A method for detecting trimethylamine hydrochloride based on chromatographic analysis

Abstract

The present invention relates to the field of chromatographic analysis, and in particular to a trimethylamine hydrochloride detection method based on chromatographic analysis, comprising: performing chromatographic peak separation on a target chromatographic image of each solution to be detected, determining whether to adjust the degassing time of the solution to be detected according to the retention time difference value of each chromatographic peak; performing standard analysis on the target chromatographic image of each solution to be detected, determining the chromatographic analysis mode of the corresponding target chromatographic image according to the abnormal analysis cycle proportion of each target chromatographic image and the number of chromatographic peaks with abnormal analysis cycles; if the abnormal analysis cycle proportion is greater than a preset abnormal analysis cycle proportion, adjusting the vortex time of the solution to be detected; if the abnormal analysis cycle proportion is less than the preset abnormal analysis cycle proportion, determining the abnormal processing mode according to the abnormal dispersion coefficient and the abnormal correlation coefficient of the target chromatographic image. The present invention improves the accuracy of the acquired chromatographic image.

Description

Technical Field

[0001] The invention relates to the field of chromatographic analysis, and in particular to a trimethylamine hydrochloride detection method based on chromatographic analysis. Background Art

[0002] Using chromatographic analysis to detect different sample solutions is currently a common means of obtaining the content of different components in the sample solution and other quality data. However, slight differences between each liquid chromatography analysis process can lead to deviations in the chromatographic analysis results. The existing method of evaluating the chromatographic analysis results is often only based on whether there are interfering peaks in the chromatographic image and the relative standard deviation of the data, ignoring the relationship between the specific conditions of each chromatographic peak in the actual working scenario and the detection process. Therefore, how to analyze the specific conditions of each chromatographic peak in the actual working scenario and make timely adjustments to the chromatographic analysis process to obtain a more accurate chromatographic image is an urgent problem to be solved by technical personnel in this field.

[0003] Chinese patent publication number CN118443858B discloses a high performance liquid chromatograph fault analysis method based on artificial intelligence, which relates to the field of data processing technology. The method comprises: collecting crop images, growth environment information and pesticide spraying parameters of target crops for pesticide residue detection using a high performance liquid chromatograph; performing pesticide residue repeatability analysis at multiple detection positions to obtain residue repeatability distribution; performing pesticide residue detection to obtain multiple chromatographic detection result sets; obtaining multiple detection repeatability parameters; obtaining multiple detection accuracy parameters, and analyzing to obtain the fault analysis results of the high performance liquid chromatograph. However, the above scheme has the following problems: it fails to make targeted selections for the adjustment methods of the subsequent chromatographic analysis process according to the actual distribution of abnormal areas in the acquired chromatographic image, resulting in low effectiveness of the subsequent adjustment methods for the liquid chromatography analysis process, and further resulting in low accuracy of the acquired chromatographic image. Summary of the invention

[0004] To this end, the present invention provides a trimethylamine hydrochloride detection method based on chromatographic analysis, so as to overcome the problem that the prior art fails to determine the chromatographic analysis method according to the proportion and distribution of abnormal analysis cycles of the target chromatographic image, resulting in low effectiveness of the subsequent adjustment method for the liquid chromatography analysis process, and further resulting in low accuracy of the acquired chromatographic image.

[0005] To achieve the above object, the present invention provides a trimethylamine hydrochloride detection method based on chromatographic analysis, comprising:

[0006] Performing chromatographic peak separation on the target chromatographic image of each solution to be detected, and determining whether to adjust the degassing time of the solution to be detected according to whether there is a chromatographic peak in the target chromatographic image with a retention time difference value greater than a preset retention time difference value;

[0007] Performing standard analysis on the target chromatographic image of each solution to be tested, and determining the chromatographic analysis method of the corresponding target chromatographic image according to the abnormal analysis period ratio of each target chromatographic image and the number of chromatographic peaks with abnormal analysis periods;

[0008] If the abnormal analysis cycle ratio is greater than the preset abnormal analysis cycle ratio, the vortex duration of the solution to be tested is adjusted;

[0009] If the abnormal analysis cycle ratio is less than the preset abnormal analysis cycle ratio, the abnormal processing method is determined according to the abnormal dispersion coefficient and the abnormal correlation coefficient of the target chromatographic image, and the abnormal processing method includes adjusting the change frequency of the mobile phase composition, the injection speed of the solution to be detected, and the elution volume ratio;

[0010] A standard image is determined according to whether the target chromatographic image meets the image screening condition.

[0011] Further, the target chromatographic image of each solution to be detected is subjected to chromatographic peak separation to obtain the chromatographic peak corresponding to each target detection component;

[0012] Detect the retention time difference value of the chromatographic peak corresponding to each target detection component, and determine whether to adjust the degassing time of the solution to be detected based on whether there is a chromatographic peak with a retention time difference value greater than a preset retention time difference value in the target chromatographic image;

[0013] If there is a chromatographic peak in the target chromatographic image whose retention time difference value is greater than the preset retention time difference value, the degassing time of the corresponding solution to be detected is increased and adjusted.

[0014] Furthermore, a standard analysis is performed on the target chromatographic image of each solution to be tested, and the process of the standard analysis includes:

[0015] The analysis period is divided for each chromatographic peak, and the abnormal coefficients of different analysis periods of each chromatographic peak are tested;

[0016] Determine the category of the analysis period according to the abnormal coefficient, and record the analysis period with an abnormal coefficient greater than the preset abnormal coefficient as an abnormal analysis period;

[0017] The chromatographic analysis method of the corresponding target chromatographic image is determined according to the abnormal analysis period ratio of each target chromatographic image.

[0018] Further, for a single analysis period, the abnormal coefficient is determined according to the change rate difference value and the curve fluctuation of the analysis period;

[0019] The chromatographic curve in the analysis period is divided into a plurality of detection curves, and a curve change reference value and a curve fluctuation degree of the analysis period are determined according to the change rate of each detection curve;

[0020] The change rate difference value is the absolute value of the difference between the curve change reference value of the analysis period and its corresponding matching analysis period, and the matching analysis period is an analysis period in the reference chromatogram record having the same target detection component and cycle order as that of the analysis period;

[0021] The curve fluctuation is determined according to the change rate of each detection curve and the curve change reference value of the analysis period.

[0022] Furthermore, for a single target chromatographic image, if the abnormal analysis period ratio is greater than a preset abnormal analysis period ratio, the vortex duration of the corresponding solution to be tested is increased and adjusted according to the average abnormal coefficient of each abnormal chromatographic peak in the target chromatographic image;

[0023] The increase in the vortex duration is positively correlated with the average anomaly coefficient.

[0024] Furthermore, for a single target chromatogram image, if the abnormal analysis period ratio is less than or equal to the preset abnormal analysis period ratio, the abnormality handling method is determined according to the abnormal dispersion coefficient and abnormal correlation coefficient of the target chromatogram image;

[0025] The abnormal dispersion coefficient is determined according to the number of abnormal chromatographic peaks and the number of abnormal analysis cycles in which each abnormal chromatographic peak exists;

[0026] The abnormal correlation coefficient is determined according to the interval length between adjacent abnormal analysis cycles.

[0027] Further, if the abnormal dispersion coefficient of the target chromatographic image is greater than the preset abnormal dispersion coefficient and the abnormal correlation coefficient is greater than the preset abnormal correlation coefficient, the frequency of change of the mobile phase composition is reduced and adjusted according to the abnormal correlation coefficient;

[0028] The decrease value of the change frequency is positively correlated with the abnormal correlation coefficient.

[0029] Further, if the abnormal dispersion coefficient of the target chromatographic image is greater than the preset abnormal dispersion coefficient and the abnormal correlation coefficient is less than or equal to the preset abnormal correlation coefficient, the injection speed of the solution to be detected during the detection process is reduced and adjusted according to the average abnormal coefficient;

[0030] The reduction value of the injection speed is positively correlated with the average abnormal coefficient.

[0031] Furthermore, if the abnormal dispersion coefficient of the target chromatographic image is less than or equal to the abnormal dispersion coefficient, the elution volume proportion is reduced and adjusted according to the average change rate difference value of the abnormal analysis period;

[0032] The decrease value of the elution volume ratio is positively correlated with the average change rate difference value.

[0033] Furthermore, the target detection images that meet the image screening conditions are recorded as standard images.

[0034] Compared with the prior art, the beneficial effect of the present invention lies in that, in the technical solution of the present invention, by analyzing the acquired target chromatographic image and making targeted adjustments to the liquid chromatography analysis process according to the proportion of abnormal analysis cycles and the distribution of abnormal analysis cycles, the anomalies existing in the chromatographic analysis process are locked based on the proportion of abnormal analysis cycles and the distribution of abnormal analysis cycles, and an adjustment method that is more in line with the actual working scenario is selected to ensure the effectiveness of the determined adjustment method. The present invention improves the accuracy of the acquired chromatographic image.

[0035] Furthermore, in the present invention, a standard analysis is performed on the target chromatographic image of each solution to be detected, and an abnormality coefficient is determined based on the difference value of the change rate of each analysis cycle and the curve fluctuation, so as to further determine the category of each analysis cycle, so that the determination process of the abnormality coefficient is more in line with the actual situation of the target chromatographic image, thereby making the abnormality coefficient obtained by the detection more accurate, providing a more accurate basis for determining the subsequent chromatographic analysis method.

[0036] Furthermore, in the present invention, the corresponding chromatographic analysis method is determined according to the proportion of abnormal analysis cycles. If the proportion of abnormal analysis cycles is large, adjusting the vortex duration of the solution to be detected can improve the uniformity of solute distribution, so as to improve the overall quality of the target chromatographic image. If the proportion of abnormal analysis cycles is small, the distribution of abnormal analysis cycles is detected to determine the corresponding abnormal handling method, and then determine the corresponding adjustment method. The present invention improves the effectiveness of the adjustment method for the chromatographic analysis process.

[0037] Furthermore, the present invention determines the abnormal handling method according to the abnormal dispersion coefficient and the abnormal correlation coefficient of the target chromatographic image, and determines the targeted adjustment means through the different distribution conditions of the abnormal analysis cycle, so that the adjustment means are more in line with the actual working conditions, thereby improving the effectiveness of the adjustment of the chromatographic analysis process. The present invention improves the accuracy of the acquired chromatographic image. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 It is a schematic diagram of the trimethylamine hydrochloride detection method based on chromatographic analysis of the present invention;

[0039] Figure 2 A flow chart of determining the category of an analysis cycle according to an abnormal coefficient according to the present invention;

[0040] Figure 3 A flow chart of the present invention for determining a chromatographic analysis method corresponding to a target chromatographic image according to the abnormal analysis period ratio of the target chromatographic image;

[0041] Figure 4 The present invention is a flow chart for determining an abnormality processing method according to an abnormal dispersion coefficient and an abnormal correlation coefficient of the target chromatographic image. DETAILED DESCRIPTION

[0042] In order to make the objects and advantages of the present invention more clearly understood, the present invention is further described below in conjunction with embodiments; it should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0043] The preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only used to explain the technical principles of the present invention and are not intended to limit the protection scope of the present invention.

[0044] It should be noted that, in the description of the present invention, terms such as "up", "down", "left", "right", "inside" and "outside" indicating directions or positional relationships are based on the directions or positional relationships shown in the drawings. This is merely for the convenience of description and does not indicate or imply that the device or element must have a specific orientation, be constructed and operated in a specific orientation. Therefore, it cannot be understood as a limitation on the present invention.

[0045] In addition, it should be noted that in the description of the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For those skilled in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0046] See also Figures 1 to 4 As shown, the present invention provides a trimethylamine hydrochloride detection method based on chromatographic analysis, comprising:

[0047] Performing chromatographic peak separation on the target chromatographic image of each solution to be detected, and determining whether to adjust the degassing time of the solution to be detected according to whether there is a chromatographic peak in the target chromatographic image with a retention time difference value greater than a preset retention time difference value;

[0048] Performing standard analysis on the target chromatographic image of each solution to be tested, and determining the chromatographic analysis method of the corresponding target chromatographic image according to the abnormal analysis period ratio of each target chromatographic image and the number of chromatographic peaks with abnormal analysis periods;

[0049] If the abnormal analysis cycle ratio is greater than the preset abnormal analysis cycle ratio, the vortex duration of the solution to be tested is adjusted;

[0050] If the abnormal analysis cycle ratio is less than the preset abnormal analysis cycle ratio, the abnormal processing method is determined according to the abnormal dispersion coefficient and the abnormal correlation coefficient of the target chromatographic image, and the abnormal processing method includes adjusting the change frequency of the mobile phase composition, the injection speed of the solution to be detected, and the elution volume ratio;

[0051] A standard image is determined according to whether the target chromatographic image meets the image screening condition.

[0052] The solution to be tested in the present invention comprises a blank solution, a control solution and a test solution. The blank solution is composed of 1 ml of sodium tetraborate decahydrate solution, 1.5 ml of fluorenylmethoxycarbonyl chloride solution, 2.5 ml of acetonitrile, 0.3 ml of citric acid solution and 4.7 ml of water. The control solution is composed of 1 ml of a mixed solution, 1 ml of a trimethylamine hydrochloride solution, 1 ml of sodium tetraborate decahydrate solution, 1.5 ml of fluorenylmethoxycarbonyl chloride solution, 2.5 ml of acetonitrile and 0.3 ml of citric acid solution. The test solution is composed of The solution is composed of 1 ml trimethylamine hydrochloride solution, 1 ml sodium tetraborate decahydrate solution, 1.5 ml fluorenylmethoxycarbonyl chloride solution, 2.5 ml acetonitrile and 0.3 ml citric acid solution. Vortex treatment is required when preparing blank solution, control solution and test solution. The mixed solution is composed of 1 ml methylamine hydrochloride solution, 1 ml dimethylamine hydrochloride solution and 98 ml water. The concentration of the sodium tetraborate decahydrate solution is 19 mg / ml, and the concentration of the fluorenylmethoxycarbonyl chloride solution is 10 mg / ml. g / ml, the concentration of the citric acid solution is 0.4g / ml, the concentration of the methylamine hydrochloride solution is 0.5mg / ml, the concentration of the dimethylamine hydrochloride solution is 0.5mg / ml, the concentration of the trimethylamine hydrochloride solution is 5mg / ml, the target detection components in the present invention include: methylamine hydrochloride, dimethylamine hydrochloride, trimethylamine hydrochloride, sodium tetraborate decahydrate, fluorenylmethoxycarbonyl chloride, acetonitrile and citric acid, and the present invention performs liquid chromatography analysis on each solution to be detected to obtain a corresponding target chromatographic image, wherein the user can set the detection process of the high performance liquid chromatography according to the actual working scenario, and provide a parameter setting for the liquid chromatography detection process, the mobile phase is formic acid solution and acetonitrile methanol mixed solution, the concentration of the formic acid solution is 1mg / ml, the acetonitrile methanol mixed solution is a mixture of 450ml of acetonitrile and 150ml of methanol, and gradient elution is performed based on the two solutions during the liquid chromatography analysis process, and the proportion of the two mobile phases changes with time, and the chromatographic column is Waters XBridge C18, with a size of 4.6 mm × 150 mm, a filler particle size of 3.5 μm, a column temperature of 35 °C, and a detection wavelength of 264 nm.

[0053] Several test history records are applied in the present invention, and any one of the test history records at least one abnormal coefficient, the number of abnormal analysis cycles, the proportion of abnormal analysis cycles, the abnormal dispersion coefficient and the abnormal correlation coefficient in the liquid chromatography analysis process of the solution to be detected, and each test history record corresponds to a qualified mark, which records whether the accuracy of the chromatographic analysis result meets the user's requirements.

[0054] Specifically, the target chromatographic image of each solution to be detected is subjected to chromatographic peak separation to obtain the chromatographic peak corresponding to each target detection component;

[0055] Detect the retention time difference value of the chromatographic peak corresponding to each target detection component, and determine whether to adjust the degassing time of the solution to be detected based on whether there is a chromatographic peak with a retention time difference value greater than a preset retention time difference value in the target chromatographic image;

[0056] If there is a chromatographic peak in the target chromatographic image whose retention time difference value is greater than the preset retention time difference value, the degassing time of the corresponding solution to be detected is increased and adjusted.

[0057] Among them, in the present invention, chromatographic peak separation can be performed for each target chromatographic image through wavelet transform method, Fourier deconvolution method or curve fitting method. The user can select a suitable chromatographic peak separation method according to the actual working scenario. How to use the above three methods to separate chromatographic peaks is easy for technicians in this field to understand and will not be described in detail here. For the chromatographic peak of a single target detection component, the retention time difference value is the absolute value of the difference between the retention time of the chromatographic peak and its corresponding reference retention time. The reference retention time is the chromatographic peak of the corresponding target detection component in each detection historical record that meets the user's requirements for the accuracy of the chromatographic analysis results. The average value of the retention time, the value of the preset retention time difference value can be determined by the user according to the actual working scenario, for example, the user can set it according to the detection history record, the higher the user's accuracy requirement for the chromatographic analysis result, the smaller the value of the preset retention time difference value, and a method for determining the preset retention time difference value is provided, the maximum value of the retention time difference value of each chromatographic peak in the detection history record that meets the user's accuracy requirement for the chromatographic analysis result is recorded as the preset retention time difference value, and a value of the preset retention time difference value is provided, and the value of the preset retention time difference value is 5% of the corresponding reference retention time;

[0058] If there is a chromatographic peak in the target chromatographic image whose retention time difference is greater than the preset retention time difference, the degassing time of the solution to be detected corresponding to the target chromatographic image is increased and adjusted. The degassing time is the time for degassing the solution to be detected before high performance liquid chromatography analysis. If there are bubbles in the solution to be detected, it will lead to instability of the flow rate during the injection process of the solution to be detected, and the instability of the flow rate will directly affect the retention time of the chromatographic peak. Therefore, if there is a chromatographic peak with a retention time difference greater than the preset retention time difference, extending the degassing time of the solution to be detected can effectively improve this phenomenon. The present invention does not make specific limitations on the method used in the degassing process, and users can choose according to their actual working scenarios. How to complete the degassing treatment for the solution to be detected is content that technicians in this field have mastered and will not be elaborated here.

[0059] Specifically, a standard analysis is performed on the target chromatographic image of each solution to be tested. The process of the standard analysis includes:

[0060] Each chromatographic peak is divided to obtain a number of analysis cycles, and the abnormal coefficients of different analysis cycles of each chromatographic peak are detected;

[0061] Determine the category of the analysis period according to the abnormal coefficient, and record the analysis period with an abnormal coefficient greater than the preset abnormal coefficient as an abnormal analysis period;

[0062] The chromatographic analysis method of the corresponding target chromatographic image is determined according to the abnormal analysis period ratio of each target chromatographic image.

[0063] Among them, for a single chromatographic peak, the number of analysis cycles obtained by division is positively correlated with the retention time of the chromatographic peak, and the number of analysis cycles obtained by division is consistent with the number of analysis cycles contained in the chromatographic peak corresponding to the same target detection component in the reference chromatographic record. The durations corresponding to the analysis cycles contained in a chromatographic peak are all the same. The categories of analysis cycles include abnormal analysis cycles and regular analysis cycles. The analysis cycle with an abnormal coefficient less than or equal to a preset abnormal coefficient is recorded as a regular analysis cycle. The value of the preset abnormal coefficient can be determined by the user according to the actual working scenario. For example, the user can set it according to the detection history record. The higher the user's accuracy requirement for the chromatographic analysis result, the smaller the value of the preset abnormal coefficient. A method for determining the value of the preset abnormal coefficient is provided, and the minimum value of the abnormal coefficient of each abnormal analysis cycle in the detection history record that meets the user's accuracy requirement for the chromatographic analysis result is recorded as the preset abnormal coefficient. The abnormal analysis cycle proportion = the number of abnormal analysis cycles in the target chromatographic image / the number of analysis cycles in the target chromatographic image.

[0064] Specifically, for a single analysis period, the abnormal coefficient is determined according to the change rate difference value and the curve fluctuation of the analysis period;

[0065] The chromatographic curve in the analysis period is divided into a plurality of detection curves, and a curve change reference value and a curve fluctuation degree of the analysis period are determined according to the change rate of each detection curve;

[0066] The change rate difference value is the absolute value of the difference between the curve change reference value of the analysis period and its corresponding matching analysis period, and the matching analysis period is an analysis period in the reference chromatogram record having the same target detection component and cycle order as that of the analysis period;

[0067] The curve fluctuation is determined according to the change rate of each detection curve and the curve change reference value of the analysis period.

[0068] Among them, for a single analysis cycle, the chromatographic curve within the analysis cycle is divided into several detection curves, and the time lengths corresponding to the divided detection curves are all the same. The average value of the change rate of each detection curve is recorded as the curve change reference value of the analysis cycle. The cycle order is used to represent the arrangement order of each analysis cycle in the chromatographic peak. The reference chromatogram record is a record of the chromatographic peak corresponding to each target detection component in the detection history record that meets the user's requirements for the accuracy of the chromatographic analysis results. For a single analysis cycle, the curve fluctuation = the sum of the absolute values ​​of the differences between the change rates of each detection curve and the curve change reference value of the analysis cycle / the number of detection curves of the analysis cycle. For a single analysis cycle, the curve change reference value is the average value of the change rates of each detection curve, and the anomaly coefficient is the natural logarithm of the product of the change rate difference value and the curve fluctuation.

[0069] Specifically, for a single target chromatographic image, if the abnormal analysis period ratio is greater than the preset abnormal analysis period ratio, the vortex time of the corresponding solution to be tested is increased and adjusted according to the average abnormal coefficient of each abnormal chromatographic peak in the target chromatographic image;

[0070] The increase in the vortex duration is positively correlated with the average anomaly coefficient.

[0071] The value of the preset abnormal analysis cycle ratio can be determined by the user according to the actual working scenario. For example, the user can set it according to the detection history record, and a method for setting the value of the preset abnormal analysis cycle is provided. The detection history record that is adjusted only for the vortex duration is recorded as the ratio reference record, and the average value of the ratio of each abnormal analysis cycle in the ratio reference record that meets the user's requirements for the accuracy of the chromatographic analysis result is recorded as the preset abnormal analysis cycle ratio. A value of the preset abnormal analysis cycle ratio is provided, and the value of the preset abnormal analysis cycle ratio is 0.3;

[0072] The abnormal chromatographic peak is a chromatographic peak with an abnormal analysis cycle. For a single abnormal chromatographic peak, the average abnormal coefficient is the average value of the abnormal coefficients of each abnormal analysis cycle contained in the abnormal chromatographic peak. If the vortex mixing is insufficient, it will lead to uneven distribution of solutes in the solution to be detected, resulting in inconsistent solute concentrations during injection, or causing the concentration of certain components in the solution to be detected to be too high, exceeding the load capacity of the chromatographic column, and additional peaks, peak splitting or peak shape changes will be generated on the acquired chromatogram. Therefore, the abnormal degree of the target chromatographic image is reflected by the proportion of abnormal analysis cycles, so as to adjust the vortex duration in a targeted manner. The vortex duration is the duration of vortex treatment for the solution to be detected. Extending the vortex duration ensures uniform distribution of solutes in the solution to be detected, so as to avoid affecting the quality of the target chromatographic image due to the preparation effect of the solution to be detected. Vortex treatment refers to generating a strong vortex motion through high-speed rotation to fully disperse the substances in the solution and achieve a state of uniform mixing. In the present invention, an automatic vortex instrument is used to perform vortex treatment on the solution to be detected.

[0073] Specifically, for a single target chromatographic image, if the abnormal analysis period ratio is less than or equal to the preset abnormal analysis period ratio, the abnormality handling method is determined according to the abnormal dispersion coefficient and abnormal correlation coefficient of the target chromatographic image;

[0074] The abnormal dispersion coefficient is determined according to the number of abnormal chromatographic peaks and the number of abnormal analysis cycles in which each abnormal chromatographic peak exists;

[0075] The abnormal correlation coefficient is determined according to the interval length between adjacent abnormal analysis cycles.

[0076] Among them, the abnormal dispersion coefficient = ln (the number of abnormal chromatographic peaks / abnormal difference value), the abnormal dispersion coefficient is positively correlated with the number of abnormal chromatographic peaks, and the abnormal dispersion coefficient is negatively correlated with the abnormal difference value. For a single target chromatographic image, the abnormal difference value = the sum of the absolute values ​​of the differences between the number of abnormal analysis cycles of each abnormal chromatographic peak and the average number of abnormal cycles / the number of abnormal chromatographic peaks; the abnormal correlation coefficient is negatively correlated with the average cycle interval duration, and the average cycle interval duration is the average value of the interval durations between adjacent abnormal analysis cycles. If there is no other analysis cycle between two abnormal analysis cycles belonging to different chromatographic peaks, the two chromatographic peaks are determined to be adjacent abnormal analysis cycles.

[0077] Specifically, if the abnormal dispersion coefficient of the target chromatographic image is greater than the preset abnormal dispersion coefficient and the abnormal correlation coefficient is greater than the preset abnormal correlation coefficient, the frequency of change of the mobile phase composition is reduced and adjusted according to the abnormal correlation coefficient;

[0078] The decrease value of the change frequency is positively correlated with the abnormal correlation coefficient.

[0079] Among them, the values ​​of the preset abnormal dispersion coefficient and the preset abnormal correlation coefficient can be determined by the user according to the actual working scenario. For example, the user can set them according to the detection history records, and a method for taking the value of the preset abnormal dispersion coefficient is provided, in which the detection history record adjusted for the elution volume ratio is recorded as the dispersion reference record, and the maximum value of the abnormal dispersion coefficient in the analysis reference record that meets the user's requirements for the accuracy of the chromatographic analysis result is recorded as the preset abnormal dispersion coefficient. A method for taking the value of the preset abnormal correlation coefficient is provided, in which the detection reference record adjusted for the injection speed of the solution to be detected is recorded as the correlation reference record, and the maximum value of the abnormal correlation coefficient in the correlation reference record that meets the user's requirements for the accuracy of the chromatographic analysis result is recorded as the preset abnormal correlation coefficient;

[0080] If the abnormal correlation coefficient is greater than the preset abnormal correlation coefficient and the abnormal dispersion coefficient is greater than the preset abnormal dispersion coefficient, it can be shown that the abnormal area of ​​the target chromatographic image is mainly concentrated in the overlapping area of ​​each chromatographic peak. By reducing the change frequency of the mobile phase composition, the separation of each chromatographic peak in the target chromatographic image can be effectively improved. The change frequency is the change coefficient of the mobile phase composition in liquid chromatography analysis.

[0081] Specifically, if the abnormal dispersion coefficient of the target chromatographic image is greater than the preset abnormal dispersion coefficient and the abnormal correlation coefficient is less than or equal to the preset abnormal correlation coefficient, the injection speed of the solution to be tested is reduced and adjusted according to the average abnormal coefficient;

[0082] The reduction value of the injection speed is positively correlated with the average abnormal coefficient.

[0083] Among them, the average abnormal coefficient is the average value of the abnormal coefficients of each abnormal analysis period in the target chromatographic image. If the abnormal dispersion coefficient is greater than the preset abnormal dispersion coefficient, but the abnormal correlation coefficient is less than or equal to the preset abnormal correlation coefficient, it can be shown that the abnormal analysis periods in the target chromatographic image are evenly dispersed in more chromatographic peaks, but the abnormal analysis periods are not concentrated at the junction of the chromatographic peaks. By reducing the injection speed of the solution to be detected during the liquid chromatography analysis process, the stability of the injection speed of the solution to be detected is ensured, and the presence of abnormal analysis periods in the chromatographic peaks caused by fluctuations in the injection speed is avoided.

[0084] Specifically, if the abnormal dispersion coefficient of the target chromatographic image is less than or equal to the abnormal dispersion coefficient, the elution volume ratio is reduced and adjusted according to the average change rate difference value of the abnormal analysis period;

[0085] The decrease value of the elution volume ratio is positively correlated with the average change rate difference value.

[0086] Among them, the average change rate difference value is the average value of the change rate difference values ​​of each abnormal analysis period in the target chromatographic image, and the elution volume ratio = gradient volume / chromatographic column volume. If the abnormal dispersion coefficient of the target chromatographic image is small, that is, the abnormal analysis period is concentrated in a small part of the chromatographic peak, the peak shape of the chromatographic peak can be further improved and the abnormal analysis period of the target chromatographic image can be reduced by reducing the elution volume ratio.

[0087] Specifically, the target detection images that meet the image screening conditions are recorded as standard images.

[0088] Among them, the image screening condition is that the number of abnormal analysis cycles in the target detection image is less than or equal to the preset number of abnormal cycles and the retention time difference values ​​of each chromatographic peak in the target detection image are less than or equal to the preset retention time difference value. The value of the preset number of abnormal cycles can be determined by the user according to the actual working scenario. For example, the user can set it according to the detection history record. The higher the user's requirement for the accuracy of the chromatographic analysis results, the smaller the value of the preset number of abnormal cycles. A method for determining the value of the preset number of abnormal cycles is provided, and the average value of the number of abnormal analysis cycles in the standard image in the detection history record that meets the user's requirement for the accuracy of the chromatographic analysis results is recorded as the preset number of abnormal cycles. A value of the preset number of abnormal cycles is provided, and the value of the preset number of abnormal cycles is 3.

[0089] So far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the accompanying drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A trimethylamine hydrochloride detection method based on chromatographic analysis, characterized in that, include: Performing chromatographic peak separation on the target chromatographic image of each solution to be detected, and determining whether to adjust the degassing time of the solution to be detected according to whether there is a chromatographic peak in the target chromatographic image with a retention time difference value greater than a preset retention time difference value; Performing standard analysis on the target chromatographic image of each solution to be tested, and determining the chromatographic analysis method of the corresponding target chromatographic image according to the abnormal analysis period ratio of each target chromatographic image and the number of chromatographic peaks with abnormal analysis periods; If the abnormal analysis cycle ratio is greater than the preset abnormal analysis cycle ratio, the vortex duration of the solution to be tested is adjusted; If the abnormal analysis cycle ratio is less than the preset abnormal analysis cycle ratio, the abnormal processing method is determined according to the abnormal dispersion coefficient and abnormal correlation coefficient of the target chromatographic image. The abnormal processing method includes: If the abnormal dispersion coefficient is greater than the preset abnormal dispersion coefficient and the abnormal correlation coefficient is greater than the preset abnormal correlation coefficient, the frequency of change of the mobile phase composition is adjusted; If the abnormal dispersion coefficient is greater than the preset abnormal dispersion coefficient and the abnormal correlation coefficient is less than or equal to the preset abnormal correlation coefficient, the injection speed of the solution to be tested during the detection process is adjusted; If the abnormal dispersion coefficient is less than or equal to the preset abnormal dispersion coefficient, the elution volume ratio is adjusted, where the elution volume ratio = gradient volume / chromatographic column volume; Determine a standard image according to whether the target chromatographic image meets the image screening condition, wherein the image screening condition is that the number of abnormal analysis cycles in the target detection image is less than or equal to the preset number of abnormal cycles and the retention time difference value of each chromatographic peak in the target detection image is less than or equal to the preset retention time difference value; For a single chromatographic peak, the number of analysis cycles obtained by division is positively correlated with the retention time of the chromatographic peak, and the number of analysis cycles obtained by division is consistent with the number of analysis cycles contained in the chromatographic peak corresponding to the same target detection component in the reference chromatographic record, and the duration of each analysis cycle contained in a chromatographic peak is the same; The abnormal coefficient is the natural logarithm of the product of the difference value of the change rate and the curve fluctuation. The analysis period with an abnormal coefficient greater than the preset abnormal coefficient is recorded as an abnormal analysis period. The abnormal analysis period ratio = the number of abnormal analysis periods in the target chromatogram image / the number of analysis periods in the target chromatogram image; The change rate difference value is the absolute value of the difference between the curve change reference value of the analysis period and its corresponding matching analysis period, and the matching analysis period is an analysis period in the reference chromatogram record having the same target detection component and cycle order as that of the analysis period; The curve fluctuation is determined according to the change rate of each detection curve and the curve change reference value of the analysis period. For a single analysis period, the curve fluctuation=the sum of the absolute values ​​of the differences between the change rates of each detection curve and the curve change reference value of the analysis period / the number of detection curves of the analysis period. For a single analysis period, the curve change reference value is the average value of the change rates of each detection curve. The abnormal dispersion coefficient = ln (the number of abnormal chromatographic peaks / abnormal difference value), the abnormal difference value = the sum of the absolute values ​​of the differences between the number of abnormal analysis cycles of each abnormal chromatographic peak and the average number of abnormal cycles / the number of abnormal chromatographic peaks, the abnormal correlation coefficient is negatively correlated with the average cycle interval length, and the average cycle interval length is the average value of the interval lengths between adjacent abnormal analysis cycles; If there is no other analysis cycle between two abnormal analysis cycles belonging to different chromatographic peaks, the two chromatographic peaks are determined to be adjacent abnormal analysis cycles.

2. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 1, characterized in that, Performing chromatographic peak separation on the target chromatographic image of each solution to be detected to obtain the chromatographic peak corresponding to each target detection component; Detect the retention time difference value of the chromatographic peak corresponding to each target detection component, and determine whether to adjust the degassing time of the solution to be detected based on whether there is a chromatographic peak with a retention time difference value greater than a preset retention time difference value in the target chromatographic image; If there is a chromatographic peak in the target chromatographic image whose retention time difference value is greater than the preset retention time difference value, the degassing time of the corresponding solution to be detected is increased and adjusted.

3. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 2, characterized in that, A standard analysis is performed on the target chromatographic image of each solution to be tested. The standard analysis process includes: The analysis period is divided for each chromatographic peak, and the abnormal coefficients of different analysis periods of each chromatographic peak are tested; Determine the category of the analysis period according to the abnormal coefficient, and record the analysis period with an abnormal coefficient greater than the preset abnormal coefficient as an abnormal analysis period; The chromatographic analysis method of the corresponding target chromatographic image is determined according to the abnormal analysis period ratio of each target chromatographic image.

4. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 3, characterized in that, For a single analysis period, the abnormal coefficient is determined according to the change rate difference value and the curve fluctuation of the analysis period; The chromatographic curve within the analysis period is divided into a number of detection curves, and the curve change reference value and the curve fluctuation degree of the analysis period are determined according to the change rate of each detection curve.

5. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 4, characterized in that, For a single target chromatographic image, if the abnormal analysis period ratio is greater than the preset abnormal analysis period ratio, the vortex time of the corresponding solution to be tested is increased and adjusted according to the average abnormal coefficient of each abnormal chromatographic peak in the target chromatographic image; The increase in the vortex duration is positively correlated with the average anomaly coefficient; For a single abnormal chromatographic peak, the average abnormal coefficient is the average value of the abnormal coefficients of each abnormal analysis period contained in the abnormal chromatographic peak.

6. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 5, characterized in that, For a single target chromatographic image, if the abnormal analysis period ratio is less than or equal to the preset abnormal analysis period ratio, the abnormality handling method is determined according to the abnormal dispersion coefficient and abnormal correlation coefficient of the target chromatographic image; The abnormal dispersion coefficient is determined according to the number of abnormal chromatographic peaks and the number of abnormal analysis cycles in which each abnormal chromatographic peak exists; The abnormal correlation coefficient is determined according to the interval length between adjacent abnormal analysis cycles.

7. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 6, characterized in that, The process of adjusting the frequency of change of the mobile phase composition is to reduce the frequency of change of the mobile phase composition according to the abnormal correlation coefficient; The decrease value of the change frequency is positively correlated with the abnormal correlation coefficient.

8. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 7, characterized in that, The process of adjusting the injection speed of the solution to be detected during the detection process is to reduce the injection speed of the solution to be detected during the detection process according to the average abnormal coefficient; The reduction value of the injection speed is positively correlated with the average abnormal coefficient; The average abnormal coefficient is the average value of the abnormal coefficients of each abnormal analysis period in the target chromatographic image.

9. The trimethylamine hydrochloride detection method based on chromatographic analysis according to claim 8, characterized in that, The process of adjusting the elution volume ratio is to reduce the elution volume ratio according to the average change rate difference value of the abnormal analysis cycle; The decrease value of the elution volume ratio is positively correlated with the average change rate difference value; The average change rate difference value is the average value of the change rate difference values ​​of each abnormal analysis period in the target chromatographic image.

10. The method for detecting trimethylamine hydrochloride based on chromatographic analysis according to claim 9, characterized in that: The target detection image that meets the image screening conditions is recorded as the standard image.

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