JP6901376B2 - Data processing device for mass spectrometry and data processing method for mass spectrometry - Google Patents

Description

The present invention relates to a mass spectrometric data processing apparatus and a mass spectrometric data processing method.

Conventionally, chromatographic mass spectrometry is known as a method for quantitative analysis of known components and qualitative analysis of unknown components. In chromatographic mass spectrometry, components separated in time using a chromatography method are sequentially ionized, and then ions are separated according to a mass-to-charge ratio [m / z] by a mass spectrometer and detected by a detector. It is an analysis method. A mass spectrometer that performs such an analysis includes a data processing device for data processing the mass spectrum of each component detected with the elapsed time (holding time).

In qualitative analysis, for example, this data processing device first plots the signal intensity, which is the total amount of ions of an unknown component, with the retention time (Total Ion Current Chromatogram: hereinafter referred to as TICC). create. The data processor then searches for peaks on the TICC and extracts the mass spectrum at the detected peak position. In addition, the data processor identifies the sample components of this chromatographic peak by comparing the extracted mass spectrum with the spectrum of the library.

On the other hand, in the quantitative analysis, the data processing device plots the signal intensities of ions of known components from the mass spectrum data, which is the data of the mass spectrum, with the retention time. (Also referred to as "EIC") is created, and the peak area obtained from this EIC is applied to the calibration curve to quantify the known components.

In Patent Document 1, a mass spectrometric unit that mass spectrometrically analyzes ions, a detection unit that detects ions mass-selectively discharged from the mass spectrometric unit, and an ion intensity derived from a substance to be detected have a predetermined dark value. A hazardous material detection device including a data processing unit that determines that a substance to be detected exists when the amount exceeds the limit and an output unit that outputs a determination by the data processing unit is disclosed. Further, in Patent Document 1, the output unit is a display unit that displays the presence of the substance to be detected, and the output unit sounds an alarm when the data processing unit determines that the substance to be detected exists. Is disclosed. According to such a technique, it is possible to determine the presence or absence of a substance corresponding to an ion to be detected in the sample. Then, when the presence of the substance is confirmed, it becomes possible to carry out a detailed re-examination or the like.

Japanese Unexamined Patent Publication No. 2008-262922

However, in the technique described in Patent Document 1, information on whether or not the intensity of the quantification ion of the quantification target compound to be quantitatively analyzed exceeds a predetermined reference value (threshold) is obtained from the quantification ion of the quantification target compound. It could not be confirmed in association with the extracted ion chromatogram.

The present invention has been made to solve the above problems. An object of the present invention is to associate information on whether or not the intensity of a quantification target compound to be quantitatively analyzed exceeds a predetermined reference value (threshold value) with an extracted ion chromatogram of quantification ions of the quantification target compound. The purpose is to be able to confirm.

In order to solve the above problems, a mass spectrometric data processing apparatus reflecting one aspect of the present invention is based on data obtained by sequentially mass spectrometrically analyzing sample components separated according to the holding time by a chromatograph. A data processing device for mass spectrometry for identifying and quantifying sample components, which is a chromatogram preparation unit that creates an extraction ion chromatogram of the quantitative ion of the compound to be quantitatively analyzed, and a chromatogram preparation unit for the quantitative ion. On the screen displaying the extracted ion chromatogram and the screening condition setting unit that sets the reference value line intensity corresponding to the height of the intensity of the predetermined reference value set in the above with respect to the concentration of the standard sample containing the compound to be quantified. The reference is based on the image data creation unit that creates image data for superimposing and displaying the reference value intensity line corresponding to the reference value line intensity, and the peak intensity of the quantification ion of the quantification target compound for which the extracted ion chromatogram is generated. It is provided with a screening unit that screens whether or not the value line strength is exceeded and notifies the fact when the intensity of the quantitative ion exceeds the reference value.

The mass spectrometric data processing method that reflects one aspect of the present invention is the mass spectrometric data processing method in the mass spectrometric data processing apparatus.

According to the present invention, information on whether or not the intensity of the quantification target compound to be quantitatively analyzed exceeds a predetermined reference value (threshold value) is used as an extraction ion chromatogram of quantification ions of the quantification target compound. You will be able to check it in correspondence.

It is a block diagram which shows the outline of the mass spectrometer which concerns on one Embodiment of this invention. It is a figure for demonstrating the structure of the data processed in the mass spectrometry data processing apparatus which concerns on one Embodiment of this invention. It is a figure which shows an example of a mass spectrum. It is explanatory drawing which shows the structural example of the display area of the screen of the display part which concerns on one Embodiment of this invention. It is a flowchart which shows the procedure of the main processing of the mass spectrometry data processing by the mass spectrometry data processing apparatus which concerns on one Embodiment of this invention. It is a flowchart which shows the procedure of the screening executed in the main process of the data processing for mass spectrometry which concerns on one Embodiment of this invention. It is a flowchart which shows the procedure of the screening executed in the main process of the data processing for mass spectrometry which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the mass spectrometric data processing apparatus and the mass spectrometric data processing method of the present invention will be described in detail with reference to the drawings. In each embodiment, the same components are designated by the same reference numerals, and duplicate description will be omitted.

[First Embodiment]
<Mass spectrometer>
FIG. 1 is a block diagram showing an outline of a mass spectrometer according to an embodiment of the present invention. The mass spectrometer 1 according to the first embodiment shown in FIG. 1 sequentially mass-analyzes the sample components separated by the chromatograph, and together with the sample separation unit 101 and the mass spectrometry unit 102, the first mass spectrometer 1 The mass spectrometric data processing device 1a of the embodiment is provided. Hereinafter, the details of these components included in the mass spectrometer 1 will be described.

(Sample separator)
The sample separation unit 101 is an example of a chromatograph that separates a mixture sample to be analyzed for each component. The sample separation unit 101 includes a sample introduction unit 101a for introducing a mixture sample to be analyzed, and a column 101b for separating the sample introduced from the sample introduction unit 101a for each component. The column 101b is filled with a stationary phase that allows the sample introduced from the sample introduction unit 101a to pass through. The components temporally separated according to the speed of passing through the stationary phase are supplied to the mass spectrometer 102 with a retention time [RT: Retention Time] peculiar to each component.

In the present embodiment, for example, a gas chromatograph is used as the sample separation unit 101, but the present invention is not limited thereto. For example, a liquid chromatograph or another chromatograph may be used.

(Mass spectrometry)
The mass spectrometer 102 is separated by the sample separation unit 101, sequentially ionizes each component supplied with a time lag, and further separates the ions of each ionized component according to the mass-to-charge ratio [m / z]. To detect. The mass spectrometer 102 includes an ionization unit 102a, a mass separation unit 102b, and a detector 102c.

The ionization unit 102a sequentially ionizes the components supplied from the sample separation unit 101. In the ionization unit 102a, molecular ions of the components supplied from the sample separation unit 101 and a plurality of fragment ions in which the molecular ions are cleaved are generated.

The mass separation unit 102b separates each ion supplied from the ionization unit 102a for each mass-to-charge ratio [m / z], passes only ions having a specific mass-to-charge ratio [m / z], and reaches the detector 102c. Let me. In this mass separation unit 102b, by scanning the mass-to-charge ratio [m / z] of the ions to reach the detector 102c, each ion reaches the detector 102c sequentially for each mass-to-charge ratio [m / z]. The process of causing is repeated at regular intervals. As the mass separation unit 102b, an appropriate method is used depending on the combination with the ionization unit 102a.

The detector 102c detects the signal intensity [I] of the ions separated according to the mass-to-charge ratio [m / z] in the mass separation unit 102b. Then, the detector 102c obtains a mass spectrum signal for each scan by taking out the obtained signal intensity [I] in correspondence with the scan of the mass-to-charge ratio [m / z]. The mass spectrum signal obtained by the detector 102c is supplied to the mass spectrometric data processing device 1a.

(Data processing device for mass spectrometry)
The data processing apparatus 1a for mass spectrometry performs qualitative analysis for identifying that the compound contained in the sample is the compound to be quantified for quantitative analysis, and the concentration of the compound to be quantified exceeds a predetermined reference value. Perform screening to confirm whether or not. Then, when it is detected as a result of the screening that the concentration of the compound to be quantified exceeds a predetermined reference value concentration, the user is notified by voice or the like to that effect. In the mass spectrometric data processing device 1a of the present embodiment, for example, is the content (concentration) of explosives, pollutants, etc. in an unknown sample within an allowable range, that is, an amount equal to or less than a reference value? It can be applied to a device or the like that needs to determine whether or not it is present.

The mass spectrometry data processing device 1a includes an input / output control unit 10, a storage unit 11, a mass spectrum extraction unit 12, a chromatogram creation unit 13, a screening condition setting unit 14, a screening unit 15, an identification unit 16, and an image data creation unit 17. , A speaker 18, an operation unit 19, and a display unit 20.

The input / output control unit 10 controls the timing of operations in each of the other units according to a preset program and an operation from the operation unit 19 by the user, and executes mass spectrometry data processing by the control. The input / output control unit 10 is connected to each of the other units constituting the mass spectrometry data processing device 1a and the detector 102c of the mass spectrometry unit 102.

The storage unit 11 stores data in which the mass spectrum signal detected by the detector 102c is associated with the holding time [RT].

Here, a configuration example of data stored in the mass spectrometry data processing apparatus 1a will be described with reference to FIG. FIG. 2 is an explanatory diagram showing a configuration example of data stored in the mass spectrometric data processing device 1a. The horizontal axis of FIG. 2 is time, and the vertical axis is signal strength [I].

The mass spectrum signals detected by the detector 102c for each of the repeated scans described above are sequentially input to the input / output control unit 10 according to the holding time [RT]. Then, the storage unit 11 stores a chromatogram (EIC: extracted ion chromatogram) for each mass-to-charge ratio [m / z] created by the chromatogram preparation unit 13 described later. The EIC is a graph showing the signal intensity [I] of an ion having a specific mass-to-charge ratio with respect to the holding time [RT], and is shown by a broken line in FIG. In FIG. 2, for simplification of the description, only four EICs corresponding to the mass-to-charge ratios [m / z] at four locations are shown.

The EIC has a peak at a predetermined extraction time position [tp] in the retention time range [Tw] set for the retention time [RT].

Further, in the storage unit 11, data in which the mass spectrum of a known substance is associated with the compound name and the structural formula is stored in advance as a library. Here, an example of a mass spectrum will be described with reference to FIG. FIG. 3 is an explanatory diagram showing an example of a mass spectrum. The horizontal axis of FIG. 3 is the mass-to-charge ratio [m / z], and the vertical axis is the signal strength [I]. The mass spectrum shown in FIG. 3 has a strong mass spectrum component at m / z 200, and has a relatively strong mass spectrum component at m / z 77 and m / z 106. Even if the same data as the data stored in the NIST (National Institute of Standards and Technology) library is used as the data stored as a library in the storage unit 11 (hereinafter, also referred to as "library data"). Good.

The mass spectrum extraction unit 12 integrates the signal intensity [I] detected by the detector 102c for each holding time [RT] based on the data stored in the storage unit 11 (TICC: (See Fig. 2).

Then, the mass spectrum extraction unit 12 carries out a series of spectrum extractions based on the TICC according to a normal automatic peak detection (so-called peak search) program based on the created TICC. The mass spectrum extraction unit 12 extracts the mass spectrum for each holding time [RT] corresponding to each peak on the TICC by the above-mentioned automatic peak detection, and generates mass spectrum data.

The chromatogram creation unit 13 creates an EIC from the mass spectrum data generated by the mass spectrum extraction unit 12.

The screening condition setting unit 14 creates screening conditions, which are conditions used in screening for determining whether or not the concentration of the compound to be quantified exceeds the reference value, according to the following procedure.
(1) Measure a standard sample containing the compound to be quantified.
(2) A qualitative analysis of the standard sample is performed using the preset quantitative conditions and the measurement result of the standard sample performed in (1).
(3) Screening conditions are created using the actually measured values obtained as a result of the qualitative analysis of the standard sample performed in (2) and the measured values of the quantitative analysis performed based on the quantitative conditions. The details of the screening condition creation process by the screening condition setting unit 14 will be described in detail with reference to FIG. 5, which shows the procedure of the main process performed by the mass spectrometric data processing device 1a.

The quantitative condition referred to by the screening condition setting unit 14 is created in advance by the user as a quantitative condition setting file (not shown). The quantitative conditions set in the quantitative condition setting file are composed of, for example, the following items.
-Compound name-Retention time [RT]
-Mass-to-charge ratio of quantitative ions [m / z]
・ Reference value ・ Peak detection time range

The name of the compound to be quantified is set in the "compound name". In the "retention time [RT]", the retention time [RT] of the compound to be quantified is set in minutes. The mass-to-charge ratio [m / z] of the quantitative ions of the compound to be quantified is set in the "mass-to-charge ratio [m / z] of the quantitative ions". In the "reference value", the reference concentration as a threshold value used by the screening unit 15 when screening the compound to be quantified is set in units of ppm.

The peak detection time range is a set value that defines the peak detection time, which is the time for detecting the peak of the compound to be quantified, and is represented by the retention time [RT] ± (peak detection range ÷ 2). For example, when the holding time [RT] is 3 minutes and the peak detection range is 0.5 minutes (30 seconds), the peak detection time range is between 2 minutes 45 seconds and 3 minutes 15 seconds. Any time can be set in the peak detection range.

The quantitative condition setting file including each of the above items is stored in the storage unit 11.

The screening condition setting unit 14 creates the following items as screening conditions.
-Compound name-Measured value of retention time [RT] -Mass-to-charge ratio of quantitative ions [m / z]
・ Peak detection time range ・ Peak intensity ・ Standard substance concentration ・ Reference value ・ Reference value Line intensity

For the "compound name", "mass-to-charge ratio of quantitative ions [m / z]", "reference value", and "peak detection time range", each set value set in the quantitative conditions can be diverted.

The “measured value of holding time” and “peak intensity” are set to the measured values obtained as a result of the qualitative analysis performed in (3) above. The concentration of the standard sample is set in the "standard substance concentration".

The "reference value line intensity" is a value indicated as the height of the intensity of the reference value with respect to the concentration of the standard sample, and the reference value line intensity is described below using the information of the standard substance concentration, the peak intensity and the reference value. It can be calculated by the formula (1) of.

Reference value Line strength = Peak strength x Reference value / Standard substance concentration ... Equation (1)

The reference value line intensity obtained here is calculated based on the measurement result of the standard sample, and the standard sample contains a noise component. Therefore, it is assumed that the reference value line intensity calculated here also includes the noise component.

The screening condition consisting of the above items set by the screening condition setting unit 14 is stored in the storage unit 11 as, for example, a screening condition setting file (not shown).

The screening unit 15 performs screening for determining whether or not the concentration of the compound to be quantified exceeds a predetermined reference value line intensity based on the screening conditions created by the screening condition setting unit 14. Then, the screening unit 15 reflects the screening result in the screening result list (not shown), which is a list in which the screening result is stored. When the screening unit 15 detects that the concentration of the compound to be quantified exceeds the reference value line intensity by screening, the screening unit 15 describes the fact in the screen result list and notifies and / or informs from the speaker 18. , Notify the user via the screen of the display unit 20.

The identification unit 16 determines whether or not the compound under measurement for which the EIC is prepared by the chromatogram preparation unit 13 is a compound to be quantified. Specifically, the identification unit 16 performs a peak search on the compound whose peak detection start time has come, and when the peak can be detected before the peak detection end time, the compound being measured is the compound to be quantified. Identify as. The peak detection start time is the start time of the “peak detection time range” set in the quantitative conditions, and is represented by the holding time [RT] − (peak detection range ÷ 2). The peak detection end time is the end time of the “peak detection time range” and is represented by the holding time [RT] + (peak detection range ÷ 2).

In the present embodiment, the identification unit 16 identifies the compound based only on the information on whether or not the peak is detected within the peak detection time range, but the present invention is not limited to this. .. For example, as a condition for the identification unit 16 to identify the compound, information on whether or not the retention time [RT] of the top position of the peak detected as a result of the peak search is within the preset RT tolerance is used. You may. In this case, the identification unit 16 identifies the compound under measurement as the compound to be quantified when the retention time [RT] at the top position of the peak is within the RT tolerance, and is within the RT tolerance. If not, it is determined that the compound under measurement is not a compound to be quantified (compound to be quantified is not detected).

Alternatively, as a condition for the identification unit 16 to identify the compound, information on the I / Q ratio indicating the ratio of the intensity of the reference ion to the intensity of the quantitative ion of the compound may be used. In this case, the identification unit 16 compares the measured I / Q ratio (measured I / Q ratio) with the I / Q ratio set in the quantitative conditions (set I / Q ratio), and the result of the comparison. When the difference between the obtained I / Q ratios is within the preset tolerance range, the compound under measurement is identified as the compound to be quantified. If the error between the measured I / Q ratio and the set I / Q ratio is out of the margin of error, it is determined that the compound being measured is not a quantification target compound (quantification target compound not detected).

Alternatively, as a condition for the identification unit 16 to identify the compound, information on the spectral similarity obtained by comparing the mass spectrum created by the mass spectrum extraction unit 12 with the mass spectrum of the compound hit by the library search can be obtained. You may use it. In this case, the identification unit 16 identifies the compound under measurement as the compound to be quantified when the similarity between the mass spectrum and the library data is equal to or higher than a predetermined threshold value. When the similarity between the mass spectrum and the library data is less than a predetermined threshold value, it is determined that the compound under measurement is not a quantification target compound (quantification target compound not detected).

The above-mentioned conditions listed by the identification unit 16 as the conditions that can be used for the identification of the compound may be used alone, or some or all of the above-mentioned conditions may be used in combination. By using the RT tolerance information, the spectral similarity information, and / or the I / Q ratio information in addition to the peak detection time range information used by the identification unit 16 in the present embodiment, the identification unit 16 The accuracy of compound identification can be further improved.

The image data creation unit 17 includes the TICC generated by the mass spectrum extraction unit 12, the EIC of the compound for which the peak search is performed in the peak detection time range by the identification unit 16, and each information stored in the screening result list. Is converted into image data to be displayed on the display unit 20. Further, the image data creation unit 17 generates a reference value intensity line to be displayed in the image in which the screening result is displayed, based on the information of the reference value line intensity set in the screening condition by the screening condition setting unit 14.

Each image data generated by the image data creation unit 17 is displayed as an image in each area divided by the screen of the display unit 20. The image based on the image data generated by the image data creation unit 17 is displayed on the screen of the display unit 20 in real time (in parallel in time) at the same time as the mass spectrometry data processing device 1a analyzes the data. ) It is done. A configuration example of the display area of the screen of the display unit 20 will be described in detail with reference to FIG. 4 below.

The operation unit 19 inputs various settings related to data processing to be executed in the mass spectrometry data processing device 1a. The various settings related to data processing include, for example, setting of a holding time range [Tw] for creating a chromatogram in the chromatogram creating unit 13. The operation unit 19 may be composed of, for example, a keyboard, a mouse, or the like.

The display unit 20 displays an image based on the image data created by the image data creation unit 17. The operation unit 19 and the display unit 20 may be integrally formed with each other as a touch panel capable of touch input by the user.

<Example of configuration of display area on the screen of the display unit>
Next, a configuration example of the display area of the screen of the display unit 20 will be described with reference to FIG. FIG. 4 is an explanatory diagram showing a configuration example of a display area of the screen of the display unit 20.

As shown in FIG. 4, the screen display area of the display unit 20 is composed of a chromatogram display area Ar1 and a screening condition and screening result display area Ar2. The chromatogram display area Ar1 further includes a TICC display area Ar11 and an EIC display area Ar12.

In the TICC display area Ar11, the TICC being measured created by the mass spectrum extraction unit 12 is displayed. In the EIC display area Ar12, the EIC of the compound whose elapsed time from the start of measurement exceeds the peak detection start time set as the quantitative condition, that is, the screening unit 15, performs a peak search in the peak detection time range. EIC is displayed. When there are a plurality of compounds whose peak search is performed in the peak detection time range by the screening unit 15, a plurality of EICs are displayed in the EIC display area Ar12.

In the example shown in FIG. 4, the EIC of compound C having a mass-to-charge ratio [m / z] of "129" is displayed in the upper part of the EIC display region Ar12, and the mass-to-charge ratio [m / z] is displayed in the lower part. The EIC of compound D of "57" is displayed. Further, in each area of the EIC display area Ar12, the reference value intensity lines L1 and L2 are superimposed on the EIC and are displayed by broken lines, respectively. The reference value intensity lines L1 and L2 are generated by the image data creation unit 17 based on the information of the reference value line intensity set in the screening conditions.

In the example shown in FIG. 4, the concentration of compound C having a mass-to-charge ratio [m / z] of “129” exceeds the reference value intensity line L1. Therefore, a warning sound is emitted from the speaker 18 (see FIG. 1) under the control of the screening unit 15.

The screening conditions and the screening result display area Ar2 contain information on the screening conditions set by the screening condition setting unit 14 and the screening result list showing the results of the screening performed by the screening unit 15. Specifically, the following items are displayed.

-Compound name-Retention time [RT] (minutes)
-Mass-to-charge ratio of quantitative ions [m / z] (denoted as "quantitative ions" in the figure)
・ Peak detection time range (minutes)
・ Standard substance concentration (ppm)
・ Peak intensity (peak height)
・ Reference value (ppm)
・ Reference value line strength ・ Detection result

In "Compound name", the name of the compound contained in the standard sample is described. In the example shown in FIG. 4, since the standard sample contains compound A, compound B, compound C, and compound D, the names of these four compounds are described.

In the "retention time [RT] (minutes)", the actually measured value of the retention time [RT] obtained as a result of the qualitative analysis performed by the screening condition setting unit 14 is described. "Mass-to-charge ratio of quantitative ions [m / z]", "Peak detection time range (minutes)", "Standard substance concentration (ppm)", "Reference value (ppm)", "Reference value line strength" The value described in the screening condition setting file is described.

In the "detection result", the result of screening by the screening unit 15 is described. Specifically, as a result of screening by the screening unit 15, when the concentration of the compound to be quantified exceeds the reference value, "D." is described, and when it is below the reference value, "ND. Is described. In the example shown in FIG. 4, it is shown that the concentrations of Compound B and Compound C above the reference value were detected.

<Data processing method for mass spectrometry using a data processing device for mass spectrometry>
Next, with reference to FIGS. 5 to 7, a mass spectrometry data processing method by the mass spectrometry data processing apparatus 1a according to the present embodiment will be described. FIG. 5 is a flowchart showing a procedure of main processing of mass spectrometry data processing by the mass spectrometry data processing apparatus 1a according to the present embodiment. 6 and 7 are flowcharts showing a screening procedure performed in the main process of mass spectrometric data processing.

First, the quantitative condition is set by the user, and the quantitative condition setting file is created (step S1). As described above, the quantitative conditions set in the quantitative condition setting file are "compound name", "retention time [RT]", "mass-to-charge ratio of quantitative ions [m / z]", "reference value" and "reference value". It consists of each item of "Peak detection time range".

Next, the screening condition setting unit 14 measures a standard sample containing the compound to be quantified (step S2). In this embodiment, in step S2, the screening condition setting unit 14 measures only one standard sample containing a known single concentration of target component. As a result, the time and labor required for measuring the standard sample can be significantly reduced as compared with the conventional case. For the purpose of improving the accuracy of the quantitative analysis performed in the subsequent step, it is desirable to use a standard sample having a high concentration of the compound to be quantified as the standard sample to be measured in step S2. ..

Next, the screening condition setting unit 14 performs a qualitative analysis of the standard sample based on the standard sample measurement result obtained by the measurement in step S2 and the quantitative conditions described in the quantitative condition setting file created in step S1. (Step S3).

In the qualitative analysis in step S3, information on the retention time [RT] of each compound to be quantified contained in the standard sample and information on the peak intensity are also acquired. In acquiring this information, the screening condition setting unit 14 first detects the peak of the EIC of each quantification target compound contained in the standard sample generated by the chromatogram preparation unit 13. Next, the screening condition setting unit 14 acquires the measured value of the holding time [RT] and the peak intensity from the detected peak information.

Next, the screening condition setting unit 14 sets the screening conditions using the actually measured values obtained as a result of the qualitative analysis in step S3 and the set values of the quantitative conditions set in the quantitative condition setting file (step S4). ).

As described above, the screening conditions set in step S4 are "compound name", "measured value of retention time [RT]", "mass-to-charge ratio of quantitative ions [m / z]", and "peak detection time range". , "Peak intensity", "Standard substance concentration", "Reference value" and "Reference value line intensity".

For the "compound name", "mass-to-charge ratio of quantitative ions [m / z]", "reference value", and "peak detection time range", each set value set in the quantitative condition setting file can be used. it can. Further, in the "measured value of holding time" and "peak intensity", each measured value obtained as a result of the qualitative analysis performed in step S3 is set. The concentration of the standard sample is set in the "standard substance concentration". Further, the "reference value line strength" can be obtained by using the above formula (1).

Next, the screening unit 15 screens the compound to be quantified using the screening conditions set in step S4 (step S5). When the screening unit 15 performs the screening in step S5, information on the screening result and the measurement result of the compound to be quantified can be obtained.

<Screening method by screening unit 15>
Next, the details of the screening process executed in step S5 of FIG. 5 will be described with reference to FIGS. 6 and 7.

First, the user activates the measurement monitor displayed on the display unit 20 (step S11). After the process of step S11, three processes (first sub-process to third sub-process) are executed in parallel. Therefore, a fork node Fn indicating that the three processes are started to be executed at the same time is connected to step S11.

In the first sub-processing shown on the left side of FIG. 6, the mass spectrometric unit 102 (see FIG. 1) measures the compound to be quantified, and the measurement result is stored in the storage unit 11. Specifically, the mass spectrum extraction unit 12 extracts the mass spectrum from the TICC based on the data read from the storage unit 11 and acquires the mass spectrum data of the extracted mass spectrum (step S12). The mass spectrum data acquired by the mass spectrum extraction unit 12 in step S12 is supplied to the chromatogram creation unit 13.

Next, the mass spectrum extraction unit 12 determines whether or not the measurement by the mass spectrometry unit 102 is completed (step S13). When it is determined in step S13 that the measurement has not been completed (when the determination in step S13 is NO), the mass spectrum extraction unit 12 performs the process of step S12 again. On the other hand, when it is determined in step S13 that the measurement is completed (when the determination in step S13 is YES), the join node Jn at the lower side of FIG. Move. The join node Jn represents combining a plurality of processes into one.

In the second subtreatment shown in the center of FIG. 6, screening of the compound to be quantified is performed. Specifically, first, using the mass spectrum data extracted by the mass spectrum extraction unit 12 in step S12, the chromatogram creation unit 13 creates an EIC, and the created EIC updates the display on the measurement monitor (step). S15). The EIC displayed on the measurement monitor (the display is updated) in step S15 is an EIC in which the peak is detected when the peak detection start time has come, and the procedure for extracting the EIC is described. , Will be described in detail with reference to FIG. 7 described later.

Next, the screening unit 15 compares the intensity of the peak extracted from the EIC whose display has been updated in step S15 with the reference value line intensity (step S16). Next, the screening unit 15 determines whether or not the intensity of the peak extracted from the EIC is larger than the reference value line intensity (step S17). When it is determined in step S17 that the peak intensity is larger than the reference value line intensity (when the determination in step S17 is YES), the screening unit 15 determines that the concentration of the compound to be quantified on which EIC is displayed exceeds the reference value. This is notified to the user by sound emission from the speaker 18 or the like (step S18). Next, the screening unit 15 updates the content of the screening result written in the screening result list (step S19).

Next, the screening unit 15 determines whether or not the measurement of the compound to be quantified has been completed (step S20). When it is determined in step S20 that the measurement has not been completed (when the determination in step S20 is NO), the screening unit 15 returns the process to step S15. On the other hand, when it is determined in step S20 that the measurement is completed (when the determination in step S20 is YES), the process proceeds to the join node Jn.

On the other hand, when it is determined in step S17 that the peak intensity is equal to or less than the reference value line intensity (when the determination in step S17 is NO), the screening unit 15 shifts the process to step S20.

In the third sub-treatment shown on the right side of FIG. 6, the EIC of the compound to be quantified is displayed on the measurement monitor, deleted from the measurement monitor, and the screening results obtained in the second sub-treatment are reflected in the screening result list. The process of causing (updating the screening result) is performed. Specifically, first, the screening unit 15 determines whether or not there is a quantification target compound that does not display EIC on the measurement monitor (step S21). If it is determined in step S21 that there is no compound to be quantified that does not display EIC (when the determination in step S21 is NO), the process proceeds to join node Jn.

On the other hand, when it is determined in step S21 that there is a compound to be quantified that does not display EIC (when the determination in step S21 is YES), the screening unit 15 measures the peak detection start time and the measurement based on the screening conditions. Compare with the elapsed time from the start (step S22). Next, the screening unit 15 determines whether or not the peak detection start time is equal to or longer than the elapsed time from the start of measurement (step S23).

The peak detection start time is the start time of the “peak detection time range” set in the quantitative conditions, and is represented by the holding time [RT] − (peak detection range ÷ 2) as described above. That is, in step S23, whether or not the compound determined to have not yet displayed EIC in step S21 is a compound whose elapsed time from the start of measurement is within the peak detection time range, that is, EIC is measured. It is determined whether or not the EIC should be displayed on the monitor.

When it is determined in step S23 that the peak detection start time is equal to or longer than the elapsed time from the start of measurement (when the determination in step S23 is YES), the screening unit 15 measures the EIC of the quantitative ion of the compound to be quantified. Control is performed to add to the EIC display area Ar12 (see FIG. 4) of the monitor (step S24). By controlling step S24, the image data creation unit 17 newly draws the EIC of the quantification ion of the quantification target compound in the EIC display area Ar12 of the measurement monitor. Next, the screening unit 15 adds compound information of the compound whose EIC is being drawn to the screening result list (step S25).

Next, the screening unit 15 determines whether or not the measurement of the compound to be quantified has been completed (step S26). When it is determined in step S26 that the measurement has not been completed (when the determination in step S26 is NO), the screening unit 15 returns the process to step S21. On the other hand, when it is determined in step S26 that the measurement is completed (when the determination in step S26 is YES), the process proceeds to the join node Jn.

When it is determined in step S23 that the peak detection start time is less than the elapsed time from the start of measurement (when the determination in step S23 is NO), the screening unit 15 performs the process of step S31 in FIG. In step S31 of FIG. 7, the peak detection end time and the elapsed time from the measurement start are compared. As described above, the peak detection end time is the end time of the “peak detection time range” and is represented by the holding time [RT] + (peak detection range ÷ 2).

Next, the screening unit 15 determines whether or not the peak detection start time is equal to or less than the elapsed time from the start of measurement (step S32). When it is determined in step S32 that the peak detection start time is equal to or less than the elapsed time from the start of measurement (when the determination in step S32 is YES), the screening unit 15 is displaying in the EIC display area Ar12 of the measurement monitor. Control to delete the EIC is performed (step S33). Next, the screening unit 15 updates the screening conditions of the measurement monitor and the values of each item of the screening result display area Ar2 with the information of the result obtained by the screening (step S34). After the processing of step S34, the screening unit 15 shifts the processing to step S26 of FIG.

Then, when all of the first to third sub-processes are completed and the process moves to the join node Jn, the main process of the mass spectrometry data processing device 1a is completed, and the display of the measurement monitor is terminated (step S14). ).

<Various effects>
In the above embodiment, the screening condition setting unit 14 sets the reference value line intensity corresponding to the height of the reference value with respect to the concentration of the standard sample containing the compound to be quantified. Then, the image data creation unit 17 creates image data for displaying by superimposing the reference value intensity line corresponding to the reference value line intensity on the screen displaying the extracted ion chromatogram of the quantification ion of the compound to be quantified. Will be done. Therefore, according to the above embodiment, the information on whether or not the intensity of the quantified ion of the quantification target compound exceeds a predetermined reference value (threshold value) is made to correspond to the extracted ion chromatogram of the quantification ion of the quantification target compound. Can be confirmed.

Further, in the above embodiment, when the intensity of the quantitative ion of the extracted ion chromatogram exceeds the reference value, the screening unit 15 notifies the user via the speaker 18 or the like. Therefore, according to the present embodiment, the user can immediately grasp that the intensity of the quantitative ion exceeds the reference value.

Further, in the above embodiment, the screening condition setting unit 14 measures only one standard sample containing the target component having a known single concentration when setting the reference value line intensity. Therefore, according to the present embodiment, it is not necessary to measure a plurality of standard samples including a plurality of concentration target components as in the conventional case, so that the labor and time required for measuring the standard sample can be saved. In addition, since it is not necessary to set the quantification conditions in detail, it is possible to easily screen the compound to be quantified without the trouble of opening the quantification condition setting screen separately.

Further, in the above embodiment, the screening unit 15 is a quantification target in a peak detection time range having a predetermined time width centered on the retention time [RT] of the quantification target compound, which is preset for the quantification target compound. Perform a peak search for quantitative ions of the compound. Then, the image data creation unit 17 creates image data for displaying the extracted ion chromatogram in which the peak search for quantitative ions is performed by the screening unit 15 on the screen (EIC display area Ar12). Therefore, according to the present embodiment, the user can efficiently confirm only the extracted ion chromatogram of the compound for which the peak search for quantitative ions is performed in the screening unit 15 on the screen of the display unit 20. it can.

Further, in the above embodiment, when the identification unit 16 detects the peak of the quantification ion of the quantification target compound within the peak detection time range, the compound in which the peak is detected is identified as the quantification target compound. Therefore, according to the present embodiment, the compound for which it is desired to determine whether or not the intensity exceeds the reference value can be easily identified.

Further, in the embodiment of the regulation, the identification unit 16 adds the measured I / Q ratio and the set I / Q ratio in addition to the information on whether or not the peak of the quantitative ion of the compound to be quantified is detected within the peak detection time range. The compound to be quantified can be identified by using the information as to whether or not the difference between the above is within a predetermined error range. Therefore, according to the present embodiment, the identification accuracy of the compound to be quantified can be further improved.

It should be noted that the present invention is not limited to the above-described embodiments, and it goes without saying that various other application examples and modifications can be taken as long as the gist of the present invention described in the claims is not deviated.

For example, in the above embodiment, when the intensity of the quantitative ion of the compound to be quantified exceeds the reference value line intensity, the screening unit 15 notifies the user via the speaker 18 or the like. The invention is not limited to this. For example, not only not only the user is notified, or instead of the notification process to the user, control may be performed to forcibly stop the operation of the mass spectrometry target device to which the mass spectrometer is connected. As a result, for example, when a pollutant or a residual substance exceeding a reference value is detected in the process of process analysis, the operation of the apparatus can be stopped quickly.

Further, for example, the above-described embodiment describes the configuration of the device in detail and concretely in order to explain the present invention in an easy-to-understand manner, and is not necessarily limited to the one including all the described configurations. Further, the control lines or information lines shown by solid lines in FIG. 1 show those considered necessary for explanation, and do not necessarily show all the control lines and information lines in the product. In practice, it can be considered that almost all configurations are interconnected.

1 ... Mass spectrometer, 1a ... Data processing device for mass spectrometry, 10 ... Input / output control unit, 11 ... Storage unit, 12 ... Mass spectrum extraction unit, 13 ... Chromatogram creation unit, 14 ... Screening condition setting unit, 15 ... Screening unit, 16 ... identification unit, 17 ... image data creation unit, 18 ... speaker, 19 ... operation unit, 20 ... display unit, 102 ... mass spectrometry unit, Ar1 ... chromatogram display area, Ar11 ... TICC display area, Ar12 ... EIC display area, Ar2 ... Screening result display area, L1 ... Reference value intensity line

Claims (6)

A mass spectrometric data processing device for identifying and quantifying the sample components based on the data obtained by sequentially mass spectrometrically analyzing the sample components separated according to the retention time by a chromatograph.
Extraction of quantitative ions of the compound to be quantified A chromatogram preparation unit that creates an ion chromatogram,
A screening condition setting unit that sets a reference value line intensity corresponding to the height of the intensity of a predetermined reference value set for the quantification ion with respect to the concentration of the standard sample containing the compound to be quantified.
An image data creation unit that creates image data for superimposing and displaying a reference value intensity line corresponding to the reference value line intensity on a screen displaying the extracted ion chromatogram, and an image data creation unit.
It is screened whether or not the intensity of the quantitative ion of the compound to be quantified from which the extracted ion chromatogram is generated exceeds the reference value line intensity, and when the intensity of the quantitative ion exceeds the reference value, the same is performed. A mass spectrometric data processing device including a screening unit for notifying the fact. The screening condition setting unit according to claim 1, measures one standard sample containing a known single concentration of a target component, and sets the reference value line intensity using the measurement result of the standard sample. Data processing device for mass spectrometry. The screening unit peaks the quantification ions of the quantification target compound in a peak detection time range including a predetermined time width before and after the retention time of the quantification target compound, which is preset for the quantification target compound. Do a search and
The mass spectrometry for mass spectrometry according to claim 1 or 2, wherein the image data creation unit creates image data for displaying an extracted ion chromatogram in which a peak search for quantitative ions is performed in the screening unit on the screen. Data processing device. An identification unit for identifying that the sample component is the compound to be quantified is further provided.
The mass spectrometry according to claim 3, wherein the identification unit identifies the compound in which the peak is detected as the quantification target compound when the peak of the quantification ion of the quantification target compound is detected within the peak detection time range. Data processing device. The identification unit includes an actually measured I / Q ratio which is an actually measured value of an I / Q ratio indicating the ratio of the intensity of the reference ion to the intensity of the quantifying ion of the quantification target compound, and a quantification for quantifying the quantification target compound. Compare with the set I / Q ratio, which is the I / Q ratio set in the condition,
When the difference between the two I / Q ratios obtained as a result of the comparison is within the preset tolerance range, and / or the peak of the quantification ion of the quantification target compound is detected within the peak detection time range. The mass spectrometric data processing apparatus according to claim 4, wherein the compound being measured is identified as a compound to be quantified. A mass spectrometric data processing method for identifying and quantifying the sample components based on the data obtained by sequentially mass spectrometrically analyzing the sample components separated according to the retention time by a chromatograph.
Extraction of quantitative ions of the compound to be quantified Creating an ion chromatogram and
To set the reference value line intensity corresponding to the height of the intensity of the predetermined reference value set for the quantification ion with respect to the concentration of the standard sample containing the compound to be quantified.
Creating image data for superimposing and displaying a reference value intensity line corresponding to the reference value line intensity on a screen displaying the extracted ion chromatogram, and generating the extracted ion chromatogram. Mass spectrometry including screening whether or not the intensity of the quantitative ion of the compound to be quantified exceeds the reference value line intensity, and notifying the fact when the intensity of the quantitative ion exceeds the reference value. Data processing method.

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