Chromatographic analysis device and chromatographic analysis program

Abstract

To provide the analysis results of polyspecimen multicomponents in such a manner as easy for users to understand and efficiently confirmable.SOLUTION: The present invention comprises: an analysis processing unit (22) that finds, for each specimen, multiple kinds of numerical value information on the basis of measured data, that are measurement and analysis results with regard to multiple kinds of compounds; a flag condition setting unit 230 that sets a condition for flagging based on a threshold, for each of two or more kinds of multiple kinds of numerical value information, in accordance with user operation; an acceptance condition setting unit 231 that sets a plurality of categories for each of which a combination of whether two or more kinds of numerical value information are flagged or not is made to be a determination condition, in accordance with user operation; an acceptance determination unit 232 that checks whether flagged or not in accordance with the determination condition of the plurality of categories, and identifies a combination of specimen and compound that are relevant to the plurality of categories; and a display processing unit 24 that displays the identified combination in association with the relevant category or in a manner in which the category is visually discriminable.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a chromatographic analyzer and a computer program for use with the chromatographic analyzer, which includes liquid chromatographs (LC), gas chromatographs (GC), liquid chromatograph mass spectrometers (LC-MS), gas chromatograph mass spectrometers (GC-MS), and supercritical fluid chromatographs (SFC). [Background technology]

[0002] In recent years, quantitative analysis of multiple samples and components using LC-MS and GC-MS has been used in various fields, such as testing for pesticide residues in food, testing for contaminants in environmental water, pharmacokinetic studies in pharmaceutical development, and clinical testing. Generally, the amount of measurement data, such as chromatograms, obtained from multi-sample, multi-component analysis, and the quantitative results obtained by quantitative analysis of such measurement data are quite large. Therefore, to improve the efficiency of analytical work, allowing users to confirm and verify multi-sample, multi-component measurement and quantitative results, it is important to display measurement and quantitative results in a manner that is easy to operate, efficient, and less prone to errors or oversights.

[0003] To meet these demands, multi-analyte quantification support software has been commercialized, as described in Non-Patent Documents 1 and 2. As disclosed in Non-Patent Documents 1 and 2, this multi-analyte quantification support software is capable of collectively displaying on a screen information such as the quantification results of all samples, the quantification results of all compounds, or a two-dimensional table summarizing the quantification results of all compounds in all samples, chromatograms for each compound in each sample, and even calibration curves used for the quantification of each compound.

[0004] Furthermore, in multi-analyte, multi-component analysis, the amount of information displayed is so large that it is difficult for users to know which quantification results or peak detection results to check. Therefore, the multi-analyte quantification support software described above is equipped with a flagging function that alerts users by displaying colored flags on analysis results or measurement results, such as quantification values ​​that do not meet a threshold preset by the user. For example, Non-Patent Document 2 describes an example in which, as flagging criteria, the water quality standard value for a musty odor-causing substance is set as a warning concentration value, and a value 1 / 10 of the water quality standard value is set as a caution concentration value. Compounds with quantification values ​​exceeding 1 / 10 of the water quality standard value are colored orange to indicate caution, and compounds with quantification values ​​exceeding the water quality standard value are colored red to indicate a warning. [Prior art documents] [Non-patent literature]

[0005] [Non-Patent Document 1] "LabSolutions Insight: Multi-analyte quantification support software for GC / MS & LC / MS," [Online], Shimadzu Corporation, [Retrieved February 1, 2022], Internet<URL:https: / / www.an.shimadzu.co.jp / data-net / labsolutions / labsolutions-insight / features.htm> [Non-patent document 2] "LabSolutions Insight GCMS Multi-analyte Quantitation Support Software," [Online], Shimadzu Corporation, [Retrieved February 1, 2022], Internet<URL:https: / / www.an.shimadzu.co.jp / gcms / insight.htm> Summary of the Invention [Problem to be solved by the invention]

[0006] In the quantitative analysis of multiple samples and components, in addition to quantitative values ​​such as concentration values, the measurement and analysis results include the peak area value for each compound, the SN ratio, the symmetry coefficient (a coefficient indicating the symmetry of the peak), and the coefficient of determination (R 2 Various types of numerical information can be obtained, such as the retention time difference (the difference between the actual retention time and the standard retention time), and the like. In the conventional multi-analyte quantification support software described above, thresholds are set for each of these different types of numerical information, and a flag is set when the obtained numerical value exceeds the threshold.

[0007] However, for example, if a certain compound in a certain sample is flagged for multiple different types of numerical information, even an experienced analyst has difficulty in properly interpreting the results. This is because the reasons for flagging vary depending on the type of numerical information, and there are various possible reasons, such as the sample simply containing too much or too little, as well as inappropriate measurement conditions, inappropriate instrument conditions, or inappropriate standard samples for creating a calibration curve. Therefore, even if a certain numerical information for a certain compound in a certain sample is flagged, it is not necessarily possible to immediately determine that the sample has a problem, and it is difficult to automatically interpret the results.

[0008] In other words, while conventional flagging functions are suitable for allowing users to check at a glance whether a particular type of numerical information exceeds a threshold, they are not necessarily suitable for, for example, determining the quality of a sample based on multiple types of numerical information, or for selecting samples that require detailed examination by an analyst.

[0009] On the other hand, quantitative analysis of multiple samples and multiple components is often used for sample screening, etc., and for such purposes, there is a strong demand for operators without specialized knowledge to mechanically extract samples that are likely to be defective or samples that require detailed confirmation by a technician. However, the above-mentioned conventional multi-sample quantitative support software has not necessarily been able to fully meet such demands.

[0010] The present invention has been made in view of the above problems, and its main object is to provide a chromatographic analyzer and a computer program for chromatographic analysis that can accurately and flexibly utilize various numerical information obtained in the course of measurement and analysis, and provide the user with a multi-analyte, multi-component analysis result that requires user confirmation or that is clearly abnormal, in a state that allows the user to easily and efficiently confirm the result. [Means for solving the problem]

[0011] One aspect of the chromatographic analyzer according to the present invention, which has been made to solve the above problems, is a chromatographic analyzer that performs measurements of a plurality of types of compounds for a plurality of samples, each of which includes: an analysis processing unit that calculates, for each sample, measurement results for a plurality of types of compounds and a plurality of types of numerical information that are analysis results using the measurement results, based on data obtained by measurement; a flag condition setting unit that sets conditions for assigning a flag based on a threshold value to each of two or more types of numerical information among the plurality of types of numerical information in response to an operation by a user; a judgment result category setting unit that sets a plurality of judgment result categories, each of which has a judgment condition based on a combination of the presence or absence of a flag for the two or more types of numerical information, in response to an operation by a user; a judgment processing unit that checks whether or not the multiple types of numerical information for each sample and each compound obtained by the analysis processing unit meets the flag conditions set in the flag condition setting unit, and if so, assigns a flag, and also checks the presence or absence of a flag in accordance with the judgment conditions for multiple judgment result categories set in the judgment result category setting unit, and identifies combinations of samples and compounds that meet the multiple judgment result categories; a display processing unit that displays the combination of sample and compound identified by the determination processing unit in association with the determination result category to which the combination falls, or in a manner that allows the determination result category to be visually identified; Equipped with.

[0012] One aspect of the chromatographic analysis program according to the present invention, which has been made to solve the above-mentioned problems, is a data processing program used in a chromatographic analysis apparatus that performs measurements of a plurality of types of compounds for a plurality of samples, the program comprising: an analytical processing step of determining, for each sample, measurement results for a plurality of types of compounds and a plurality of types of numerical information that are analysis results using the measurement results, based on data obtained by measurement; a flag condition setting step of setting conditions for assigning a flag based on a threshold value to each of two or more types of numerical information among the plurality of types of numerical information in response to an operation by a user; a judgment result category setting step of setting a plurality of judgment result categories, each of which has a judgment condition based on a combination of the presence or absence of a flag for the two or more types of numerical information, in response to an operation by a user; a determination processing step of checking whether or not the multiple types of numerical information for each sample and each compound obtained in the analysis processing step meets the flag conditions set in the flag condition setting step, and assigning a flag if the multiple types of numerical information meets the flag conditions, and checking the presence or absence of a flag according to the determination conditions for the multiple determination result categories set in the determination result category setting step, and identifying combinations of samples and compounds that meet the multiple determination result categories; a display processing step of displaying the combination of sample and compound identified in the determination processing step on a display unit in association with the determination result category to which the combination falls or in a manner that allows the determination result category to be visually identified; Run To make. [Effects of the Invention]

[0013] In the above-described aspects of the chromatographic analyzer and chromatographic analysis program according to the present invention, by freely combining flags that are assigned when different types of numerical information exceed or fall below a threshold, it is possible to determine whether each combination of sample and compound falls into one of the judgment result categories, such as "pass," "fail," or "confirmation required." Then, for example, in a list of quantitative results or a chromatogram display for each sample and each compound, combinations of sample and compound that fall into such judgment result categories, i.e., "pass" or "fail," can be visually presented to the user in an easy-to-understand manner.

[0014] In this way, the above-described aspects of the chromatographic analyzer and chromatographic analysis program according to the present invention enable the user to efficiently and without mistakes such as oversights to identify, among the analysis results of a multi-analyte, multi-component analysis, those that require confirmation, those that are clearly abnormal, those that are clearly normal, etc. Furthermore, as long as a person with specialized knowledge appropriately defines the judgment result categories and their judgment conditions, even an operator without such knowledge can analyze the quantitative results. [Brief explanation of the drawings]

[0015] [Figure 1] 1 is a schematic diagram of an LC-MS system according to one embodiment of the present invention. [Figure 2] 10 is a flowchart showing an example of the procedure of a pass / fail determination process based on the quantification results in the LC-MS system of the present embodiment. [Figure 3] FIG. 2 is a diagram showing an example of a flag condition setting screen in the LC-MS system of the present embodiment. [Figure 4] FIG. 2 is a diagram showing an example of a pass / fail condition setting screen in the LC-MS system of the present embodiment. [Figure 5] FIG. 2 is a diagram showing a state in which conditions are set on a pass / fail condition setting screen in the LC-MS system of the present embodiment. [Figure 6]FIG. 10 is a diagram showing an example of a color bar setting screen for pass / fail judgment results in the LC-MS system of this embodiment. [Figure 7] FIG. 2 is a diagram showing an example of a table listing the quantification results of one sample in the LC-MS system of this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0016] An LC-MS system, which is one embodiment of a chromatographic analyzer according to the present invention, will now be described with reference to the accompanying drawings.

[0017] FIG. 1 is a schematic diagram of the LC-MS system of this embodiment. This LC-MS system includes a measurement unit 1 , a data processing unit 2 , an operation unit 3 , and a display unit 4 .

[0018] The measurement unit 1 includes an autosampler 10 that has the function of selecting a large number of pre-prepared samples in a predetermined order, a liquid chromatograph (LC) unit 11 that temporally separates compounds contained in the samples, and a mass spectrometer (MS) unit 12 that ionizes and detects the compounds. Note that, although the MS unit 12 is described here as a single-type quadrupole mass spectrometer, a tandem mass spectrometer such as a triple quadrupole mass spectrometer or a quadrupole-time-of-flight mass spectrometer can also be used.

[0019] The data processing unit 2 includes, as functional blocks, a data storage unit 20, a chromatogram creation unit 21, a quantitative analysis unit 22, an analysis work support unit 23, and a display processing unit 24. The analysis work support unit 23 includes, as subordinate functional blocks, a flag condition setting unit 230, a pass / fail condition setting unit 231, a pass / fail determination unit 232, and an analysis result table creation unit 233.

[0020] The data processing unit 2 can be configured to use a personal computer including a CPU, RAM, ROM, etc. as hardware, and to realize at least part of its functions by executing dedicated data processing software (computer program) installed on the computer.

[0021] The computer program can be provided to the user by being stored on a non-transitory computer-readable recording medium, such as a CD-ROM, DVD-ROM, memory card, or USB memory (dongle). The program can also be provided to the user in the form of data transfer via a communication line such as the Internet. Furthermore, the program can be pre-installed on a computer that is part of the system (strictly speaking, a storage device that is part of the computer) when the user purchases the system.

[0022] First, we will briefly explain the measurement operation in the measurement unit 1 when performing quantitative analysis of multiple samples and multiple components in the LC-MS system of this embodiment. In this case, multiple (usually a large number of) compounds to be measured are predetermined, and the retention time and the mass-to-charge ratio m / z of the ions to be measured are known for each compound. In other words, this information is given in advance.

[0023] A large number of samples (analytes) are loaded into the autosampler 10, and under the control of a control unit (not shown), the autosampler 10 selects the samples in a predetermined order and sends the selected samples to the LC unit 11. Although not shown, in the LC unit 11, a liquid delivery pump delivers a mobile phase to the column at a substantially constant flow rate, and an injector injects a predetermined amount of sample into the mobile phase at a predetermined timing. The injected sample is introduced into the column with the flow of the mobile phase, and the compounds in the sample are separated over time as they pass through the column.

[0024] The eluate exiting the column is introduced into the MS section 12. Although not shown, in the MS section 12, an ion source ionizes compounds in the eluate. The generated ions are separated according to their m / z values ​​by a quadrupole mass filter, and ions having specific m / z values ​​are selected and detected by an ion detector. The detection signal from the ion detector is converted into a digital signal, sent to the data processing section 2, and stored in the data storage section 20.

[0025] During quantitative analysis of multiple components, the quadrupole mass filter in the MS unit 12 is driven to selectively pass ions having m / z values ​​corresponding to the target compounds within a predetermined time range around the retention time at which the target compounds are introduced into the MS unit 12. That is, for each of the multiple target compounds, a selected ion monitoring (SIM) measurement is performed on the ions corresponding to each target compound. After the LC / MS measurement for one sample within the predetermined measurement time range is completed, the autosampler 10 selects the next sample and sends it to the LC unit 11. The LC unit 11 and the MS unit 12 then repeat the LC / MS measurement described above. Note that when a tandem mass spectrometer is used as the MS unit 12, instead of a SIM measurement, a multiple reaction monitoring (MRM) measurement targeting the MRM transition corresponding to the target compounds may be performed.

[0026] In this way, measurement data showing the time change in intensity of ions having specific m / z values ​​in a predetermined time range around the retention times corresponding to a large number of target compounds for each sample, that is, measurement data constituting an extracted ion chromatogram (EIC), are stored in the data storage unit 20. This measurement data is used to perform quantitative calculations for the target compounds.

[0027] Next, the quantitative analysis of multiple samples and multiple components performed in the data processing unit 2 will be described. In the data processing unit 2, the chromatogram creation unit 21 reads the measurement data corresponding to each sample from the data storage unit 20 and creates an extracted ion chromatogram for each target compound. If a target compound is contained in a sample, a peak will appear in the extracted ion chromatogram corresponding to that target compound. The quantitative analysis unit 22 performs peak detection processing on each extracted ion chromatogram, and if a peak is detected, calculates the peak area (or peak height). At this time, numerical information such as the measured retention time corresponding to the peak top position of the peak and a symmetry coefficient indicating the symmetry of the peak waveform is also calculated. The quantitative analysis unit 22 calculates the concentration value from the peak area value for each target compound by referring to a calibration curve created by analyzing a standard sample. As a result, the concentration value of each target compound is determined as a quantitative value for each sample.

[0028] The quantitative analysis unit 22 stores various types of numerical information, such as the concentration value calculated for each target compound, the peak area value determined in the process, the measured retention time, and the symmetry coefficient, in association with the measurement data or in the same file or folder as the measurement data, in the data storage unit 20. The quantitative analysis process by the quantitative analysis unit 22 may be performed in a batch manner after the measurements of all of the multiple samples have been completed, or may be performed sequentially when the measurements of some of the multiple samples have been completed (i.e., during a series of measurements).

[0029] In any case, when the quantitative analysis of multiple samples and multiple components is completed, a large amount of measurement data and quantitative results for multiple samples will be stored in the data storage unit 20. In this state, the characteristic analysis processing that is carried out mainly by the analysis work support unit 23 will be described with reference to Figures 2 to 7.

[0030] Fig. 2 is a flowchart showing an example of the procedure for pass / fail judgment processing in the LC-MS system of this embodiment. Fig. 3 is a diagram showing an example of a flag condition setting screen, Fig. 4 is a diagram showing an example of a pass / fail condition setting screen, Fig. 5 is a diagram showing a state in which conditions have been set on the pass / fail condition setting screen, Fig. 6 is a diagram showing an example of a color bar setting screen for pass / fail judgment results, and Fig. 7 is a diagram showing an example of a table listing the quantitation results of one sample.

[0031] When the user performs a predetermined operation using the operation unit 3, the flag condition setting unit 230 displays a flag setting screen 5 as shown in Fig. 3 on the screen of the display unit 4 via the display processing unit 24. As shown in Fig. 3, a compound table 50 showing a list of compounds to be measured is arranged on the flag setting screen 5. This compound table 50 shows, for each compound, the compound name, the m / z value of the compound to be measured, and the standard retention time, and further, items for which a flag can be set (numerical information that is the measurement result or analysis result) are arranged horizontally.

[0032] Items for which flags can be set include, for example, concentration values, peak area values, peak height values, SN ratios, peak symmetry coefficients, retention time differences, and coefficients of determination (R 2 ), accuracy percentage indicating the degree of deviation from a predetermined concentration setting, or the ratio of ion intensities at multiple m / z values. Because the primary objective here is quantitative analysis, the concentration value, which is the most important numerical information, is given two flags for the upper and lower concentration limits: "Caution," which prompts the user to check the value, and "Warning," which indicates the possibility of a serious problem with the concentration itself or its calculation or measurement process. In other words, there are four flags for concentration: "Upper concentration limit (Caution)," "Upper concentration limit (Warning)," "Lower concentration limit (Caution)," and "Lower concentration limit (Warning)." Based on the thresholds set for each flag, concentration values ​​can be classified into five levels (one of which is no flag).

[0033] Here, flags can be set for all compounds for each sample type. The sample type indicates the type of sample, such as unknown sample, standard sample, etc., and can be set on the flag setting screen shown in Figure 3. 5 In the [Sample Type] dialog box, the sample type can be specified by switching tabs. When the user clicks the "Edit" button 53 on the operation unit 3, input into the threshold value field 51 for each item becomes possible. The user then inputs or modifies the threshold value appropriately for each compound, thereby setting the items to be flagged and the conditions (threshold value) for flagging those items (Step S1).

[0034] In the example in Figure 3, a concentration lower limit (warning) flag has been set for each of the seven compounds with compound names aaa, ..., hhh, and the threshold for each is 2.5. The user can also set flags for other items as appropriate. This method of setting flags is similar to that used in conventional LC-MS using the multi-analyte quantitation software described above.

[0035] After setting all the desired flags, the user operates the operation unit 3 to display the flag setting screen. 5 top 4 on the display unit 4. The pass / fail condition setting screen 6 includes a pass / fail condition setting table 60 and a pass / fail judgment result output condition setting section 61. The pass / fail condition setting table 60 shows the types of flags that are currently set vertically, and provides check boxes for each flag to select whether or not to add it to the judgment conditions in the two judgment result categories of "fail" and "confirmation required."

[0036] Typically, the "Fail" result category is used when it is assumed that there is an abnormality in the data. For example, this is a result of a problem with the quantitative results of the sample relative to the purpose of the measurement (such as when a marker component exceeding the reference value for metabolic syndrome is detected for the purpose of a health check), a problem with the signal processing or calculation based on the data obtained from the sample (such as when the symmetry coefficient exceeds the threshold), or a problem with the measurement of the sample itself (such as when the signal-to-noise ratio is below the threshold, the retention time is significantly off, or the peak cannot be detected).

[0037] Furthermore, the "Confirmation Required" judgment result category is a judgment result when there is a possibility that there is a problem with the data, even if it is not a "fail." For example, if the concentration value is significantly below the threshold and the retention time is significantly different from the set value, it is estimated with a high degree of certainty to be a "fail." However, even if the concentration value is below the threshold, if the retention time is correct, the measurement may have been performed correctly, and it is difficult to determine whether there is a problem without checking the waveform of the chromatogram. Therefore, in such cases, the "Confirmation Required" judgment result is effective. Furthermore, even if a flag is set, all results that do not fall under the categories of "fail" or "confirmation required" can be classified into the "pass" judgment result category.

[0038] In this example, "Fail" is a judgment conditional on all specified flags being set (i.e., a logical product), and "Verification Required" is a judgment conditional on at least one of the specified flags being set (i.e., a logical sum), but this can be changed as appropriate. However, if the judgment condition is that all flags are set, it is not permissible to simultaneously set warning and caution flags of the same direction (upward for the upper limit, downward for the lower limit) as conditions. In other words, for example, it is not possible to specify both a concentration upper limit (warning) flag and a concentration upper limit (caution) flag. This is because multiple flags of the same direction cannot be assigned at the same time.

[0039] The user selects the flags to be used as judgment conditions by checking the checkboxes for "Fail" and "Confirmation Required" or either one of them on the pass / fail condition setting screen 6 (step S2). Figure 5 shows an example of selecting flags as judgment conditions. Here, a "Fail" judgment is made on the condition that both the "Upper concentration limit (warning)" flag and the "Symmetry coefficient" flag are set. Also, a "Confirmation Required" judgment is made on the condition that either the "Lower concentration limit (caution)" flag, the "Upper concentration limit (caution)" flag, or the "Symmetry coefficient" flag are set.

[0040] Next, the user sets conditions for outputting (displaying) the pass / fail judgment results on the pass / fail condition setting screen 6 (step S3). Specifically, the text "fail," "Inconclusive," and "Pass" are normally output for judgment results of "Fail," "Verification Required," and "Pass," respectively, but if a different text is desired to be output, the user checks one or more of the top three checkboxes in the pass / fail judgment result output condition setting section 61 and inputs the text string they wish to output. There is also an option to not display the judgment results in text.

[0041] Furthermore, if the user wishes to display the judgment result not only in text but also in color, the user checks the "Display judgment color bar" checkbox. Then, by performing a predetermined operation, the pass / fail condition setting unit 231 displays a display color selection screen 7 on the display unit 4, as shown in FIG. 6. In this screen, the user can select the color to be used for each of the judgment results "Fail," "Confirmation Required," and "Pass." After making a selection, the user clicks the "OK" button 72 to register the selected color. Furthermore, when the user clicks the "OK" button 62 on the pass / fail condition setting screen 6, the pass / fail conditions currently set are registered.

[0042] When the user performs a predetermined operation using the operation unit 3 with the flag conditions and pass / fail conditions set as described above, the pass / fail determination unit 232 judges the numerical information, which is the measurement results and analysis results stored in the data storage unit 20, in accordance with the flag setting conditions registered as described above, and assigns a flag to the numerical information that meets the set conditions. Furthermore, the pass / fail determination unit 232 identifies sample and compound combinations that respectively correspond to "fail" and "confirmation required" by checking the presence or absence of flags in accordance with the pass / fail conditions registered as described above. In addition, it determines other sample and compound combinations as "pass" (step S4).

[0043] The analysis result table creation unit 233 creates a table listing, for each sample, the numerical information representing the analysis results or measurement results corresponding to all compounds, a table listing, for each compound, the numerical information representing the analysis results or measurement results corresponding to all samples, or a table arranging one analysis result or numerical information representing the measurement result corresponding to each combination of all samples and all compounds. In this case, the table is provided with columns showing the flag information assigned as described above and the pass / fail judgment results based on the flag. The display processing unit 24 displays the analysis result screen including the created quantitative result list table on the display unit 4 (step S5).

[0044] In addition to the table, the analysis result screen including the quantitative result list table can also display other information, such as the peak waveforms of extracted ion chromatograms corresponding to all or some of the compounds in a specific sample, and calibration curves used to calculate concentrations.

[0045] FIG. 7 is an example of a table listing the numerical information for each compound for one sample. In the quantitative results list table shown in Figure 7, compounds for which a flag has been set are marked with a flag in the "Flag" column, and the type of flag is indicated by a symbol in the "Flag ID" column. The "RT (Actual Measurement)" and "Concentration" columns show the actual retention time and concentration value corresponding to each compound. The "Flag Pass / Fail Result" column displays either "Pass," "Fail," or "Inconclusive," along with a rectangular mark of the color specified in the judgment color bar. Furthermore, for compounds ccc that have been judged as failing, the background of the numerical information to which the flag that caused the failure has been assigned—in this case, the concentration value—is filled in with the color corresponding to the judgment result of "Fail."

[0046] As described above, in the LC-MS system of this embodiment, the pass / fail judgment results are displayed individually for each sample and compound in the quantitative result list table, so the user can see at a glance which compounds in which samples have failed or require further confirmation. Therefore, for example, even an operator without specialized knowledge can extract only failed samples, or extract combinations of samples and compounds that require further confirmation and forward them to another person with specialized knowledge.

[0047] Furthermore, the LC-MS system of this embodiment can set different combinations of flag conditions for different judgment result categories, such as "fail," "check required," and "pass." This provides flexibility and scalability, allowing various conditions to be grasped depending on the content and purpose of the judgment result category. Furthermore, when flags are set for various items, it is generally difficult to interpret whether a problem lies with the sample, the instrument, or the measurement conditions, simply by looking at the flag status. In contrast, the LC-MS system of this embodiment can make judgments on multiple types of flags at once, making it easier to grasp the status of abnormalities and malfunctions.

[0048] Furthermore, by filtering by judgment result category such as "fail," "needs confirmation," or "pass," it is possible to display only samples or compounds, or combinations thereof, that fall within a specific judgment result category. Even when filtering in this way to display only some of the quantitative results, the presence or absence of flags that are not directly related to the filtering can be displayed, allowing the user to check the presence or absence of those flags even in the narrowed-down results.

[0049] 7, the threshold value for flagging can be adjusted by returning to the flag setting screen 5. In this case, if the threshold value is changed, the presence or absence of a flag and the pass / fail judgment result based on the flag will also be changed. This makes it possible to adjust the flagging conditions themselves so that, for example, the analysis result of a certain compound in a certain sample is judged to be a fail.

[0050] In the LC-MS system of this embodiment, pass / fail judgment conditions are defined for two judgment result categories, "fail" and "check required," and results that do not meet these criteria are classified as "pass." However, the names of these judgment result categories can be changed as appropriate and may be freely set by the user. For example, in the case of quantitative analysis aimed at testing for pesticide residues, the name may be "shipment suspension" rather than "fail," or in the case of quantitative analysis aimed at health checkups, the name may be "treatment required" rather than "fail." The name may be chosen according to the purpose.

[0051] Although the above embodiment is an application of the present invention to an LC-MS, it is clear that the present invention can be applied to any chromatographic device that can acquire a chromatogram and perform quantitative analysis based on the chromatogram. That is, the present invention can be widely applied to not only LC-MS but also GC-MS, LC, GC, SFC, etc.

[0052] Furthermore, since the above-described embodiments and the various modifications described above are all examples of the present invention, it is natural that any modifications, changes, or additions made within the spirit of the present invention will also be encompassed within the scope of the claims of the present application.

[0053] [Various aspects] It will be apparent to those skilled in the art that the above-described exemplary embodiments are examples of the following aspects.

[0054] (Item 1) One aspect of the chromatographic analyzer according to the present invention is a chromatographic analyzer that performs measurements of multiple types of compounds for multiple samples, each of which includes: an analysis processing unit that calculates, for each sample, measurement results for a plurality of types of compounds and a plurality of types of numerical information that are analysis results using the measurement results, based on data obtained by measurement; a flag condition setting unit that sets conditions for assigning a flag based on a threshold value to each of two or more types of numerical information among the plurality of types of numerical information in response to an operation by a user; a judgment result category setting unit that sets a plurality of judgment result categories, each of which has a judgment condition based on a combination of the presence or absence of a flag for the two or more types of numerical information, in response to an operation by a user; a judgment processing unit that checks whether or not the multiple types of numerical information for each sample and each compound obtained by the analysis processing unit meets the flag conditions set in the flag condition setting unit, and if so, assigns a flag, and also checks the presence or absence of a flag in accordance with the judgment conditions for multiple judgment result categories set in the judgment result category setting unit, and identifies combinations of samples and compounds that meet the multiple judgment result categories; a display processing unit that displays the combination of sample and compound identified by the determination processing unit in association with the determination result category to which the combination falls, or in a manner that allows the determination result category to be visually identified; Equipped with.

[0055] (Item 4) One aspect of the chromatographic analysis program according to the present invention is a data processing program used in a chromatographic analyzer that performs measurements of multiple types of compounds for multiple samples, the program comprising: an analytical processing step of determining, for each sample, measurement results for a plurality of types of compounds and a plurality of types of numerical information that are analysis results using the measurement results, based on data obtained by measurement; a flag condition setting step of setting conditions for assigning a flag based on a threshold value to each of two or more types of numerical information among the plurality of types of numerical information in response to an operation by a user; a judgment result category setting step of setting a plurality of judgment result categories, each of which has a judgment condition based on a combination of the presence or absence of a flag for the two or more types of numerical information, in response to an operation by a user; a determination processing step of checking whether or not the multiple types of numerical information for each sample and each compound obtained in the analysis processing step meets the flag conditions set in the flag condition setting step, and assigning a flag if the multiple types of numerical information meets the flag conditions, and checking the presence or absence of a flag according to the determination conditions for the multiple determination result categories set in the determination result category setting step, and identifying combinations of samples and compounds that meet the multiple determination result categories; a display processing step of displaying the combination of sample and compound identified in the determination processing step on a display unit in association with the determination result category to which the combination falls or in a manner that allows the determination result category to be visually identified; Run To make.

[0056] The chromatographic analyzer described in paragraph 1 includes a liquid chromatographic analyzer, a gas chromatographic analyzer, a liquid chromatographic mass spectrometer, a gas chromatographic mass spectrometer, and a supercritical fluid chromatographic analyzer.

[0057] In the chromatographic analysis device described in paragraph 1 and the chromatographic analysis program described in paragraph 4, by freely combining flags that are assigned when different types of numerical information exceed or fall below a threshold, it is possible to determine whether each combination of sample and compound falls into one of the judgment result categories, such as "pass," "fail," or "confirmation required." Then, for example, in a list of quantitative results or a chromatogram display for each sample and each compound, combinations of samples and compounds that fall into such judgment result categories, i.e., "pass" or "fail," can be visually presented to the user in an easy-to-understand manner.

[0058] In this way, with the chromatographic analyzer described in paragraph 1 and the chromatographic analysis program described in paragraph 4, the user can efficiently and without making mistakes such as oversights to identify, among the analysis results of a multi-analyte, multi-component analysis, those that require confirmation, those that are clearly abnormal, and those that are clearly normal. Furthermore, as long as a person with specialized knowledge appropriately defines the judgment result categories and their judgment conditions, even an operator without such knowledge can analyze the quantitative results.

[0059] (Item 2) In the chromatographic analysis device described in item 1, the judgment result categories may be multiple, including a judgment result category that is at least either pass or fail, and other judgment result categories.

[0060] (Item 5) In the chromatographic analysis program described in item 4, the judgment result categories may be multiple, including judgment result categories that are at least either pass or fail, and other judgment result categories.

[0061] The "other determination result categories" may correspond to instructions that prompt the user to check information other than numerical information such as chromatogram waveforms and calibration curves, for example.

[0062] The chromatographic analysis device described in paragraph 2 and the chromatographic analysis program described in paragraph 5 make it possible to extract combinations of samples and compounds that require confirmation of chromatogram waveforms, for example, using criteria that are completely different from pass / fail criteria.

[0063] (Item 3) In the chromatographic analysis device described in item 1 or 2, the plurality of determination result categories can be associated with colors designated by the user, and the display processing unit can display the combination of the sample and compound using the color associated with the determination result category.

[0064] (Item 6) In addition, in the chromatographic analysis program described in Items 4 or 5, the plurality of determination result categories can be associated with colors designated by the user, and in the display processing step, the combination of the sample and the compound can be displayed in a color associated with the determination result category.

[0065] According to the chromatographic analysis device described in paragraph 3 and the chromatographic analysis program described in paragraph 6, the user can easily find samples or compounds that fall into judgment result categories such as pass, fail, or require confirmation in a quantitative result table or the like that displays numerical values ​​such as concentration values ​​in a list. [Explanation of symbols]

[0066] 1...Measuring part 10...Autosampler 11...Liquid chromatograph section (LC section) 12...Mass spectrometry section (MS section) 2...Data processing unit 20...Data storage section 21...Chromatogram creation section 22…Quantitative analysis department 23…Analysis work support department 230...Flag condition setting unit 231... Pass / fail condition setting section 232... Pass / Fail Judgment Section 233...Analysis result table creation unit 24...Display processing unit 3...Operation unit 4...Display section

Claims

1. A chromatographic analyzer for measuring a plurality of types of compounds for a plurality of samples, an analysis processing unit that calculates, for each sample, measurement results for a plurality of types of compounds and a plurality of types of numerical information that are analysis results using the measurement results, based on data obtained by measurement; a flag condition setting unit that sets conditions for assigning a flag based on a threshold value to each of two or more types of numerical information among the plurality of types of numerical information in response to an operation by a user; a judgment result category setting unit that sets a plurality of judgment result categories, each of which has a judgment condition based on a combination of the presence or absence of a flag for the two or more types of numerical information, in response to an operation by a user; a judgment processing unit that checks whether or not the multiple types of numerical information for each sample and each compound obtained by the analysis processing unit meets the flag conditions set in the flag condition setting unit, and if so, assigns a flag, and also checks the presence or absence of a flag in accordance with the judgment conditions for multiple judgment result categories set in the judgment result category setting unit, and identifies combinations of samples and compounds that meet the multiple judgment result categories; a display processing unit that displays the combination of sample and compound identified by the determination processing unit in association with the determination result category to which the combination falls, or in a manner that allows the determination result category to be visually identified; A chromatographic analysis device comprising:

2. 2. The chromatographic analyzer according to claim 1, wherein the judgment result categories are plural and include a judgment result category that is at least either pass or fail, and other judgment result categories.

3. 3. The chromatographic analyzer according to claim 2, wherein the plurality of determination result categories are associated with colors designated by a user, and the display processing unit displays the combinations of the samples and compounds in the colors associated with the determination result categories.

4. A data processing program used in a chromatographic analyzer that performs measurements of multiple types of compounds for multiple samples, the program comprising: an analytical processing step of determining, for each sample, measurement results for a plurality of types of compounds and a plurality of types of numerical information that are analysis results using the measurement results, based on data obtained by measurement; a flag condition setting step of setting conditions for assigning a flag based on a threshold value to each of two or more types of numerical information among the plurality of types of numerical information in response to an operation by a user; a judgment result category setting step of setting a plurality of judgment result categories, each of which has a judgment condition based on a combination of the presence or absence of a flag for the two or more types of numerical information, in response to an operation by a user; a determination processing step of checking whether or not the plurality of types of numerical information for each sample and each compound obtained in the analysis processing step corresponds to the flag conditions set in the flag condition setting step, and assigning a flag if the plurality of types of numerical information corresponds to the flag conditions, and checking the presence or absence of a flag according to the determination conditions of the plurality of determination result categories set in the determination result category setting step, and identifying combinations of samples and compounds that correspond to the plurality of determination result categories; a display processing step of displaying the combination of sample and compound identified in the determination processing step on a display unit in association with the determination result category to which the combination falls or in a manner that allows the determination result category to be visually identified; A chromatographic analysis program that executes the above.

5. 5. The chromatographic analysis program according to claim 4, wherein the judgment result categories are plural and include a judgment result category that is at least either pass or fail, and other judgment result categories.

6. 6. The chromatographic analysis program according to claim 4, wherein the plurality of determination result categories are associated with colors designated by a user, and the display processing step displays the combinations of the samples and compounds in the colors associated with the determination result categories.

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