Data processing method, data processing system and computer program

Abstract

To acquire simulation data of a three-dimensional chromatogram of a sample including plural components, with a desired separation degree.SOLUTION: The present invention includes: a data preparation step of preparing chromatogram data and spectrum data of each of plural components; a parameter determination step of determining a parameter including respective ratios of the concentrations of the components in the sample and respective separation degrees of peaks of the component on a chromatogram; a data adjusting step of adjusting a peak area and a peak position of the chromatogram data of each composition on the basis of the parameter determined by the parameter determination step; and a matrix product step of calculating a matrix product of a spectrum data group made of the spectrum data of each composition and a chromatogram data group made of chromatogram data of each composition adjusted in the data adjustment step and preparing simulation data of a three-dimensional chromatogram of the sample on the basis of the calculation result.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a data processing method, a data processing system, and a computer program. [Background technology]

[0002] In a liquid chromatograph using a multichannel detector such as a photodiode array (PDA) detector (hereinafter referred to as LC-PDA), three-dimensional chromatogram data having three dimensions, time, wavelength, and signal intensity (absorbance), can be obtained by continuously acquiring the absorption spectrum of a sample eluting from an analytical column.

[0003] When quantifying a target component in a sample using a liquid chromatograph, it is common to create a chromatogram using the wavelength at which the target component has the greatest absorbance, and then determine the area value of the target component's peak on that chromatogram to perform quantification. However, a sample may contain impurities other than the target component, and the peaks of those impurities may overlap with the peak of the target component on the chromatogram. In such cases, if multiple peaks remain overlapping, it is not possible to determine the peak area values ​​of the target component and the impurities, and quantitative results cannot be obtained. Therefore, it is necessary to separate the multiple components whose peaks overlap on the chromatogram.

[0004] One method for separating overlapping peaks of multiple components is to estimate the chromatogram of each component by applying a model function (peak model) such as an EMG (Exponential Modified Gaussian) function to the waveform of the actual chromatogram (see Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 035167 Summary of the Invention [Problem to be solved by the invention]

[0006] When impurities are present in a sample at concentrations several hundredths to several thousandths of the concentration of the main component and the peaks of these components overlap, the peak separation method using the model function described above will result in the peak area value of the low-concentration component (impurity) being buried in the error between the actual component peak of the low-concentration component and the model function that simulates it, making it impossible to accurately determine the correct peak shape and size of the low-concentration component.

[0007] There is a demand for analysis of samples containing multiple components under analytical conditions that allow each component peak to be separated from the other components with a desired degree of resolution. However, when the peaks of multiple components with significantly different concentrations overlap, as described above, peak separation techniques using model functions cannot accurately estimate the shape and size of the peaks of low-concentration components, making it difficult to verify whether the degree of resolution of each component peak in the analytical data obtained by actually performing the analysis is as desired.

[0008] The inventors considered that if it were possible to accurately know in advance what kind of three-dimensional chromatogram data would be obtained depending on the concentrations of the multiple components contained in a sample and the degree of separation of the peaks of those components, it would be possible to verify whether the analytical data actually obtained has the desired degree of separation.

[0009] Therefore, an object of the present invention is to obtain simulation data of a three-dimensional chromatogram with a desired degree of resolution for a sample containing multiple components at desired concentrations. [Means for solving the problem]

[0010] A data processing method according to the present invention is a data processing method for creating simulation data of a three-dimensional chromatogram for a sample containing multiple components, and includes the following steps: a data preparation step for preparing chromatogram data and spectral data for each of the multiple components; a parameter determination step for determining parameters including the ratio of the concentrations of the multiple components in the sample to each other and the degree of resolution of the peaks of the multiple components to each other on the chromatogram; a data adjustment step for adjusting the peak areas and peak positions of the chromatogram data for each of the multiple components based on the parameters determined in the parameter determination step; and a matrix multiplication step for calculating the matrix product of a spectral data group consisting of the spectral data for each of the multiple components and a chromatogram data group consisting of the chromatogram data for each of the multiple components adjusted in the data adjustment step, and creating simulation data of a three-dimensional chromatogram for the sample based on the calculation results.

[0011] A data processing system according to the present invention is a data processing system that creates simulation data of a three-dimensional chromatogram for a sample containing multiple components, and includes a data storage unit that stores chromatogram data and spectral data for each of the multiple components, and a calculation processing unit that performs calculations using the data stored in the data storage unit. The calculation processing unit is configured to execute the following steps: a parameter determination step that determines parameters including the ratio of the concentrations of the multiple components in the sample and the degree of resolution of the peaks of the multiple components on the chromatogram, based on information input by a user; a data adjustment step that adjusts the peak areas and peak positions of the chromatogram data for each of the multiple components based on the parameters determined in the parameter determination step; and a matrix multiplication step that calculates the matrix product of a spectral data group consisting of the spectral data for each of the multiple components and a chromatogram data group consisting of the chromatogram data for each of the multiple components adjusted in the data adjustment step, and creates simulation data of a three-dimensional chromatogram for the sample based on the calculation results. [Effects of the Invention]

[0012] In the data processing method according to the present invention, chromatogram data for each of the multiple components is adjusted using parameters including the concentration and resolution of each of the multiple components, and the matrix product of the adjusted chromatogram data group and the spectral data group is calculated to obtain simulation data for a three-dimensional chromatogram. This allows for the acquisition of simulation data for a three-dimensional chromatogram when a sample containing multiple components at desired concentrations is analyzed so as to obtain the desired resolution.

[0013] In the data processing method according to the present invention, chromatogram data and spectral data of multiple components are prepared, and simulation data of a three-dimensional chromatogram corresponding to the determined parameters is obtained simply by determining parameters including the concentrations and resolution of each of the multiple components. Therefore, simulation data of a three-dimensional chromatogram obtained when a sample containing multiple components at desired concentrations is analyzed so as to obtain a desired resolution can be easily obtained. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 1 is a diagram illustrating the concept of a data processing method. [Figure 2] FIG. 1 is a schematic diagram illustrating an embodiment of a data processing system. [Figure 3] 3 is a flowchart showing a procedure of data processing executed in the embodiment. [Figure 4] 10 is a graph showing the verification results of the data processing in the same embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0015] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a data processing method and a data processing system according to the present invention will now be described with reference to the accompanying drawings.

[0016] First, the concept of data processing in this embodiment will be explained with reference to FIG.

[0017] Figure 1 shows the concept for generating simulated data of a three-dimensional chromatogram that would be obtained when a sample containing two components A and B is analyzed by LC-PDA.

[0018] To obtain the desired simulation data, it is necessary to prepare chromatogram data C(A) and spectrum data S(A) for component A, and chromatogram data C(B) and spectrum data S(B) for component B. The chromatogram data C(A) and C(B) and spectrum data S(A) and S(B) for components A and B, respectively, can be created by analyzing components A and B separately by LC-PDA, or by analyzing a sample containing components A and B under analytical conditions that completely separate the peaks of components A and B from each other, and then extracting the wavelengths and retention times at which the chromatogram information and spectrum information for each of components A and B can be read from the resulting three-dimensional chromatogram data.

[0019] The matrix of the chromatogram data group consisting of the prepared chromatogram data C(A) and C(B) of components A and B is TIFF0007732327000001.tif7151, and the matrix of the spectral data set consisting of spectral data S(A) and S(B) is TIFF0007732327000002.tif7151 The matrix of the three-dimensional chromatogram data obtained by analyzing components A and B using LC-PDA is TIFF0007732327000003.tif7151 Then, the following equation holds: TIFF0007732327000004.tif8151 Here, T is the transpose of a matrix. Therefore, the simulated data of a three-dimensional chromatogram for a sample containing components A and B is expressed as the matrix of the chromatogram data group: TIFF0007732327000005.tif7151 and the matrix of spectral data sets TIFF0007732327000006.tif7151 matrix multiplication of TIFF0007732327000007.tif8151 It can be found by calculating

[0020] Before calculating the matrix product, the peak areas in each chromatogram data can be adjusted so that the concentrations of components A and B contained in the sample are desired, and the positions of the peaks in each chromatogram data can be adjusted so that the degree of resolution between the peaks of components A and B is desired. Then, by performing the matrix product calculation using the adjusted data, it is possible to obtain simulation data of a three-dimensional chromatogram assuming that a sample containing components A and B at desired concentrations has been analyzed under analysis conditions such that the peaks of components A and B are separated from each other with the desired degree of resolution.

[0021] Next, an embodiment of a data processing system for executing the above data processing will be described with reference to FIG.

[0022] The data processing system 2 includes a data storage unit 4 and an arithmetic processing unit 6. The data processing system 2 can be constructed by installing a predetermined computer program in a computer device such as a personal computer that includes a CPU (Central Processing Unit) and a data storage device such as a hard disk drive or flash memory. The data storage unit 4 is a function realized by a partial storage area of ​​the data storage device, and the arithmetic processing unit 6 is a function realized by the CPU executing a predetermined program.

[0023] The data storage unit 4 stores chromatogram data and spectrum data for each of the multiple components contained in a sample for which simulation data of a three-dimensional chromatogram is to be generated. The chromatogram data and spectrum data for each of the multiple components stored in the data storage unit 4 may be extracted from the three-dimensional chromatogram data acquired by the LC-PDA, as described above, or may be read from a database connected to the data processing system 2 via a network. The data processing system 2 may also have a function for extracting the chromatogram data and spectrum data for each of the multiple components from the three-dimensional chromatogram data acquired by the LC-PDA.

[0024] The arithmetic processing unit 6 is configured to generate simulation data of a three-dimensional chromatogram using the data stored in the data storage unit 4. When generating the simulation data, the arithmetic processing unit 6 determines parameters, such as the concentrations of each of the multiple components contained in the sample and the resolution of the peaks of those components, based on information input by the user via an input device 8, such as a keyboard or mouse, and adjusts the peak areas and peak positions of the chromatogram data for each of the multiple components based on those parameters. That is, the arithmetic processing unit 6 changes each value of the chromatogram data matrix group C or adjusts the position of the values. The arithmetic processing unit 6 then calculates the matrix product of a matrix consisting of the adjusted chromatogram data group and a matrix consisting of the spectrum data group, thereby generating simulation data of a three-dimensional chromatogram for a sample containing multiple components at concentrations specified by the user, in which the peaks of those components are separated at the resolution specified by the user.

[0025] That is, the simulation data of the three-dimensional chromatogram is created by the procedure shown in FIG.

[0026] First, chromatogram data and spectrum data for each of the multiple components contained in the sample are prepared (stored in the data storage unit 4) (step 101). Parameters such as the concentration of each component in the sample and the degree of resolution of each component are determined by having the user input them (step 102). Once the parameters are determined, the chromatogram data for each component is adjusted by the calculation processing unit 6 so that the peak area and peak position correspond to the determined parameters (step 103).

[0027] Next, if desired by the user, or always, the calculation processing unit 6 adds a predetermined noise to each data (step 104). The noise can be added to the adjusted chromatogram data and / or spectrum data. Examples of the added noise include randomly generated noise and noise components measured when a blank solution is run through the LC analysis flow path. The type of noise to be added may be selected by the user.

[0028] Then, the calculation processing unit 6 is made to calculate the matrix product of the matrix of the chromatogram data group consisting of the adjusted chromatogram data and the matrix of the spectrum data group consisting of the spectrum data (step 105), and further, the calculation result is used to create simulation data of a three-dimensional chromatogram (step 106).

[0029] 4 shows a chromatogram at a certain wavelength showing the results of verification of simulation data created for a sample containing two components with a concentration ratio of 100:0.05. In this verification, simulation data (Example) created using the chromatogram data and spectrum data of each of the two components, and simulation data (Comparative Example) of a chromatogram created by combining the chromatograms of each of the two components simulated by a model function (Gaussian), were compared with chromatogram data (measurement data) obtained by actually analyzing the sample using LC-PDA.

[0030] The verification results show that the data of the comparative example reproduced using the model function deviates from the measured data at both ends of the peak where two components overlap. On the other hand, the data of the example matches the measured data over the entire peak. Therefore, by processing the data of the above example, it is possible to create highly accurate simulation data of a three-dimensional chromatogram for a sample containing multiple components with very large concentration differences.

[0031] The above-described embodiment is merely an example of an embodiment of the present invention. The following are embodiments of a data processing method, a data processing system, and a computer program according to the present invention.

[0032] One embodiment of the data processing method according to the present invention is a data processing method for creating simulation data of a three-dimensional chromatogram for a sample containing multiple components, and includes: a data preparation step for preparing chromatogram data and spectral data for each of the multiple components; a parameter determination step for determining parameters including the ratio of the concentrations of the multiple components in the sample to each other and the degree of resolution of the peaks of the multiple components to each other on the chromatogram; a data adjustment step for adjusting the peak areas and peak positions of the chromatogram data for each of the multiple components based on the parameters determined in the parameter determination step; and a matrix multiplication step for calculating the matrix product of a spectral data group consisting of the spectral data for each of the multiple components and a chromatogram data group consisting of the chromatogram data for each of the multiple components adjusted in the data adjustment step, and creating simulation data of a three-dimensional chromatogram for the sample based on the calculation results.

[0033] In the above embodiment, in the data adjustment step, a predetermined noise can be added to the chromatogram data and / or spectrum data of each of the plurality of components, thereby making it possible to obtain simulation data that is closer to the actual measurement data.

[0034] One embodiment of a data processing system according to the present invention is a data processing system that creates simulation data of a three-dimensional chromatogram for a sample containing multiple components, and includes a data storage unit that stores chromatogram data and spectral data for each of the multiple components, and a calculation processing unit that performs calculations using the data stored in the data storage unit. The calculation processing unit is configured to execute the following steps: a parameter determination step that determines parameters including the ratio of the concentrations of the multiple components in the sample and the degree of resolution of the peaks of the multiple components on the chromatogram based on information input by a user; a data adjustment step that adjusts the peak areas and peak positions of the chromatogram data for each of the multiple components based on the parameters determined in the parameter determination step; and a matrix multiplication step that calculates the matrix product of a spectral data group consisting of the spectral data for each of the multiple components and a chromatogram data group consisting of the chromatogram data for each of the multiple components adjusted in the data adjustment step, and creates simulation data of a three-dimensional chromatogram for the sample based on the calculation results.

[0035] In the above embodiment, the calculation processing unit may be configured to add a predetermined noise to the chromatogram data and / or spectrum data of each of the plurality of components in the data adjustment step, thereby obtaining simulation data that is closer to actual measurement data.

[0036] A computer program according to the present invention is configured to cause a computer to function as the above-described data processing system when installed in the computer. [Explanation of symbols]

[0037] 2. Data Processing System 4 Data storage unit 6. Processing unit 8 Input Devices

Claims

1. A data processing method for generating simulation data of a three-dimensional chromatogram for a sample containing multiple components using a computer, comprising: a data preparation step of storing chromatogram data and spectral data for each of the plurality of components in a data storage device of the computer; a parameter determination step of determining parameters including a ratio of the concentrations of the plurality of components in the sample and a degree of resolution of the peaks of the plurality of components on a chromatogram by having a user input the parameters to the computer; a data adjustment step of adjusting peak areas of the chromatogram data of each of the multiple components based on the ratios of the concentrations of the multiple components determined in the parameter determination step, and adjusting peak positions of the chromatogram data of each of the multiple components based on the resolution of the peaks of the multiple components determined in the parameter determination step; a matrix multiplication step of calculating a matrix product of a spectral data group consisting of spectral data for each of the plurality of components and a chromatogram data group consisting of chromatogram data for each of the plurality of components adjusted in the data adjustment step, and, based on the calculation result, creating simulation data of a three-dimensional chromatogram in which the peaks of the plurality of components are separated at the resolution input by the user to the computer in the parameter determination step for the sample containing the plurality of components in the concentration ratio input by the user to the computer in the parameter determination step.

2. 2. The data processing method according to claim 1, wherein the data adjustment step adds a predetermined noise to the chromatogram data and / or spectrum data of each of the plurality of components.

3. A data processing system for generating simulation data of a three-dimensional chromatogram for a sample containing multiple components, comprising: a data storage unit that stores chromatogram data and spectral data for each of the plurality of components; a calculation processing unit that performs calculation processing using the data stored in the data storage unit, The arithmetic processing unit a parameter determination step of requesting a user to input parameters including the ratio of the concentrations of the plurality of components in the sample to each other and the degree of resolution of the peaks of the plurality of components to each other on a chromatogram, and having the user input the parameters to determine the parameters; a data adjustment step of adjusting peak areas of the chromatogram data of each of the multiple components based on the ratios of the concentrations of the multiple components determined in the parameter determination step, and adjusting peak positions of the chromatogram data of each of the multiple components based on the resolution of the peaks of the multiple components determined in the parameter determination step; a matrix multiplication step of calculating a matrix product of a spectral data group consisting of spectral data of each of the plurality of components and a chromatogram data group consisting of chromatogram data of each of the plurality of components adjusted in the data adjustment step, and, based on the calculation result, creating simulation data of a three-dimensional chromatogram in which the peaks of the plurality of components are separated with the degree of resolution determined in the parameter determination step for the sample containing the plurality of components in the concentration ratio determined in the parameter determination step.

4. 4. The data processing system according to claim 3, wherein the arithmetic processing unit is configured to add a predetermined noise to the chromatogram data and / or the spectrum data of each of the plurality of components in the data adjustment step.

5. A computer program configured to cause a computer to function as the data processing system according to claim 3 or 4 when installed in the computer.