A mass axis calibration method, device and medium thereof

Abstract

The present application discloses a mass axis calibration method, device and medium, relating to the technical field of mass spectrometer calibration, for calibrating the offset of the mass axis. Aiming at the problem of low efficiency of the current mass axis calibration method, a mass axis calibration method is provided. Since the calibration of the mass axis is mainly for the maximum value of the mass spectrum peak, this method does not need to obtain the mass curve of the entire mass spectrum peak, but makes the maximum value of the mass spectrum peak fall into the sampling point range by means of left and right translation, and then fits a local mass curve according to the sampling data, and finally realizes the calibration of the mass axis, reducing the number of samplings required. In addition, since the left and right translation method is adopted, the entire range of the mass spectrum peak can be quickly traversed to find the maximum value, which is simpler and faster than the method of taking the average of multiple samplings, and the number of samplings required is less, simplifying the steps of mass axis calibration and greatly improving the calibration efficiency.

Description

Technical Field

[0001] The present application relates to the technical field of mass spectrometer calibration, and particularly to a mass axis calibration method, device and medium thereof. Background Art

[0002] An HPLC triple quadrupole mass spectrometer is a precision instrument. Due to factors such as component aging and changes in the environment (temperature, humidity, etc.), the mass axis of the mass spectrometer will drift, resulting in a decrease in system sensitivity. Excessive deviation will cause the system to be unable to collect effective mass spectrometry signals. Therefore, mass axis calibration is usually required regularly.

[0003] Currently, there is a method of obtaining data through sampling, and then fitting a mass curve through the sampling points to achieve mass axis calibration based on the obtained mass curve. This method requires the sampling points to cover the range of a mass spectrometry peak as much as possible. When there are too many sampling points, the sampling difficulty is large and the sampling efficiency is low; when there are fewer sampling points, the distance between the sampling points is too large and the dispersion degree is too high, resulting in poor fitting effect. Therefore, currently, three-point sampling is usually repeated (generally more than 10 times), and the sampling data is averaged, and finally the mass curve is fitted and determined to calibrate the mass axis. However, this method of repeated sampling is still time-consuming and is not conducive to improving the efficiency of the mass axis calibration process.

[0004] Therefore, those skilled in the art now urgently need a mass axis calibration method to solve the problem of low efficiency of the current mass axis calibration method. Summary of the Invention

[0005] The purpose of the present application is to provide a mass axis calibration method, device and medium thereof, to solve the problem of low efficiency of the current mass axis calibration method.

[0006] To solve the above technical problems, the present application provides a mass axis calibration method, including:

[0007] Determine a preset number of sampling points according to the target mass number and perform sampling to obtain sampling data; wherein, the target mass number is the mass number of the mass axis to be calibrated; the sampling points are within the range of the same mass spectrometry peak, and the distance between each other is the same and is a first preset distance;

[0008] Judge whether the maximum value of the mass spectrometry peak falls within the range of the sampling points according to the sampling data. If not, repeat the sampling by shifting the sampling points left or right by a second preset distance until the maximum value falls within the range of the sampling points; wherein, the second preset distance is the distance between the first sampling point and the last sampling point;

[0009] Fit a mass curve according to the sampling data and calibrate the mass axis according to the mass curve.

[0010] Preferably, it is determined whether the maximum value of the mass spectrometry peak falls within the sampling point range according to the sampling data. If not, sampling is repeatedly performed by shifting the sampling point left or right by a second preset distance until the maximum value falls within the sampling point range, including:

[0011] According to the sampling data, determine the mass spectrometry intensity values of each sampling point;

[0012] If the mass spectrometry intensity values increase successively, shift the sampling point to the right by the second preset distance to repeat sampling;

[0013] If the mass spectrometry intensity values decrease successively, shift the sampling point to the left by the second preset distance to repeat sampling;

[0014] If the mass spectrometry intensity values show a non-monotonic increasing form, determine that the maximum value falls within the sampling point range.

[0015] Preferably, the first preset distance is determined by the resolution of the mass spectrometer.

[0016] Preferably, the preset number satisfies the first formula;

[0017] wherein, the first formula is: (preset number - 1) * first preset distance * 5 = 1.

[0018] Preferably, the preset number is an odd number and greater than 3.

[0019] Preferably, determining the preset number of sampling points according to the target mass number includes:

[0020] Taking the target mass number as the mass number of the center point among the sampling points, and the mass numbers of the remaining sampling points differ from the mass numbers of adjacent sampling points by the first preset distance.

[0021] Preferably, performing sampling to obtain sampling data includes:

[0022] The mass spectrometer operates in the MRM mode and scans according to the sampling points to obtain sampling data.

[0023] To solve the above technical problems, the present application further provides a mass axis correction device, including:

[0024] A sampling module, configured to determine a preset number of sampling points according to the target mass number and perform sampling to obtain sampling data; wherein, the target mass number is the mass number of the mass axis to be corrected; the sampling points are within the range of the same mass spectrometry peak, and the intervals between them are the same and are the first preset distance;

[0025] A judgment module, configured to judge whether the maximum value of a mass spectrometry peak falls within the range of sampling points according to sampling data. If not, sampling is repeatedly performed by shifting the sampling points left or right by a second preset distance until the maximum value falls within the range of sampling points. The second preset distance is the distance between the first sampling point and the last sampling point.

[0026] A calibration module, configured to fit a mass curve according to sampling data and calibrate the mass axis according to the mass curve.

[0027] To solve the above technical problems, the present application further provides a mass axis calibration device, including:

[0028] A memory, configured to store a computer program;

[0029] A processor, configured to implement the steps of the mass axis calibration method as described above when executing the computer program.

[0030] To solve the above technical problems, the present application further provides a computer-readable storage medium, on which a computer program is stored. When the computer program is executed by a processor, the steps of the mass axis calibration method as described above are implemented.

[0031] For the mass axis calibration method provided by the present application, since the calibration of the mass axis is mainly the calibration of the maximum value of the mass spectrometry peak, specifically, it is to determine the offset between the target mass number and the mass number corresponding to the maximum value of the mass spectrometry peak. Therefore, this method does not need to obtain the mass curve of the entire mass spectrometry peak, but makes the maximum value of the mass spectrometry peak fall within the range of sampling points by shifting left and right, and then fits a local mass curve according to the sampling data, and finally realizes the calibration of the mass axis, reducing the number of samplings required. In addition, since the left and right shifting method is adopted, the entire range of the mass spectrometry peak can be quickly traversed to find the maximum value, which is simpler and faster than the method of taking the average of multiple samplings, and the required number of samplings is less, simplifying the steps of mass axis calibration and greatly improving the calibration efficiency.

[0032] The mass axis calibration device and the computer-readable storage medium provided by the present application correspond to the above method, and have the same effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] To more clearly illustrate the embodiments of the present application, the following will briefly introduce the drawings required in the embodiments. Obviously, the drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0034] Figure 1 It is a mass spectrometry schematic diagram of an existing three-point fitting mass axis calibration method;

[0035] Figure 2 Flow chart of a mass axis calibration method provided by the present invention;

[0036] Figure 3 Schematic diagram of a mass spectrum with a left - shifted sampling point provided by the present invention;

[0037] Figure 4 Schematic diagram of a mass spectrum with a right - shifted sampling point provided by the present invention;

[0038] Figure 5 Structural diagram of a mass axis calibration device provided by the present invention;

[0039] Figure 6 Structural diagram of another mass axis calibration device provided by the present invention. Detailed implementation manners

[0040] Next, the technical solutions in the embodiments of the present application will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the protection scope of the present application.

[0041] The core of the present application is to provide a mass axis calibration method, device and its medium.

[0042] In order to enable those skilled in the art to better understand the solution of the present application, the present application will be further described in detail below in conjunction with the drawings and specific implementation manners.

[0043] During the use of a mass spectrometer, it is necessary to calibrate the offset mass axis to ensure the accuracy of the mass spectrometry signals collected by the mass spectrometer. Usually, to check whether the mass axis is offset, an injection pump is used for injection and a special calibration solution is used. This requires separating the mass spectrometer from the liquid chromatography instrument, that is, the mass spectrometer enters the offline state. In the offline state, a mass spectrometry peak shape with a complete profile is obtained in the full - scan mode, and it is determined whether the mass axis has shifted according to the vertices of the profile diagram. Then, the mass spectrometer is calibrated according to the offset amount. After calibration, the mass spectrometry is connected to the chromatography again, switched to the online state, and the normal operation of the mass spectrometer is restored.

[0044] The above method requires disconnecting the connection between the chromatography and the mass spectrometry, and then the user uses an injection pump for injection to perform calibration, resulting in a reduction in the system detection efficiency, which is not conducive to the automation of the calibration work and does not meet the requirements of clinical applications. Moreover, a specific calibration solution can only correct specific mass numbers and cannot accurately cover the mass numbers concerned by users.

[0045] Therefore, a new mass axis calibration method, a method based on three-point fitting of the mass axis, is proposed to calibrate the mass axis. This method is as follows Figure 1 As shown, the mass curve is fitted through three points within the same mass spectrometry peak range. The distance between the three points is too large, usually 0.2 - 0.4 Da (Da is the unit of atomic mass, defined as one-twelfth of the mass of a carbon-12 atom). The degree of discretization between the points is relatively high, resulting in a large deviation between the fitting equation and the true value, which also affects the authenticity of the maximum value.

[0046] Therefore, the above method usually reduces errors by means of multiple samplings (generally more than 10 times). The instrument needs to repeat at least 10 injections and scans, and perform averaging processing based on the data of each sampling, so as to calculate the average position of the inflection point (maximum value) for mass axis calibration, making the entire calibration process time-consuming.

[0047] Based on the above problems, the present application provides a mass axis calibration method, as follows Figure 2 shown, including:

[0048] S11: Determine a preset number of sampling points according to the target mass number and perform sampling to obtain sampling data.

[0049] Among them, the target mass number is the mass number of the mass axis to be calibrated; the sampling points are within the same mass spectrometry peak range, and the distance between each other is the same and is the first preset distance.

[0050] Considering that the multiple reaction monitoring mode (MRM mode) is a mass spectrometry technique that selectively collects mass spectrometry signals based on known or assumed reaction ion information, records signals of ions that meet the rules, and removes interference from signals of ions that do not meet the rules; and obtains mass spectrometry quantitative information through statistical analysis of the data. The MRM mode has characteristics such as high sensitivity and high specificity. Also, since the triple quadrupole mass spectrometer is the most sensitive mass spectrometry system for single mass-to-charge ratio scanning, it is the most suitable mass spectrometry instrument for the MRM mode.

[0051] Based on the above advantages, the present embodiment provides a preferred sampling scheme. The above-mentioned performing sampling to obtain sampling data includes:

[0052] The mass spectrometer operates in the MRM mode and scans according to the sampling points to obtain sampling data.

[0053] S12: Determine whether the maximum value of the mass spectrometry peak falls within the sampling point range according to the sampling data. If not, repeat sampling by shifting the sampling points left or right by a second preset distance until the maximum value falls within the sampling point range.

[0054] Among them, the second preset distance is the distance between the first sampling point and the last sampling point.

[0055] The above-mentioned setting method of the second preset distance ensures that the range covered by the sampling points can traverse the entire mass spectrometry peak range, thereby avoiding missing the maximum value. And it ensures that the required number of traversals is the least (that is, the number of samplings is the least).

[0056] Furthermore, for how to determine whether the maximum value falls within the sampling point range, this embodiment provides a preferred implementation scheme, which specifically includes:

[0057] S121: Determine the mass spectrometry intensity values of each sampling point according to the sampling data.

[0058] S122: If the mass spectrometry intensity values increase successively, shift the sampling points to the right by the second preset distance to repeat the sampling.

[0059] S123: If the mass spectrometry intensity values decrease successively, shift the sampling points to the left by the second preset distance to repeat the sampling.

[0060] S124: If the mass spectrometry intensity values show a non-monotonic increasing form, determine that the maximum value falls within the sampling point range.

[0061] It can be known from the mathematical theorem that the curves on both sides of the maximum value are in a monotonically increasing trend. Among them, the left side of the maximum value is monotonically increasing, and the right side is monotonically decreasing. Therefore, according to the above derivation, it can be determined according to the sampling data of the sampling points the growth trend of the mass spectrometry intensity values corresponding to the sampling points, and further determine whether the maximum value is within the sampling point range. And if it is not within the sampling point range, it can be determined whether the sampling range is to the left or to the right, and whether to shift left or right for the next sampling.

[0062] According to the preferred scheme provided by the above embodiment, it is possible to simply determine whether the maximum value is within the sampling point range, and even further obtain the conclusion of whether to shift the second preset distance to the left or to the right for the next sampling, which is convenient for quickly determining the position of the maximum value, thereby completing the calibration work of the mass axis.

[0063] S13: Fit a mass curve according to the sampling data and correct the mass axis according to the mass curve.

[0064] The sampled data are the mass numbers and mass spectrometry intensity values of the sampling points. Based on the sampled data of each sampling point, a mass curve can be fitted to determine the maximum value. As described above, for the sampled data used by the method provided in this application to fit the mass curve, the maximum value is within the range corresponding to the sampling point. Therefore, based on the sampling points obtained above, even if the sampling points cannot completely cover the mass spectrometry peak range, the position of the maximum value can still be determined. Thus, a smaller spacing can be adopted during sampling to obtain a lower degree of dispersion and a better fitting effect.

[0065] In addition, it should also be noted that for the calibration solution used for mass axis calibration, since this method only fits a small number of sampling points to determine the mass axis and does not need to reproduce the entire mass curve, there is no need to use a special calibration solution. The analyte, standard sample, or internal standard can be selected as the calibration solution, and liquid phase injection can be used to achieve online calibration without a special calibration solution, without offline operation, and without manual intervention.

[0066] A mass axis calibration method provided in this application calibrates the mass axis by fitting the sampling points within the range that includes the maximum value, so that the sampling points do not need to cover a large range of the mass spectrometry peak, and the position of the maximum value can still be guaranteed to be determined. Further, by means of left and right translation, only a small number of samplings are required to traverse the entire mass spectrometry peak range, complete the determination of the maximum value position, and achieve the calibration of the mass axis. Compared with the current method of obtaining the mass curve by taking the average of multiple samplings, the efficiency of this method is higher. Also, because the sampling points do not need to cover the entire or most of the mass spectrometry peak range, the spacing between the sampling points can be made smaller, thereby obtaining a lower degree of dispersion, and the fitted mass curve is also more accurate. Compared with the method of taking the average of multiple samplings, the calibration accuracy is also better, improving the entire mass axis calibration process in terms of both accuracy and efficiency.

[0067] As can be seen from the above embodiments, the accuracy and efficiency of mass axis calibration are related to the selection of sampling points. Among them, the first preset distance affects the accuracy of the fitted curve. The smaller the first preset distance, the lower the degree of dispersion between the sampling points, and correspondingly, the higher the accuracy of the fitted curve. Therefore, this embodiment provides a preferred implementation: the first preset distance is determined by the resolution of the mass spectrometer.

[0068] Furthermore, that is, the first preset distance is the smallest mass number unit that the mass spectrometer can resolve. For example, in actual application scenarios, the resolution of common mass spectrometers is mostly 0.05 Da. According to the above preferred scheme, the first preset distance should be selected as 0.05 Da.

[0069] After determining the value of the first preset distance, the specific value of the preset number can be further determined. It is easy to know that the more the preset number, the more accurate the mass curve fitted by the sampling points. However, too many sampling points pose challenges to sampling. Therefore, at present, the mass axis calibration is performed by the method of three-point fitting through repeated sampling.

[0070] Therefore, this embodiment provides a preferred solution for the method of determining the preset number: the preset number satisfies the first formula.

[0071] Among them, the first formula is: (preset number - 1) * first preset distance * 5 = 1.

[0072] It should be noted that the 1 in the above first formula represents that the range of the current mass spectrum peak is 1 Da. As can be seen from the above, the calibration of the mass axis is carried out within the range of the current mass spectrum peak. The core is to find the maximum value of the mass spectrum peak, so as to determine the offset from the target mass number, and then calibrate the mass axis.

[0073] Considering the actual application, the offset of the mass axis is not very large and is usually within the range of the current mass spectrum peak. Therefore, the sampling points need to cover the mass spectrum peak range as much as possible. And through the preferred solution provided by this embodiment, it is ensured that the sampling point range can cover one-fifth of the current mass spectrum peak, so that the position of the maximum value can be determined with at most 2 translations (that is, at most 3 samplings) without too many sampling points.

[0074] Exemplarily, when the first preset distance is 0.05 Da, the preset number determined according to the above preferred solution is 5. Compared with the commonly used three-point sampling fitting method, it does not increase too many sampling points, but the required number of samplings is greatly reduced (from at least 10 times to at most 3 times), thus greatly improving the efficiency of mass axis calibration. At the same time, the spacing between sampling points is reduced from 0.2 - 0.4 Da to 0.05 Da, greatly reducing the discreteness of sampling points, so that the mass curve obtained by fitting does not require multiple samplings to obtain an average value and can also obtain higher accuracy.

[0075] The preferred solution provided by this embodiment further explains the determination of the first preset distance and the preset number. The sampling points determined by this embodiment require fewer sampling times than the currently commonly used methods during the process of sampling to fit the mass curve, and the spacing between sampling points is also greatly reduced. Therefore, there is a significant improvement in both sampling efficiency and fitting accuracy, optimizing the mass axis calibration process in terms of both efficiency and accuracy.

[0076] As can be seen from the above embodiments, a preferred solution for determining a preset number through a first preset distance is provided in the above embodiments. The purpose is to ensure that the maximum value position can be obtained with fewer translation times, which is an improvement from the perspective of improving the quality axis calibration efficiency.

[0077] Correspondingly, from the perspective of improving the quality axis calibration accuracy, a preferred implementation solution provided in this embodiment is: the preset number is an odd number greater than 3.

[0078] Based on the above preferred solution, each sampling point can be further determined, that is, the sampling mass number of each sampling point can be determined. A preferred implementation solution is as follows:

[0079] Taking the target mass number as the mass number of the center point among the sampling points, the mass numbers of the remaining sampling points differ from the mass numbers of adjacent sampling points by a first preset distance.

[0080] Exemplarily, taking the preset number as 5 as an example, the mass axis to be corrected is 609.5 Da, that is, there are 5 sampling points, which are called the first point to the fifth point from left to right in sequence, and the target mass number is 609.5 Da. Also as an example, taking the first preset distance as 0.05 Da, that is, determining the second preset distance as 0.2 Da. At this time, the mass numbers of the initial five sampling points can be determined according to the above embodiments. The mass numbers of the first point to the fifth point from top to bottom are shown in the following table:

[0081] Table 1. Mass numbers of initial sampling points

[0082] Five-channel mass number (Da) 609.40 609.45 609.50 609.55 609.60

[0083] It can be known from the mass spectrum that the sampling range of the above determined sampling points is the center of the entire mass spectrum peak, and there is still a range of 0.4 Da on each side that has not been sampled, while the second preset distance is 0.2 Da, that is, each translation is 0.2 Da. Therefore, even if the maximum value point is not found in this sampling, at most two translations can be performed to find the maximum value. Greatly reducing the number of samplings required to determine the maximum value position.

[0084] In addition, there is another reason for the preferred solution provided in this embodiment to take the target mass number as the mass number of the center point of the sampling point: Generally speaking, the offset of the mass axis will not be too large, that is, the offset mass axis is more likely to fall to a position closer to the target mass number than to a position farther from the target mass number. Determining the position of the initial sampling point according to the above preferred solution can more likely obtain the maximum value position in the initial sampling, reduce the required number of samplings, and further improve the efficiency of mass axis calibration.

[0085] Further, to clearly and detailedly describe the mass axis calibration method provided in the above embodiments, the mass axis calibration method provided in the present application will be further described below with reference to examples:

[0086] Take the target mass number as 609.5 Da; the resolution of the mass spectrometer is 0.05 Da.

[0087] As can be seen from the above embodiments, the first preset distance is 0.05 Da, that is, the spacing between sampling points is 0.05 Da; the preset number is 5, that is, the number of sampling points is 5; the second preset distance is 0.2 Da, that is, the distance of each translation is 0.2 Da; the mass numbers of the initial 5 sampling points are shown in Table 1.

[0088] As Figure 3 shown, when the mass spectrometry intensity values scanned through the 5 sampling channels shown in Table 1 are monotonically increasing, it indicates that the overall sampling range is biased to the left, and the position of the maximum value cannot be determined through these 5 sampling points. At this time, it is necessary to shift 0.2 Da to the right as a whole, and the mass numbers of the new 5 sampling points from the first point to the fifth point, from top to bottom, are as shown in Table 2 below:

[0089] Table 2. Mass numbers of sampling points after right shift

[0090] Five-channel mass number (Da) 609.60 609.65 609.70 609.75 609.80

[0091] Similarly, as Figure 4 shown, if when the mass spectrometry intensity values scanned through the 5 sampling channels shown in Table 1 are monotonically decreasing, it indicates that the overall sampling range is biased to the right, and the position of the maximum value cannot be determined through these 5 sampling points. At this time, it is necessary to shift 0.2 Da to the left as a whole, and the mass numbers of the new 5 sampling points from the first point to the fifth point, from top to bottom, are as shown in Table 3 below:

[0092] Table 3. Mass numbers of sampling points after left shift

[0093] Five-channel mass number (Da) 609.20 609.25 609.30 609.35 609.40

[0094] Regarding the further determination of whether the maximum value is within the sampling range and the further translation method, the same principle applies, so it will not be elaborated again. Until the position of the maximum value is determined through at most two translations (that is, three samplings), the mass axis can be calibrated.

[0095] In the above embodiments, a mass axis calibration method is described in detail. The present application also provides an embodiment corresponding to a mass axis calibration device. It should be noted that the present application describes the embodiments of the device part from two perspectives, one is from the perspective of functional modules, and the other is from the perspective of hardware.

[0096] From the perspective of functional modules, as Figure 5As shown in the figure, this embodiment provides a mass axis correction device, including:

[0097] A sampling module 21, configured to determine a preset number of sampling points according to a target mass number and perform sampling to obtain sampling data; wherein, the target mass number is the mass number of the mass axis to be corrected; the sampling points are within the same mass spectrometry peak range, and the distance between each other is the same and is a first preset distance;

[0098] A judgment module 22, configured to judge whether the maximum value of the mass spectrometry peak falls within the sampling point range according to the sampling data. If not, sampling is repeated by shifting the sampling points left or right by a second preset distance until the maximum value falls within the sampling point range; wherein, the second preset distance is the distance between the first sampling point and the last sampling point;

[0099] A correction module 23, configured to fit a mass curve according to the sampling data and correct the mass axis according to the mass curve.

[0100] Since the embodiments of the device part correspond to the embodiments of the method part, for the embodiments of the device part, please refer to the description of the embodiments of the method part, which will not be elaborated here for the time being.

[0101] The mass axis correction device provided in this embodiment obtains sampling data through the sampling module, and judges whether the sampling range contains the maximum value point through the judgment module. If it contains, the sampling points are fitted to correct the mass axis, so that the sampling points do not need to cover a large range of mass spectrometry peaks, and the determination of the maximum value position can still be ensured. When there is no maximum value within the sampling range, by means of left and right translation, only a few samplings are required to traverse the entire mass spectrometry peak range, complete the determination of the maximum value position, and realize the correction of the mass axis. Compared with the current mass axis correction method, the number of samplings required for correction in this embodiment is less, and the correction efficiency is higher. Also, since the sampling points do not need to cover the entire or most of the mass spectrometry peak range, the distance between the sampling points can be made smaller, so as to obtain a lower dispersion, and the fitted mass curve is also more accurate. Compared with the method of taking the average by multiple samplings, the accuracy of the correction is also better, so that the entire mass axis correction process is improved in terms of both accuracy and efficiency.

[0102] Figure 6 This is a structural diagram of a mass axis correction device provided in another embodiment of the present application. As Figure 6 shown, a mass axis correction device includes: a memory 30, configured to store a computer program;

[0103] A processor 31, configured to implement the steps of the mass axis correction method in the above embodiment when executing the computer program.

[0104] A quality axis calibration device provided in this embodiment may include, but is not limited to, a smart phone, a tablet computer, a notebook computer, a desktop computer, etc.

[0105] Among them, the processor 31 may include one or more processing cores, such as a 4-core processor, an 8-core processor, etc. The processor 31 may be implemented in at least one hardware form of a digital signal processor (DSP), a field-programmable gate array (FPGA), and a programmable logic array (PLA). The processor 31 may also include a main processor and a coprocessor. The main processor is a processor for processing data in the wake state, also known as a central processing unit (CPU); the coprocessor is a low-power processor for processing data in the standby state. In some embodiments, the processor 31 may be integrated with a graphics processing unit (GPU), and the GPU is responsible for rendering and drawing the content to be displayed on the display screen. In some embodiments, the processor 31 may further include an artificial intelligence (AI) processor, and the AI processor is used to process computational operations related to machine learning.

[0106] The memory 30 may include one or more computer-readable storage media, and the computer-readable storage media may be non-transitory. The memory 30 may further include a high-speed random access memory and a non-volatile memory, such as one or more disk storage devices and a flash storage device. In this embodiment, the memory 30 is at least used to store the following computer program 301. After the computer program is loaded and executed by the processor 31, it can implement the relevant steps of a quality axis calibration method disclosed in any of the foregoing embodiments. In addition, the resources stored in the memory 30 may further include an operating system 302 and data 303, etc., and the storage method may be temporary storage or permanent storage. Among them, the operating system 302 may include Windows, Unix, Linux, etc. The data 303 may include, but is not limited to, a quality axis calibration method, etc.

[0107] In some embodiments, a quality axis calibration device may further include a display screen 32, an input / output interface 33, a communication interface 34, a power supply 35, and a communication bus 36.

[0108] Those skilled in the art can understand that Figure 6 the structure shown in does not constitute a limitation on a quality axis calibration device, and it may include more or fewer components than shown in the figure.

[0109] A mass axis calibration device provided by an embodiment of the present application includes a memory and a processor. When the processor executes the program stored in the memory, the following method can be implemented: A mass axis calibration method.

[0110] The mass axis calibration device provided in this embodiment realizes fitting of sampling points containing maxima within the sampling range through the processor executing a computer program stored in the memory, so as to calibrate the mass axis, enabling the determination of the maximum value position without the sampling points needing to cover a large range of mass spectrometry peaks. When there is no maximum value within the sampling range, through the method of left and right translation, only a small number of samplings are required to traverse the entire mass spectrometry peak range and complete the determination of the maximum value position, thereby realizing the calibration of the mass axis. Compared with the current mass axis calibration method, the number of samplings required for calibration in this embodiment is less, and the calibration efficiency is higher. Also, since the sampling points do not need to cover the entire or most of the mass spectrometry peak range, the spacing between sampling points can be made smaller, thereby obtaining a lower dispersion, and the fitted mass curve is also more accurate. Compared with the method of taking the average of multiple samplings, the calibration accuracy is also better, improving the entire mass axis calibration process in terms of both accuracy and efficiency.

[0111] Finally, the present application also provides an embodiment corresponding to a computer-readable storage medium. A computer program is stored on the computer-readable storage medium, and when the computer program is executed by a processor, the steps recorded in the above method embodiment are implemented.

[0112] It can be understood that if the method in the above embodiments is implemented in the form of a software functional unit and sold or used as an independent product, it can be stored in a computer-readable storage medium. Based on this understanding, the technical solution of the present application, in essence, or the part that contributes to the prior art, or all or part of this technical solution, can be embodied in the form of a software product. This computer software product is stored in a storage medium and executes all or part of the steps of the methods described in various embodiments of the present application. The aforementioned storage medium includes: various media such as USB flash drives, mobile hard disks, read-only memory (ROM), random access memory (RAM), magnetic disks, or optical discs that can store program codes.

[0113] A computer-readable storage medium provided by this embodiment, when the computer program stored therein is executed, can fit the sampling points containing the maximum value within the sampling range to correct the mass axis, so that the sampling points do not need to cover a large range of mass spectrometry peaks, and still can ensure the determination of the maximum value position. When there is no maximum value within the sampling range, by means of left and right translation, only a small number of samplings are required to traverse the entire mass spectrometry peak range, complete the determination of the maximum value position, and achieve the correction of the mass axis. Compared with the current mass axis correction method, the number of samplings required for correction in this embodiment is less, and the correction efficiency is higher. Also, since the sampling points do not need to cover the entire or most of the mass spectrometry peak range, the spacing between the sampling points can be made smaller, so as to obtain a lower dispersion, and the fitted mass curve is also more accurate. Compared with the method of taking the average of multiple samplings, the accuracy of the correction is also better, so that the entire mass axis correction process is improved in terms of both accuracy and efficiency.

[0114] The above has introduced in detail a mass axis correction method, device and medium provided by this application. The various embodiments in the specification are described in a progressive manner. Each embodiment focuses on the differences from other embodiments. The same or similar parts among the various embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the description of the method part. It should be noted that for those of ordinary skill in the art in this technical field, without departing from the principle of this application, several improvements and modifications can be made to this application, and these improvements and modifications also fall within the protection scope of the claims of this application.

[0115] It should also be noted that in this specification, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or also includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "including a..." does not exclude the existence of another identical element in the process, method, article or device including the said element.

Claims

1. A method for mass axis calibration, characterized in that, it includes: Determine a preset number of sampling points according to the target mass number and perform sampling to obtain sampling data; wherein, the target mass number is the mass number of the mass axis to be calibrated; the sampling points are within the same mass spectrometry peak range, and the distance between each other is the same and is a first preset distance; Judge whether the maximum value of the mass spectrometry peak falls within the range of the sampling points according to the sampling data. If not, repeat the sampling by shifting the sampling points left or right by a second preset distance until the maximum value falls within the range of the sampling points; wherein, the second preset distance is the distance between the first sampling point and the last sampling point; Fit a mass curve according to the sampling data including the maximum value of the mass spectrometry peak, and calibrate the mass axis according to the mass curve.

2. The mass axis calibration method according to claim 1, characterized in that, Judging whether the maximum value of the mass spectrometry peak falls within the range of the sampling points according to the sampling data. If not, repeating the sampling by shifting the sampling points left or right by a second preset distance until the maximum value falls within the range of the sampling points includes: Determine the mass spectrometry intensity values of each sampling point according to the sampling data; If the mass spectrometry intensity values increase in sequence, shift the sampling points to the right by the second preset distance to repeat the sampling; If the mass spectrometry intensity values decrease in sequence, shift the sampling points to the left by the second preset distance to repeat the sampling; If the mass spectrometry intensity values show a non-monotonic increasing form, determine that the maximum value falls within the range of the sampling points.

3. The mass axis calibration method according to claim 1, characterized in that, The first preset distance is determined by the resolution of the mass spectrometer.

4. The mass axis calibration method according to claim 3, characterized in that, The preset number satisfies the first formula; wherein, the first formula is: (preset number - 1) * first preset distance * 5 = 1.

5. The mass axis calibration method according to claim 1, characterized in that, The preset number is odd and greater than 3.

6. The mass axis calibration method according to claim 5, characterized in that, Determining a preset number of sampling points according to the target mass number includes: Taking the target mass number as the mass number of the center point among the sampling points, and the mass numbers of the remaining sampling points differ from the mass numbers of adjacent sampling points by the first preset distance.

7. The mass axis calibration method according to any one of claims 1 to 6, characterized in that, The performing sampling to obtain sampling data includes: The mass spectrometer operates in the MRM mode, and scans according to the sampling points to obtain the sampling data.

8. A mass axis calibration device, characterized in that, it includes: A sampling module, configured to determine a preset number of sampling points according to the target mass number and perform sampling to obtain sampling data; wherein, the target mass number is the mass number of the mass axis to be calibrated; the sampling points are within the same mass spectrometry peak range, and the distance between each other is the same and is a first preset distance; A judgment module, configured to judge whether the maximum value of a mass spectrometry peak falls within the range of the sampling points according to the sampling data. If not, sampling is repeatedly performed by shifting the sampling points left or right by a second preset distance until the maximum value falls within the range of the sampling points; wherein, the second preset distance is the distance between the first sampling point and the last sampling point; A calibration module, configured to fit a mass curve based on the sampling data including the maximum value of the mass spectrometry peak, and calibrate the mass axis according to the mass curve.

9. A mass axis calibration device, characterized in that, it includes: a memory, configured to store a computer program; a processor, configured to implement the steps of the mass axis calibration method according to any one of claims 1 to 7 when executing the computer program.

10. A computer-readable storage medium, characterized in that, a computer program is stored on the computer-readable storage medium, and when the computer program is executed by a processor, the steps of the mass axis calibration method according to any one of claims 1 to 7 are implemented.

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