Mass spectrometry method for rapid analysis of poisons and explosives

Abstract

The application discloses a mass spectrum detection method for rapid analysis of poisons and explosives, and comprises the following steps: providing a sampling carrier for collecting a sample to be measured and placing the sampling carrier in an ion source area; reading identification information associated with the carrier and automatically obtaining preset analysis parameters; dynamically adjusting the heating temperature of the carrier based on the parameters to make the sample to be measured desorb; performing plasma ionization on the sample to be measured in the ion source area; performing mass spectrum analysis on the ionized sample to be measured and outputting a result. The application realizes time dimension separation by automatically calling parameters to execute a dynamic program temperature rising, effectively blocks ionization competition among complex mixtures in a physical time sequence. The method does not need complex pretreatment, is specific, has high resolution and sensitivity, and is suitable for rapid and accurate screening of mixed poisons and explosives on site.

Description

Technical Field

[0001] This invention belongs to the field of mass spectrometry detection technology. Specifically, this invention relates to a mass spectrometry detection method that can be used for rapid analysis of toxic substances and explosives. Background Technology

[0002] In recent years, drug manufacturers have frequently mixed various drugs to create new types of hybrid drugs with enhanced effects. These hybrid drugs, where different drugs are mixed to enhance each other's efficacy, are highly dangerous and place higher demands on rapid on-site drug identification technology. However, current traditional detection instruments, including spectroscopy, chromatography-mass spectrometry, and immunoassay, are not suitable for the requirements of rapid and accurate on-site detection.

[0003] Explosive detection technology is widely used in customs, aviation, subway stations, prisons, and explosion sites to prevent explosions and provide timely information to public security departments for rapid source tracing and analysis. Due to the wide variety of explosives and the fact that most are non-volatile, explosives are highly concealed, making accurate detection of trace explosives remaining on object surfaces extremely important. Currently, a common method for on-site analysis of trace explosives is the paper swab method combined with ion mobility spectrometry, but this method suffers from low sensitivity, resolution, and a limited analytical range.

[0004] Therefore, there is an urgent need to develop a mass spectrometry detection method with high sensitivity, high resolution, and a wide analytical range. Summary of the Invention

[0005] This application aims to at least partially address one of the technical problems existing in the prior art. To this end, this application provides a mass spectrometry detection method.

[0006] In one aspect of this application, a mass spectrometry detection method is proposed. According to an embodiment of this application, the mass spectrometry detection method includes: providing a sampling carrier for collecting a sample to be tested; placing the sampling carrier carrying the sample to be tested in an ion source region; dynamically adjusting the heating temperature of the sampling carrier based on preset analytical parameters corresponding to the sample to be tested, so as to desorb the analyte; performing plasma ionization on the desorbed analyte in the ion source region; performing mass spectrometry analysis on the ionized analyte and outputting the detection results; wherein the preset analytical parameters are automatically obtained based on identification information associated with the sampling carrier. The mass spectrometry detection method of this application embodiment has the advantages of high sensitivity, high resolution, and a large analytical range, enabling rapid sampling and efficient analysis. The method of this application embodiment can be conveniently implemented using a dedicated reagent kit, which typically includes a sampling carrier and a tooling structure for positioning and support. The tooling structure may integrate a magnetic positioning component and an RFID tag storage module; when the reagent kit is inserted into the mass spectrometer, the magnetic positioning component guides the sampling carrier to precisely align and dock with the heating module and discharge electrode of the mass spectrometer host. These components are preferred tools for implementing methods, rather than limitations of the methods themselves.

[0007] In some embodiments of this application, the identification information is a radio frequency identification (RFID) tag, a QR code, or a barcode, preferably an RFID tag.

[0008] In some embodiments of this application, the step of placing the sampling carrier in the ion source region includes: positioning and docking by magnetic adsorption so that the sample area on the sampling carrier is aligned with the pyrolysis adsorption module and discharge electrode of the ion source.

[0009] In some embodiments of this application, the step of dynamically adjusting the heating temperature includes: executing a programmed heating process according to the pre-set desorption temperatures of at least two different analytes, and using the difference in desorption temperatures of the different analytes to sequentially perform desorption and mass spectrometry analysis on the at least two different analytes to achieve separation and detection of mixed samples.

[0010] In some embodiments of this application, the programmed heating process is a heating process automatically generated based on the parameters of the test object in the database, or a manually set heating program.

[0011] In some embodiments of this application, the steps of collecting the sample to be tested include: for liquid samples, dropping them onto the organic solvent-repellent labeling area at the front end of the sampling carrier; for solid samples, wiping the surface of the sample to be tested with the sampling carrier.

[0012] In some embodiments of this application, the desorption is carried out in a temperature range of 30-350°C; and / or, the discharge voltage of the plasma ionization treatment is 1 kV-10 kV; and / or, the discharge frequency of the plasma ionization treatment is 10 kHz-100 kHz.

[0013] In some embodiments of this application, the working gas used for plasma ionization can be an inert gas such as helium, argon, or nitrogen to achieve higher ionization efficiency. Preferably, to meet the needs of portable and rapid on-site detection, the plasma ionization directly uses ambient air as the discharge working gas. The preferred discharge voltage and frequency conditions of this invention (e.g., high frequency and high voltage) ensure the generation of stable low-temperature plasma even in an air environment, eliminating the dependence of portable devices on external gas cylinders. As an example, the plasma ionization can specifically employ ambient pressure open ionization techniques such as low-temperature plasma (LTP) probes or dielectric barrier discharge (DBD).

[0014] In some embodiments of this application, the mass spectrometry analysis includes tandem mass spectrometry analysis, used for qualitative confirmation of the analyte.

[0015] In some embodiments of this application, the sample to be tested includes at least one of explosives, poisons, drugs, and food contaminants.

[0016] In some embodiments of this application, the sampling carrier includes at least one of a glass slide, a paper slide, and a cloth slide.

[0017] In some embodiments of this application, the preset parameters invoked by the identification information include at least one of the following: target desorption temperature, programmed heating rate, holding time, sample type, analyte type, calibration curve, and detection mode information.

[0018] In some embodiments of this application, the output detection result includes at least one of the following: output mass spectrum, target concentration range, detection limit, and confidence interval.

[0019] The beneficial effects of this application are as follows: 1. Fast and efficient: The entire analysis process can be completed in a short time by automatically calling parameters through RFID tags and combining dynamic temperature-dependent desorption, making it suitable for field applications; 2. High sensitivity: Optimized thermal desorption and plasma ionization conditions are particularly suitable for the detection of trace substances; 3. Wide applicability: By adjusting the parameters, it can be applied to a variety of analytes such as explosives, poisons, narcotics, drugs, and food contaminants; 4. Simple operation: It can be quickly analyzed after sampling, reducing the technical threshold for operators.

[0020] In another aspect of this application, a control method for a mass spectrometry detection device is proposed. According to an embodiment of this application, the method is executed by the control unit of the device and includes the following steps: acquiring identification information of a sampling carrier placed in the ion source region; automatically calling preset analysis parameters corresponding to the sample to be tested based on the identification information; controlling a heating module to dynamically adjust the heating temperature of the sampling carrier according to the preset analysis parameters to desorb the analyte; controlling a discharge electrode to perform plasma ionization of the desorbed analyte in the ion source region; acquiring the mass spectrometry data of the ionized analyte for mass spectrometry analysis and outputting the detection results. This embodiment of the mass spectrometry detection method, from the perspective of automatic device control, achieves a high degree of automation and intelligence in the detection process. Through closed-loop control with coordinated hardware and software, it effectively eliminates subjective differences caused by human operation, further improving the reproducibility, stability, and response speed of the on-site detection results. The method of this embodiment can be conveniently implemented using a control unit integrated with a microprocessor, industrial computer, or related control software program. This control unit typically communicates with an identification reading component (such as an RFID reader), a temperature control component, and a mass spectrometry analysis component to achieve automatic command issuance and execution. It should be noted that this control command flow-based implementation architecture allows the core logic of this invention—dynamic temperature variation and detection—to be independently established at the hardware and software interaction level, which is more conducive to the standardized operation and intelligent upgrading of portable mass spectrometry equipment.

[0021] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0022] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 This is a schematic diagram of one implementation process of the mass spectrometry detection method of the present invention (corresponding to automatic temperature rise mode).

[0023] Figure 2 This is a schematic diagram of another implementation process of the mass spectrometry detection method of the present invention (corresponding to manual heating mode).

[0024] Figure 3 This is a schematic diagram illustrating the working principle of a reagent kit that can be used to implement the method of the present invention.

[0025] Figure 4 This is a schematic diagram of the reagent kit structure for liquid samples in Example 1.

[0026] Figure 5 This is a schematic diagram of the reagent kit structure for solid samples in Example 2.

[0027] Figure 6 This is a flowchart of the mass spectrometry detection method in Example 1.

[0028] Figure 7 This is a flowchart of the mass spectrometry detection method in Example 2.

[0029] Figure 8 These are the test parameters used in Example 2 for detecting explosives TNT, PETN, RDX, HMX, NG, DNT, PA, CE, and ETN.

[0030] Figure 9 This is a mass spectrometry result of the detection of explosives TNT, PETN, RDX, HMX, NG, DNT, PA, CE, and ETN in Example 2.

[0031] Figure 10 These are the test parameters used in Example 2 for detecting the drugs cocaine, ketamine, morphine, and methamphetamine.

[0032] Figure 11 This is a mass spectrometry result of the detection of cocaine, ketamine, morphine and methamphetamine in Example 2.

[0033] Figure 12 These are the test parameters used in Example 2 to detect the poisons cypermethrin, deltamethrin, and fenvalerate.

[0034] Figure 13 This is a mass spectrometry result of the detection of the poisons cypermethrin, deltamethrin, and fenvalerate in Example 2.

[0035] Figure 14 This is a graph showing the relationship between the signal strength of the mixture of various explosives in Example 3 and temperature.

[0036] Figure 15 These are the test parameters for detecting various explosives by programmed temperature rise separation in Example 3.

[0037] Figure 16 This is a tandem mass spectrum (MS2 and MS3) of the explosive picric acid (PA) in Example 4. Detailed Implementation

[0038] The embodiments of this application are described in detail below, with examples of these embodiments shown in the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0039] Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the terminology used in this application is for the purpose of describing particular embodiments only and is not intended to limit this application; unless otherwise stated, the values ​​of the parameters mentioned in this application can be measured using various measurement methods commonly used in the art (e.g., they can be tested according to the methods given in the embodiments of this application).

[0040] The terms “comprising” and “having”, and any variations thereof, in the specification and claims of this application are open-ended expressions, meaning they include what is specified in this application but do not exclude other aspects.

[0041] In the description of this application, it should be understood that the terms "width", "thickness", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing this application and 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, and therefore should not be construed as a limitation of this application.

[0042] In the description of this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. "First feature" and "second feature" may include one or more of the indicated feature.

[0043] In the description of this application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc., indicating the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, are only for the convenience of describing this application and 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, and therefore should not be construed as a limitation of this application.

[0044] In the description of this application, unless otherwise expressly specified and limited, "above" or "below" the second feature can mean that the first and second features are in direct contact, or that the first and second features are in indirect contact through an intermediate medium. Furthermore, "above," "on top of," and "over" the second feature can mean that the first feature is directly above or diagonally above the second feature, or simply that the first feature is at a higher horizontal level than the second feature. "Below," "below," and "under" the second feature can mean that the first feature is directly below or diagonally below the second feature, or simply that the first feature is at a lower horizontal level than the second feature.

[0045] In the description of this application, "multiple" means two or more.

[0046] In the description of this application, "A and / or B" can include any of the cases of A alone, B alone, or A and B, where A and B are merely examples and can be any technical feature connected by "and / or" in this application.

[0047] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0048] This application proposes a mass spectrometry detection method and a control method for a mass spectrometry detection device, which will be described in detail below.

[0049] Mass spectrometry detection method In one aspect of this application, a mass spectrometry detection method is proposed. According to an embodiment of this application, the mass spectrometry detection method includes: providing a sampling carrier for collecting a sample to be tested; placing the sampling carrier carrying the sample to be tested in an ion source region; dynamically adjusting the heating temperature of the sampling carrier based on preset analytical parameters corresponding to the sample to be tested, so as to desorb the analyte; performing plasma ionization on the desorbed analyte in the ion source region; performing mass spectrometry analysis on the ionized analyte and outputting the detection results; wherein the preset analytical parameters are automatically obtained based on identification information associated with the sampling carrier. Compared to ion mobility spectrometry, spectroscopy, mass spectrometry, and immunoassay, portable mass spectrometers offer better specificity and effectively avoid false positives and false negatives. They also possess high sensitivity, high resolution, fast analysis speed, and a wider analytical range, making them more suitable for rapid and accurate trace analysis on-site. Furthermore, this method combines rapid sampling with a portable mass spectrometer, enabling faster and more accurate results on-site, which is highly advantageous for scenarios requiring rapid on-site analysis in special environments. The mass spectrometry detection method of this application has the advantages of high sensitivity, high resolution and large analysis range, and can perform rapid sampling and efficient analysis.

[0050] According to embodiments of this application, the identification information is a radio frequency identification (RFID) tag, a QR code, or a barcode, preferably an RFID tag.

[0051] It should be explained that RFID is an abbreviation for Radio Frequency Identification.

[0052] According to an embodiment of this application, the step of placing the sampling carrier in the ion source region includes: positioning and docking by magnetic adsorption so that the sample area on the sampling carrier is aligned with the pyrolysis adsorption module and discharge electrode of the ion source.

[0053] According to an embodiment of this application, the step of dynamically adjusting the heating temperature includes: executing a programmed heating process based on the pre-set desorption temperatures of at least two different analytes, and using the difference in desorption temperatures of the different analytes to sequentially perform desorption and mass spectrometry analysis on the at least two different analytes to achieve separation and detection of mixed samples.

[0054] Furthermore, the mechanism in this application that automatically invokes and executes dynamic temperature changes (such as programmed temperature rise processes) through identification information is not only for automation, but also fundamentally overcomes the technical bottlenecks in existing on-site mass spectrometry detection. As described in the background art, traditional portable mass spectrometry or ion mobility spectrometry often faces the problem of low resolution when dealing with complex mixtures (such as mixed drugs or residues of multiple explosives). The fundamental reason is that when mixed samples are instantaneously desorbed together at a fixed temperature, a large number of different types of molecules will simultaneously flood into the ion source region, thereby triggering severe ionization competition and matrix inhibition effects, resulting in the inability to effectively detect poorly ionized or trace substances (producing false negatives).

[0055] This application achieves a miniaturized, column-free "pyrolysis-adsorption gas chromatography separation" at the ion source front end by dynamically adjusting the heating temperature and utilizing the inherent differences in vapor pressure and pyrolysis adsorption temperature of different analytes in the mixture. During the programmed temperature rise, different components in the mixture are sequentially stripped and enter the plasma region for individual ionization over time (temperature gradient), effectively blocking the ionization competition between different molecules from a physical temporal perspective. This principle not only endows portable mass spectrometers with extremely high resolution without the need for large-volume pretreatment hardware such as chromatographic columns, but also greatly improves the sensitivity of trace component detection in complex matrices.

[0056] According to embodiments of this application, the programmed heating process is either an automatically generated heating process based on the analyte parameters in the database, or a manually set heating program. It should be noted that the dynamic adjustment of the heating temperature of the sampling carrier (i.e., the programmed heating process) includes not only "linear heating" which continuously increases the temperature at a constant or variable rate, but also "step heating (or gradient holding)" which switches between multiple different temperature nodes and holds each for a specific time. Any method that utilizes temperature differences to achieve sequential desorption of the mixture components over time falls within the scope of this invention.

[0057] According to an embodiment of this application, the steps for collecting a sample to be tested include: for liquid samples, dropping them onto the organic solvent-repellent labeling area at the front end of the sampling carrier; for solid samples, wiping the surface of the sample to be tested with the sampling carrier.

[0058] According to embodiments of this application, the desorption is carried out in a temperature range of 30-350℃, for example, the temperature can be 30℃, 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, or a range between the two, such as 40-350℃ or 50-350℃. A suitable desorption temperature is beneficial to improving the ionization efficiency of the analyte and enhancing the detection sensitivity; excessively high desorption temperatures will cause some of the analyte to decompose and increase the power consumption of the instrument, while excessively low desorption temperatures cannot achieve effective thermal desorption.

[0059] According to embodiments of this application, the discharge voltage of the plasma ionization treatment is 1 kV-10 kV, for example, it can be 1 kV, 1.5 kV, 2 kV, 2.5 kV, 3 kV, 3.5 kV, 4 kV, 4.5 kV, 5 kV, 6 kV, 7 kV, 8 kV, 9 kV, 10 kV, or a range between the two, 1.5 kV-10 kV, 2 kV-10 kV. A suitable discharge voltage is beneficial for portable mass spectrometry trace detection; excessively high discharge voltages may affect other components of the instrument and pose safety hazards; excessively low discharge voltages will prevent plasma generation.

[0060] According to embodiments of this application, the discharge frequency of the plasma ionization treatment is 10 kHz-100 kHz, for example, it can be 10 kHz, 15 kHz, 20 kHz, 25 kHz, 30 kHz, 35 kHz, 40 kHz, 45 kHz, 50 kHz, 55 kHz, 60 kHz, 65 kHz, 70 kHz, 75 kHz, 80 kHz, 85 kHz, 90 kHz, 95 kHz, 100 kHz, and the range between the two, 15 kHz-100 kHz, 20 kHz-100 kHz. A suitable discharge frequency is beneficial for portable mass spectrometry trace detection, and high-voltage modules in this frequency range are relatively easy to implement, inexpensive, and small in size.

[0061] It should be particularly noted that the operating parameter range defined in this invention (temperature 30-350℃, discharge voltage 1kV-10kV, discharge frequency 10 kHz-100 kHz) was determined based on extensive experimental exploration, and both extreme values ​​have clear physical meaning and are supported by specific application scenarios. (1) Regarding the temperature range (30-350℃): In practical applications, for highly volatile target substances (such as some volatile drug precursors, organic solvent residues, or specific explosives such as TATP), using an initial low temperature of 30℃ can achieve smooth desorption of the target substance, avoiding excessively rapid heating that would cause the sample to evaporate in large quantities and exceed the linear range of the detector; while at the high temperature end, for analytes that are extremely difficult to volatilize and have high thermal stability (such as high melting point explosives such as HMX or macromolecular pesticide residues), the experiments of this invention have confirmed that raising the thermal desorption temperature to 350℃ can ensure the complete desorption of such non-volatile substances, and in this specific plasma environment, due to the extremely rapid desorption and ionization process, it effectively avoids the deep carbonization or thermal decomposition of such substances on the carrier surface, thereby ensuring the complete detection of characteristic precursor ions.

[0062] (2) Regarding discharge voltage (1 kV-10 kV): For highly polar compounds that are easily ionized, a low discharge voltage of 1 kV is sufficient to form a stable plasma to achieve soft ionization, effectively reducing excessive fragmentation and preserving the molecular ion peak of the target substance; while for difficult-to-ionize substances with extremely low proton affinity or electron affinity (or extremely trace samples existing in a high matrix interference environment), applying a discharge voltage of up to 10 kV can greatly increase plasma density and energy, significantly improve the ionization efficiency of such inert samples, and ensure that there are no false negatives or missed detections of trace toxic substances or explosives.

[0063] (3) Regarding the discharge frequency (10 kHz-100 kHz): At a low frequency of 10 kHz, the plasma discharge exhibits excellent long-term stability, which is suitable for continuous and stable signal acquisition of samples with high concentrations; while at a high frequency of 100 kHz, the transient energy density generated by the discharge is extremely high, which can cope with rapid desorption events at the microsecond level, and is particularly suitable for instantaneous pulsed efficient ionization of extremely small amounts (picogram level) of wiped samples on site.

[0064] According to embodiments of this application, the mass spectrometry analysis includes tandem mass spectrometry analysis, used for qualitative confirmation of the analyte.

[0065] According to embodiments of this application, the sample to be tested includes at least one of explosives, poisons, drugs, and food contaminants.

[0066] According to embodiments of this application, the explosives include TNT, PETN, RDX, HMX, etc., and are used in security screening scenarios.

[0067] According to embodiments of this application, the poisons include narcotics (such as cocaine, ketamine, etc.) and other toxic substances (such as pesticide residues), covering illegal drugs and environmental pollutants, or referring to harmful substances that may exist in food. This method can be adapted to such detections through parameter calls.

[0068] According to embodiments of this application, the drug includes legal drugs (such as verapamil, reserpine) or abused drugs, for use in pharmaceutical monitoring or toxicological analysis.

[0069] According to embodiments of this application, the sampling carrier includes at least one of a glass slide, a paper slide, and a cloth slide.

[0070] According to embodiments of this application, the preset parameters invoked by the identification information include at least one of the following: target desorption temperature, programmed heating rate, holding time, sample type, analyte type, calibration curve, and detection mode information.

[0071] According to an embodiment of this application, the output detection result includes at least one of the following: output mass spectrum, target concentration range, detection limit, and confidence interval.

[0072] According to a specific embodiment of this application, a heating process is automatically generated based on the parameters of the analyte in the database for detection. The method includes: S1) installing the sampling carrier within the tooling support structure; S2) collecting the sample to be tested into a designated area of ​​the sampling carrier: solids can be sampled by wiping, and liquids can be added dropwise to the sampling area; S3) docking the reagent kit with the ion source of the portable mass spectrometer using a magnet positioning process; S4) calling preset parameters based on an RFID tag and issuing the execution command; S5) setting the initial temperature, starting the heating process, and determining if the temperature is within acceptable limits. S6) If the temperature reaches the initial temperature, turn on the motor switch and move the heating platform and discharge electrode to the designated position; S7) Control the temperature to reach and maintain the desorption temperature of the analyte; S8) Perform mass spectrometry analysis; S9) After completing the detection of the sample, determine whether all analytes have been detected. If not, set the corresponding analysis parameters for the next analyte and perform temperature rise and mass spectrometry analysis; S10) After all analytes have been analyzed, compare the collected mass spectra with the database; S11) Output the detection report and corresponding mass spectra. See details. Figure 1 .

[0073] According to a specific embodiment of this application, the heating program can also be manually set to control the heating rate and temperature holding time, and the corresponding mass spectrometry scanning sequence within the temperature range can be set for scanning. Manual setting offers greater flexibility, allowing for alternating scanning of multiple analytes within a unified time period, resulting in higher sample utilization. The detection process of the method is as follows: S1) Install the sampling carrier within the tooling support structure; S2) Collect the sample to be tested into the designated area of ​​the sampling carrier: solids can be sampled by wiping, and liquids can be added dropwise to the sampling area; S3) Connect the reagent kit to the ion source of the portable mass spectrometer using a magnet for positioning; S4 S5) Based on the RFID tag, call the preset parameters and issue the execution; S6) Set the initial temperature, start heating, and determine if the temperature has reached the starting temperature; S7) When the temperature reaches the starting temperature, turn on the motor switch, move the heating platform and discharge electrode to the designated position, and start timing; S8) Control the temperature to rise according to the specified heating program; perform mass spectrometry analysis according to the set order of the analytes; S9) Determine if the time has reached the end time. If yes, proceed to the next step; otherwise, continue to perform temperature control and mass spectrometry analysis according to the set order; S10) When the time reaches the end time, compare the collected mass spectra with the database; S11) Output the test report and corresponding mass spectra. See details. Figure 2 . Figure 2This diagram illustrates another implementation flow of the mass spectrometry detection method of the present invention, corresponding to the manual heating mode. In certain special analytical scenarios or R&D testing phases, operators can disable the RFID automatic call function through the device's operating interface and manually input analytical parameters such as the target desorption temperature and heating rate. The device then executes the subsequent dynamic heating and mass spectrometry detection process according to the manually issued instructions.

[0074] According to the embodiments of this application, the core method flow of the present invention can be summarized as follows: 1. Sampling: Collect the sample to be tested using a suitable sampling carrier (such as a glass slide, paper, cloth, etc.); 2. Sample loading and positioning: Place the sampling carrier in the analysis area of ​​the ion source of the mass spectrometer. Preferably, rapid and accurate positioning can be achieved through magnetic adsorption or other methods; 3. Parameter calling and setting: Read the RFID tag related to this detection and automatically call the preset analysis parameters (such as sample type, target analyte, desorption temperature program, ionization parameters, etc.); 4. Variable temperature desorption and ionization: Control the heating module according to the parameters, and raise the temperature according to the program or manually, so that the analytes with different volatility are desorbed sequentially at the optimal temperature. The desorbed molecules are ionized under the action of plasma generated by the discharge electrode; 5. Mass spectrometry analysis and result output: The ionized analyte enters the mass spectrometer for analysis, the obtained mass spectrum is compared with the database, and qualitative results are output.

[0075] To better implement the method of the present invention, a dedicated reagent kit can be preferably used. The working principle of the reagent kit is as follows: Figure 3 As shown, the reagent kit is inserted into the designated position of the ion source. Using the positioning function of the magnet in the reagent kit and the magnet in the ion source structure, the sample area of ​​the sampling carrier is placed above the desorption heating module. The rapid thermal desorption of the sample on the sampling carrier is achieved by heating. The sample that has been thermally desorbed will be ionized by the plasma generated by the discharge electrode above the sample carrying area. Figure 3 A schematic diagram illustrating the working principle of a reagent kit that can be used to implement the method of the present invention is shown. Figure 3 As shown, the kit not only serves as the physical medium for carrying the sample, but its overall configuration is also compatible with the ion source interface at the front end of the portable mass spectrometer. Through non-destructive positioning and docking methods such as mechanical limiting or magnetic attraction, it ensures that the sampling carrier is precisely positioned within the optimal working area of ​​the discharge electrode and heating module each time it is inserted, thereby guaranteeing high reproducibility of the detection signal. This kit is not a necessary limitation of this method, but it greatly improves the convenience and standardization of operation. For kits for liquid samples, please refer to [link to kit]. Figure 4 Sampling carrier: can be a glass slide with a marking ring at the front end that is resistant to organic solvents (such as polytetrafluoroethylene) to define the position of the droplet; Tooling structure: includes a structure for fixing the sampling carrier and a structure for positioning with the mass spectrometer, and is equipped with an RFID tag pasting area.

[0076] See kits for solid samples. Figure 5 Sampling carrier: can use paper of a specific shape for easy installation and positioning; Tooling structure: includes devices for fixing the paper (such as top cover limit, positioning hole), the handle can be designed as a rotatable structure to provide support during wiping, and also integrates magnetic positioning function and RFID tag area.

[0077] Control methods for mass spectrometry detection equipment In another aspect of this application, a control method for a mass spectrometry detection device is proposed. According to an embodiment of this application, the method is executed by the control unit of the device and includes the following steps: acquiring identification information of a sampling carrier placed in the ion source region; automatically calling preset analysis parameters corresponding to the sample to be tested based on the identification information; controlling a heating module to dynamically adjust the heating temperature of the sampling carrier according to the preset analysis parameters to desorb the analyte; controlling a discharge electrode to perform plasma ionization of the desorbed analyte in the ion source region; acquiring the mass spectrometry data of the ionized analyte for mass spectrometry analysis and outputting the detection results. This embodiment of the mass spectrometry detection method, from the perspective of automatic device control, achieves a high degree of automation and intelligence in the detection process. Through closed-loop control with coordinated hardware and software, it effectively eliminates subjective differences caused by human operation, further improving the reproducibility, stability, and response speed of the on-site detection results. The method of this embodiment can be conveniently implemented using a control unit integrated with a microprocessor, industrial computer, or related control software program. This control unit typically communicates with an identification reading component (such as an RFID reader), a temperature control component, and a mass spectrometry analysis component to achieve automatic command issuance and execution. It should be noted that this control command flow-based implementation architecture allows the core logic of this invention—dynamic temperature variation and detection—to be independently established at the hardware and software interaction level, which is more conducive to the standardized operation and intelligent upgrading of portable mass spectrometry equipment.

[0078] The following will explain the solution of this application with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0079] Example 1: Detection of liquid samples This example demonstrates a method for detecting liquid mixed drug samples using a dedicated reagent kit.

[0080] (1) Using a reagent kit for liquids, drop the liquid sample to be tested into the marked circle on the sampling slide.

[0081] (2) After the solvent has evaporated, insert the kit into the ion source interface of the portable mass spectrometer and position it by magnetic force.

[0082] (3) The instrument automatically reads the parameters in the RFID tag and executes the temperature change program.

[0083] (4) After mass spectrometry analysis, the qualitative results of each drug are output. The kit designed in this embodiment is for liquid samples; see the schematic diagram below. Figure 4 The consumables are glass slides or other carriers capable of collecting liquids. This embodiment exemplifies the use of a sampling glass slide, characterized by an 8mm printed circle at the front end, printed using a hydrophobic organic solvent (hydrophobic and oleophobic material). The reagent kit includes a positioning structure for the ion source, a sampling carrier fixing structure, and an RFID tag attachment area. The kit functions as follows: the positioning structure ensures consistent sample loading position each time; the sampling carrier fixing structure secures the sampling carrier to the handle; and the RFID tag allows identification of preset parameters for the sample, enabling rapid analysis. The mass spectrometry detection method's usage process is as follows: First, prepare the sample to be tested. Place the sampling slide inside the kit, add the sample to the sample collection area, and after the solvent evaporates, it can be sent to a small mass spectrometer for mass spectrometry analysis. See details... Figure 6 .

[0084] Example 2: Detection of trace explosives on solid surfaces The kit designed in this embodiment is for solid samples. See the schematic diagram below for details. Figure 5 The consumables are paper sheets or other carriers capable of collecting surface samples. This embodiment exemplifies the use of sampling paper sheets, whose shape facilitates assembly and positioning. The reagent kit fixture includes: a paper sheet fixing device; an RFID tag pasting area; and a rotatable handle that can be rotated under the paper sheet for support during wiping. It achieves the following functions: fixing the paper sheet, performing wiping operations, a positioning structure that interacts with the ion source structure for positioning, and the ability to identify preset parameters of the sample under test by attaching an RFID tag, enabling rapid analysis.

[0085] The procedure for using the mass spectrometry detection method is as follows: First, install and secure the sampling paper in the reagent kit, flip it over, and then wipe the surface of the analyte. After wiping, return the turntable to its original position and insert it into the miniature mass spectrometer for mass spectrometry analysis. See details... Figure 7 .

[0086] This kit can be used to detect explosives TNT, PETN, RDX, HMX, NG, DNT, PA, CE, and ETN. Test parameters are detailed below. Figure 8 See results Figure 9 .

[0087] Use this kit to detect cocaine, ketamine, morphine, and methamphetamine. Test parameters are as follows: Figure 10 See results Figure 11 .

[0088] This kit was used to detect the poisons cypermethrin, deltamethrin, and fenvalerate. Test parameters are as follows: Figure 12 See results Figure 13 .

[0089] Example 3: A one-time detection method for multiple explosive mixtures based on programmed temperature rise This embodiment aims to demonstrate the ability of the method of the present invention to effectively separate and detect complex mixtures through dynamic temperature control.

[0090] Detection method steps: 1. Sample preparation: Prepare a mixed standard solution containing multiple explosives such as PETN, CE (Tai'an), RDX, HMX, and PA (picric acid).

[0091] 2. Sampling and loading: Following the method described in Example 1 or 2, the mixed sample is loaded onto the sampling carrier and installed into the kit, and then docked with the ion source of the portable mass spectrometer.

[0092] 3. Setting Analytical Parameters and Establishing a Database: To demonstrate the method's ability to separate complex mixtures, this example first explores the method by manually setting the heating program (setting a heating process covering 30℃ to 300℃, and setting the order of alternating mass spectrometry scans of different explosives within different temperature ranges). In acquiring... Figure 14 After optimizing the parameters as shown, this set of programmed temperature rise parameters is written into the database as "preset analysis parameters" and associated with the corresponding reagent kit's RFID tag. In subsequent field applications, the instrument only needs to read the RFID tag to automatically invoke the temperature rise program.

[0093] 4. Data Acquisition and Analysis: Initiate the analysis process. The instrument heats up according to the preset program and acquires mass spectrometry signals from the target explosive at the corresponding temperature points.

[0094] For the temperature rise curve and mass spectrometry scanning material settings, please refer to [link / reference]. Figure 15 The test results are as follows Figure 14 As shown. Figure 14The curves showing the signal intensity of each explosive as a function of temperature are clearly displayed. The results indicate that, due to differences in thermal stability and volatility, different explosives exhibit distinct independent signal peaks sequentially within different characteristic temperature ranges (e.g., PETN and CE desorb at low temperatures, while RDX, HMX, and PA sequentially peak at high temperatures). This data objectively demonstrates that the programmed temperature control method of this embodiment can effectively separate mixture components over time, avoiding signal interference caused by simultaneous desorption, and achieving the resolution of multiple explosives in a single injection.

[0095] Example 4: A method for qualitative identification and confirmation of explosives based on tandem mass spectrometry (MS2 / MS3) This embodiment aims to demonstrate how the method of the present invention, after completing the initial mass spectrometry (MS1) detection, utilizes tandem mass spectrometry technology to perform fragment ion analysis on the target analyte, thereby achieving a higher level of qualitative confirmation and effectively avoiding false positive results.

[0096] Detection method steps: 1. Sample and Preliminary Detection: Taking the explosive picric acid (PA) as an example. First, following the method described in Example 1 or 2, a sample containing PA was subjected to conventional mass spectrometry (MS1) scanning, and its precursor ion signal was detected (e.g., m / z 227.99 [MH)). - ).

[0097] 2. Tandem Mass Spectrometry Analysis: Subsequently, the tandem mass spectrometry analysis process is automatically or manually triggered by the operator. MS2 analysis is performed first: the parent ion at m / z 229 undergoes collision-induced dissociation to generate characteristic fragment ions (such as...). Figure 16 The m / z value shown is 197.99 [MHO]. - (etc.), and obtained MS2 mass spectra.

[0098] 3. Multi-stage mass spectrometry analysis (optional): To further confirm the structure, a key MS2 fragment ion (e.g., m / z 197.99) can be selected for MS3 analysis, and collisional dissociation can be performed again to obtain information on the next level of fragment ions (m / z 154.01).

[0099] Analysis results as follows Figure 16As shown in the figure, the MS2 and MS3 mass spectra of picric acid (PA) are clearly displayed. The MS2 spectrum shows characteristic fragment peaks resulting from the loss of NO2 or other groups from the parent ion, while the MS3 spectrum provides more detailed information on the fragmentation pathway. These characteristic fragment ion fingerprints match information in the standard substance database, providing strong evidence for the presence of PA and greatly improving the accuracy of qualitative analysis. The embodiments of this invention demonstrate that the method is not only rapid and sensitive but also possesses strong compound structure confirmation capabilities, making it particularly suitable for safety screening fields where the accuracy of detection results is extremely important.

[0100] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0101] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A mass spectrometry detection method, characterized in that, include: A sampling carrier is provided, which is used to collect the sample to be tested; The sampling carrier carrying the sample to be tested is placed in the ion source region; Based on preset analytical parameters corresponding to the sample to be tested, the heating temperature of the sampling carrier is dynamically adjusted to desorb the analyte. In the ion source region, the desorbed analyte is subjected to plasma ionization; Mass spectrometry analysis is performed on the ionized analyte, and the detection results are output. The preset analysis parameters are automatically obtained based on the identification information associated with the sampling carrier.

2. The method according to claim 1, characterized in that, The identification information is a radio frequency identification (RFID) tag, QR code, or barcode information, preferably an RFID tag.

3. The method according to claim 1, characterized in that, The step of placing the sampling carrier in the ion source region includes: positioning and docking by magnetic adsorption so that the sample area on the sampling carrier is aligned with the pyrolysis adsorption module and discharge electrode of the ion source.

4. The method according to claim 1, characterized in that, The steps of dynamically adjusting the heating temperature include: executing a programmed heating process based on the pre-set desorption temperatures of at least two different analytes, and using the difference in desorption temperatures of the different analytes to sequentially perform desorption and mass spectrometry analysis on the at least two different analytes in order to achieve separation and detection of mixed samples.

5. The method according to claim 4, characterized in that, The programmed heating process is either an automatically generated heating process based on the parameters of the test object in the database, or a manually set heating program.

6. The method according to claim 1, characterized in that, The steps for collecting the sample to be tested include: for liquid samples, dropping them onto the organic solvent-repellent labeling area at the front end of the sampling carrier; for solid samples, wiping the surface of the sample to be tested with the sampling carrier.

7. The method according to claim 1, characterized in that, The desorption is carried out in a temperature range of 30-350℃; and / or, the discharge voltage of the plasma ionization treatment is 1 kV-10 kV; and / or, the discharge frequency of the plasma ionization treatment is 10 kHz-100 kHz.

8. The method according to claim 1, characterized in that, The mass spectrometry analysis includes tandem mass spectrometry, which is used for qualitative confirmation of the analyte. And / or, the sample to be tested includes at least one of explosives, poisons, drugs, and food contaminants.

9. The method according to claim 1, characterized in that, The sampling carrier includes at least one of glass slides, paper slides, and cloth slides; Optionally, the preset parameters invoked by the identification information include at least one of the following: target desorption temperature, programmed heating rate, holding time, sample type, analyte type, calibration curve, and detection mode information; Optionally, the output detection result includes at least one of the following: output mass spectrum, target concentration range, detection limit, and confidence interval.

10. A control method for a mass spectrometry detection device, characterized in that, Performed by the control unit of the device, the steps include: Obtain the identification information of the sampling carrier placed in the ion source region; Based on the identification information, the preset analysis parameters corresponding to the sample to be tested are automatically called. According to the preset analysis parameters, the heating module is controlled to dynamically adjust the heating temperature of the sampling carrier so as to desorb the analyte. The discharge electrode is controlled to perform plasma ionization of the desorbed analyte in the ion source region; The mass spectrometry data of the ionized analyte are acquired, analyzed by mass spectrometry, and the detection results are output.

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