JP2009229150A - Chromatograph mass analyzer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a chromatograph mass analyzer which enables an operator to easily confirm and correct the area value of a whole sample or whole compound. <P>SOLUTION: The chromatograph mass analyzer is constituted by connecting a chromatograph device, which separates and refines a compound corresponding to the size and physical properties of a molecule, and a mass analyzer, which separates and detects the ions ionized from the compound corresponding to a mass/charge ratio, to each other in series and provided with a graphic-user interface equipped with the function of arranging the mass chromatograms of a plurality of different samples, which are observed with respect to one predetermined component of the mass chromatogram obtained by measurement, in parallel to each other. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a chromatographic mass spectrometer used for analyzing trace substances such as agricultural chemicals and dioxins contained in soil, water, foods and the like.

  A chromatographic mass spectrometer is an instrumental analyzer in which a chromatograph that separates compounds according to molecular size and physical properties and a mass spectrometer that separates and detects ions according to mass-to-charge ratio are connected in series.

  This analyzer can qualitatively and quantitatively analyze trace amounts of compounds contained in mixtures, and is intended for the analysis of chemical substances that are actually harmful to the human body, such as pesticides and dioxins contained in soil, drinking water, and food. Widely used.

  In a chromatographic mass spectrometer, a mixture subjected to measurement as a sample is first separated as much as possible according to the molecular size and physical properties of individual compounds. Next, the mass spectrometer converts the compounds separated by the chromatograph into single or plural ions, and separates and detects them according to the mass-to-charge ratio.

  FIG. 1 shows the basic configuration of a chromatographic mass spectrometer. In the figure, reference numeral 1 denotes a chromatograph such as a gas chromatograph (GC) or a liquid chromatograph (LC). The compound separated by the chromatograph is introduced into the mass spectrometer 2 placed in the latter stage, ionized, and mass separated for each mass to charge ratio.

  Information on the amount of ions mass-separated by the mass spectrometer 2 is sent to the data processing device 3 at the subsequent stage, and is created in a mass chromatogram together with information on the mass-to-charge ratio, and stored in a storage device 4 such as a hard disk. Is done. Information stored in the storage device 4 can be displayed on a display device 5 such as a CRT or a liquid crystal panel as necessary.

  The results measured in this way are expressed in a chart called a total ion chromatogram (TIC), and the TIC is composed of a plurality of charts called mass chromatograms (MC) (FIG. 2).

  On these TIC and MC, the separated and purified compound is expressed by one peak (vertex), and the content of the compound can be known by calculating a certain area of a chart including this peak.

  Normally, when acquiring the peak area value, either TIC or MC may be used, but MC is generally used. This is because the peaks of all compounds in the mixture measured on TIC are mixed and displayed, whereas on MC, only a specific compound or an ion with the same mass-to-charge ratio happens to be converted to an ion with the mass spectrometer. This is because only a plurality of compounds are displayed, and simpler information can be obtained.

  Even if the peak displayed on the TIC is separated as a single peak by a chromatographic apparatus, there are cases in which compounds having similar sizes and physical properties cannot be sufficiently separated from each other. Even in that case, these different compounds are displayed with different MCs if they are detected as ions having different mass-to-charge ratios by the mass spectrometer.

  When determining the peak area value, if the number of target samples and target compounds is small, the operator manually operates and executes them, but if the number of samples or compounds is large, obtaining the area values can help the program. Borrow and do it automatically. However, the operator confirms whether or not the automatically calculated area value is correct. If the calculation result is incorrect, the operator manually corrects the area value (FIG. 3).

JP-A-2-141655, FIGS. 5 and 6. FIG.

Japanese Patent Laid-Open No. 2-47549, FIG.

Japanese Patent Laid-Open No. Sho 63-111461, FIG.

  Although the area value of the MC acquired by the chromatographic mass spectrometer of the prior art is automatically calculated by the program, the operator must check the result and correct it if it is incorrect.

  At that time, the peak area value is confirmed and corrected by displaying only one MC containing the peak of one compound contained in the sample on the graphic user interface (GUI) of the program. The MCs to be displayed are sequentially switched each time, but this method has a problem that it takes time when the number of MCs to be confirmed is large (FIG. 4).

  In view of the above points, an object of the present invention is to provide a chromatographic mass spectrometer that allows an operator to easily check and correct the area values of all samples or all compounds.

In order to achieve this object, a chromatographic mass spectrometer according to the present invention includes:
A chromatographic apparatus for separating compounds according to molecular size and physical properties;
In a chromatograph mass spectrometer comprising a mass spectrometer for introducing and ionizing compounds separated by the chromatograph and performing mass spectrometry,
Mass chromatogram creation means for obtaining chromatogram data for predetermined N types of mass-to-charge ratios based on data obtained from a mass spectrometer and comprising data obtained by arranging the intensities of ions having a predetermined mass-to-charge ratio over time When,
Storage means for storing N × M mass chromatogram data for the predetermined N kinds of mass-to-charge ratios obtained by the mass chromatogram creating means for M different samples;
A graphic user interface having a function of displaying the mass chromatograms of different samples in parallel for a desired mass-to-charge ratio based on the mass chromatogram data stored in the storage means Yes.

  In addition, the graphic user interface displays another mass when the region setting range for obtaining the peak area value derived from ions in one desired mass chromatogram among the mass chromatograms arranged in parallel is corrected. The corrected region setting range is also set for the peak of the chromatogram.

According to the chromatograph mass spectrometer of the present invention,
In a chromatograph mass spectrometer in which a chromatograph that separates and purifies a compound according to the size and physical properties of a compound and a mass spectrometer that separates and detects ions obtained by ionizing the compound according to a mass-to-charge ratio are connected in series.
A chromatographic apparatus for separating compounds according to molecular size and physical properties;
In a chromatograph mass spectrometer comprising a mass spectrometer for introducing and ionizing compounds separated by the chromatograph and performing mass spectrometry,
Mass chromatogram creation means for obtaining chromatogram data for predetermined N types of mass-to-charge ratios based on data obtained from a mass spectrometer and comprising data obtained by arranging the intensities of ions having a predetermined mass-to-charge ratio over time When,
Storage means for storing N × M mass chromatogram data for the predetermined N kinds of mass-to-charge ratios obtained by the mass chromatogram creating means for M different samples;
Since it has a graphic user interface having a function of displaying mass chromatograms of different samples in parallel for a desired mass-to-charge ratio based on the mass chromatogram data stored in the storage means,
It has become possible to provide a chromatographic mass spectrometer that allows an operator to easily check and correct the area values of all samples or all compounds.

  Embodiments of the present invention will be described below with reference to the drawings. The basic configuration of the new chromatograph mass spectrometer according to the present invention is exactly the same as that of the conventional chromatograph mass spectrometer shown in FIG. 1 except for the GUI displayed on the display device. The description will be focused on a GUI that is different from the prior art.

  FIG. 5 shows an example of a GUI mounted on a new chromatographic mass spectrometer according to the present invention. In this embodiment, a GUI (multiple sample display mode) that collects MCs derived from a desired compound from a plurality of samples, stores them in a storage device such as a memory, and then displays them together. Displayed so that the operator can easily check and correct the area values of all samples.

The MC acquisition method includes:
(1) By measuring a mass spectrum over a region of a desired mass-to-charge ratio every predetermined time and connecting the values of ionic strengths of ions having a predetermined mass-to-charge ratio with the passage of time from those data Synthesize a mass chromatogram.
(2) In order to increase the sensitivity, only one or several specific ion peak intensities are monitored, and the obtained ion peak intensity values are connected with the passage of time to synthesize a mass chromatogram.
However, the present embodiment can be applied to the MC obtained by either method.

  As shown in FIG. 5, in this example, for example, for one compound having a desired mass-to-charge ratio contained in three samples (sample 1, sample 2, sample 3), the area value of each ion peak is obtained, With the time axis or peak position aligned, each mass chromatogram is displayed in parallel on the GUI.

  Thereby, for example, for each of Compound A, Compound B, and Compound C, the size of the area value can be confirmed at a glance between Sample 1, Sample 2, and Sample 3. For example, in the case of Compound A, the peak area value is large in the order of Sample 1> Sample 2> Sample 3. In the case of Compound B, the peak area value is large in the order of Sample 1> Sample 2> Sample 3. In the case of Compound C, the peak area value is large in the order of Sample 1> Sample 2> Sample 3.

  As described above, in this embodiment, since the operator can compare at a glance a large amount and a small amount of the predetermined components in all the samples, the large burden conventionally required for the MC confirmation work is remarkably reduced. Became.

  In this embodiment, as an example, the MC of a predetermined compound is collectively displayed in all samples. However, in the present invention, the MC of all measured samples must be displayed at one time. Not a translation. It goes without saying that only the MC of one desired compound in the number of samples desired by the operator may be collectively displayed on the GUI according to the judgment of the operator.

  Conventionally, as shown in FIG. 3, with respect to correction in the case where the peak area value in the MC is an erroneous result due to inappropriate setting conditions or setting ranges, the setting conditions and settings for each individual MC are also provided. The conventional method that had to correct the range was revised, and as shown in FIG. 6, the ion peak setting condition and the setting range were corrected for one of the MCs of each sample displayed in a lump. The correction results are applied to the setting conditions and setting ranges of ion peaks in the MC of other samples, and the corrections are made together.

  Thus, for example, if the setting conditions and setting range of a desired ion peak in compound A are corrected to optimum conditions, the setting conditions and setting ranges of the corresponding ion peaks of compound B and compound C are automatically linked accordingly. The same correction will be made. As a result, a quantitative value of ions reflecting the corrected setting condition and setting range is newly calculated and automatically displayed at a predetermined location.

  As described above, in this embodiment, the operator does not have to input the peak setting conditions and setting ranges one by one with respect to the MCs of all the samples. The large burden has been significantly reduced.

  FIG. 7 shows another embodiment of the GUI installed in the new chromatograph mass spectrometer according to the present invention. In this example, after a plurality of MCs contained in a desired sample are once stored in a storage device such as a memory, they are collectively displayed on a GUI (multiple compound display mode) that can be displayed at one time. The peak area values of all the compounds contained in one sample can be easily confirmed.

As described above, the MC acquisition method is as follows.
(1) By measuring a mass spectrum over a region of a desired mass-to-charge ratio every predetermined time and connecting the values of ionic strengths of ions having a predetermined mass-to-charge ratio with the passage of time from those data Synthesize a mass chromatogram.
(2) In order to increase the sensitivity, only one or several specific ion peak intensities are monitored, and the obtained ion peak intensity values are connected with the passage of time to synthesize a mass chromatogram.
The present embodiment is also applicable to the MC obtained by either method.

  As shown in FIG. 7, in this example, for example, for three components (compound A, compound B, and compound C), the area value of each ion peak in one sample desired by the operator is obtained, and the time axis or peak The mass chromatograms are displayed together in parallel on the GUI in the same position.

  Thereby, for example, in each of Sample 1, Sample 2, and Sample 3, the size of the area value can be confirmed at a glance between Compound A, Compound B, and Compound C. For example, in the case of sample 1, compound A≈compound B≈compound C. In the case of sample 2, compound A≈compound B≈compound C. In the case of Sample 3, Compound A≈Compound B≈Compound C.

  As described above, in this embodiment, since the operator can compare at a glance a large amount and a small number of a plurality of components in one sample, the large burden conventionally required for the MC confirmation work is significantly reduced. It became so.

  In this example, as an example, the MC of all the compounds in a desired sample has been described as being collectively displayed. However, the present invention does not necessarily display all the measured MCs of the compounds at one time. It's not necessary. It goes without saying that only the desired number of compound MCs in one sample desired by the operator may be collectively displayed on the GUI according to the judgment of the operator.

  Can be widely used in chromatographic mass spectrometers.

It is a figure which shows the basic composition of a chromatograph mass spectrometer. It is a figure which shows the relationship between TIC and MC. It is a figure which shows the flow of the conventional peak area value measuring method. It is a figure which shows an example of the conventional MC confirmation method. It is a figure which shows one Example of the MC confirmation method concerning this invention. It is a figure which shows one Example of the MC area value correction method concerning this invention. It is a figure which shows another Example of the MC confirmation method concerning this invention.

Explanation of symbols

1: Chromatographic device, 2: Mass spectrometer, 3: Data processing device, 4: Storage device, 5: Display device

Claims (2)

A chromatographic apparatus for separating compounds according to molecular size and physical properties;
In a chromatograph mass spectrometer comprising a mass spectrometer for introducing and ionizing compounds separated by the chromatograph and performing mass spectrometry,
Mass chromatogram creation means for obtaining chromatogram data for predetermined N types of mass-to-charge ratios based on data obtained from a mass spectrometer and comprising data obtained by arranging the intensities of ions having a predetermined mass-to-charge ratio over time When,
Storage means for storing N × M mass chromatogram data for the predetermined N kinds of mass-to-charge ratios obtained by the mass chromatogram creating means for M different samples;
A graphic user interface having a function of displaying the mass chromatograms of different samples in parallel for a desired mass to charge ratio based on the mass chromatogram data stored in the storage means; Chromatograph mass spectrometer. When the region setting range for obtaining the peak area value derived from ions in one desired mass chromatogram among the mass chromatograms arranged in parallel is corrected, the graphic user interface may display another mass chromatogram. The chromatograph mass spectrometer according to claim 1, wherein the corrected region setting range is also set for the peak of.

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