control device. Attached Figure Description

[0016] Figure 1 This is a structural diagram of a mass spectrometry preparation apparatus in one embodiment;

[0017] Figure 2 A detailed structural diagram of the mass spectrometry preparation apparatus in one embodiment;

[0018] Figure 3 A detailed structural diagram of the mass spectrometry preparation apparatus in another embodiment;

[0019] Figure 4 This is a control timing diagram of a mass spectrometry preparation apparatus in one embodiment. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this application clearer, the following description, in conjunction with embodiments and accompanying drawings, provides a more comprehensive overview of the application. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of the application.

[0021] In one embodiment, a mass spectrometry preparation apparatus is provided. This apparatus is used to connect to a mass spectrometer, and after processing a sample using this apparatus, the prepared sample is transferred to the mass spectrometer for analysis. Please refer to [link to previous document]. Figure 1The mass spectrometry preparation device includes a cavity 100, a pulsed thermal desorption module 200, a sample introduction module 300, an ionization module 400, and a mass spectrometry interface 500. The ionization module 400 is disposed within the cavity 100. The sample introduction module 300 includes a sample target 301 for receiving samples. The sample target 301 is disposed within the effective area of ​​the pulsed thermal desorption module 200. The pulsed thermal desorption module 200 is used to thermally desorb the sample in the sample target 301 to generate sample molecules. The output port of the sample introduction module 300 is connected to the cavity 100 to introduce sample molecules into the ionization module 400. The ionization module 400 is used to ionize sample molecules to generate sample ions. The mass spectrometry interface 500 is used to connect the cavity 100 and the mass spectrometer and introduce sample ions into the mass spectrometer. The sample introduction module 300 receives the sample through the sample target 301. The pulse thermal desorption module 200 can rapidly desorb the sample into a gaseous state, generating sample molecules. The output port of the sample introduction module 300 is connected to the cavity 100, introducing the sample molecules into the ionization module 400. The ionization module 400 is set inside the cavity 100 to ionize the sample molecules. The generated sample ions enter the mass spectrometer for analysis and detection through the mass spectrometry interface 500. This device can achieve rapid sample introduction, improve ionization efficiency, and also realize positive and negative ion detection of the sample, effectively improving sensitivity and analysis speed. Moreover, this device is easy to automate, convenient for on-site and real-time online analysis, and can meet the needs of rapid and efficient analysis of various samples. It is reliable in use.

[0022] Specifically, cavity 100 can be a semi-enclosed cavity. This device encloses the ionization module 400 within cavity 100, and cavity 100 is connected to the mass spectrometry interface 500 of the mass spectrometer. A semi-enclosed cavity means that the cavity is not connected to other devices except for other components of the mass spectrometry preparation apparatus and the mass spectrometer, and cannot receive other substances from other devices. The interface between cavity 100 and sample introduction module 300 is sealed, and the inside of the mass spectrometer is usually also sealed, so that cavity 100 is in a semi-enclosed state, not easily affected by other factors, thereby improving its working performance. Since mass spectrometers typically use mechanical and molecular pumps to create a vacuum, the pressure inside chamber 100 is lower than atmospheric pressure. The pressure at the atmospheric pressure interface of the mass spectrometer is approximately 100–130 Pa. The pressure inside chamber 100 is between the pressure at the mass spectrometer interface and atmospheric pressure. Therefore, the internal pressure of chamber 100 can be maintained at a relatively low level, which can improve the ability to control the energy of reagent ions, reduce the dependence of the sample on humidity during the ionization process, and enhance the sensitivity of the instrument.

[0023] The sample target 301 is positioned within the effective area of ​​the pulse thermal desorption module 200, such as within its focusing region. The pulse thermal desorption module 200 rapidly desorbs the sample from the sample target 301 into a gaseous state. Combined with the spotting injection method, this improves the sample desorption efficiency and thus enhances sensitivity. Specifically, the pulse thermal desorption module 200 only begins thermal desorption when the sample target 301 is positioned at the desorption location. The pulse thermal desorption module 200 can instantly reach temperatures exceeding 300 degrees Celsius, effectively vaporizing the sample and delivering it into the ionization region, thereby improving sensitivity and repeatability.

[0024] The sample introduction module 300 includes a sample target 301 for receiving samples, and the sample can be placed on the sample target 301. After the sample introduction module 300 receives the sample through the sample target 301, the pulse thermal desorption module 200 quickly desorbs the sample in the sample target 301 into a gaseous state, generating sample molecules, which are generally neutral gaseous molecules. The output port of the sample introduction module 300 is connected to the cavity 100, and can transfer the vaporized sample molecules into the cavity 100, specifically to the active area of ​​the ionization module 400 within the cavity 100. Furthermore, the sample introduction module 300 can also be used to introduce an auxiliary gas, which can be an inert gas such as compressed air, nitrogen, or helium, or other special reactive gases such as methane or heated compressed air. The type of auxiliary gas can be selected according to the type of sample, as long as it is deemed feasible by those skilled in the art. In addition, the auxiliary gas can also include a certain proportion of water vapor to buffer the influence of the actual sample humidity on the measurement results and improve the accuracy of the measurement results. After receiving the gaseous neutral molecules and the auxiliary gas, the auxiliary gas drives the gaseous neutral molecules to move. The gaseous neutral molecules are then transported to the cavity 100 through the output port of the sample introduction module 300, and specifically transported to the working area of ​​the ionization module 400 in the cavity 100 for ionization.

[0025] The ionization module 400 is used to ionize gaseous neutral molecules transmitted into the cavity 100 to generate sample ions. The mass spectrometry interface 500 connects the cavity 100 and the mass spectrometer, and the sample ions enter the mass spectrometer for analysis and detection through the mass spectrometry interface 500. The structure of the ionization module 400 and the mass spectrometry interface 500 is not unique, as long as they can achieve the corresponding functions.

[0026] In one embodiment, see Figure 2 Alternatively, cavity 100 includes a metal cavity 102, an insulating cavity 101, an exhaust port 105, and a vacuum pump 106. Ionization module 400 is disposed inside metal cavity 102. The output port of sample injection module 300 is connected to metal cavity 102. Mass spectrometry interface 500 is used to introduce sample ions into mass spectrometer. Insulating cavity 101 is connected to mass spectrometry interface and is provided with exhaust port 105, which is connected to vacuum pump 106.

[0027] Specifically, the ionization module 400 is disposed within the metal cavity 102, and the output port of the sample injection module 300 is connected to the metal cavity 102. The metal cavity 102 encloses the ionization module 400 and the output port of the sample injection module 300, forming an ionization chamber in the hollow region. The insulating cavity 101 is connected to the mass spectrometry interface 500 of the mass spectrometer. The insulating cavity 101 is provided with an exhaust port 105, which is connected to a vacuum pump 106. The vacuum port can be located below the insulating cavity 101 and connected to the vacuum pump 106 for exhaust. When the mass spectrometer preparation device is connected to the auxiliary gas, the auxiliary gas is used to deliver gaseous neutral molecules to the ionization region inside the metal cavity 102. Therefore, the unionized gaseous neutral molecules and the auxiliary gas can be drawn away through the exhaust pipe, that is, discharged outside the mass spectrometer preparation device through the exhaust port 105 and the vacuum pump 106. This helps to maintain the pressure of the sealed cavity 100 and reduces interference, including background interference and interference from other samples, thereby improving the working performance of the mass spectrometer preparation device.

[0028] In one embodiment, see Figure 2 Alternatively, the mass spectrometry preparation apparatus also includes a heater 103 and a temperature sensor 104 disposed within the chamber 100. Specifically, the heater 103 heats the chamber 100 to prevent the vaporized sample (gaseous neutral molecules) from condensing. The type of heater 103 is not unique; it can be a heating rod, heating wire, heating plate, etc., depending on the actual requirements. The heating temperature of the heater 103 is also not fixed and can be selected according to the sample properties. Generally, a heater 103 with a heating upper limit of 300℃ can meet most testing requirements. The temperature sensor 104 is used to detect the temperature inside the chamber 100. Expandably, the temperature sensor 104 can be connected to a control device 600 or other devices to monitor the temperature inside the chamber 100 in real time. When the temperature inside the chamber 100 is too high or too low, alarms or other measures can be taken to remind the staff to handle the situation promptly, improving the reliability of the mass spectrometry preparation apparatus.

[0029] In one embodiment, see Figure 2 Alternatively, the pulsed thermal desorption module 200 includes a laser 201, a laser driving power supply 202, and a focusing lens 203. The laser driving power supply 202 is connected to the laser 201, and the focusing lens 203 focuses the laser emitted by the laser 201. The sample target 301 is set in the effective area of ​​the focusing lens 203.

[0030] Specifically, the laser driver power supply 202 is used for powering and setting the power of the laser 201. It can be set manually, via a host computer, or controlled by the control device 600. Host computer control enables rapid programmed temperature control, allowing for the rapid decomposition of substances with different thermal stability. The focusing lens 203 focuses the laser emitted by the laser 201. The sample target 301 is positioned within the effective area of ​​the focusing lens 203. The focusing lens 203 can adjust the size of the heating area on the sample target 301, improving thermal decomposition efficiency. The type of laser 201 is not unique; it can be an adjustable pulsed high-power laser diode, a diode laser array, or a pulse-controlled halogen lamp, as long as it can achieve rapid heating with pulsed control. In this embodiment, the laser 201 is a laser diode, specifically an adjustable pulsed laser diode with a power >10W and a wavelength range of 915nm to 1550nm. The laser diode is pulsed, high-power, and adjustable in power, with an instantaneous temperature exceeding 300 degrees Celsius. It also allows for faster and more precise temperature control via a host computer program. It is understood that in other embodiments, the pulse thermal desorption module 200 may also have other structures, as long as those skilled in the art believe it is feasible.

[0031] In one embodiment, see Figure 2 Alternatively, the sample introduction module 300 may also include a sealing gasket 302, an ion transmission tube 303, and an auxiliary gas heating line 304. The sealing gasket 302 is disposed on the sample target 301 and has a through hole. The ion transmission tube 303 is connected to the sample target 301 through the through hole and is connected to the auxiliary gas heating line 304. The auxiliary gas heating line is used to access the auxiliary gas. The end of the ion transmission tube 303 away from the sealing gasket 302 is connected to the cavity 100.

[0032] Specifically, the sample target 301 includes a sampling orifice. The sample target 301 can be a pull-out type, and can be operated manually or using an automatic transmission device such as a stepper motor for sample injection, achieving automated, high-throughput operation. The type of sample target 301 is not unique; for example, it can be a ceramic-welded metal structure with the sampling orifice made of metal and the rest of the material made of ceramic. A sealing gasket 302 is used to seal the sample target 301. This sealing gasket 302 has a through-hole, the size of which can be the same as the sampling orifice, and the gasket is coaxial in position. The type of sealing gasket 302 is not unique; for example, it can be a sealing gasket 302 made of insulating materials such as polytetrafluoroethylene (PTFE).

[0033] Ion transmission tube 303 is connected to sample target 301 through a through hole. Further, the cross-sectional radius of ion transmission tube 303 is smaller than the radius of the spotting hole, and ion transmission tube 303 extends vertically into the spotting hole. The mounting hole of ion transmission tube 303 is a stepped hole, with the larger diameter end facing outwards, forming a hollow channel with a certain gap with the ion transmission tube 303. This hollow channel is connected to the sealing gasket 302, and its diameter is consistent with the diameter of the spotting hole. Small holes are opened on the side wall of ion transmission tube 303 for connecting to auxiliary gas heating pipe 304 to introduce heating auxiliary gas. After entering from the auxiliary gas heating pipe 304, the heating auxiliary gas is blown into the bottom of the spotting hole, backflushing the vaporized sample into ion transmission tube 303. The end of ion transmission tube 303 away from the sealing gasket 302 is connected to cavity 100, sending the vaporized sample into the ionization chamber. It is understood that in other embodiments, the sample introduction module 300 can also have other structures, as long as those skilled in the art believe it is feasible.

[0034] In one embodiment, see Figure 2 Alternatively, the auxiliary gas heating pipeline 304 includes a gas pipe 3041, a flow controller 3042, a gas temperature sensor 3043, a heating pipe 3044, and a heat insulation sleeve 3045. The heating pipe 3043, the gas pipe 3041, and the heat insulation sleeve 3045 are nested together. The flow controller 3042 and the gas temperature sensor 3043 are both located in the gas pipe 3041. The heat insulation sleeve 3045 is used to keep the heating auxiliary gas warm and provide insulation.

[0035] Specifically, the gas tube 3041 can be a metal gas tube, which is robust and durable. The heating tube 3044 can be a ceramic heating tube, which has high temperature resistance. The heating tube 3044 is fitted inside the gas tube 3041, nested with the metal gas tube, and can heat the auxiliary gas transported inside the metal gas tube. The heating temperature is unlimited, for example, up to 350°C. The heat insulation sleeve 3045 is nested with the heating tube 3043 and the gas tube 3041, and is generally installed on the outermost layer. From the outside to the inside, the sequence is heat insulation sleeve 3045, heating tube 3043, and gas tube 3041. The heat insulation sleeve 3045 can keep the heating auxiliary gas warm and insulated. The gas temperature sensor 3043 can be installed inside or outside the gas tube 3041 to monitor the temperature of the reactants transported inside the gas tube 3041. Both the gas temperature sensor 3043 and the flow controller 3042 can be connected to the control device 600. The gas temperature sensor 3043 transmits the detected temperature of the reactant to the control device 600. The control device 600 can control the flow rate of the reactant through the flow controller 3042 and can also achieve on / off linkage with other devices. For example, during sample injection, the control device 600 will control the working state of the flow controller 3042 based on the received control signal (such as a TTL injection signal), thereby improving the automation level of the mass spectrometry preparation device. The type of reactant transported in the gas tube 3041 is not unique; for example, it can be compressed air, nitrogen, helium, or other inert gases, as well as other special reactive gases such as methane.

[0036] In one embodiment, see Figure 2 Alternatively, the ionization module 400 includes a discharge element 401, an adjustment base 402, a focusing electrode 403, and a heating pad 404 disposed within the cavity 100. The discharge element 401 is connected to the adjustment base 402, the focusing electrode 403 is disposed at the outlet position of the discharge element 401, and the heating pad 404 is disposed on the focusing electrode 403 for heating the focusing electrode.

[0037] Specifically, a required voltage is applied to the discharge element 401 to ionize neutral gaseous molecules. This voltage can be provided by the control device 600 and can be controlled in conjunction with the laser 201 and the auxiliary gas flow controller 3042. The adjustment base 402 can be an insulated withstand voltage adjustment base 402, used to mount the discharge element 401, connected to the discharge element 401, and mounted on the cavity 100. Specifically, it can be mounted inside the metal cavity 102. The position of the ionization region can be adjusted by precisely rotating and adjusting the front-to-back distance of the discharge element 401. The focusing electrode 403 is generally a metal focusing electrode 403. A DC voltage is applied to the focusing electrode 403 to focus the generated sample ions and push them into the mass spectrometry interface 500. The type of focusing electrode 403 is not unique; for example, it can be a conical focusing electrode 403, which has a better focusing effect. A heating pad 404 is disposed on the focusing electrode 403 to heat the focusing electrode 403. The shape and type of the heating pad 404 are not unique. In this embodiment, the heating pad 404 can be a ring-shaped ceramic heating element. The ring-shaped ceramic heating element can not only heat the focusing electrode 403, but also serve as insulation to prevent leakage. It is understood that in other embodiments, the ionization module 400 can also have other structures, as long as those skilled in the art believe it is feasible.

[0038] In one embodiment, the discharge element 401 is a corona discharge needle or a plasma generating module. The corona discharge needle can be fitted with an adjustable voltage and current of 2–6 kV to ionize reactive ions, resulting in good ionization. The plasma generating module can employ a glass tube-insulated metal wire structure, generating plasma by applying a radio frequency voltage of 3–7 kVpp, which then reacts with the reactive ions, achieving high ionization efficiency. It is understood that in other embodiments, the discharge element 401 can also be other types of devices, as long as those skilled in the art deem it feasible.

[0039] In one embodiment, see Figure 2 Alternatively, the mass spectrometry interface 500 includes a sample injection element 501, an insulating pad 502, and an interface base 503 disposed within the cavity 100. The sample injection element 501 is disposed on the interface base 503 via the insulating pad 502, and the sample injection element 501 connects the cavity 100 and the mass spectrometer.

[0040] Specifically, the sample injector 501 is used to connect to the mass spectrometer, introducing the sample ions generated by the ionization module 400 into the mass spectrometer. The type of sample injector 501 is not unique; it can be, for example, a sample capillary, a sampling cone, or a flat sampling cone. When the sample injector 501 is a flat sampling cone, the inner diameter of the orifice can be any value within the range of 0.5 to 2 mm. The interface base 503 supports the sample injector 501 and the insulating pad 502, serving to fix their positions. The insulating pad 502 insulates the sample injector 501 and the interface base 503, preventing leakage and improving safety.

[0041] In one embodiment, see Figure 1 The mass spectrometry preparation apparatus also includes a control device 600, with the ionization module 400 and sample injection module 300 all connected to the control device 600. The ionization module 400 and sample injection module 300 can operate under the control of the control device 600, improving the intelligence level of the mass spectrometry preparation apparatus. Furthermore, the control device 600 can also be connected to other devices to achieve other functions, such as powering the plasma generation module, heating element, heating tube 3044, heating pad 404, flow controller 3042, etc., and also performing timing control of the ionization module 400, laser drive power supply 202, and auxiliary gas flow controller 3042, as shown in the timing control diagram. Figure 4 As shown.

[0042] To better understand the above embodiments, a detailed explanation is provided below with reference to a specific embodiment. In one embodiment, the mass spectrometry preparation device is a pulsed sample introduction and ionization device for rapid mass spectrometry analysis, including: a cavity 100, a pulsed thermal desorption module 200, a sample introduction module 300, an ionization module 400, a mass spectrometry interface 500, and a control device 600. This device encloses the ionization module 400 and the mass spectrometry interface 500 within the cavity 100. The pulsed thermal desorption module 200 rapidly desorbs the sample to a gaseous state. Neutral gaseous molecules are transported to the ionization region for ionization using heated compressed air or an auxiliary gas (selected according to the sample type). The resulting sample ions are focused by a cone-shaped focusing electrode 403 and, under the influence of the axial electric field generated by the pressure difference between the electrode and the sample introduction element 501, enter the mass spectrometer for analysis and detection. The mass spectrometry preparation device realizes a pulsed sample introduction direct ionization-mass spectrometry rapid analysis technology, which can realize the detection of positive and negative ions in the sample, effectively improving the sensitivity and analysis speed. Moreover, the device is easy to automate, convenient for on-site and real-time online analysis, and can meet the needs of rapid and efficient analysis of various samples such as pesticide residues and drugs.

[0043] This application provides a pulsed sample introduction and ionization device for rapid mass spectrometry analysis, comprising: a cavity 100, a pulsed thermal desorption module 200, a sample introduction module 300, an ionization module 400, a mass spectrometry interface 500, and a control device 600. The device encloses the ionization module 400 within the cavity 100. The pulsed thermal desorption module 200 rapidly desorbs the sample to a gaseous state. Neutral gaseous molecules are transported to the ionization region for ionization via heated compressed air or a reactant gas (selected according to the sample type). The resulting sample ions are focused by a conical focusing electrode 403 and, under the influence of the axial electric field generated by the pressure difference between the electrode and the sample introduction element 501, enter the mass spectrometer for analysis and detection. This invention realizes a pulsed sample introduction direct ionization-mass spectrometry rapid analysis technology, enabling the detection of both positive and negative ions in samples, effectively improving sensitivity and analysis speed. Furthermore, this device is easily automated, convenient for on-site and real-time online analysis, and can meet the needs of rapid and efficient analysis of various samples such as pesticide residues and narcotics.

[0044] Specifically, the cavity 100 includes: a metal cavity 102, an insulating cavity 101, a heating element, a temperature sensor 104, an exhaust port 105, and a vacuum pump 106. The metal cavity 102 encloses the ionization module 400 and the sample delivery tube, with the hollow area forming an ionization chamber. The insulating cavity 101 has an exhaust port at its bottom, connected to the vacuum pump 106, for exhausting air. The heater 103 and the temperature sensor 104 are used to heat the cavity 100, preventing the vaporized sample from condensing; the maximum heating temperature can reach 300°C.

[0045] The pulsed thermal desorption module 200 includes a laser 201, a laser driver power supply 202, and a focusing lens 203. The laser 201 is an adjustable pulsed high-power laser diode or a pulsed laser array. The laser driver power supply 202 is controlled by the control device 600 and is used for powering and setting the power of the laser 201. It can be set manually or by a host computer. Through host computer control, rapid programmed temperature control can be achieved to enable rapid desorption of substances with different thermal stability. The focusing lens 203 is used to focus the light emitted by the laser 201 and adjust the size of the heating area on the sample target 301.

[0046] The sample introduction module 300 includes a sample target 301, a sealing gasket 302, an ion transfer tube 303, and an auxiliary gas heating line 304. The sample target 301 has a ceramic-welded metal structure, with the sample spotting orifice made of metal and the rest of the material being ceramic. The sample target 301 can be operated manually or using an automatic transmission device such as a stepper motor for sample introduction, achieving automated, high-throughput operation. The sealing gasket 302 is made of insulating material such as polytetrafluoroethylene and is used to seal the sample target 301. The sealing gasket 302 has a small hole with the same size as the sample spotting orifice and is coaxial in position. The ion transfer tube 303 is smaller than the radius of the sample spotting orifice and extends vertically into the sample spotting orifice. The mounting hole of the transmission tube on the cavity 100 is a stepped hole, with the larger diameter end facing outwards, forming a hollow channel with a certain gap with the transmission tube. This hollow channel is connected to the sealing gasket 302, and its diameter is consistent with the diameter of the sample spotting hole. Small holes are opened on the side wall of the channel to introduce heating auxiliary gas. After entering the channel, the heating auxiliary gas is blown into the bottom of the sample spotting hole, backflushing the vaporized sample into the transmission tube and sending it into the ionization chamber. The auxiliary gas heating pipeline 304 includes a gas pipe 3041, a flow controller 3042, a gas temperature sensor 3043, a heating tube 3044, and a heat insulation sleeve 3045. The heating tube 3043, the gas pipe 3041, and the heat insulation sleeve 3045 are nested together to heat the auxiliary gas, with a maximum heating temperature of 350°C. The flow controller 3042 is controlled by the control device 600 and is used to set the flow rate of the auxiliary gas and to link with the switching on and off of the laser 201. The auxiliary gas can be compressed air, nitrogen, helium, or other inert gases, as well as other special reactive gases such as methane. The injection module 300 sends a TTL injection signal to the control device 600 during injection.

[0047] The ionization module 400 includes a discharge element 401, an adjustment base 402, a conical focusing electrode 403, and an annular ceramic heating element. The discharge element 401 can be an ionization module such as a corona discharge needle or a plasma generation module, and a corresponding required voltage is applied to it for ionizing sample ions. The voltage is provided by a control circuit and is linked to the laser 201 and the auxiliary gas flow controller 3042 for control. The adjustment base 402 is made of insulating and voltage-resistant material and is used to mount the discharge element 401 on the metal cavity 102. The distance between the discharge element 401 and the base can be precisely adjusted by rotation. The conical focusing electrode 403 is made of metal, and a DC voltage is applied to it to focus the generated sample ions and push them into the mass spectrometry interface 500. The annular ceramic heating element heats the conical focusing electrode 403 and also provides insulation.

[0048] The mass spectrometer interface 500 includes an injection element 501, an insulating pad 502, and an interface base 503, which are used to introduce sample ions generated by the ionization module 400 into the mass spectrometer. The injection element 501 can be an injection capillary, a sampling cone, a flat sampling cone, etc.

[0049] The control device 600 is used to supply power and control the entire device, including power supply to the ionization module 400, heating device, etc., and timing control of the ionization module 400, laser 201 and auxiliary gas flow controller 3042.

[0050] The mass spectrometry preparation device employs a rapid spotting injection method under normal pressure. A controllable pulsed thermal desorption module 200 instantly desorbs the sample within the sample target 301 into a gaseous state. Heated compressed air or a reactive gas (selected according to sample type) then transports the gaseous neutral molecules to the discharge region for ionization. The resulting sample ions are focused by a conical focusing electrode 403 and, under the influence of the axial electric field generated by the pressure difference between this electrode and the injection element 501, enter the mass spectrometer for analysis. The mass spectrometry preparation device uses a closed chamber 100, maintaining relatively low internal pressure. This improves the ability to control reagent ion energy, reduces the sample's dependence on humidity during ionization, and enhances instrument sensitivity. The voltage applied to the conical focusing electrode 403 helps control ion distribution. An additional proportion of water vapor can be added as an auxiliary reactive gas to buffer the influence of actual sample humidity on the measurement results.

[0051] In one embodiment, the structure and working principle of the mass spectrometry preparation device are as follows:

[0052] The cavity 100 includes: an insulating cavity 101, a metal cavity 102, a heater 103, a temperature sensor 104, an exhaust port 105, and a vacuum pump 106. The metal cavity 101 encloses the ionization module 400 and the sample delivery tube 303, and the hollow area forms an ionization chamber. The insulating cavity 101 has an exhaust port 105 at its bottom, connected to the vacuum pump 106, for exhausting air. The heating device 103 and the temperature sensor 104 are used to heat the cavity, preventing the vaporized sample from condensing. The maximum heating temperature can reach 300 degrees Celsius, depending on the sample properties.

[0053] The pulsed thermal desorption module 200 includes a laser diode 201, a laser driver power supply 202, and a focusing lens 203. The laser diode 201 is an adjustable pulsed laser diode with a power >10W and a wavelength range of 915nm to 1550nm. The laser driver power supply 202 is used for powering and controlling the laser diode. It can be set manually or by a host computer. It can be controlled by a host computer through a control device to achieve rapid program temperature control, thereby enabling rapid desorption of substances with different thermal stability. The focusing lens 203 is used to focus the light emitted by the laser diode and adjust the size of the heating area on the sample target.

[0054] The sample introduction module 300 includes a pull-out sample target 301, a sealing gasket 302, an ion transfer tube 303, and an auxiliary gas heating pipeline 304. The pull-out sample target 301 has a ceramic-welded metal structure, with the sampling holes made of metal and the rest of the material being ceramic. The sampling hole size is 5-8 mm, and the number of sampling holes on each sample target is not limited to 5, 48, or 96; the specific number depends on actual needs. The sealing gasket 302 is made of insulating materials such as polytetrafluoroethylene (PTFE) and is used to seal the sample target. The sealing gasket has small holes with the same size as the sampling holes and are coaxial in position. The ion transfer tube 303 is smaller than the radius of the sampling holes and extends vertically into them. The mounting hole of the transfer tube 303 on the cavity is a stepped hole, with the larger diameter end facing outwards, forming a 1 mm gap hollow channel with the transfer tube 303. This hollow channel and the sealing gasket 304... The sample injection module 304 is connected to the sample spotting hole 305, and its diameter is consistent with the diameter of the sample spotting hole. A small hole with a diameter of 3mm is opened on the side wall of the channel to introduce heating auxiliary gas. After entering the channel, the heating auxiliary gas is blown into the bottom of the sample spotting hole, backflushing the vaporized sample into the transfer tube 303 and then into the ionization chamber. The auxiliary gas heating pipeline 304 includes a gas pipe 3041, a flow controller 3042, a temperature sensor 3043, a heating tube 3044, and a heat insulation sleeve 3045. The heating tube 3043, gas pipe 3041, and heat insulation sleeve 3045 are nested together to heat the auxiliary gas, with a maximum heating temperature of 350 degrees Celsius. The flow controller 3042 is controlled by the control device 600 to set the flow rate of the auxiliary gas and to link with the on / off state of the laser 201. The auxiliary gas can be compressed air, nitrogen, helium, or other inert gases and other special reactive gases, such as methane. When the sample is injected, the injection module 300 sends a TTL injection signal to the control device 600.

[0055] The ionization module 400 includes a corona discharge needle 401, an adjusting base 402, a conical focusing electrode 403, and a heating pad 404. A 2-6kV high voltage with adjustable voltage and current is applied to the corona discharge needle for ionizing reactive ions. This voltage is provided by the control circuit 600 and is linked to the laser 201 and the auxiliary gas flow controller 3042 for control. The adjusting base 402 is made of insulating and voltage-resistant material and is used to mount the corona discharge needle on the metal cavity 102. The distance between the corona discharge needle and the base can be precisely adjusted by rotation. The conical focusing electrode 403 is made of metal, with an outlet orifice diameter of 3-5mm. A DC voltage is applied to the electrode to focus the generated sample ions and push them into the mass spectrometry interface. The heating pad 404 heats the conical focusing electrode 403 and also provides insulation.

[0056] The mass spectrometer interface 500 includes a flat sampling cone 501, an insulating pad 502, and an interface base 503, which is used to introduce sample ions generated by the ionization module into the mass spectrometer. The inner diameter of the orifice of the flat sampling cone 501 is 0.5 to 2 mm.

[0057] The control device 600 provides power and control for the entire device, including power supply to the corona discharge needle, heater 103, heating tube 3044, heating pad 404, flow controller 3042, etc., and timing control of the ionization module 400, laser drive power supply 202, and auxiliary gas flow controller 3042, etc. The timing control diagram is shown below. Figure 4 As shown.

[0058] In another embodiment, the structure and working principle of the mass spectrometry preparation device are as follows:

[0059] The cavity 100 includes: an insulating cavity 101, a metal cavity 102, a heater 103, a temperature sensor 104, an exhaust port 105, and a vacuum pump 106. The metal cavity 101 encloses the ionization module 200 and the sample delivery tube 303, and the hollow area forms an ionization chamber. The insulating cavity 101 has an exhaust port 105 at its bottom, connected to the vacuum pump 106, for exhausting air. The heating device 103 and the temperature sensor 104 are used to heat the cavity, preventing the vaporized sample from condensing. The maximum heating temperature can reach 300 degrees Celsius, depending on the sample properties.

[0060] The pulsed thermal desorption module 200 includes a laser diode 201, a laser driver power supply 202, and a focusing lens 203. The laser diode 201 is an adjustable pulsed laser diode with a power >10W and a wavelength range of 915nm to 1550nm. The laser driver power supply 202 is used for powering and controlling the laser diode. It can be set manually or by a host computer. It can be controlled by a host computer through a control device to achieve rapid program temperature control, thereby enabling rapid desorption of substances with different thermal stability. The focusing lens 203 is used to focus the light emitted by the laser diode and adjust the size of the heating area on the sample target.

[0061] The sample introduction module 300 includes a pull-out sample target 301, a sealing gasket 302, an ion transfer tube 303, and an auxiliary gas heating pipeline 304. The pull-out sample target 301 has a ceramic-welded metal structure, with the sampling holes made of metal and the rest of the material being ceramic. The sampling hole size is 5-8 mm, and the number of sampling holes on each sample target is not limited to 5, 48, or 96; the specific number depends on actual needs. The sealing gasket 302 is made of insulating materials such as polytetrafluoroethylene (PTFE) and is used to seal the sample target. The sealing gasket has small holes with the same size as the sampling holes and are coaxial in position. The ion transfer tube 303 is smaller than the radius of the sampling holes and extends vertically into them. The mounting hole for the transfer tube 303 on the cavity is a stepped hole, with the larger diameter end facing outwards, forming a 1 mm gap hollow channel with the transfer tube 303. This hollow channel is connected to the sealing gasket 302. The sample injection module 304 is connected to the sample spotting hole, and its diameter is consistent with the diameter of the sample spotting hole. A 3mm diameter hole is opened on the side wall of the channel to introduce heating auxiliary gas. After entering the channel, the heating auxiliary gas is blown into the bottom of the sample spotting hole, backflushing the vaporized sample into the transfer tube 303 and sending it into the ionization chamber. The auxiliary gas heating pipeline 304 includes a gas pipe 3041, a flow controller 3042, a temperature sensor 3043, a heating pipe 3044, and a heat insulation sleeve 3045. The heating pipe 3043, gas pipe 3041, and heat insulation sleeve 3045 are nested together to heat the auxiliary gas, with a maximum heating temperature of 350 degrees Celsius. The flow controller 3042 is controlled by the control device 600 to set the flow rate of the auxiliary gas and to link with the on / off state of the laser 201. The auxiliary gas can be compressed air, nitrogen, helium, or other inert gases and other special reactive gases, such as methane. When the sample is injected, the injection module 300 sends a TTL injection signal to the control device 600.

[0062] The ionization module 400 includes a plasma generation module, an adjustment base 402, a conical focusing electrode 403, and a heating pad 404. The plasma generation module adopts a glass tube-insulated metal wire structure. It generates plasma by applying a radio frequency voltage with an amplitude of 3-7 kVpp, which reacts with reactive ions. This voltage is provided by the control circuit 600 and is linked to the laser 201 and the auxiliary gas flow controller 3042 for control. The adjustment base 402 is made of insulating and pressure-resistant material and is used to install the plasma generation module on the metal cavity 102. The front and rear distance of the plasma generation module can be precisely adjusted by rotation. The conical focusing electrode 403 is made of metal, and the diameter of the outlet orifice is 3-5 mm. A DC voltage is applied to the electrode to focus the generated sample ions and push them into the mass spectrometry interface. The heating pad 404 is used to heat the conical focusing electrode 403 and also serves as insulation.

[0063] The mass spectrometer interface 500 includes a flat sampling cone 501, an insulating pad 502, and an interface base 503, which is used to introduce sample ions generated by the ionization module into the mass spectrometer. The inner diameter of the orifice of the flat sampling cone 501 is 0.5 to 2 mm.

[0064] Control device 600 is used to power and control the entire device, including powering the plasma generation module 401, heater 103, heating tube 3044, heating pad 404, flow controller 3042, etc., and timing control of ionization module 400, laser drive power supply 202, and auxiliary gas flow controller 3042, etc., as shown in the timing control diagram. Figure 4 As shown.

[0065] This mass spectrometry preparation device implements a pulsed-injection direct ionization-mass spectrometry rapid analysis technique, achieving instantaneous temperatures exceeding 300°C within 2 seconds. It effectively resolves non-volatile and highly viscous samples, enabling the detection of both positive and negative ions, significantly improving sensitivity and analysis speed. The ionization module and auxiliary reaction gas can be selected according to sample type and properties to achieve effective ionization of various samples. Furthermore, a certain proportion of water vapor can be added to the auxiliary reaction gas to buffer the influence of actual sample humidity on the measurement results. The device employs a closed ionization chamber, maintaining relatively low internal pressure, which improves the ability to control ion energy, reduces the sample's dependence on humidity during ionization, and enhances instrument sensitivity. This device is easily automated, convenient for on-site, and allows for real-time online analysis, meeting the needs for rapid and efficient analysis of various samples, including pesticide residues and narcotics.

[0066] The device was applied to a mass spectrometer. During the experiment, compressed air with a water content of 30%–60% was used as the auxiliary gas at a flow rate of 1 L / min. The heating temperature was 200°C. A high voltage of 3 kV was applied to the corona discharge needle, 60V to the conical focusing electrode, and 50V to the flat conical sample injector. Avermectin concentrations of 50 μg / L, 100 μg / L, 500 μg / L, and 1 mg / L were spotted onto the sample target. The power of the laser diode was set, and activation of the laser diode enabled thermal desorption and detection analysis of the sample within 1 second. Six injections were performed for each concentration. The peak area of ​​the MIC (micron emission index) for the sample ion m / z 890 ([M+NH4]+) was statistically analyzed, and the average value was used as the signal intensity for that concentration. The test results showed that avermectin exhibited good linearity in the concentration range of 50 ppb–1 ppm, with an R² of 0.9983.

[0067] The aforementioned mass spectrometry preparation device includes a cavity, a pulsed thermal desorption module, a sample introduction module, an ionization module, and a mass spectrometry interface. The ionization module is disposed within the cavity. The sample introduction module includes a sample target for receiving samples. The sample target is disposed within the effective area of ​​the pulsed thermal desorption module. The pulsed thermal desorption module is used to thermally desorb the sample in the sample target to generate sample molecules. The output port of the sample introduction module is connected to the cavity to introduce the sample molecules into the ionization module. The ionization module is used to ionize the sample molecules. The mass spectrometry interface is used to connect the cavity and the mass spectrometer. The sample introduction module receives the sample through the sample target, and the pulse thermal desorption module can rapidly desorb the sample into a gaseous state, generating sample molecules. The output port of the sample introduction module is connected to the cavity, introducing the sample molecules into the ionization module. The ionization module is located in the cavity and is used to ionize the sample molecules. The generated sample ions enter the mass spectrometer for analysis and detection through the mass spectrometry interface. This device can achieve rapid sample introduction, improve ionization efficiency, and also realize the detection of positive and negative ions of the sample, effectively improving sensitivity and analysis speed. Moreover, this device is easy to automate, convenient for on-site and real-time online analysis, and can meet the needs of rapid and efficient analysis of various samples. It is reliable in use.

[0068] In one embodiment, a mass spectrometry device is provided, including a mass spectrometer and a mass spectrometry preparation apparatus as described above.

[0069] The aforementioned mass spectrometry preparation device includes a cavity, a pulsed thermal desorption module, a sample introduction module, an ionization module, and a mass spectrometry interface. The ionization module is disposed within the cavity. The sample introduction module includes a sample target for receiving samples, which is disposed within the effective area of ​​the pulsed thermal desorption module. The pulsed thermal desorption module is used to thermally desorb the sample in the sample target to generate sample molecules. The output port of the sample introduction module is connected to the cavity to introduce the sample molecules into the ionization module. The ionization module is used to ionize the sample molecules to generate sample ions. The mass spectrometry interface is used to connect the cavity and the mass spectrometer and introduce the sample ions into the mass spectrometer. The sample introduction module receives the sample through the sample target, and the pulse thermal desorption module can rapidly desorb the sample into a gaseous state, generating sample molecules. The output port of the sample introduction module is connected to the cavity, introducing the sample molecules into the ionization module. The ionization module is located in the cavity and is used to ionize the sample molecules. The generated sample ions enter the mass spectrometer for analysis and detection through the mass spectrometry interface. This device can achieve rapid sample introduction, improve ionization efficiency, and also realize the detection of positive and negative ions of the sample, effectively improving sensitivity and analysis speed. Moreover, this device is easy to automate, convenient for on-site and real-time online analysis, and can meet the needs of rapid and efficient analysis of various samples. It is reliable in use.

[0070] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0071] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A mass spectrometry preparation device, characterized by, The device includes a cavity, a pulsed thermal desorption module, a sample introduction module, an ionization module, and a mass spectrometry interface. The ionization module is located within the cavity, which contains a heater for heating the cavity. The sample introduction module includes a sample target for receiving samples, an ion transmission tube, and an auxiliary gas heating line. The output port of the sample introduction module is connected to the cavity. The sample target is located within the active area of ​​the pulsed thermal desorption module, which thermally desorbs the sample in the sample target to generate sample molecules. The auxiliary gas heating line is used to connect heated auxiliary gas. The auxiliary gas backflushs the thermally desorbed sample molecules through the spotting orifice of the sample target into the ion transmission tube, and then introduces the sample molecules into the ionization module within the cavity via the ion transmission tube. The ionization module includes a discharge element and a focusing electrode located within the cavity. The focusing electrode has a heating pad for heating the focusing electrode. The ionization module ionizes the sample molecules to generate sample ions. The mass spectrometry interface connects the cavity and the mass spectrometer and introduces the sample ions into the mass spectrometer.

2. The mass spectrometry preparation device of claim 1, wherein, The cavity includes a metal cavity, an insulating cavity, an exhaust port, and a vacuum pump. The ionization module is disposed in the metal cavity. The output port of the sample injection module is connected to the metal cavity. The mass spectrometry interface is used to introduce the sample ions into the mass spectrometer. The insulating cavity is connected to the mass spectrometry interface and is provided with the exhaust port, which is connected to the vacuum pump.

3. The mass spectrometry preparation device of claim 1, wherein, It also includes a temperature sensor disposed within the cavity.

4. The mass spectrometry preparation device of claim 1, wherein, The pulsed thermal desorption module includes a laser, a laser driving power supply, and a focusing lens. The laser driving power supply is connected to the laser, and the focusing lens is used to focus the laser beam. The sample target is disposed in the effective area of ​​the focusing lens.

5. The mass spectrometry preparation device of claim 1, wherein, The sample introduction module also includes a sealing gasket, which is disposed on the sample target. The sealing gasket has a through hole, and the ion transmission tube is connected to the sample target through the through hole. The ion transmission tube is connected to the auxiliary gas heating pipeline, which is used to connect to the auxiliary gas. The end of the ion transmission tube away from the sealing gasket is connected to the cavity.

6. The mass spectrometry preparation device of claim 5, wherein, The auxiliary gas heating pipeline includes a gas pipe, a flow controller, a gas temperature sensor, a heating pipe, and a heat insulation sleeve. The heating pipe, the gas pipe, and the heat insulation sleeve are nested together. The flow controller and the gas temperature sensor are both located on the gas pipe. The heat insulation sleeve is used to keep the auxiliary gas warm and provide insulation.

7. The mass spectrometry preparation device of claim 1, wherein, The ionization module includes an adjustment base disposed within the cavity, the discharge element is connected to the adjustment base, and the focusing electrode is disposed at the outlet position of the discharge element.

8. The mass spectrometry preparation apparatus according to claim 7, characterized in that, The discharge device is a corona discharge needle or a plasma generation module.

9. The mass spectrometry preparation device of claim 1, wherein, The mass spectrometry interface includes a sample injection element, an insulating pad, and an interface base. The sample injection element is disposed on the interface base through the insulating pad, and the sample injection element is used to connect the cavity and the mass spectrometer.

10. The mass spectrometry preparation device of claim 1, wherein, It also includes a control device, and both the ionization module and the sample injection module are connected to the control device.

Images