JP2011153966A - Data processing method and data processor for three-dimensional chromatogram - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a data processing method and a data processor for three-dimensional chromatograms capable of error identification in the component comparison of a plurality of samples. <P>SOLUTION: In the data processor 20 for three-dimensional chromatograms, a max plot extraction part 31, a peak information acquisition part 32, a pole information acquisition part 33, and a first peak list creation part 34 list up information including the peak top time (retention time) and a local maximum wavelength of each peak to three-dimensional chromatograms of the plurality of samples to create a first peak list. A list comparison part 35 compares peaks between the samples on the first peak list and determines whether compares peaks are a peak of the same and one component on the basis of whether a displacement of the retention time and a displacement in the maximum wavelength are both included in prescribed allowable ranges to list up the peak intensity of each peak in a second peak list creation part 36 for each sample to crate a second peak list. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a chromatograph mass spectrometer combining a chromatograph such as a gas chromatograph (GC) or a liquid chromatograph (LC) and a mass spectrometer, or a liquid chromatograph using a photodiode array detector as a detector. The present invention relates to a data processing method and a data processing apparatus for a chromatograph capable of acquiring three-dimensional chromatogram data having a third dimension such as m / z and wavelength in addition to time and intensity.

  Gas chromatograph mass spectrometer (GC / MS) and liquid chromatograph mass spectrometer (LC / MS) separate sample components temporally with a GC or LC column and ionize each separated component. It has a configuration in which ions are separated and detected according to m / z. Here, a mass spectrum is created by taking m / z on the horizontal axis and intensity on the vertical axis, focusing on a specific time, and focusing on time on the horizontal axis, focusing on one specific m / z. A mass chromatogram is created by taking the vertical axis. Also, by integrating these, a three-dimensional chromatogram with axes of time, intensity (ion intensity), and m / z can be created.

  In addition, a GC analyzer or LC analyzer allows a mobile phase to flow through a GC column or LC column at a constant flow rate, injects a sample into the mobile phase, and temporally passes each component while passing through the column. It has a configuration in which a sample separated and eluted from the column is detected by a detector. Here, by using, for example, a detector having a photodiode array (hereinafter referred to as “PDA detector”) as a detector, the time, intensity (absorbance of sample components, fluorescence intensity, emission intensity, etc.), wavelength, etc. A three-dimensional chromatogram with axes can be created.

  In these three-dimensional chromatograms, the wavelength and m / z at which the maximum intensity appears generally differ for each sample component. Therefore, when performing quantitative analysis of a target component from a three-dimensional chromatogram in a conventional chromatograph data processing device, a two-dimensional chromatogram of a specific wavelength or m / z where the maximum intensity of the target component appears is drawn. The peaks of the two-dimensional chromatogram are separated by waveform processing, and each peak intensity (peak height or area) is calculated.

  On the other hand, there are cases where it is desired to use a three-dimensional chromatogram acquired for each of a plurality of samples to compare the components (peaks) contained in those samples and to analyze changes in the component amount (peak intensity). Examples of this include pre- and post-comparison in accelerated degradation tests such as heating and UV irradiation, good / defective product discrimination in product inspection and acceptance inspection, quality prediction model construction, investigation of the cause of defective products, comparison of products from other companies in the same industry, food production areas There is discrimination. In these inspections and discriminations, it is necessary to compare not only the components showing characteristic peaks but also the overall similarity. However, as described above, if only the main peaks are picked up from the entire 3D chromatogram and only 2D chromatograms of those specific wavelengths and m / z are drawn, it is possible to miss minute changes. Sometimes. In addition, when the number of two-dimensional chromatograms created for one sample increases, the calculation time increases and the analysis becomes difficult.

  On the other hand, in Non-Patent Document 1, for example, the maximum intensity (absorbance) in each holding time in a predetermined wavelength range (400-600 nm) is plotted from a three-dimensional chromatogram obtained by a PDA detector. By creating a dimensional chromatogram for each sample, components are compared among a plurality of samples. Here, a two-dimensional chromatogram in which the intensity at a wavelength (m / z in an analyzer equipped with a mass spectrometer) showing the maximum intensity of each holding time in this predetermined wavelength range is generally referred to as a “max plot”. is called. The two-dimensional chromatogram of this Max Plot can capture a minute change in the three-dimensional chromatogram, and since only one is created for one sample, it is suitable for analysis between a plurality of samples.

"Application of high-speed and high-separation analysis (5) Analysis of synthetic colorants" Shimadzu Application News No. L349, [Online], Shimadzu Corporation, [Search January 18, 2010], Internet <URL: https: //solutions.shimadzu.co.jp/cgi/ac?cmd=1&url=/solnavi/s/apl/a-news/1/l/pdf/l349.pdf>

  When comparing components between a plurality of samples, it is necessary to first check whether the unknown components detected in each sample are the same. Even in the comparison between the max plots for each sample in Non-Patent Document 1, this confirmation compares the time at the peak top of the peak detected for each sample, and the deviation is within a predetermined allowable range. This is done by determining whether it is included. However, in this determination method, different components having the same or very close peak top time may be regarded as the same component, which has caused erroneous identification.

  The problem to be solved by the present invention is to provide a three-dimensional chromatogram data processing method and data processing apparatus capable of preventing erroneous identification in component comparison of a plurality of samples.

A data processing method for a three-dimensional chromatogram according to the present invention made to solve the above-mentioned problems,
A data processing method for a three-dimensional chromatogram obtained from each of a plurality of samples and having a third variation in addition to time and intensity,
a) Max plot rendering process for creating a two-dimensional chromatogram by plotting the maximum value of the intensity of each holding time against a three-dimensional chromatogram of one sample selected from a plurality of samples;
b) Peak information acquisition process for detecting peaks from the two-dimensional chromatogram and acquiring the peak top time and peak intensity of each peak;
c) In the three-dimensional chromatogram of the selected sample, for each peak top time, an extreme point information obtaining process for obtaining a value of a third change amount at which the intensity becomes maximum and / or minimum;
d) A first peak for creating a first peak list including at least information on the peak top time of each peak and the value of the third variation obtained in the pole information acquisition process for the selected sample. List creation process,
e) Each peak in the first peak list is compared between different samples, and whether the compared peaks are peaks of the same component or not is obtained in the peak top time and peak information acquisition process of the peak. A list comparison process for discriminating based on the value of the change amount of 3,
f) a second peak list creation process for creating a second peak list in which the peak intensities of the peaks classified in the list comparison process are listed for each sample;
It is characterized by having.

In addition, a data processing apparatus for a three-dimensional chromatogram according to the present invention made to solve the above problems is
A data processing apparatus for a three-dimensional chromatogram obtained from each of a plurality of samples and having a third variation in addition to time and intensity,
a) Max plot drawing means for creating a two-dimensional chromatogram by plotting the maximum value of the intensity of each holding time against a three-dimensional chromatogram of one sample selected from a plurality of samples;
b) Peak information acquisition means for detecting a peak from the two-dimensional chromatogram and acquiring the peak top time and peak intensity of each peak;
c) In the three-dimensional chromatogram of the selected sample, for each peak top time, extreme point information acquisition means for acquiring a value of a third change amount at which the intensity becomes maximum and / or minimum;
d) A first peak for creating a first peak list including at least information on the peak top time of each peak and the value of the third variation obtained by the pole information acquisition means for the selected sample. List creation means;
e) Each peak of the first peak list is compared between different samples, and whether the compared peaks are peaks of the same component or not is obtained by the peak top time of the peak and the pole information acquisition means. List comparison means for discriminating based on the value of the change amount of 3,
f) second peak list creating means for creating a second peak list in which the peak intensities of the peaks classified by the list comparing means are listed for each sample;
It is characterized by having.

  The “three-dimensional chromatogram” in the present invention is obtained continuously (or almost continuously) in the axial direction of the third variation, as in a chromatogram obtained from a PDA detector. Alternatively, a small number of chromatograms may be intermittently arranged in the axial direction of the third change amount. The third change amount typically includes the above-described wavelength and m / z. The “peak intensity” in the present invention is a peak area and / or a peak height.

  In the three-dimensional chromatogram data processing method and data processing apparatus according to the present invention, it is desirable to perform multivariate analysis based on the second peak list created in the second peak list creation process. As a method of multivariate analysis, principal component analysis, PLS regression analysis, discriminant analysis, and cluster analysis can be suitably used. Also, multiple regression analysis can be used as a technique other than multivariate analysis.

According to the data processing method and data processing apparatus for a three-dimensional chromatogram according to the present invention, in comparing peaks between a plurality of samples, the peak top time and the intensity of the three-dimensional chromatogram at the peak top time are maximized and / or The value of the third change amount that is the minimum is used for the determination. The value of the third change amount used for this determination represents the waveform information in the axial direction of the third change amount, and is unique to each component. Therefore, erroneous identification is performed rather than using only the peak top time. It becomes possible to prevent.

The whole block diagram of the analysis system provided with one Example of the data processing apparatus for three-dimensional chromatogram which concerns on this invention. The figure which shows an example of a three-dimensional chromatogram (a), the figure which shows the max plot created from this three-dimensional chromatogram (b), and the figure which shows the spectrum waveform in the specific time of this three-dimensional chromatogram (c). The flowchart which shows the procedure of the data processing in a present Example. The figure which shows an example of the 1st peak list produced by a present Example (a), and the figure which shows an example of the 2nd peak list created from this 1st peak list (b). The graph which shows the max plot created with respect to each of three types of coffee drinks used as a sample. The figure which shows the 1st peak list | wrist of each sample produced by the conventional method. The figure which shows the 2nd peak list produced by the conventional method. The figure which shows the 1st peak list | wrist of each sample created by a present Example. The figure which shows the 2nd peak list produced by a present Example. The graph which shows the result of having performed the principal component analysis based on the 2nd peak list created by the present Example.

  The case where the three-dimensional chromatogram data processing apparatus according to the present invention is applied to a liquid chromatograph analysis apparatus using a PDA detector as a detector will be described as an example. FIG. 1 is an overall configuration diagram of the analysis system of this embodiment.

  The analysis system in FIG. 1 is roughly divided into an analysis device 10 and a data processing device 20. The analyzer 10 includes an eluent tank 11 that stores an eluent (mobile phase), a liquid feed pump 12 that sucks the mobile phase from the eluent tank 11, and a mobile phase that is aspirated by the liquid feed pump 12. An interface including an injector 13 for injecting a sample solution, a column oven 16 including a guard column 14 and a main column 15, a PDA detector 17 provided at the outlet of the main column 15, an amplifier, an A / D converter, and the like (I / F) 18 and a control unit 19 that controls the operation of each unit described above.

  On the other hand, the data processing device 20 is embodied by, for example, a personal computer in which a dedicated control / data processing program is installed, and a main processing unit 21 including a CPU and a ROM, and a storage unit 22 including a large-capacity storage device such as a hard disk. And a monitor (display unit) 24 composed of an LCD (Liquid Crystal Display) or the like and an input unit 25 composed of a keyboard, a mouse or the like are connected via an input / output control unit 23. The storage unit 22 is provided with a three-dimensional chromatogram storage unit 221 and a control / data processing program 222.

  When performing chromatographic analysis in the above analysis system, first, the mobile phase is caused to flow into the main column 15 at a constant flow rate by the liquid feed pump 12, and the sample liquid is injected into the mobile phase from the injector 13. 15 While the injected sample passes through the main column 15, the components in the sample are separated with different retention times. The PDA detector 17 disperses the absorbance, fluorescence intensity, emission intensity, and the like of each component eluted from the main column 15 in the wavelength direction at predetermined time intervals and detects them as detection signals at the respective wavelengths. This detection signal is converted into a digital signal by the I / F 18 and sent to the main processing unit 21. For example, a three-dimensional chromatogram composed of time, absorbance (intensity), and wavelength as shown in FIG. Is created, and the data is stored in the three-dimensional chromatogram storage unit 221 in the storage unit 22. These processes are sequentially performed on a plurality of samples, and data constituting each three-dimensional chromatogram is stored in the three-dimensional chromatogram storage unit 221 as a data file for each sample.

  Further, in the data processing device 20 of the present embodiment, as a characteristic feature of the present invention, a max plot rendering unit 31, a peak information acquisition unit 32, a pole information acquisition unit 33, a first peak list creation unit 34, a list comparison unit 35, a second peak list creation unit 36 is provided. These are realized by software by the main processing unit 21 executing the control / data processing program 222, and for the three-dimensional chromatograms of a plurality of samples stored as data files in the three-dimensional chromatogram storage unit 221, Data processing is executed according to the flowchart of FIG. Hereinafter, the data processing procedure will be described with reference to the flowchart of FIG.

First, the main processing unit 21 selects one of three-dimensional chromatogram data files created for each of a plurality of samples, and reads it from the storage unit 22 (step S1). And with respect to this selected three-dimensional chromatogram, the max plot drawing part 31 plots the maximum intensity | strength of each holding time in the predetermined wavelength range which the user set, and produces a two-dimensional chromatogram (step S2). . As a result, a two-dimensional chromatogram (max plot) obtained by projecting the three-dimensional chromatogram onto a plane including the time axis and the intensity axis can be obtained (FIG. 2B). Here, the wavelength range for creating the max plot can be appropriately selected by the user according to the components that can be included in the sample. Also, when using a liquid chromatograph and an organic buffer such as formic acid or acetic acid as the mobile phase, absorption by the mobile phase occurs in the short wavelength region, so avoid the short wavelength region in this case. Is preferred.
When drawing the max plot, as described above, plot the maximum intensity at each time in the predetermined wavelength range, but the average value of the intensity in the vicinity of the wavelength showing the maximum intensity for the purpose of noise removal etc. May be plotted.

  In step S3, each peak appearing in the two-dimensional chromatogram created in step S2 is detected by the peak information acquisition unit 32, and its retention time (peak top time) and peak intensity (peak area and / or peak height, etc.). Is acquired.

  In step S4, a two-dimensional graph (spectrum waveform shown in FIG. 2 (c)) is cut out for each holding time acquired in step S3 from the three-dimensional chromatogram read out in step S1, and a pole information acquisition unit is extracted. 33 obtains the wavelength at which the intensity is maximum in the two-dimensional graph (hereinafter referred to as “maximum wavelength”). The results obtained in step S3 and step S4 are listed by the first peak list creation unit 34, and a first peak list having information on the retention time and maximum wavelength of each peak as shown in FIG. It is created (step S5). In the first peak list shown in FIG. 4A, in addition to the retention time (second column) and the maximum wavelength (third column) of each peak, the peak intensity (fourth column) of each sample is also shown. It is described.

  Note that a plurality of maximum wavelengths may be obtained for one peak as shown in FIG. In this embodiment, only the maximum wavelength is acquired. However, only the minimum point of the wavelength (hereinafter referred to as “minimum wavelength”) at a specific holding time may be acquired. Moreover, you may make it acquire both a maximum wavelength and a minimum wavelength.

  Next, in step S6, it is determined whether or not the first peak list has been created for the three-dimensional chromatograms of all the samples. If there is a data file that is not yet listed, the remaining data files are stored. Similarly, the processes of steps S1 to S5 are performed.

  In step S7, each peak in the first peak list created in steps S1 to S6 is compared between different samples, and it is determined whether the compared peaks are peaks of the same component. This determination method will be described with reference to the table of FIG. In the table shown in FIG. 4A, the ch1 to ch3 peaks are detected for the sample A, and the ch4 to ch6 peaks are detected for the sample B. Here, the list comparison unit 35 determines whether or not the component corresponding to each peak of the sample A is included in the sample B. It should be noted that the allowable range of holding time shift used for determination is 0.1 min, and the allowable range of maximum wavelength shift is 3 nm.

  First, comparing the holding time of ch1 of sample A and the holding times of ch4 to ch6 of sample B, the peak of sample B having the holding time closest to the holding time of ch1 is ch4, and holding of ch1 and ch4 It can be seen that the time lag is within the allowable range. Here, when comparing the maximum wavelengths of ch1 and ch4, the number of maximum wavelengths obtained for these peaks is one, and the shift of the maximum wavelength is included in the allowable range. Therefore, the ch1 peak of sample A and the ch4 peak of sample B are determined to be peaks of the same component.

  Next, the ch2 holding time of sample A is compared with the holding times of the remaining peaks (ch5 and ch6) of sample B, respectively. As a result, it can be seen that the peak of the sample B having the retention time closest to the retention time of ch2 is ch5, and the deviation of the retention times of ch1 and ch4 is included in the allowable range. Here, when the maximum wavelengths of ch2 and ch5 are compared, the number of maximum wavelengths obtained for these peaks is two, and the shift of each maximum wavelength is included in the allowable range. Accordingly, the ch2 and ch5 peaks are also determined to be the same component.

Finally, when the holding time of ch3 of sample A and the holding time of ch6 of sample B are compared, the deviations of these holding times are included in the allowable range. However, the number of maximum wavelengths of ch3 is one while the number of maximum wavelengths of ch6 is two. The maximum wavelength of ch3 shows a value very close to one of the maximum wavelengths of ch6, but since there is no maximum wavelength corresponding to the other of ch6, these are determined to be different components.
As described above, whether or not each peak in the first peak list for each sample is the peak of the same component in step S7 is determined by the peak top time and the maximum obtained by the extreme point information acquisition unit 33. This is performed based on the value of the third change amount that is minimal. That is, the determination is made based on whether or not the peak top time between the peaks in the list to be compared and the deviation of each of the third change amounts are within a predetermined allowable range.

The above is the determination method by the list comparison unit 35. The results are compiled by the second peak list creation unit 36, and as a result, the second peak list shown in FIG. 4B is created (step S8). In the second peak list of FIG. 4B, ch1 and 4 are grouped together in one row as peaks of the same component, and ch2 and 5 are similarly grouped in one row as peaks of the same component. On the other hand, since it is determined that ch3 and ch6 are peaks of different components, they are separated into different lines. Since the component corresponding to the peak of ch3 does not exist in sample B, the peak intensity of ch3 in sample B is input as zero. Similarly, in sample A, the peak intensity of ch6 is input as zero.
The peaks of ch3 and ch6 are peaks that are determined to be the same component in the determination performed only for the conventional holding time. In the data processing apparatus of the present invention, it is possible to appropriately determine a different component even for such a peak that is easily misidentified.

  Although the processing characteristic of the data processing apparatus of the present embodiment is as described above, a data analysis method such as multivariate analysis can be further used based on the second peak list created in step S8. Since the second peak list created by the data processing apparatus of this embodiment is more appropriately compared between components than the conventional data processing apparatus, the analysis accuracy can be improved in the subsequent analysis.

  Next, each peak list created by the data processing apparatus of this embodiment is compared with a peak list created by a conventional method while referring to actual experimental data. In this experiment, three types of coffee beverages (freeze-dried solution, can beverage, and bean extract) were prepared, and the components contained in each coffee beverage were compared. The analysis conditions are as follows.

  The liquid chromatograph analyzer used was the Prominence UFLC series (manufactured by Shimadzu Corporation). 10 mM phosphate buffer / AcN is used as the mobile phase, and the ratio is 90/10 from the start of analysis for 5 min, 70/30 from 5 min to 15 min, 30/70 from 15 min to 18 min, from 30/70, 18 min. Up to 25 min was 90/10. The flow rate was 1.0 mL / min. Shim-pack VP-ODS (Shimadzu Corporation, 4.6 mm I.D. × 150 mm L., 5 μm) is used for the main column 15, and Shim-pack GVP-ODS (Shimadzu Corporation, 4.6 mm I.D) is used for the guard column 14. . × 10 mmL) was used. The temperature of the column oven 16 was 40 ° C. Further, the detection wavelength range of the PDA detector 17 was 190-800 nm and the bandwidth was 4 nm.

  FIG. 5 shows the results of analyzing the three types of coffee beverages under the above-described analysis conditions and drawing the max plot for the three-dimensional chromatograms created for each sample. The wavelength range of the max plot was 220-400 nm. In addition, LC Solution (manufactured by Shimadzu Corporation), which is an LC workstation for liquid chromatographs, was used for creating the max plot.

For each of the max plots (two-dimensional chromatograms) of FIG. 5, a conventional method creates a first peak list as shown in FIG. The first peak list shown in FIG. 6 is a list that does not have the maximum wavelength column in the first peak list of this embodiment. In the conventional method, each peak is compared between samples from the first peak list created as shown in FIG. 6, and the peaks that are compared depending on whether or not the deviation of the retention time is included in the allowable range are peaks of the same component. Are integrated into one peak list. FIG. 7 is a second peak list created when the allowable range of holding time deviation is 0.1 min. In the second peak list created by the conventional method shown in FIG. 7, it can be seen that it is determined that 31 types of ingredients are included in the 3 types of coffee beverages.
Note that the ch number of the first peak list of each sample shown in FIG. 6 and the ch number of the second peak list shown in FIG. 7 do not correspond in particular. The channel numbers of the second peak list in FIG. 7 are obtained by arranging the peaks in the order of holding time when the first peak list is combined into one list, and numbering them in order from 1.

On the other hand, in the method of the present embodiment, the maximum wavelength data for each holding time is also input to the first peak list. FIG. 8 is a first peak list of each sample created by the method of this example. Further, FIG. 9 shows a result obtained by comparing these three first peak lists with each other by the determination method shown in step S6 and collecting them into one list.
Note that the determination condition in step S6 was that the allowable range of holding time deviation was 0.1 min, and the allowable range of maximum wavelength deviation was 3 nm. Further, in the second peak list of FIG. 9, columns of retention time and maximum wavelength are added so that the correspondence relationship with the peak lists of FIGS. 7 and 8 can be easily understood. Furthermore, the channel numbers in FIG. 9 are the same as the peak list in FIG. 7, but are simply renumbered from 1 in order of retention time when the first peak list in FIG. 8 is combined into one list. The channel numbers in FIG. 7 do not particularly correspond.

  As shown in the second peak list of FIG. 9, the data processing device 20 of this embodiment determines that 36 types of ingredients are included in 3 types of coffee beverages, and 10 types of ingredients in the conventional method. Is misidentified as 5 components. Specifically, the peaks of ch4 and 5 in the second peak list of FIG. 9 created in the present embodiment are determined to be the same component peak in the peak list of FIG. 7 (corresponding to ch4 of FIG. 7). . In addition, ch8, 9, 12, 13, 16, 17, 18, and 19 in FIG. 9 are erroneously identified in the peak list in FIG.

  Further, FIG. 10 shows the result of principal component analysis which is one of multivariate analysis based on the second peak list of FIG. Here, the score plot of FIG. 10A shows the difference between the samples. In FIG. 10 (a), it can be seen that the can beverage, the freeze-dried solution, and the bean extract are arranged in this order in the direction of the first main component. This result shows that the can beverage and the bean extract are the most different among the three types of coffee beverages, and the freeze-dried solution is in the middle. Note that the contribution ratios of the first principal component and the second principal component were 70.2% and 29.8%, respectively, indicating that the first principal component contributed greatly.

  In addition, the loading plot shown in FIG. 10B shows the difference between the main components of each peak. Each number in FIG. 10B corresponds to the ch number in the second peak list in FIG. As shown in FIG. 10B, many peaks appear on the positive side of the first main component. It can be seen from FIG. 10 (a) that the components corresponding to these peaks are more in canned beverages and less in bean extract.

  The component of ch17 shown in FIG. 10 (b) is a peak that is erroneously identified only by the holding time. From these results, it is understood that when identification is performed only with the holding time, there is a possibility that the characteristic peak may be overlooked and the original difference may be overlooked.

  In the example described above, in the determination condition in step S6, the allowable range of deviation of the holding time was 0.1 min and the allowable range of deviation of the maximum wavelength was 3 nm. It can be appropriately changed according to the result.

DESCRIPTION OF SYMBOLS 10 ... Analyzer 11 ... Eluent tank 12 ... Liquid feed pump 13 ... Injector 14 ... Guard column 15 ... Main column 16 ... Column oven 17 ... PDA detector 18 ... Interface (I / F)
DESCRIPTION OF SYMBOLS 19 ... Control part 20 ... Data processing device 21 ... Main processing part 22 ... Storage part 221 ... Three-dimensional chromatogram storage part 222 ... Control / data processing program 23 ... Input / output control part 24 ... Monitor (display part)
25 ... Input unit 31 ... Maxplot drawing unit 32 ... Peak information acquisition unit 33 ... Pole information acquisition unit 34 ... First peak list creation unit 35 ... List comparison unit 36 ... Second peak list creation unit

Claims (8)

A data processing method for a three-dimensional chromatogram obtained from each of a plurality of samples and having a third variation in addition to time and intensity,
a) Max plot rendering process for creating a two-dimensional chromatogram by plotting the maximum value of the intensity of each holding time against a three-dimensional chromatogram of one sample selected from a plurality of samples;
b) Peak information acquisition process for detecting peaks from the two-dimensional chromatogram and acquiring the peak top time and peak intensity of each peak;
c) In the three-dimensional chromatogram of the selected sample, for each peak top time, an extreme point information obtaining process for obtaining a value of a third change amount at which the intensity becomes maximum and / or minimum;
d) A first peak for creating a first peak list including at least information on the peak top time of each peak and the value of the third variation obtained in the pole information acquisition process for the selected sample. List creation process,
e) Each peak in the first peak list is compared between different samples, and whether the compared peaks are peaks of the same component or not is obtained in the peak top time and peak information acquisition process of the peak. A list comparison process for discriminating based on the value of the change amount of 3,
f) a second peak list creation process for creating a second peak list in which the peak intensities of the peaks classified in the list comparison process are listed for each sample;
A data processing method for a three-dimensional chromatogram, comprising:   The three-dimensional chromatogram data processing method according to claim 1, wherein the third change amount is a wavelength or m / z.   3. The three-dimensional chromatogram data processing method according to claim 1, wherein multivariate analysis is performed based on the second peak list.   3. The data processing method for a three-dimensional chromatogram according to claim 1, wherein multiple regression analysis is performed based on the second peak list. A data processing apparatus for a three-dimensional chromatogram obtained from each of a plurality of samples and having a third variation in addition to time and intensity,
a) Max plot drawing means for creating a two-dimensional chromatogram by plotting the maximum value of the intensity of each holding time against a three-dimensional chromatogram of one sample selected from a plurality of samples;
b) Peak information acquisition means for detecting a peak from the two-dimensional chromatogram and acquiring the peak top time and peak intensity of each peak;
c) In the three-dimensional chromatogram of the selected sample, for each peak top time, extreme point information acquisition means for acquiring a value of a third change amount at which the intensity becomes maximum and / or minimum;
d) A first peak for creating a first peak list including at least information on the peak top time of each peak and the value of the third variation obtained by the pole information acquisition means for the selected sample. List creation means;
e) Each peak of the first peak list is compared between different samples, and whether the compared peaks are peaks of the same component or not is obtained by the peak top time of the peak and the pole information acquisition means. List comparison means for discriminating based on the value of the change amount of 3,
f) second peak list creating means for creating a second peak list in which the peak intensities of the peaks classified by the list comparing means are listed for each sample;
A data processing apparatus for a three-dimensional chromatogram, comprising:   6. The three-dimensional chromatogram data processing apparatus according to claim 5, wherein the third change amount is a wavelength or m / z.   7. The three-dimensional chromatogram data processing apparatus according to claim 5, wherein multivariate analysis is performed based on the second peak list.   7. The three-dimensional chromatogram data processing apparatus according to claim 5, wherein multiple regression analysis is performed based on the second peak list.

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