JP3938086B2 - Chromatographic data processor - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a data processing apparatus for a chromatograph such as a liquid chromatograph (hereinafter abbreviated as “LC”) and a gas chromatograph (hereinafter abbreviated as “GC”).
[0002]
[Prior art]
Generally, in chromatographic analysis, a chromatogram is created with the retention time (retention time) of each component separated by the column on the horizontal axis and the relative intensity (concentration) of each component detected by the detector on the vertical axis. Is done.
[0003]
In such chromatographic analysis, an automatic sample changer such as an autosampler is often used for continuous analysis over a long period of time while automatically exchanging a number of samples prepared in advance. In such an analysis, if an analyst creates a schedule table that lists analysis procedures, that is, analysis file names indicating sample numbers and analysis conditions in a list format, samples are selected and analyzed sequentially according to the schedule. Conditions are changed, and analysis of a large number of samples is automatically executed (see, for example, Patent Document 1). The chromatogram data as the analysis result is stored in one data file for each analysis of each sample and stored in an external storage device or the like.
[0004]
FIG. 6 is a diagram schematically showing a data file creation operation in a conventional LC data processing apparatus. As shown in FIG. 6, in general, the starting point of chromatogram data collected by analyzing one sample is at the time of sample injection (or when it has been delayed by a predetermined time), and predetermined data from the time t0 of the starting point. The chromatogram data is collected during the period (t1-t0) up to time t1 when the collection time has elapsed, and is collected as data to be accommodated in one file. Therefore, in such a conventional data processing apparatus, for example, when N samples are analyzed (that is, N sample injections) in a certain automatic analysis, a total of N data files are created. Become.
[0005]
[Patent Document 1]
JP-A-10-318803 (paragraphs 0017 to 0019)
[0006]
[Problems to be solved by the invention]
In the conventional data processing apparatus, chromatogram data for each analysis set in the schedule table is reliably collected and remains as a data file. However, normally, a period during which no data was collected between a chromatogram for one analysis and a chromatogram for the analysis immediately after that (from time t1 to the start time t0 of the next analysis in FIG. 6). The chromatogram does not have temporal continuity before and after that portion. Therefore, for example, even if a malicious third party falsifies a chromatogram for one of these continuous analyses, such a chromatogram is modified from the viewpoint of continuity with the preceding and subsequent chromatograms. And finding anomalies is very difficult.
[0007]
In addition, in chromatogram analysis, there may be sample components that elute after a predetermined data collection time has elapsed, but in the above data processor, chromatogram data corresponding to these components remains. As a result, component detection omissions occur. Even if it is guaranteed that there are no sample components in the data non-collection period as described above, for example, abnormal signs that the baseline of the chromatogram is significantly disturbed may appear in this data non-collection period. Therefore, if there is a gap in the data collection period, there is a possibility that it will hinder verification of the validity of the analysis or investigation of the cause of the abnormality.
[0008]
The present invention has been made in order to solve such problems, and its main purpose is to provide temporal continuity of chromatograms acquired by each analysis in chromatographic analysis in which a plurality of analyzes are continuously performed. It is an object of the present invention to provide a chromatographic data processing device that ensures easy analysis of chromatogram waveforms in each analysis.
[0009]
[Means for solving the problems and effects]
In order to solve the above problems, the present invention is a data processing apparatus for a chromatograph that sequentially introduces a plurality of samples into a column and continuously analyzes various components contained in each sample.
Data collected sequentially with respect to the plurality of sample introductions are aggregated as a chromatogram data group constituting one chromatogram, and one data file is added together with analysis incidental information such as analysis conditions corresponding to the plurality of analyzes. A parent file creation means to create;
When an individual chromatogram creation request for each sample introduction is received, data in a predetermined time range is extracted from the chromatogram data included in the parent file, and the data and corresponding analysis supplementary information are extracted. A child file creation means for creating a child file including:
It is characterized by having.
[0010]
In the chromatograph data processing apparatus according to the present invention, the parent file creation means constitutes a single chromatogram without selecting a lot of data sequentially collected by a plurality of sample introductions on the way. The data is aggregated as a data group, and analysis-related information such as analysis conditions corresponding to the plurality of analyzes is merged to create one parent file. On the other hand, when the child file creation means receives a request for creating an individual chromatogram for each sample introduction, for example, a chromatogram in a predetermined time range instructed by an analyst from among the chromatogram data included in the parent file. Data is extracted, and a child file including the chromatogram data and corresponding analysis supplementary information is created separately from the parent file. That is, this child file corresponds to a data file for each analysis created in a conventional data processing apparatus.
[0011]
Therefore, according to the chromatographic data processing apparatus of the present invention, chromatogram data without a blank period in time remains in the parent file even between the analyzes in a series of continuous analysis. The data of the portion continuously connecting between the stored chromatograms can be confirmed as necessary. As a result, it becomes easy to find fraud such as alteration of some chromatograms, and the validity and validity of the analysis result can be verified more smoothly.
[0012]
Moreover, even if there is a sample component that appears at a holding time position that is not intended by the analyst, the peak due to such sample component can be reliably captured and used for data analysis. Conventionally, even if any signs of abnormality appear during a period in which no chromatogram data remains, since such signs can be reliably captured, analysis of abnormal conditions can be verified more smoothly. Furthermore, since the child file stores chromatogram data and analysis supplementary information corresponding to each analysis as before, analysis of waveform processing, quantitative calculation, report output, etc. using the data of this child file It can be performed.
[0013]
As one embodiment of the chromatograph data processing apparatus according to the present invention,
A chromatogram creation means for receiving data sequentially collected by the plurality of sample introductions and creating a chromatogram as the analysis proceeds;
Display means for displaying the chromatogram;
Range indicating means for instructing an arbitrary clipping range of the chromatogram on the display screen of the display means in accordance with the operation of the analyst;
And the child file creation means creates a child file including chromatogram data belonging to the cutout range designated by the range designation means.
[0014]
In this configuration, the analyst can instruct an arbitrary cutout range on the screen by the range instruction unit while confirming the peak of the chromatogram sequentially drawn on the display screen of the display unit as time elapses. . Accordingly, appropriate chromatograms corresponding to each analysis can be acquired in parallel with the progress of the continuous analysis, and the analysis can be performed efficiently.
[0015]
Further, when such a plurality of analyzes are continuously performed and the type of the component contained in the sample to be analyzed is known, before the previous sample component is completely discharged from the column. In addition, so-called overlap injection can be performed in which the next sample is introduced into the column (see, for example, JP-A-11-201961). That is, if the retention time of the contained component is known, for example, the injection timing is such that the peak of the component contained in the next sample appears between the positions of the peaks of the two components contained in the previous sample. To allow portions of the chromatogram to overlap for the two analyses. Even in the case of continuous analysis by such overlap injection, according to the above configuration, if it is instructed to cut out two chromatograms each including an overlapped portion in the chromatograms sequentially drawn on the display screen, they are separately provided. Child files can be easily obtained.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, a case where the chromatographic data processing apparatus according to the present invention is applied to an LC analyzer will be described as an example.
[0017]
FIG. 1 is an overall configuration diagram of an LC analyzer according to the present embodiment. The configuration of this analyzer can be broadly divided into an LC analyzer that performs actual analysis on a liquid sample and collects data necessary for the analysis, and performs predetermined waveform processing and arithmetic processing on the collected data. And a data processing unit for deriving a qualitative analysis or quantitative analysis result.
[0018]
In the LC analyzer, the eluent is sucked from the eluent (mobile phase) tank 1 by the operation of the liquid feed pump 2 and supplied to the column 5 through the autoinjector 3 at a constant flow rate. The autosampler 4 holds a large number of samples and selects the samples in a predetermined order, and the autoinjector 3 injects the selected samples into the eluent at a predetermined timing. This sample rides on the eluent and is introduced into the column 5, and each component in the sample is temporally separated while passing through the column 5. The detector 6 sequentially detects the sample components eluted from the column 5 as time elapses, and the detection signal is converted into a digital signal by the A / D converter 7 and then a personal computer (hereinafter referred to as a data processing unit). (Referred to as “computer”). Various detectors 6 are used depending on the purpose, but a spectrophotometric detector, a spectrofluorescence detector, an electrical conductivity detector, or the like is usually used.
[0019]
FIG. 2 is a block diagram functionally showing the components necessary for achieving the operations characteristic of the data processing apparatus of the present embodiment in the personal computer 8. That is, the detection signal converted into a digital signal by the A / D converter 7 is input in parallel to the chromatogram creation unit 11 and the chromatogram data collection unit 13. The chromatogram creation unit 11 performs predetermined data processing on sequentially input signals to create a chromatogram, and the chromatogram is displayed on the screen of the display unit 19 via the chromatogram display processing unit 12 and the display control unit 17. Display a gram.
[0020]
On the other hand, among the data collected by the chromatogram data collection unit 13, data within a time range specified by the control unit 10 is extracted by the chromatogram extraction unit 14 as described later. The analysis information collection unit 15 includes analysis results such as analysis conditions (for example, pressure of the liquid feed pump 2, column oven temperature, etc.), parameters of data analysis processing, operation logs indicating a history of changes in analysis conditions during the analysis, and the like. Various incidental information other than certain data (herein, these data are collectively referred to as analysis incidental information) is collected. The chromatogram data collection unit 13, the chromatogram extraction unit 14 and the analysis information collection unit 15 pass the collected data to the file management unit 16 under the control of the control unit 10, and the file management unit 16 organizes these data. And stored in the external storage device 20 such as a hard disk drive as a parent file or a child file. The contents of the parent file and child file will be described later. The operation of each unit is controlled by the control unit 10, and an input unit 18 that is a pointing device such as a keyboard or a mouse is connected to the control unit 10.
[0021]
Next, an example of a data file creation operation at the time of continuous analysis in the LC analyzer having the above configuration will be described with reference to FIGS. FIG. 3 is an explanatory diagram of this data file creation operation, and FIG. 4 is a diagram showing an example of the display screen of the display unit.
[0022]
First, before performing the analysis, the analyst inputs and sets a schedule table indicating the procedure of the continuous analysis from the input unit 18 as in the conventional analysis. This schedule table includes, for example, a sample number, a sample name, a sample injection amount, an analysis condition file name, and the like, and an analysis condition for each analysis is determined by this. The analyst also sets the total collection period for continuous chromatogram data. However, this whole collection period is not necessarily determined by the analyst, for example, from the start of calibration analysis to the end of continuous analysis, from the start point of the first analysis set in the schedule table to the end point of the last analysis. Alternatively, it is possible to arbitrarily determine from login to logout to the personal computer 8 or data processing software. Here, as an example, the entire collection period of chromatogram data is defined from the start point of the first analysis set in the schedule table to the end point of the last (Nth) analysis.
[0023]
When the analyst instructs the start of analysis, and in response to this, a series of continuous analysis is actually started, the chromatogram data collection unit 13 starts collecting chromatogram data from time t0. Once the collection of chromatogram data is started, the data is continuously collected regardless of a plurality of analysis breaks, and this operation is continued until a predetermined collection end time t1. That is, as shown in FIG. 3A, chromatogram data constituting a long-time chromatogram in which all chromatograms in which various peaks appear in a plurality of analyzes are connected are collected.
[0024]
The chromatogram data is also input to the chromatogram creation unit 11 in parallel, whereby a chromatogram 30 that is sequentially updated as time passes is rendered on the screen of the display unit 19 as shown in FIG. . The analyst designates the start point and the end point of the time range desired to be a chromatogram for each analysis (sample injection) by moving the cursors 31 and 32 from the input unit 18 while visually confirming the chromatogram 30. The chromatogram extraction unit 14 that has received this instruction from the control unit 10 selects data belonging to the period from the time corresponding to the instructed start point to the time corresponding to the end point among the data collected by the chromatogram data collection unit 13. Extracted as chromatogram data corresponding to each analysis.
[0025]
For example, as shown in FIG. 3B, for the first analysis (sample injection), a time range starting from time t2 and ending at time t3 is designated, and for the second analysis (sample injection). If a time range starting from time t4 and ending at time t5 is designated, chromatogram data collected in each time range is extracted. This means that individual chromatograms corresponding to the respective time ranges are cut out from the entire chromatogram of the continuous analysis.
[0026]
On the other hand, the analysis information collection unit 15 is performed by the input unit 18 to change analysis condition file data for each analysis set by the control unit 10 in the schedule table or the like while the analyst performs analysis. Information accompanying various types of analysis such as an operation log representing a history of operation details or a status log for monitoring the state of an apparatus under analysis is collected.
[0027]
When a series of continuous analysis is completed, the file management unit 16 receives all the chromatogram data from the chromatogram data collection unit 13, receives the analysis supplementary information as described above from the analysis information collection unit 15, and stores them according to a predetermined format. The parent file 40 accommodated in the same file is created and stored in the external storage device 20. The analysis supplementary information accommodated in the parent file 40 corresponds to all of the continuous analysis.
[0028]
In addition, the file management unit 16 receives chromatogram data corresponding to each analysis from the chromatogram extraction unit 14, and for each analysis, the chromatogram data and the individual analysis supplementary information related to the analysis are stored in the same file according to a predetermined format. .. Are stored and associated with the parent file, for example, stored in the same folder and stored in the external storage device 20.
[0029]
That is, the parent file 40 includes all the chromatogram data collected during the series of continuous analysis executions, and the child files 411, 412,. Chromatogram data constituting a chromatogram for each analysis is included. Therefore, since the parent file 40 has chromatogram data of periods between individual chromatograms that are not included in the child files 411, 412,. It can be used when creating a summary report. On the other hand, since each child file 411, 412,... Includes analysis-accompanying information including parameters necessary for analyzing chromatogram data, it is possible to perform chromatogram waveform processing and quantitative calculation.
[0030]
In the above description, information (start point and end point) for the analyst to cut out individual chromatograms is input from the input unit 18 in parallel with the continuous analysis. It is also possible to read the stored parent file 40, display the entire chromatogram on the screen of the display unit 19, and instruct the start point and end point of the individual chromatograms in that state. In addition, a time range for acquiring individual chromatograms for each analysis may be designated in advance in a schedule table or the like, and the chromatogram extracting unit 14 may automatically select and collect necessary data according to the time ranges. In any case, individual chromatograms for each analysis can be cut out in any time range within the total chromatogram of the continuous analysis.
[0031]
In addition, when performing overlap injection in which the next sample is injected into the mobile phase before the components contained in the previously injected sample are completely eluted from the column 5, the second half of the chromatogram and the next As shown in FIG. 5, the peak P2 from the next analysis may appear before the peak P3 from the previous analysis as shown in FIG. Even in such a case, in the data processing apparatus according to the present embodiment, the cursor 33 indicating the start point of the chromatogram of the next analysis can be set before the cursor 32 indicating the end point of the chromatogram of the previous analysis. The chromatogram corresponding to the analysis can be appropriately cut out. The individual chromatograms cut out in this way include, for example, the peak P2 from the next analysis in addition to the original peaks P1 and P3 from the analysis. Such unwanted peaks can be eliminated by data processing.
[0032]
It should be noted that the above embodiment is merely an example of the present invention, and it is obvious that the present invention is encompassed by the present invention even if appropriate modifications and additions are made within the scope of the present invention.
[Brief description of the drawings]
FIG. 1 is an overall configuration diagram of an LC analyzer which is an embodiment of a chromatograph including a data processing apparatus according to the present invention.
FIG. 2 is a block diagram functionally showing constituent elements necessary to achieve an operation characteristic of the data processing apparatus according to the present embodiment.
FIG. 3 is an explanatory diagram of a data file creation operation in the data processing apparatus of the present embodiment.
FIG. 4 is a diagram illustrating an example of a display screen of a display unit during a data file creation operation in the data processing apparatus according to the embodiment.
FIG. 5 is a diagram showing another example of the display screen of the display unit during the data file creation operation in the data processing apparatus of the embodiment.
FIG. 6 is a schematic diagram showing a data file creation operation in a conventional LC data processing apparatus.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Eluent tank 2 ... Liquid feed pump 3 ... Auto injector 4 ... Auto sampler 5 ... Column 6 ... Detector 7 ... A / D converter 8 ... Personal computer (data processing part)
DESCRIPTION OF SYMBOLS 10 ... Control part 11 ... Chromatogram preparation part 12 ... Chromatogram display processing part 13 ... Chromatogram data collection part 14 ... Chromatogram extraction part 15 ... Analysis information collection part 16 ... File management part 17 ... Display control part 18 ... Input part 19: Display unit 20: External storage device

Claims (2)

In a data processing apparatus for a chromatograph that sequentially introduces a plurality of samples into a column and continuously analyzes various components contained in each sample,
Data collected sequentially with respect to the plurality of sample introductions are aggregated as a chromatogram data group constituting one chromatogram, and one data file is added together with analysis incidental information such as analysis conditions corresponding to the plurality of analyzes. A parent file creation means to create;
When an individual chromatogram creation request for each sample introduction is received, data in a predetermined time range is extracted from the chromatogram data included in the parent file, and the data and corresponding analysis supplementary information are extracted. A child file creation means for creating a child file including:
A chromatograph data processing apparatus comprising: A chromatogram creation means for receiving data sequentially collected by the plurality of sample introductions and creating a chromatogram as the analysis proceeds;
Display means for displaying the chromatogram;
Range indicating means for instructing an arbitrary clipping range of the chromatogram on the display screen of the display means in accordance with the operation of the analyst;
2. The chromatograph data processing apparatus according to claim 1, further comprising: a child file including the chromatogram data belonging to the cut-out range instructed by the range instructing unit. .

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