Detector-based attenuation compensation method, apparatus, terminal device, and storage medium

Abstract

The application provides a detector-based attenuation compensation method and device, terminal equipment and storage medium, the method comprising: monitoring the signal acquisition task progress of the mass spectrometer in real time, and collecting the ion signal output by the detector when the mass spectrometer is in the transition process; generating the corresponding ion signal intensity value according to the signal peak area generated by the ion signal in the mass spectrometer; whenever the mass spectrometer completes a straight-through-filtering process, suspending the current signal acquisition task and comparing the ion signal intensity value with the pre-set reference signal value, generating the attenuation coefficient of the mass spectrometer based on the comparison result; generating the voltage compensation parameter according to the attenuation coefficient and adjusting the real-time output voltage of the detector based on the voltage compensation parameter, calculating the correction attenuation coefficient according to the real-time output voltage, and restarting the signal acquisition task when the correction attenuation coefficient reaches the pre-set attenuation threshold. The application can improve the accuracy and convenience of attenuation correction of the mass spectrometer in the quantitative analysis process.

Description

Technical Field

[0001] This invention relates to the field of mass spectrometry analysis technology, and in particular to detector-based attenuation compensation methods, devices, terminal equipment, and storage media. Background Technology

[0002] A mass spectrometer is an analytical instrument used to determine the molecular mass and composition of compounds. Among the many types of mass spectrometers, the aerosol time-of-flight mass spectrometer (TOF-MS) is specifically designed for long-term quantitative analysis of analyte concentration changes. It plays an important role in fields such as environmental monitoring, and is particularly suitable for studying atmospheric aerosols. TOF-MS uses an aerodynamic lens to focus and accelerate submicron aerosol particles, which are then flash-vaporized at a high temperature of 600°C. The vaporized material is then ionized by electron bombardment and finally detected in real time. This instrument can provide the mass concentrations of components such as sulfates, nitrates, ammonium salts, and organic matter in PM1 within seconds, offering advantages such as real-time quantification, second-level response, and simultaneous particle size and composition measurement, making it suitable for long-term field observations. However, for instruments like TOF-MS used for long-term quantitative analysis of analyte concentration changes, detector degradation due to long-term use is inevitable. This degradation directly affects the accuracy of particulate matter quantitative measurements.

[0003] Two commonly used attenuation correction methods are periodic external standard calibration and vacuum noise floor calibration. Periodic external standard calibration involves inserting standard samples of known concentration or mass-to-charge ratio at fixed intervals or in fixed batches, comparing the measured values ​​with reference values, and using an external standard curve to correct subsequent data in real time if the deviation exceeds a threshold, thus ensuring long-term quantitative accuracy. Vacuum noise floor calibration, on the other hand, uses the noise floor generated by stray ions in the vacuum chamber of the mass spectrometer as a reference, adjusting the electron multiplier's operating voltage based on this noise floor to ensure stable noise measurements and thus correct the electron multiplier's gain. However, both of these existing attenuation correction methods have significant drawbacks. Periodic external standard calibration has high maintenance and operating costs. The periodic preparation and dispensing of external standard solutions or samples incurs high consumable costs. The calibration process requires on-site operation by laboratory personnel, increasing manpower and management costs. Furthermore, the instrument's downtime during calibration creates data gaps, requiring remedial measures, which leads to equipment depreciation, increased energy consumption, and greater maintenance difficulty. Vacuum noise floor calibration, on the other hand, suffers from large gain errors. The noise floor pulse is easily confused with the real ion signal, resulting in an overestimation of the gain. At the same time, environmental changes alter the noise floor level, causing calibration results to drift and failing to accurately reflect the actual attenuation of the detector. Summary of the Invention

[0004] The present invention aims to provide a detector-based attenuation compensation method, device, terminal equipment and storage medium to solve the above-mentioned technical problems and improve the accuracy and convenience of attenuation correction of mass spectrometers in quantitative analysis.

[0005] To address the aforementioned technical problems, this invention provides a detector-based attenuation compensation method, comprising:

[0006] The system monitors the progress of the mass spectrometer's signal acquisition task in real time, and acquires the ion signal output by the detector when the mass spectrometer is in the transition process; the signal acquisition task is a cyclic acquisition process that includes transition, filtering, transition, and pass-through.

[0007] The corresponding ion signal intensity value is generated based on the signal peak area generated by the ion signal in the mass spectrometer.

[0008] Each time the mass spectrometer completes a pass-through-filter process, the current signal acquisition task of the mass spectrometer is paused and the ion signal intensity value is compared with the preset reference signal value. The attenuation coefficient of the mass spectrometer is generated based on the comparison result.

[0009] The voltage compensation parameters are generated based on the attenuation coefficient, and the real-time output voltage of the detector is adjusted based on the voltage compensation parameters. The correction attenuation coefficient is calculated based on the real-time output voltage, and the signal acquisition task is restarted when the correction attenuation coefficient reaches the preset attenuation threshold.

[0010] In the above scheme, the corresponding ion signal intensity value is generated by the signal peak area. The signal peak area is directly related to the number of ions, which can more accurately reflect the strength of the ion signal. This peak area-based calculation method reflects the true situation of the ion signal better than simple signal amplitude measurement, which helps to improve the accuracy of the detection results. Every time the mass spectrometer completes a pass-through-filter process, it compares the ion signal intensity value with the reference signal value and generates an attenuation coefficient. This periodic monitoring mechanism can detect signal attenuation in a timely manner, facilitating timely compensation measures and avoiding deviations in detection results due to signal attenuation, thus ensuring the stability and reliability of the mass spectrometer during long-term operation. By generating voltage compensation parameters based on the attenuation coefficient and adjusting the real-time output voltage of the detector, dynamic compensation for signal attenuation can be achieved. When signal attenuation is detected, increasing the detector's output voltage can enhance the response capability to the ion signal, restoring the signal intensity to a suitable range, thereby maintaining the stability of instrument performance. The entire attenuation compensation process is automated. From signal acquisition, attenuation coefficient calculation, voltage compensation parameter generation to detector output voltage adjustment, and then to the calculation of correction attenuation coefficient and restart of signal acquisition task, each link is closely connected and executed automatically, making the detection process more efficient and orderly.

[0011] In one implementation, the signal acquisition task is a cyclical acquisition process that includes transition, filtering, transition, and pass-through, specifically:

[0012] The transition process switches between the filtration process and the through-flow process via the injection valve;

[0013] The filtration process filters aerosols in the ambient gas using a filtration device, and then inputs the filtered ambient gas into the mass spectrometer.

[0014] The pass-through process is used to directly input ambient gases containing aerosols into the mass spectrometer.

[0015] In the above scheme, the transition process uses an injection valve to switch between the filtration and direct-through processes. Precise control of the injection valve ensures a smooth and seamless transition between the different processes, avoiding any adverse effects on the mass spectrometer's detection results caused by the switching process, and ensuring the continuity and stability of signal acquisition. The filtration process uses a filtration device to filter aerosols in the ambient gas, and the ambient gas obtained after filtering out the aerosols is input into the mass spectrometer. This effectively eliminates the interference of aerosols on the detection results, accurately obtains the background information of the ambient gas itself, and provides pure and reliable background data for subsequent analysis, helping to more accurately analyze the influence of aerosols on the composition of ambient gases. The direct-through process directly inputs ambient gas containing aerosols into the mass spectrometer. Combined with the background signal obtained from the filtration process, a comprehensive understanding of the composition and characteristics of the ambient gas in the presence or absence of aerosols can be achieved.

[0016] In one implementation, the corresponding ion signal intensity value is generated based on the peak area of ​​the ion signal generated in the mass spectrometer, specifically including:

[0017] Obtain the initial single-frame spectrum generated by each repulsion, and remove the initial single-frame spectrum with signal peak area lower than the preset area threshold to obtain the first single-frame spectrum;

[0018] The first single-frame spectrum and the corresponding initial single-frame spectrum are statistically analyzed for each mass-to-charge ratio. The probability of signal occurrence for a single mass-to-charge ratio is generated based on the ratio of the number of spectra in the first single-frame spectrum to the number of spectra in the initial single-frame spectrum.

[0019] When the probability of a signal occurring at a single mass-to-charge ratio is within a preset range, the first single-frame spectrum corresponding to that mass-to-charge ratio is retained to obtain an effective single-frame spectrum.

[0020] The signal peak area in the effective single-frame spectrum is statistically analyzed, and the ion signal intensity value is generated based on the average value of the signal peak area.

[0021] In the above scheme, after obtaining the initial single-frame spectrum, spectra with signal peak areas below a preset area threshold are removed. This effectively eliminates spectra corresponding to noise, interference signals, or extremely weak invalid signals, reducing the impact of these low-quality data on subsequent analysis and making the processed data more representative and reliable. The probability of signal occurrence is calculated based on the ratio of the number of spectra in the first single-frame spectrum to that in the initial single-frame spectrum. Only the first single-frame spectrum corresponding to mass-to-charge ratios (MMRs) with signal occurrence probabilities within a preset range is retained. This step further filters out MMR data with stable signal characteristics, eliminating those with unstable signals or potential random errors, thus improving the overall data quality.

[0022] In one implementation, each time the mass spectrometer completes a pass-through-filtering process, the current signal acquisition task of the mass spectrometer is paused, and the ion signal intensity value is compared with a pre-set reference signal value. Based on the comparison result, the attenuation coefficient of the mass spectrometer is generated, specifically including:

[0023] The switching status of the injection valve and the changes in the signal intensity output by the mass spectrometer are monitored in real time; the signal intensity includes the background signal intensity excluding aerosols and the signal intensity including aerosols.

[0024] When the signal intensity change is consistent with the preset signal intensity change trend and the signal intensity change matches the switching state, it is determined that the mass spectrometer has completed one pass-through-filtering process; wherein, the signal intensity change trend is from the background signal intensity to the signal intensity containing aerosols and then back to the background signal intensity;

[0025] When the mass spectrometer detects that it has completed one pass-through-filter process, a sample pause detection command is sent and the current signal acquisition task of the mass spectrometer is interrupted based on the sample pause detection command.

[0026] The ion signal intensity value is compared with the reference signal value, and an attenuation coefficient is generated based on the comparison result; the expression for the attenuation coefficient is as follows:

[0027] ;

[0028] In the formula, The attenuation coefficient; This represents the ion signal intensity value. This is the reference signal value.

[0029] In the above scheme, the switching status of the injection valve and the changes in the signal intensity output by the mass spectrometer are monitored in real time. The signal intensity changes are required to be consistent with a preset trend and match the switching status to determine whether the mass spectrometer has completed a single pass-through-filtering process. This multi-factor combined judgment method improves the accuracy of process determination, avoids errors in subsequent operations due to misjudgment caused by a single factor, and ensures that subsequent signal analysis and processing are only performed after a complete process has been truly completed. When the mass spectrometer is detected to have completed a pass-through-filtering process, a sample pause detection command is promptly sent, and the current signal acquisition task is interrupted. This avoids continuing signal acquisition at inappropriate times, ensures that the acquired data is based on a complete pass-through-filtering process, prevents data corruption, and allows subsequent data processing and analysis to proceed in an orderly manner.

[0030] In one implementation, generating voltage compensation parameters based on the attenuation coefficient and adjusting the detector's output voltage based on the voltage compensation parameters specifically includes:

[0031] When the attenuation coefficient is less than the preset attenuation threshold, voltage compensation parameters are generated according to the preset compensation formula; where the expression of the preset compensation formula is:

[0032] ;

[0033] In the formula, These are voltage compensation parameters; is the current output voltage of the detector; k is the attenuation coefficient;

[0034] By adding voltage compensation parameters to the current output voltage, a corrected output voltage is obtained, and the detector's output voltage is adjusted based on the corrected output voltage.

[0035] In the above scheme, by comparing the attenuation coefficient with a preset attenuation threshold, it is possible to accurately determine whether the mass spectrometer signal has attenuated. Once signal attenuation is detected, a voltage compensation parameter is immediately generated according to a preset compensation formula to quickly respond to the signal attenuation. Based on the calculated voltage compensation parameter, the corrected output voltage is obtained by increasing the current output voltage. This targeted voltage adjustment method can effectively compensate for signal attenuation, restoring the signal strength output by the detector to an appropriate level. By adjusting the detector's output voltage, the response capability to ion signals can be enhanced, effectively compensating for the impact of signal attenuation and maintaining the signal strength within a stable range. This helps ensure that the mass spectrometer can consistently provide accurate and reliable detection results during long-term operation.

[0036] In one implementation, a correction attenuation coefficient is calculated based on the real-time output voltage. When the correction attenuation coefficient reaches a preset attenuation threshold, the signal acquisition task is restarted. Specifically, this includes:

[0037] Calculate the correction value for the ion signal intensity output by the detector under the real-time output voltage;

[0038] The correction attenuation coefficient is calculated based on the comparison between the ion signal intensity correction value and the reference signal value.

[0039] When the correction attenuation coefficient reaches the preset attenuation threshold, record the voltage compensation parameters and restart the signal acquisition task.

[0040] In the above scheme, by calculating the ion signal intensity correction value output by the detector under the real-time output voltage, the actual situation of the ion signal after voltage compensation can be accurately reflected. A correction attenuation coefficient is calculated based on the comparison between the ion signal intensity correction value and the reference signal value. This coefficient intuitively reflects the degree of signal attenuation after correction. Comparing it with the previous attenuation coefficient clearly determines whether the voltage compensation has effectively improved the signal attenuation problem. The voltage compensation parameters are recorded when the signal acquisition task is restarted; these parameters can provide a reference for subsequent detection processes. If a similar signal attenuation problem occurs again, the previous compensation parameters can be used for quick and effective adjustments, improving detection efficiency and stability.

[0041] Secondly, this application also provides a detector-based attenuation compensation device, including a signal acquisition module, a signal generation module, an attenuation detection module, and an attenuation compensation module;

[0042] The signal acquisition module is used to monitor the progress of the mass spectrometer's signal acquisition task in real time. When the mass spectrometer is in the transition process, it acquires the ion signal output by the detector. The signal acquisition task is a cyclic acquisition process that includes transition, filtering, transition, and pass-through.

[0043] The signal generation module is used to generate the corresponding ion signal intensity value based on the signal peak area generated by the ion signal in the mass spectrometer;

[0044] The attenuation detection module is used to pause the current signal acquisition task of the mass spectrometer and compare the ion signal intensity value with the preset reference signal value whenever the mass spectrometer completes a pass-through-filter process, and generate the attenuation coefficient of the mass spectrometer based on the comparison result;

[0045] The attenuation compensation module is used to generate voltage compensation parameters based on the attenuation coefficient and adjust the real-time output voltage of the detector based on the voltage compensation parameters. It calculates the correction attenuation coefficient based on the real-time output voltage and restarts the signal acquisition task when the correction attenuation coefficient reaches the preset attenuation threshold.

[0046] In the above scheme, the corresponding ion signal intensity value is generated by the signal peak area. The signal peak area is directly related to the number of ions, which can more accurately reflect the strength of the ion signal. This peak area-based calculation method reflects the true situation of the ion signal better than simple signal amplitude measurement, which helps to improve the accuracy of the detection results. Every time the mass spectrometer completes a pass-through-filter process, it compares the ion signal intensity value with the reference signal value and generates an attenuation coefficient. This periodic monitoring mechanism can detect signal attenuation in a timely manner, facilitating timely compensation measures and avoiding deviations in detection results due to signal attenuation, thus ensuring the stability and reliability of the mass spectrometer during long-term operation. By generating voltage compensation parameters based on the attenuation coefficient and adjusting the real-time output voltage of the detector, dynamic compensation for signal attenuation can be achieved. When signal attenuation is detected, increasing the detector's output voltage can enhance the response capability to the ion signal, restoring the signal intensity to a suitable range, thereby maintaining the stability of instrument performance. The entire attenuation compensation process is automated. From signal acquisition, attenuation coefficient calculation, voltage compensation parameter generation to detector output voltage adjustment, and then to the calculation of correction attenuation coefficient and restart of signal acquisition task, each link is closely connected and executed automatically, making the detection process more efficient and orderly.

[0047] In one implementation, the signal acquisition task is a cyclical acquisition process that includes transition, filtering, transition, and pass-through, specifically:

[0048] The transition process switches between the filtration process and the through-flow process via the injection valve;

[0049] The filtration process filters aerosols in the ambient gas using a filtration device, and then inputs the filtered ambient gas into the mass spectrometer.

[0050] The pass-through process is used to directly input ambient gases containing aerosols into the mass spectrometer.

[0051] In the above scheme, the transition process uses an injection valve to switch between the filtration and direct-through processes. Precise control of the injection valve ensures a smooth and seamless transition between the different processes, avoiding any adverse effects on the mass spectrometer's detection results caused by the switching process, and ensuring the continuity and stability of signal acquisition. The filtration process uses a filtration device to filter aerosols in the ambient gas, and the ambient gas obtained after filtering out the aerosols is input into the mass spectrometer. This effectively eliminates the interference of aerosols on the detection results, accurately obtains the background information of the ambient gas itself, and provides pure and reliable background data for subsequent analysis, helping to more accurately analyze the influence of aerosols on the composition of ambient gases. The direct-through process directly inputs ambient gas containing aerosols into the mass spectrometer. Combined with the background signal obtained from the filtration process, a comprehensive understanding of the composition and characteristics of the ambient gas in the presence or absence of aerosols can be achieved.

[0052] In one implementation, the signal generation module is used to generate a corresponding ion signal intensity value based on the signal peak area generated by the ion signal in the mass spectrometer, specifically including:

[0053] Obtain the initial single-frame spectrum generated by each repulsion, and remove the initial single-frame spectrum with signal peak area lower than the preset area threshold to obtain the first single-frame spectrum;

[0054] The first single-frame spectrum and the corresponding initial single-frame spectrum are statistically analyzed for each mass-to-charge ratio. The probability of signal occurrence for a single mass-to-charge ratio is generated based on the ratio of the number of spectra in the first single-frame spectrum to the number of spectra in the initial single-frame spectrum.

[0055] When the probability of a signal occurring at a single mass-to-charge ratio is within a preset range, the first single-frame spectrum corresponding to that mass-to-charge ratio is retained to obtain an effective single-frame spectrum.

[0056] The signal peak area in the effective single-frame spectrum is statistically analyzed, and the ion signal intensity value is generated based on the average value of the signal peak area.

[0057] In the above scheme, after obtaining the initial single-frame spectrum, spectra with signal peak areas below a preset area threshold are removed. This effectively eliminates spectra corresponding to noise, interference signals, or extremely weak invalid signals, reducing the impact of these low-quality data on subsequent analysis and making the processed data more representative and reliable. The probability of signal occurrence is calculated based on the ratio of the number of spectra in the first single-frame spectrum to that in the initial single-frame spectrum. Only the first single-frame spectrum corresponding to mass-to-charge ratios (MMRs) with signal occurrence probabilities within a preset range is retained. This step further filters out MMR data with stable signal characteristics, eliminating those with unstable signals or potential random errors, thus improving the overall data quality.

[0058] In one implementation, the attenuation detection module is used to pause the current signal acquisition task of the mass spectrometer and compare the ion signal intensity value with a pre-set reference signal value whenever the mass spectrometer completes a pass-through-filter process. Based on the comparison result, it generates the attenuation coefficient of the mass spectrometer, specifically including:

[0059] The switching status of the injection valve and the changes in the signal intensity output by the mass spectrometer are monitored in real time; the signal intensity includes the background signal intensity excluding aerosols and the signal intensity including aerosols.

[0060] When the signal intensity change is consistent with the preset signal intensity change trend and the signal intensity change matches the switching state, it is determined that the mass spectrometer has completed one pass-through-filtering process; wherein, the signal intensity change trend is from the background signal intensity to the signal intensity containing aerosols and then back to the background signal intensity;

[0061] When the mass spectrometer detects that it has completed one pass-through-filter process, a sample pause detection command is sent and the current signal acquisition task of the mass spectrometer is interrupted based on the sample pause detection command.

[0062] The ion signal intensity value is compared with the reference signal value, and an attenuation coefficient is generated based on the comparison result; the expression for the attenuation coefficient is as follows:

[0063] ;

[0064] In the formula, The attenuation coefficient; This represents the ion signal intensity value. This is the reference signal value.

[0065] In the above scheme, the switching status of the injection valve and the changes in the signal intensity output by the mass spectrometer are monitored in real time. The signal intensity changes are required to be consistent with a preset trend and match the switching status to determine whether the mass spectrometer has completed a single pass-through-filtering process. This multi-factor combined judgment method improves the accuracy of process determination, avoids errors in subsequent operations due to misjudgment caused by a single factor, and ensures that subsequent signal analysis and processing are only performed after a complete process has been truly completed. When the mass spectrometer is detected to have completed a pass-through-filtering process, a sample pause detection command is promptly sent, and the current signal acquisition task is interrupted. This avoids continuing signal acquisition at inappropriate times, ensures that the acquired data is based on a complete pass-through-filtering process, prevents data corruption, and allows subsequent data processing and analysis to proceed in an orderly manner.

[0066] In one implementation, the attenuation compensation module is used to generate voltage compensation parameters based on the attenuation coefficient and adjust the real-time output voltage of the detector based on the voltage compensation parameters, specifically including:

[0067] When the attenuation coefficient is less than the preset attenuation threshold, voltage compensation parameters are generated according to the preset compensation formula; where the expression of the preset compensation formula is:

[0068] ;

[0069] In the formula, These are voltage compensation parameters; is the current output voltage of the detector; k is the attenuation coefficient;

[0070] By adding voltage compensation parameters to the current output voltage, a corrected output voltage is obtained, and the detector's output voltage is adjusted based on the corrected output voltage.

[0071] In the above scheme, by comparing the attenuation coefficient with a preset attenuation threshold, it is possible to accurately determine whether the mass spectrometer signal has attenuated. Once signal attenuation is detected, a voltage compensation parameter is immediately generated according to a preset compensation formula to quickly respond to the signal attenuation. Based on the calculated voltage compensation parameter, the corrected output voltage is obtained by increasing the current output voltage. This targeted voltage adjustment method can effectively compensate for signal attenuation, restoring the signal strength output by the detector to an appropriate level. By adjusting the detector's output voltage, the response capability to ion signals can be enhanced, effectively compensating for the impact of signal attenuation and maintaining the signal strength within a stable range. This helps ensure that the mass spectrometer can consistently provide accurate and reliable detection results during long-term operation.

[0072] In one implementation, a correction attenuation coefficient is calculated based on the real-time output voltage. When the correction attenuation coefficient reaches a preset attenuation threshold, the signal acquisition task is restarted. Specifically, this includes:

[0073] Calculate the correction value for the ion signal intensity output by the detector under the real-time output voltage;

[0074] The correction attenuation coefficient is calculated based on the comparison between the ion signal intensity correction value and the reference signal value.

[0075] When the correction attenuation coefficient reaches the preset attenuation threshold, record the voltage compensation parameters and restart the signal acquisition task.

[0076] In the above scheme, by calculating the ion signal intensity correction value output by the detector under the real-time output voltage, the actual situation of the ion signal after voltage compensation can be accurately reflected. A correction attenuation coefficient is calculated based on the comparison between the ion signal intensity correction value and the reference signal value. This coefficient intuitively reflects the degree of signal attenuation after correction. Comparing it with the previous attenuation coefficient clearly determines whether the voltage compensation has effectively improved the signal attenuation problem. The voltage compensation parameters are recorded when the signal acquisition task is restarted; these parameters can provide a reference for subsequent detection processes. If a similar signal attenuation problem occurs again, the previous compensation parameters can be used for quick and effective adjustments, improving detection efficiency and stability.

[0077] Thirdly, this application also provides a terminal device, including a processor, a memory, and a computer program stored in the memory and configured to be executed by the processor, wherein the processor executes the computer program to implement the detector-based attenuation compensation method described above.

[0078] Fourthly, this application also provides a computer-readable storage medium, which includes a stored computer program, wherein, when the computer program is running, it controls the device where the computer-readable storage medium is located to perform the detector-based attenuation compensation method described above. Attached Figure Description

[0079] Figure 1 This is a schematic flowchart of a detector-based attenuation compensation method provided in one embodiment of the present invention;

[0080] Figure 2 This is a schematic diagram illustrating the cycle of a signal acquisition task provided in one embodiment of the present invention;

[0081] Figure 3 This is a flowchart illustrating a filtering process provided in one embodiment of the present invention;

[0082] Figure 4 This is a schematic diagram of a detector-based attenuation compensation method device provided in one embodiment of the present invention. Detailed Implementation

[0083] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[0084] The terms "first" and "second," etc., in the specification, claims, and drawings of this application are used to distinguish different objects, not to describe a specific order. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or apparatus that includes a series of steps or units is not limited to the listed steps or units, but may optionally include steps or units not listed, or may optionally include other steps or units inherent to such processes, methods, products, or apparatus.

[0085] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments.

[0086] Example 1

[0087] See Figure 1 , Figure 1 This is a schematic flowchart of a detector-based attenuation compensation method provided in one embodiment of the present invention. The embodiment of the present invention provides a detector-based attenuation compensation method, including steps 101 to 104, each step of which is detailed below:

[0088] Step 101: Monitor the progress of the mass spectrometer's signal acquisition task in real time. When the mass spectrometer is in the transition process, acquire the ion signal output by the detector. The signal acquisition task is a cyclic acquisition process that includes transition, filtering, transition, and pass-through.

[0089] The detector is a key component of a mass spectrometer, and its type can be an MCP (microchannel plate detector) or an electron multiplier. Its core function is to convert detected ions into electrical signals that can be processed by subsequent systems. These electrical signals contain various information about the ions, such as their quantity and type. Mass spectrometers generate ions during operation, which cannot be directly analyzed or recorded. The main role of the detector is to capture these ions and convert them into electrical signals through internal physical mechanisms. For example, when an ion strikes the detector's detection plane, it triggers a series of physical reactions, generating electrons and thus forming an electrical signal. During different stages of the mass spectrometer's signal acquisition process, when ions reach the detector, under the influence of a pre-set detection voltage, the ions collide with the detection plane with a certain kinetic energy. This embodiment of the invention also includes a signal acquisition and processing module (including an ADC converter and a digital signal processor) for acquiring the ion signals output by the detector. The high-speed ADC converter (sampling rate ≥ 1 MHz) starts working, sampling the analog electrical signals output by the detector at high speed. Because the ADC converter has a high sampling rate, it can quickly and accurately convert continuous analog electrical signals into discrete digital signals to meet the needs of subsequent digital signal processing. The digital signal processor (DSP) further processes the digital signal converted by the ADC. Throughout the signal acquisition cycle, especially after the filtering process, the ion signals acquired are stored and analyzed by the DSP.

[0090] In this embodiment of the invention, the mass spectrometer is controlled to continuously and automatically acquire signals according to a certain cyclic acquisition process. The cyclic acquisition process ensures the continuity of data acquisition, and the alternation between different processes enables the acquisition of complete information about aerosols under different states. For example, through multiple cyclic acquisitions, the changes in aerosol signal intensity over different time periods can be obtained, thereby providing a more comprehensive understanding of the dynamic characteristics of aerosols, such as the trend of concentration changes over time.

[0091] In one embodiment, the signal acquisition task is a cyclic acquisition process including transition, filtering, transition, and direct pass. Specifically, the transition process switches between the filtering process and the direct pass process through the injection valve; the filtering process filters aerosols in the ambient gas through a filtering device and inputs the filtered ambient gas into the mass spectrometer; the direct pass process is used to directly input the ambient gas containing aerosols into the mass spectrometer.

[0092] See Figure 2 , Figure 2 This is a schematic diagram illustrating the cycle of a signal acquisition task according to one embodiment of the present invention. A single signal acquisition task consists of several signal acquisition cycles. A complete signal acquisition cycle includes a transition, filtering, and pass-through process. In this embodiment, the transition process is the connecting stage between the filtering and pass-through processes, mainly achieved by switching between the two processes through an injection valve (such as a solenoid valve). During the switching process, due to a certain delay in mechanical action or signal transmission, a transition signal of 2-3 seconds is generated. This process serves to buffer and stabilize the injection channel, ensuring a smooth transition between different processes. See also... Figure 3 , Figure 3 This is a flowchart illustrating a filtration process according to one embodiment of the present invention. In the filtration process, ambient gas passes through a filtration device, which filters out aerosols from the ambient gas, allowing only the ambient gas to pass through. At this time, the signal input to the mass spectrometer is only the ambient gas, also known as the background signal. This background signal is an important reference for subsequent calculations of the aerosol signal intensity. It should be noted that ambient gas refers to the atmosphere surrounding the mass spectrometer, which contains various gaseous components and potentially present aerosol particles. Ambient gas is the fundamental substance in the entire signal acquisition process, and its composition and state affect the final signal acquisition results. The direct-through process directly inputs the ambient gas containing aerosols into the mass spectrometer. The signal acquired by the mass spectrometer includes both the ambient gas background signal and the aerosol signal. By processing the background signal acquired in the subsequent filtration process, the aerosol signal can be separated.

[0093] For example, suppose we want to monitor and analyze aerosols in the atmosphere near a factory and initiate a mass spectrometer signal acquisition task. The instrument is in the signal acquisition and filtering phase, and ambient gases from the vicinity of the factory are drawn into the instrument. These gases pass through a filtration device, such as a high-efficiency particulate air (HEPA) filter, removing aerosol particles and leaving only pure ambient gas entering the mass spectrometer. The mass spectrometer acquires the signals at this point; these signals represent the background signals of the ambient gases in that area. For example, during this process, the mass spectrometer records the signal intensities of some common gases (such as nitrogen, oxygen, and carbon dioxide), which are recorded by the software and used as the basis for subsequent calculations. Once the filtration process is complete, the host computer controls the injection valve (solenoid valve) to switch the injection channel from filtration mode to direct-flow mode. During this switching process, due to a certain delay in the mechanical action of the solenoid valve and signal transmission, a transition signal of 2-3 seconds is generated, i.e., the transition phase begins. The system automatically identifies this transition signal and excludes it from subsequent analysis to avoid interfering with the final results. After the injection channel switches to direct-flow mode, the ambient gas containing aerosols directly enters the mass spectrometer. The mass spectrometer acquires a superposition of ambient gas background signals and aerosol signals. For example, the mass spectrometer may detect additional signal peaks, which may correspond to specific pollutant aerosol particles emitted by the factory. Furthermore, the host computer averages the signals acquired in the direct pass section and the background signals acquired in the filter section. Then, subtracting the average value of the filter section signals from the average value of the direct pass signals yields the aerosol signal intensity in the atmosphere near the factory. Further analysis of this aerosol signal intensity allows for the determination of the concentrations and proportions of various components in the aerosols, thereby assessing the factory's impact on the surrounding atmospheric environment. After completing one acquisition and analysis cycle, the mass spectrometer automatically enters the next cycle, repeating the filtering, transition, and direct pass process to continuously monitor atmospheric aerosols in the area and promptly detect changes in aerosol concentration and composition.

[0094] Step 102: Generate the corresponding ion signal intensity value based on the signal peak area generated by the ion signal in the mass spectrometer.

[0095] In one embodiment, generating the corresponding ion signal intensity value based on the signal peak area generated by the ion signal in the mass spectrometer specifically includes: acquiring the initial single-frame spectrum generated each time repulsion occurs, removing the initial single-frame spectrum with a signal peak area lower than a preset area threshold to obtain a first single-frame spectrum; statistically analyzing the first single-frame spectrum and the corresponding initial single-frame spectrum for each mass-to-charge ratio, generating the signal occurrence probability for a single mass-to-charge ratio based on the ratio of the number of spectra in the first single-frame spectrum to the number of spectra in the initial single-frame spectrum; when the signal occurrence probability for a single mass-to-charge ratio is within a preset range, retaining the first single-frame spectrum corresponding to that mass-to-charge ratio to obtain a valid single-frame spectrum; statistically analyzing the signal peak area in the valid single-frame spectrum, and generating the ion signal intensity value based on the average value of the signal peak area.

[0096] To facilitate understanding of the above technical solutions by those skilled in the art, the following explanations are provided for some of the terms used:

[0097] (1) Repulsion: This refers to the process of applying a specific electric field to push ions generated in the ion source out with a certain energy and direction within a short period of time, so that they can enter the subsequent flight channel or analysis area for further separation and detection. Repulsion is usually performed periodically, and each repulsion generates a batch of ions for subsequent analysis.

[0098] (2) Single-frame spectrum: After each repulsion operation, the mass spectrometer detects and records the generated ions and related signals. These detected signals are then organized and displayed according to certain rules to form a single-frame spectrum. The single-frame spectrum shows the signal intensity information corresponding to ions with different mass-to-charge ratios during a single repulsion process. It is the basic data unit of mass spectrometry analysis. For example, performing multiple repulsion operations over a period of time will result in a series of single-frame spectra. If 50,000 repulsions are performed per second, 50,000 single-frame spectra will be generated.

[0099] (3) Signal Peaks: In a single-frame spectrum, the curve showing the change in ion signal intensity with mass-to-charge ratio will have some raised sections; these raised sections are called signal peaks. Each signal peak represents the presence of an ion with a specific mass-to-charge ratio. The height and shape of the signal peak reflect information such as the relative abundance and properties of ions with that mass-to-charge ratio. The signal peak area refers to the area enclosed by the signal peak and the baseline. It is an important parameter, directly proportional to the number of ions with a specific mass-to-charge ratio. In mass spectrometry analysis, the signal peak area can more accurately reflect the ion content because it comprehensively considers factors such as the height and width of the signal peak.

[0100] (4) Mass-to-charge ratio: The mass-to-charge ratio (m / z) is the ratio of the mass (m) of an ion to its charge (z). Different ions have different mass-to-charge ratios, and mass spectrometers separate and detect ions based on their mass-to-charge ratios. The mass-to-charge ratio is a key parameter used in mass spectrometry to identify ion types and determine the structure of compounds.

[0101] In this embodiment of the invention, after obtaining the initial single-frame spectrum generated by each repulsion, initial single-frame spectra with signal peak areas lower than a preset area threshold are discarded. This is because spectra with excessively small signal peak areas are likely generated by noise interference and do not represent true ion signals; discarding them can improve the quality of subsequent analysis data. The number of first single-frame spectra after preliminary screening for each mass-to-charge ratio is counted, along with the corresponding number of initial single-frame spectra. The ratio of these two values ​​yields the probability of signal occurrence for a single mass-to-charge ratio. This probability reflects the frequency of ion signals with a specific mass-to-charge ratio during multiple repulsion processes. When the probability of signal occurrence for a single mass-to-charge ratio is within a preset range, the ion signal corresponding to that mass-to-charge ratio is considered reliable, and its corresponding first single-frame spectrum is retained, resulting in a valid single-frame spectrum. If the probability of signal occurrence is not within this range, it may be an abnormal signal caused by accidental factors or other interference, and its corresponding spectrum is deleted. The signal peak areas in the valid single-frame spectra are statistically analyzed, and the average value of these signal peak areas is calculated. This average value is used as the ion signal intensity value, which reflects the relative content of ions with a specific mass-to-charge ratio in the sample.

[0102] For example, the mass spectrometer acquires data at a frequency of 50,000 repulsion operations per second, with each repulsion generating a single-frame spectrum. Over a period of time (e.g., 1 minute), a total of 3,000,000 initial single-frame spectra are acquired. A preset threshold for the signal peak area is set to 100 (the unit can be determined according to actual conditions). These 3,000,000 initial single-frame spectra are checked one by one, and spectra with a signal peak area lower than 100 are discarded, ultimately resulting in 2,000,000 first single-frame spectra. Taking a mass-to-charge ratio m / z = 44 as an example, the number of first single-frame spectra under this mass-to-charge ratio is 1,000, corresponding to 2,000 initial single-frame spectra. Therefore, the probability of the signal appearing under this mass-to-charge ratio is 1000 ÷ 2000 × 100% = 50%. The preset signal occurrence probability range is 0.05%-0.5%. Since the probability of a signal with a mass-to-charge ratio (m / z) of 44 is 50% outside this range, all first-frame spectra corresponding to this mass-to-charge ratio are deleted. This process is repeated for all mass-to-charge ratios, resulting in 1,500,000 valid single-frame spectra. The peak areas of the signals for a specific mass-to-charge ratio (e.g., m / z = 78) in the valid single-frame spectra are statistically analyzed. These peak areas are 120, 130, 125, 135, etc. The average of these peak areas is calculated as (120 + 130 + 125 + 135) ÷ 4 = 127.5. This 127.5 is taken as the signal intensity value for the ion with a mass-to-charge ratio (m / z = 78). Through these steps, the signal intensity values ​​for ions with various mass-to-charge ratios in the sample can be obtained.

[0103] Step 103: Each time the mass spectrometer completes a pass-through-filter process, pause the current signal acquisition task of the mass spectrometer and compare the ion signal intensity value with the preset reference signal value. Based on the comparison result, generate the attenuation coefficient of the mass spectrometer.

[0104] In this embodiment of the invention, after each direct-pass filtering process, the mass spectrometer pauses its current signal acquisition task, ceasing the acquisition of ambient gas. This pauses during the transition process, and the calculated ion signal intensity value is then compared with a pre-set reference signal value. The attenuation coefficient of the mass spectrometer is then generated based on the comparison result. The reference signal value is a pre-set standard reference value. By comparing the ion signal intensity value obtained from each measurement with this value, a unified comparison standard can be established for measurement data from different times and batches. This allows for a more accurate assessment of the sample's properties and changes during data analysis and result comparison, improving the horizontal and vertical comparability of the data.

[0105] In one embodiment, whenever the mass spectrometer completes a pass-through-filtering process, the current signal acquisition task of the mass spectrometer is paused, and the ion signal intensity value is compared with a preset reference signal value. Based on the comparison result, an attenuation coefficient for the mass spectrometer is generated. Specifically, this includes: real-time detection of the switching state of the injection valve and changes in the signal intensity output by the mass spectrometer; the signal intensity includes the background signal intensity without aerosols and the signal intensity containing aerosols; when the signal intensity change is consistent with a preset signal intensity change trend and matches the switching state, it is determined that the mass spectrometer has completed a pass-through-filtering process; wherein, the signal intensity change trend is from the background signal intensity to the signal intensity containing aerosols and then back to the background signal intensity; when the completion of a pass-through-filtering process is detected, a sample pause detection command is sent, and the current signal acquisition task of the mass spectrometer is interrupted based on the sample pause detection command; the ion signal intensity value is compared with the reference signal value, and an attenuation coefficient is generated based on the comparison result; wherein, the expression for the attenuation coefficient is:

[0106] ;

[0107] In the formula, The attenuation coefficient; This represents the ion signal intensity value. This is the reference signal value.

[0108] In this embodiment of the invention, the switching state of the injection valve and the signal intensity change of the mass spectrometer output are detected in real time. The switching state of the injection valve is one of the key indicators for judging the direct-pass filtering process, and it is also combined with the signal intensity change trend for comprehensive judgment. When the signal intensity change is consistent with the preset signal intensity change trend, and the signal intensity change matches the switching state, it is determined that the mass spectrometer has completed one direct-pass filtering process. The preset signal intensity change trend is from background signal intensity to signal intensity containing aerosols and then back to background signal intensity. Furthermore, in actual operation, it is necessary to accurately define and measure the background signal intensity and the signal intensity containing aerosols. A reasonable threshold range can be determined through multiple experiments to improve the accuracy of the judgment. To ensure the accuracy of the judgment, double verification can be performed in conjunction with the valve switching time set by the sampling method. For example, when the injection valve switching state and signal intensity change meet the requirements, and the time is within the valve switching time range set by the sampling method, it is determined that one direct-pass filtering process has been completed. When it is detected that the mass spectrometer has completed one direct-pass filtering process, a sample pause detection command is sent, and based on this command, the current signal acquisition task of the mass spectrometer is interrupted, and the attenuation correction process begins. During this process, it is crucial to ensure that the calibration procedure begins within the interval of sample introduction channel switching (typically 2-3 seconds, i.e., the transition process), as this will affect the subsequent signal acquisition process. The calculated ion signal intensity value is then compared with the reference signal value, and an attenuation coefficient is generated based on the comparison result. Furthermore, in actual calculations, to ensure the accuracy of the ion signal intensity value and the reference signal value, the reliability of the data can be improved by averaging multiple measurements.

[0109] For example, a mass spectrometer is used to detect pollutants in industrial waste gas. A reference signal value is preset. =1000 (this value was obtained through multiple measurements of standard samples and statistical analysis); background signal intensity range: 100-150; signal intensity range including aerosols: 800-1200; sampling method set injection valve switching time interval: 2.5s. The mass spectrometer begins detecting the exhaust gas, monitoring the switching status of the injection valve and signal intensity changes in real time. At a certain moment, the injection valve switches, and the signal intensity gradually rises from the background signal intensity of 120 to 900 (within the signal intensity range including aerosols), then drops back to 130 (returning to the background signal intensity range), with the entire process taking 2-3 seconds, within the valve switching time interval set by the sampling method. At this point, it is determined that the mass spectrometer has completed one pass-through-filtration process. Upon detection of the process completion, an attenuation correction process trigger command is sent, based on which a pause sample detection command is sent, switching to detector voltage calibration mode. The current ion signal intensity value is recorded. =950, and the attenuation coefficient is 0.95 according to the attenuation coefficient calculation formula.

[0110] Step 104: Generate voltage compensation parameters based on the attenuation coefficient and adjust the real-time output voltage of the detector based on the voltage compensation parameters. Calculate the correction attenuation coefficient based on the real-time output voltage. Restart the signal acquisition task when the correction attenuation coefficient reaches the preset attenuation threshold.

[0111] In this embodiment of the invention, a voltage compensation parameter is generated based on the attenuation coefficient, and this parameter is used to adjust the real-time output voltage of the detector. Then, a correction attenuation coefficient is calculated based on the adjusted real-time output voltage. When the correction attenuation coefficient reaches a preset attenuation threshold, the mass spectrometer's signal acquisition task is restarted. Real-time adjustment of the detector's output voltage effectively reduces measurement errors caused by signal attenuation. In actual detection, even slight signal attenuation can lead to significant deviations in measurement results. By continuously calculating and adjusting the correction attenuation coefficient, the signal strength is ensured to be within a suitable range, reducing the impact of errors on the measurement results and making the measurement data more reliable.

[0112] In one embodiment, generating voltage compensation parameters based on the attenuation coefficient and adjusting the detector's output voltage based on the voltage compensation parameters specifically includes: when the attenuation coefficient is less than a preset attenuation threshold, generating voltage compensation parameters according to a preset compensation formula; wherein, the expression of the preset compensation formula is:

[0113] ;

[0114] In the formula, These are voltage compensation parameters; is the current output voltage of the detector; k is the attenuation coefficient;

[0115] By adding voltage compensation parameters to the current output voltage, a corrected output voltage is obtained, and the detector's output voltage is adjusted based on the corrected output voltage.

[0116] In this embodiment of the invention, when the attenuation coefficient k is less than the preset attenuation threshold, it indicates that the signal attenuation is significant, requiring adjustment of the detector's output voltage. In the given supplementary information, the preset attenuation threshold is set to 0.95, meaning that when the attenuation exceeds 5% (i.e., k < 0.95), voltage adjustment is required; if k ≥ 0.95, the current voltage remains unchanged, thus avoiding unnecessary voltage adjustments and ensuring instrument stability. If voltage adjustment is necessary, the voltage compensation parameter is calculated according to the preset compensation formula. The voltage compensation parameter is added to the current output voltage to obtain the corrected output voltage, and the detector's output voltage is adjusted based on this corrected output voltage. As an alternative to this embodiment, the detector's current output voltage can also be directly adjusted to a fixed step value. + Fixed step value, the step value is 1-10V, the specific step value can be set according to specific needs, and is not limited here.

[0117] For example, when using a mass spectrometer to detect a chemical sample, the current output voltage of the detector... =1000V, preset attenuation threshold set to 0.95. After measurement and calculation, the current attenuation coefficient is obtained. =0.9. Since 0.9 < 0.95, it indicates that the signal attenuation exceeds 5%, and the detector's output voltage needs adjustment. The voltage compensation parameters can be obtained according to the compensation formula. = A voltage compensation parameter is added to the detector's current output voltage to compensate for signal attenuation.

[0118] In one embodiment, a correction attenuation coefficient is calculated based on the real-time output voltage. When the correction attenuation coefficient reaches a preset attenuation threshold, the signal acquisition task is restarted. Specifically, this includes: calculating the ion signal intensity correction value output by the detector under the real-time output voltage; calculating the correction attenuation coefficient based on the comparison result between the ion signal intensity correction value and the reference signal value; and recording the voltage compensation parameters and restarting the signal acquisition task when the correction attenuation coefficient reaches the preset attenuation threshold.

[0119] In this embodiment of the invention, after adjusting the detector's output voltage, i.e., based on the real-time output voltage, it is necessary to calculate the correction value of the ion signal intensity output by the detector at this time. Since voltage adjustment affects the detection intensity of the ion signal, calculating the correction value can more accurately reflect the current signal state. The calculation method of ion signal intensity has been described in detail above and will not be repeated here. The calculated ion signal intensity correction value is compared with a preset reference signal value to calculate the correction attenuation coefficient. The calculation method of the correction attenuation coefficient is similar to the previous attenuation coefficient calculation, and will not be repeated here. It reflects the degree of attenuation of the ion signal relative to the reference signal after voltage adjustment. This coefficient can be used to intuitively understand whether the voltage adjustment has effectively compensated for the signal attenuation. When the correction attenuation coefficient is within this range, it indicates that the signal attenuation has been effectively improved and the standard for continuing signal acquisition has been met. When the correction attenuation coefficient reaches the preset attenuation threshold, the host computer records the voltage compensation parameters used in this voltage adjustment. Recording these parameters helps in the subsequent analysis and maintenance of instrument performance and can also provide a reference for adjustments in similar situations. At the same time, the system switches back to sample detection mode, restarts the signal acquisition task, and waits for the next analysis cycle.

[0120] For example, suppose that during mass spectrometry detection of a sample, the initial attenuation coefficient k = 0.9, which is less than the preset attenuation threshold lower limit of 0.95, indicating that the signal is attenuating. At this time, the detector's current output voltage... =800V, reference signal value =1500. The correction voltage compensation parameter is calculated according to the compensation formula, and the real-time output voltage of the detector is adjusted based on the correction voltage compensation parameter. The correction value of the ion signal intensity output by the voltage calculation detector under the real-time output voltage is calculated. The correction attenuation coefficient is calculated by comparing the correction value of the ion signal intensity with the reference signal value. When the correction attenuation coefficient reaches the preset attenuation threshold range, the current voltage compensation parameter is recorded and the sample detection mode is switched to restart the signal acquisition task.

[0121] In this embodiment of the invention, a detector-based attenuation compensation device is also provided, including a processor, a memory, and a computer program stored in the memory and configured to be executed by the processor. When the processor executes the computer program, it implements the detector-based attenuation compensation method described above.

[0122] In this embodiment of the invention, a computer-readable storage medium is also provided, which includes a stored computer program, wherein the computer program controls the device where the computer-readable storage medium is located to execute the above-described detector-based attenuation compensation method when it is running.

[0123] For example, a computer program can be divided into one or more modules, one or more of which are stored in memory and executed by a processor to carry out the present invention. The one or more modules can be a series of computer program instruction segments capable of performing a specific function, which describe the execution process of the computer program in a detector-based attenuation compensation device.

[0124] Detector-based attenuation compensation devices can be computing devices such as desktop computers, laptops, handheld computers, and cloud servers. These devices may include, but are not limited to, processors, memory, and displays. Those skilled in the art will understand that the above-described components are merely examples of detector-based attenuation compensation devices and do not constitute a limitation on them. The device may include more or fewer components, combinations of certain components, or different components. For example, detector-based attenuation compensation devices may also include input / output devices, network access devices, buses, etc.

[0125] The processor can be a Central Processing Unit (CPU), or other general-purpose processors, digital signal processors (DSPs), application-specific integrated circuits (ASICs), field-programmable gate arrays (FPGAs), or other programmable logic devices, discrete gate or transistor logic devices, discrete hardware components, etc. A general-purpose processor can be a microprocessor or any conventional processor. The processor is the control center of the detector-based attenuation compensation device, connecting all parts of the device via various interfaces and lines.

[0126] The memory can be used to store computer programs and / or modules. The processor implements various functions of the detector-based attenuation compensation device by running or executing the computer programs and / or modules stored in the memory, and by calling data stored in the memory. The memory can mainly include a program storage area and a data storage area. The program storage area can store the operating system, at least one application program required for a function (such as sound playback function, text conversion function, etc.), etc.; the data storage area can store data created according to the use of the mobile phone (such as audio data, text message data, etc.). In addition, the memory can include high-speed random access memory, and can also include non-volatile memory, such as hard disk, RAM, plug-in hard disk, smart media card (SMC), secure digital (SD) card, flash card, at least one disk storage device, flash memory device, or other volatile solid-state storage device.

[0127] In this invention, the detector-based attenuation compensation module, if implemented as a software functional unit and sold or used as an independent product, can be stored in a computer-readable storage medium. Based on this understanding, all or part of the processes in the above embodiments can also be implemented by a computer program instructing related hardware. The computer program can be stored in a computer-readable storage medium, and when executed by a processor, it can implement the steps of the various method embodiments described above. The computer program includes computer program code, which can be in the form of source code, object code, executable files, or certain intermediate forms. The computer-readable medium can include: any entity or device capable of carrying computer program code, recording media, USB flash drives, portable hard drives, magnetic disks, optical disks, computer memory, read-only memory (ROM), random access memory (RAM), electrical carrier signals, telecommunication signals, and software distribution media, etc. Those skilled in the art can understand and implement this invention without any inventive effort.

[0128] This invention provides a detector-based attenuation compensation method. It generates corresponding ion signal intensity values ​​based on the signal peak area. The signal peak area is directly related to the number of ions, providing a more accurate representation of the ion signal strength. This peak area-based calculation method reflects the true state of the ion signal better than simple signal amplitude measurement, thus improving the accuracy of detection results. Each time the mass spectrometer completes a pass-through-filter process, it compares the ion signal intensity value with a reference signal value and generates an attenuation coefficient. This periodic monitoring mechanism can promptly detect signal attenuation, facilitating timely compensation measures and preventing deviations in detection results due to signal attenuation. This ensures the stability and reliability of the mass spectrometer during long-term operation. By generating voltage compensation parameters based on the attenuation coefficient and adjusting the detector's real-time output voltage, dynamic compensation for signal attenuation can be achieved. When signal attenuation is detected, increasing the detector's output voltage enhances the response to ion signals, restoring the signal intensity to a suitable range and maintaining stable instrument performance. The entire attenuation compensation process is automated. From signal acquisition, attenuation coefficient calculation, voltage compensation parameter generation to detector output voltage adjustment, and then to the calculation of correction attenuation coefficient and restart of signal acquisition task, each link is closely connected and executed automatically, making the detection process more efficient and orderly.

[0129] Example 2

[0130] See Figure 4 , Figure 4This is a schematic diagram of the modules of a detector-based attenuation compensation method device provided in one embodiment of the present invention. The embodiment of the present invention provides a detector-based attenuation compensation device, including a signal acquisition module 201, a signal generation module 202, an attenuation detection module 203, and an attenuation compensation module 204;

[0131] The signal acquisition module 201 is used to monitor the progress of the mass spectrometer's signal acquisition task in real time. When the mass spectrometer is in the transition process, it acquires the ion signal output by the detector. The signal acquisition task is a cyclic acquisition process that includes transition, filtering, transition, and pass-through.

[0132] The signal generation module 202 is used to generate the corresponding ion signal intensity value based on the signal peak area generated by the ion signal in the mass spectrometer;

[0133] The attenuation detection module 203 is used to pause the current signal acquisition task of the mass spectrometer and compare the ion signal intensity value with the preset reference signal value whenever the mass spectrometer completes a pass-through-filter process, and generate the attenuation coefficient of the mass spectrometer based on the comparison result.

[0134] The attenuation compensation module 204 is used to generate voltage compensation parameters based on the attenuation coefficient and adjust the real-time output voltage of the detector based on the voltage compensation parameters. It calculates the correction attenuation coefficient based on the real-time output voltage and restarts the signal acquisition task when the correction attenuation coefficient reaches the preset attenuation threshold.

[0135] In one embodiment, the signal acquisition task is a cyclic acquisition process including transition, filtering, transition, and pass-through, specifically:

[0136] The transition process switches between the filtration process and the through-flow process via the injection valve;

[0137] The filtration process filters aerosols in the ambient gas using a filtration device, and then inputs the filtered ambient gas into the mass spectrometer.

[0138] The pass-through process is used to directly input ambient gases containing aerosols into the mass spectrometer.

[0139] In one embodiment, the signal generation module 202 is used to generate a corresponding ion signal intensity value based on the signal peak area generated by the ion signal in the mass spectrometer, specifically including:

[0140] Obtain the initial single-frame spectrum generated by each repulsion, and remove the initial single-frame spectrum with signal peak area lower than the preset area threshold to obtain the first single-frame spectrum;

[0141] The first single-frame spectrum and the corresponding initial single-frame spectrum are statistically analyzed for each mass-to-charge ratio. The probability of signal occurrence for a single mass-to-charge ratio is generated based on the ratio of the number of spectra in the first single-frame spectrum to the number of spectra in the initial single-frame spectrum.

[0142] When the probability of a signal occurring at a single mass-to-charge ratio is within a preset range, the first single-frame spectrum corresponding to that mass-to-charge ratio is retained to obtain an effective single-frame spectrum.

[0143] The signal peak area in the effective single-frame spectrum is statistically analyzed, and the ion signal intensity value is generated based on the average value of the signal peak area.

[0144] In one embodiment, the attenuation detection module 203 is used to pause the current signal acquisition task of the mass spectrometer and compare the ion signal intensity value with a preset reference signal value whenever the mass spectrometer completes a pass-through-filter process, and generate the attenuation coefficient of the mass spectrometer based on the comparison result, specifically including:

[0145] The switching status of the injection valve and the changes in the signal intensity output by the mass spectrometer are monitored in real time; the signal intensity includes the background signal intensity excluding aerosols and the signal intensity including aerosols.

[0146] When the signal intensity change is consistent with the preset signal intensity change trend and the signal intensity change matches the switching state, it is determined that the mass spectrometer has completed one pass-through-filtering process; wherein, the signal intensity change trend is from the background signal intensity to the signal intensity containing aerosols and then back to the background signal intensity;

[0147] When the mass spectrometer detects that it has completed one pass-through-filter process, a sample pause detection command is sent and the current signal acquisition task of the mass spectrometer is interrupted based on the sample pause detection command.

[0148] The ion signal intensity value is compared with the reference signal value, and an attenuation coefficient is generated based on the comparison result; the expression for the attenuation coefficient is as follows:

[0149] ;

[0150] In the formula, The attenuation coefficient; This represents the ion signal intensity value. This is the reference signal value.

[0151] In one embodiment, the attenuation compensation module 204 is used to generate voltage compensation parameters based on the attenuation coefficient and adjust the real-time output voltage of the detector based on the voltage compensation parameters, specifically including:

[0152] When the attenuation coefficient is less than the preset attenuation threshold, voltage compensation parameters are generated according to the preset compensation formula; where the expression of the preset compensation formula is:

[0153] ;

[0154] In the formula, These are voltage compensation parameters; is the current output voltage of the detector; k is the attenuation coefficient;

[0155] By adding voltage compensation parameters to the current output voltage, a corrected output voltage is obtained, and the detector's output voltage is adjusted based on the corrected output voltage.

[0156] In one embodiment, a correction attenuation coefficient is calculated based on the real-time output voltage. When the correction attenuation coefficient reaches a preset attenuation threshold, the signal acquisition task is restarted. Specifically, this includes:

[0157] Calculate the correction value for the ion signal intensity output by the detector under the real-time output voltage;

[0158] The correction attenuation coefficient is calculated based on the comparison between the ion signal intensity correction value and the reference signal value.

[0159] When the correction attenuation coefficient reaches the preset attenuation threshold, record the voltage compensation parameters and restart the signal acquisition task.

[0160] Those skilled in the art will understand that, for the sake of convenience and brevity, the specific working process of the device described above can be referred to the corresponding process in the foregoing method embodiments, and will not be repeated here.

[0161] This invention provides a detector-based attenuation compensation device. It generates corresponding ion signal intensity values ​​based on the signal peak area. The signal peak area is directly related to the number of ions, providing a more accurate representation of the ion signal strength. This peak area-based calculation method reflects the true state of the ion signal better than simple signal amplitude measurement, thus improving the accuracy of detection results. Each time the mass spectrometer completes a pass-through-filter process, it compares the ion signal intensity value with a reference signal value and generates an attenuation coefficient. This periodic monitoring mechanism can promptly detect signal attenuation, facilitating timely compensation measures and preventing deviations in detection results due to signal attenuation. This ensures the stability and reliability of the mass spectrometer during long-term operation. By generating voltage compensation parameters based on the attenuation coefficient and adjusting the detector's real-time output voltage, dynamic compensation for signal attenuation can be achieved. When signal attenuation is detected, increasing the detector's output voltage enhances the response to ion signals, restoring the signal intensity to a suitable range and maintaining stable instrument performance. The entire attenuation compensation process is automated. From signal acquisition, attenuation coefficient calculation, voltage compensation parameter generation to detector output voltage adjustment, and then to the calculation of correction attenuation coefficient and restart of signal acquisition task, each link is closely connected and executed automatically, making the detection process more efficient and orderly.

[0162] The above are merely preferred embodiments of the present invention. It should be noted that those skilled in the art can make several improvements and substitutions without departing from the technical principles of the present invention, and these improvements and substitutions should also be considered within the scope of protection of the present invention.

Claims

1. A detector-based attenuation compensation method, characterized in that, include: The progress of the mass spectrometer's signal acquisition task is monitored in real time. When the mass spectrometer is in the transition process, the ion signal output by the detector is acquired. The signal acquisition task is a cyclic acquisition process that includes transition, filtering, transition, and pass-through. The corresponding ion signal intensity value is generated based on the signal peak area generated in the mass spectrometer according to the ion signal. Each time the mass spectrometer completes a pass-through-filter process, the current signal acquisition task of the mass spectrometer is paused and the ion signal intensity value is compared with a preset reference signal value. Based on the comparison result, the attenuation coefficient of the mass spectrometer is generated. A voltage compensation parameter is generated based on the attenuation coefficient, and the real-time output voltage of the detector is adjusted based on the voltage compensation parameter. A correction attenuation coefficient is calculated based on the real-time output voltage. When the correction attenuation coefficient reaches a preset attenuation threshold, the signal acquisition task is restarted. The signal acquisition task is a cyclical acquisition process that includes transition, filtering, transition, and pass-through, specifically: The transition process switches between the filtration process and the through-flow process via the injection valve; The filtration process uses a filtration device to filter aerosols in the ambient gas, and then inputs the filtered ambient gas into the mass spectrometer. The pass-through process is used to directly input ambient gases containing aerosols into the mass spectrometer.

2. The detector-based attenuation compensation method as described in claim 1, characterized in that, The step of generating a corresponding ion signal intensity value based on the signal peak area generated in the mass spectrometer according to the ion signal specifically includes: Obtain the initial single-frame spectrum generated by each repulsion, and remove the initial single-frame spectrum with signal peak area lower than the preset area threshold to obtain the first single-frame spectrum; The first single-frame spectrum and the corresponding initial single-frame spectrum are statistically analyzed for each mass-to-charge ratio. The probability of signal occurrence for a single mass-to-charge ratio is generated based on the ratio of the number of spectra in the first single-frame spectrum to the number of spectra in the initial single-frame spectrum. When the probability of a signal occurring at a single mass-to-charge ratio is within a preset range, the first single-frame spectrum corresponding to that mass-to-charge ratio is retained to obtain an effective single-frame spectrum. The signal peak area in the effective single-frame spectrum is statistically analyzed, and the ion signal intensity value is generated based on the average value of the signal peak area.

3. The detector-based attenuation compensation method as described in claim 1, characterized in that, Each time the mass spectrometer completes a pass-through-filter process, the current signal acquisition task of the mass spectrometer is paused, and the ion signal intensity value is compared with a pre-set reference signal value. Based on the comparison result, the attenuation coefficient of the mass spectrometer is generated, specifically including: The switching status of the injection valve and the changes in the signal intensity output by the mass spectrometer are monitored in real time; the signal intensity includes the background signal intensity excluding aerosols and the signal intensity including aerosols. When the signal intensity change is consistent with the preset signal intensity change trend and the signal intensity change matches the switching state, it is determined that the mass spectrometer has completed one pass-through-filtering process; wherein, the signal intensity change trend is from background signal intensity to signal intensity containing aerosols and then back to background signal intensity; When the mass spectrometer detects that it has completed one pass-through-filter process, a sample pause detection command is sent and the current signal acquisition task of the mass spectrometer is interrupted based on the sample pause detection command. The ion signal intensity value is compared with the reference signal value, and the attenuation coefficient is generated based on the comparison result; wherein, the expression for the attenuation coefficient is: ; In the formula, The attenuation coefficient; This represents the ion signal intensity value. This is the reference signal value.

4. The detector-based attenuation compensation method as described in claim 1, characterized in that, The step of generating voltage compensation parameters based on the attenuation coefficient and adjusting the detector's output voltage based on the voltage compensation parameters specifically includes: When the attenuation coefficient is less than the preset attenuation threshold, voltage compensation parameters are generated according to a preset compensation formula; wherein, the expression of the preset compensation formula is: ; In the formula, These are voltage compensation parameters; is the current output voltage of the detector; k is the attenuation coefficient; The voltage compensation parameter is added to the current output voltage to obtain a corrected output voltage, and the output voltage of the detector is adjusted based on the corrected output voltage.

5. The detector-based attenuation compensation method as described in claim 1, characterized in that, The step of calculating the correction attenuation coefficient based on the real-time output voltage and restarting the signal acquisition task when the correction attenuation coefficient reaches a preset attenuation threshold specifically includes: Calculate the correction value of the ion signal intensity output by the detector under the real-time output voltage; The correction attenuation coefficient is calculated based on the comparison result between the ion signal intensity correction value and the reference signal value; When the correction attenuation coefficient reaches the preset attenuation threshold, the voltage compensation parameters are recorded and the signal acquisition task is restarted.

6. A detector-based attenuation compensation device, characterized in that, It includes a signal acquisition module, a signal generation module, an attenuation detection module, and an attenuation compensation module; The signal acquisition module is used to monitor the progress of the mass spectrometer's signal acquisition task in real time. When the mass spectrometer is in the transition process, it acquires the ion signal output by the detector. The signal acquisition task is a cyclic acquisition process that includes transition, filtering, transition, and pass-through. The signal generation module is used to generate a corresponding ion signal intensity value based on the signal peak area generated by the ion signal in the mass spectrometer. The attenuation detection module is used to pause the current signal acquisition task of the mass spectrometer and compare the ion signal intensity value with a preset reference signal value whenever the mass spectrometer completes a pass-through-filter process, and generate the attenuation coefficient of the mass spectrometer based on the comparison result. The attenuation compensation module is used to generate voltage compensation parameters based on the attenuation coefficient and adjust the real-time output voltage of the detector based on the voltage compensation parameters, calculate the correction attenuation coefficient based on the real-time output voltage, and restart the signal acquisition task when the correction attenuation coefficient reaches a preset attenuation threshold. The signal acquisition task is a cyclical acquisition process that includes transition, filtering, transition, and pass-through, specifically: The transition process switches between the filtration process and the through-flow process via the injection valve; The filtration process uses a filtration device to filter aerosols in the ambient gas, and then inputs the filtered ambient gas into the mass spectrometer. The pass-through process is used to directly input ambient gases containing aerosols into the mass spectrometer.

7. A terminal device, characterized in that, It includes a processor, a memory, and a computer program stored in the memory and configured to be executed by the processor, wherein the processor executes the computer program to implement the detector-based attenuation compensation method as described in any one of claims 1 to 5.

8. A computer-readable storage medium, characterized in that, The computer-readable storage medium includes a stored computer program, wherein, when the computer program is executed, it controls the device on which the computer-readable storage medium resides to perform the detector-based attenuation compensation method as described in any one of claims 1 to 5.

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