JP2879782B2 - Data processor for multi-wavelength detector - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a data processing device for a multi-wavelength detector, and more particularly to an improvement in a qualitative / quantitative method and device for multiple components.

[Related Art] Liquid chromatography is widely used to analyze various components in a liquid.

This liquid chromatography is composed of a sample separation unit such as a pump, an injector and a column, and a chromatogram measurement unit, and separates a mixture sample composed of a plurality of components into each component in the sample separation unit. This is to obtain a single wavelength visible chromatogram.

In the chromatogram, peak detection is performed by a data processor, components corresponding to the peak are identified from the elution time of each peak, and a quantitative value is calculated from the peak area or height.

[Problems to be Solved by the Invention] However, conventional liquid chromatography has a problem that it is extremely difficult to detect a plurality of components by one analysis operation.

That is, each component of the mixture sample has an ultraviolet / visible absorption spectrum having a maximum absorption wavelength unique to the component.

For example, FIG. 5 shows absorption spectra of various components. FIG. 5 (A) shows the spectrum of naphthalene, FIG. 5 (B) shows the spectrum of anthracene, and FIG. 5 (C) shows the spectrum of pyrene. As is clear from the figure, the maximum absorption wavelengths of naphthalene, anthracene and pyrene are 221 nm, 251 nm and 241 nm, respectively.

However, in conventional liquid chromatography, only one chromatogram of one specific wavelength can be obtained in one analysis operation. Therefore, even for a mixture of these three components, a quantitative calculation must be performed using a chromatogram near 250 nm. Did not.

Here, as shown in FIG. 5 (B), in the case of anthracene, the absorption around 250 nm is high and there is no problem in its detection, but as shown in FIG. 5 (A), the absorption of naphthalene near 250 nm is small. It is expected that the quantification accuracy is poor.

In fact, FIG. 6 shows a calibration curve of naphthalene, wherein FIG. 6A shows a calibration curve at 251 nm, and FIG. 6B shows a calibration curve at 221 nm. As is clear from the figure, the calibration curve at 221 nm has much better quantitative accuracy. Nevertheless, conventional devices often had to perform analysis at 251 nm.

Recently, in order to solve such a problem, an ultraviolet / visible single-wavelength detector is used, and a device that changes the detection wavelength by a time program has been developed. Preliminary experiments must be performed and the detection wavelength must be time programmed to the time at which each component elutes. The necessity of such preliminary experiments becomes a serious problem particularly when the amount of the sample is extremely small, such as a biological sample.

Furthermore, peaks at a plurality of wavelengths overlap for components having substantially the same elution time, and it was impossible to analyze using the time program.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the related art, and an object of the present invention is to provide a data processing device of a multi-wavelength detector that can simultaneously and accurately analyze a plurality of components in a sample.

[Means for Solving the Problems] In order to achieve the above object, a data processing device for a multi-wavelength detector according to the present invention comprises: A multi-wavelength detection unit that repeats sampling, a storage unit that stores spectrum data at each measurement wavelength output from the multi-wavelength detection unit, and a timing, and a plurality of identical wavelength spectrum sequences stored in the storage unit A wavelength selection unit that allows a plurality of chromatogram data of a desired wavelength to be selected from the chromatogram data, a predicted component that may appear in the chromatogram at each of the measurement wavelengths, its retention time, the measurement wavelength, and the standard sample concentration, A peak identification table having peak identification data including quantitative data such as a slope of a calibration curve; From the table, read the peak identification data corresponding to the selected wavelength, and by comparing the peak identification data corresponding to the selected chromatogram and the wavelength, an identification processing unit that identifies components that appeared in the chromatogram at each selected wavelength. And an output unit for unitarily outputting analysis data including the component names and concentrations of the components identified by the identification processing unit in a predetermined order.

[Operation] Since the data processing device according to the present application has the above-described means, a plurality of chromatogram data of a desired wavelength can be selected from the chromatogram data of a plurality of wavelengths detected by the multi-wavelength detector.

Therefore, the component can be identified from the chromatogram data of the wavelength optimal for the component to be measured.

In addition, since a plurality of chromatogram data that can be used for output can be arbitrarily set, analysis of a plurality of components can be performed extremely efficiently.

Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings.

FIG. 1 shows a main configuration of the liquid chromatography used in the present invention.

In FIG. 1, a sample liquid containing a plurality of components is supplied to an inflow end 10a of a column 10, and a separated liquid separated for each component flows out of an outflow end 10b. An ultraviolet / visible multi-wavelength detector 12 is provided downstream of the outflow end 10b.

Here, the multi-wavelength detector 12 is configured as shown in FIG.

That is, the multi-wavelength detector 12 includes a light source 14, a flow cell 16 through which an effluent from the column 10 is conducted, and a polychromator 18 for dispersing transmitted light from the light source 14 passing through the cell 16.
And a photodiode array 20 for detecting light separated by the polychromator 18 for each wavelength.

Here, the photodiode array 20 has a plurality of light receiving elements, and the light of the specific wavelength that has been dispersed enters each light receiving element, and is photoelectrically converted.

Then, the charges accumulated in each light receiving element are sequentially scanned, and the spectrum of each wavelength and each timing detected by the multi-wavelength detector 12 is converted into a data processing device 22 as shown in FIG.
It is analyzed by

2, the data processing device 22 includes a storage unit 24, a wavelength selection unit 26, an identification processing unit 28, and an output unit 30.

The storage unit 24 is composed of a hard disk or the like, and stores the spectrum data at each wavelength and each timing sent from the multi-wavelength detector 12.

The wavelength selector 26 is composed of, for example, an input device such as a keyboard, and is capable of selecting a plurality of desired chromatogram data from the data stored in the storage 24.

The identification processing unit 28 retrieves the chromatogram data of each selected wavelength selected by the wavelength selection unit 26 from the storage unit 24, and identifies the contained component based on the retrieved chromatogram data.

The output unit 30 includes a display, a printer, and the like, and outputs data such as the content of the component identified by the identification processing unit.

The data processing apparatus according to this embodiment is configured as described above, and its operation will now be described with reference to FIG.

The operator separates a sample containing, for example, naphthalene, anthracene, pyrene or the like with the column 10 and analyzes the effluent with the multi-wavelength detector 12 (spectrum collecting step). Here, the multi-wavelength detector 12 takes in, for example, a spectrum of a plurality of wavelengths in steps of 5 nm in the range of 195 to 650 nm every 0.8 seconds and stores the spectrum in the storage unit 24 (storage step). Therefore, the storage unit 24 has 92 types of chromatogram data every 5 nm.

On the other hand, the operator selects the optimum wavelength of the desired component to be analyzed by the wavelength selector 26. Here, three types of naphthalene, anthracene and pyrene were analyzed, and 220,
Select 240, 250nm.

Next, the identification processing unit 28 checks how many types of wavelength data are present in the peak identification table (step 100). Here, there are three types of data of 220, 240, and 250 nm.

Then, the chromatogram data at the designated wavelength is read into the memory from the storage unit 24, and the peak detection result is stored in the peak identification table.

From the peak detection result of the chromatogram data,
The retention time (RT) at 220 nm, the area, and the height are calculated (step 102), and the same operation is performed on the chromatogram data at 240 and 250nm (identification step, step 104).

Next, a quantitative calculation is performed at each of the wavelengths 220, 240, and 250 nm (step 106), and printing is performed on the output unit 30 such as a printer (steps 108, 110).

As a result of the above operation, the following analysis data is obtained.

In the above table, ID♯ is the peak identification number, RT (mi
n) is the retention time until the component elutes, NAME is the component name, AMOUNT is the standard sample concentration, and FACTOR is the slope of the calibration curve.

As described above, according to the data processing method and apparatus according to the present embodiment, each component in the same sample is simultaneously analyzed at its optimum wavelength, such as 220 nm for naphthalene, 250 nm for anthracene, and 240 nm for pyrene. Can be measured, and the peak area and the component amount
Measurement can be performed with good quantitative accuracy as shown in the figure.

In this embodiment, the operator selects the wavelength based on the spectrum obtained in advance. However, since the wavelength is generally the absorption maximum, the apparatus can automatically set the wavelength.

Further, the method and apparatus according to the present embodiment are particularly effective in quantitative calculation using the internal standard method.

Here, the internal standard method is a method used to reduce errors in the amount injected into the liquid chromatogram.

That is, a chromatogram is obtained from a sample in which a known amount of an internal standard component is added to a sample, and the peak of the chromatogram is detected. This is a method for determining the concentration. However, conventionally, in selecting the internal standard component, at least strict conditions such as complete separation from the unknown concentration component by a column and monitoring at the same wavelength as the unknown concentration component were required at a minimum.

However, if this data processing method is used, it is not always necessary to separate the unknown concentration component and the internal standard component, and it is sufficient that the absorption spectra do not overlap each other at the wavelength specified in the peak identification table.

Therefore, when an ultraviolet / visible multi-wavelength detector is used, it becomes extremely easy to select an internal standard component used in the internal standard method of this data processing.

[Effects of the Invention] As described above, according to the data processing device of the multi-wavelength detector according to the present invention, the expected wavelength that may appear in the chromatogram at each measured wavelength is measured along with its retention time along with the measured wavelength. , A peak identification table having peak identification data including quantitative data is provided, so that the data processing load is reduced and the accuracy of peak separation is improved. In addition, the analysis data including the component name and concentration of each component is predetermined. It is possible to output in order.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a configuration diagram of a main part of a liquid chromatogram to which the present invention is applied, FIG. 2 is a configuration diagram of the multi-wavelength detector shown in FIG. 1, and FIG. FIG. 4 is a block diagram showing a configuration of a data processing apparatus according to one embodiment of the present invention; FIG. 4 is a flowchart showing a data processing method according to one embodiment of the present invention; FIG. 5 is a spectrum diagram of various components; Is a calibration curve of naphthalene prepared with a chromatogram of 251,221 nm. 12 Multi-wavelength detector 22 Data processing unit 24 Storage unit 26 Wavelength selection unit 28 Identification processing unit 30 Output unit

──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Toshinobu Hondo, 567, 2967, Ishikawa-cho, Hachioji-shi, Tokyo Inside (72) Inventor Hitomi Abe 5-Nihon, 2967, Ishikawa-cho, Hachioji-shi, Tokyo Within Spectator Kogyo Co., Ltd. (72) Inventor Yuzuru Sato 5 days at 2967, Ishikawa-cho, Hachioji-shi, Tokyo Within Spectator Kogyo Co., Ltd. (56) References JP-A-59-19839 (JP, A) JP-A-62-23116 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G01N 21/27 G01N 30/86

Claims (1)

(57) [Claims] 1. A multi-wavelength detecting section for repeatedly collecting a spectrum of a separated solution flowing out of a column at predetermined timings at different measuring wavelengths, and at each measuring wavelength and each timing output by the multi-wavelength detecting section. A storage unit that stores spectrum data, a wavelength selection unit that allows a plurality of chromatogram data of a desired wavelength to be selected from chromatogram data composed of a plurality of identical wavelength spectrum sequences stored in the storage unit, and the measurement wavelengths. Predicted components that may appear in the chromatogram, their retention times, measured wavelengths, peak identification tables having peak identification data including quantitative data, and from the peak identification table, the peak identification data corresponding to the selected wavelength. Read and compare the selected chromatogram with the peak identification data corresponding to the wavelength. With this, an identification processing unit that identifies components appearing in the chromatogram at each selected wavelength, and an output that unitarily outputs analysis data including the component name and concentration of each component identified in the identification step in a predetermined order And a data processing device for a multi-wavelength detector.