JP2015152350A - Data processing device for chromatograph mass analysis device - Google Patents

Abstract

A data processing apparatus for a chromatograph mass spectrometer capable of appropriately displaying a plurality of chromatograms that a user wants to confirm belongs to different segments. One or a plurality of masses obtained by analysis using a chromatograph mass spectrometer in a data processor for chromatograph mass spectrometry that processes data obtained by the chromatograph mass spectrometer. A chromatogram acquisition means 42 for acquiring a plurality of chromatograms representing changes in ionic strength over time, and grouping to create a plurality of chromatogram groups by grouping the plurality of chromatograms according to the acquisition time Means 43 and chromatogram rendering means 45 for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups are provided. [Selection] Figure 1

Description

  The present invention creates and displays a large number of chromatograms based on data acquired by a chromatograph mass spectrometer such as a liquid chromatograph mass spectrometer (LC / MS) or a gas chromatograph mass spectrometer (GC / MS). The present invention relates to a data processing apparatus for a chromatograph mass spectrometer.

  When performing qualitative analysis and quantitative analysis of each component in a sample containing a plurality of components (compounds), a chromatographic mass spectrometer such as LC / MS or GC / MS is often used. In these chromatograph mass spectrometers, a sample is introduced into a column of a chromatograph (LC section or GC section), various components contained in the sample are separated in a time direction, and ions derived from the separated components are separated. It detects sequentially with a mass spectrometer (MS part).

  By the way, in order to identify a substance having a large molecular weight and analyze its structure, a technique called MSMS analysis is widely known as one of mass spectrometry, and MSMS analysis is also used as an MS part in the chromatograph mass spectrometer. Is often used. There are various types of mass spectrometers that can perform MSMS analysis, but tandem quadrupole type (also called triple quadrupole type) mass spectrometry is relatively simple and widely used. There is a device.

  As disclosed in Patent Document 1 and the like, a general tandem quadrupole mass spectrometer includes a front quadrupole mass filter (quadrupole Q1) and a rear quadrupole mass filter (quadrupole). A collision cell (collision chamber) that dissociates ions by collision-induced dissociation (CID) is provided between Q3) and Q3). In this collision cell, a quadrupole (or more multipole) type ion guide (quadrupole q2) is arranged to transport ions while converging them.

  When various ions generated from the sample are introduced into the preceding quadrupole Q1, the quadrupole Q1 selectively passes only ions having a specific mass (strictly m / z) as precursor ions. . A CID gas such as argon (Ar) gas is introduced into the collision cell, and the precursor ions introduced into the collision cell collide with the CID gas and dissociate to generate various product ions. Precursor ions and various product ions are converged by the action of a high-frequency electric field formed by the quadrupole q2. When various product ions generated by the CID are introduced into the subsequent quadrupole Q3, the quadrupole Q3 can selectively pass only product ions having a specific mass and pass through the quadrupole Q3. Product ions reach the detector and are detected.

  The above tandem quadrupole mass spectrometer can perform MSMS analysis in various measurement modes such as MRM (Multiple Reaction Monitoring) measurement, product ion scan measurement, neutral loss scan measurement, and precursor ion scan measurement. is there. In the MRM measurement, the masses of ions that can pass through the front quadrupole Q1 and the rear quadrupole Q3 are fixed, and the intensity of a specific product ion generated from a specific precursor ion is measured. In the product ion scan measurement, the mass of ions passing through the front quadrupole Q1 is fixed to a certain value, while the mass of ions passing through the rear quadrupole Q3 is scanned in a predetermined mass range. . Thereby, a mass spectrum of product ions generated from a specific precursor ion can be obtained. In the precursor ion scan measurement, contrary to the product ion scan measurement, the mass of ions passing through the subsequent quadrupole Q3 is fixed to a certain value, while the mass of ions passing through the previous quadrupole Q1 is set to a predetermined value. Scan in the mass range of. Thereby, a mass spectrum of a precursor ion that generates a specific product ion can be obtained. In the neutral loss scan measurement, the difference between the mass of ions passing through the front quadrupole Q1 and the mass of ions passing through the rear quadrupole Q3 (that is, neutral loss) is kept constant while the front quadrupole Q1 and Mass scanning is performed in a predetermined mass range in the subsequent quadrupole Q3. Thereby, a mass spectrum of a precursor ion desorbing a specific neutral molecule can be obtained.

  For example, in the LC / MS described in Non-Patent Document 1, any of a plurality of measurement modes as described above is added to the analysis method describing the operation contents of the LC unit and the MS unit accompanying one sample introduction into the LC unit. It is possible to set up to 1000 measurement events that define the measurement conditions for implementing one. Each measurement event includes, in addition to the type of measurement mode executed in the measurement event, measurement parameters necessary for execution of the measurement mode, such as measurement start time and execution end time of the measurement event, measurement with mass scanning. If there is a mass at the start and end of scanning in the quadrupoles Q1 and Q3, a combination of masses that pass through the quadrupoles Q1 and Q3 (called transitions or channels) if measurement without mass scanning (MRM measurement), etc. Is set. Overlap of time ranges in which a plurality of measurement events are executed is allowed, and in the overlapped time ranges, the measurement modes set for the plurality of measurement events are executed while being switched at a predetermined short cycle. As a result, apparently a plurality of measurement modes are executed in parallel.

  The result of the sample measurement by the chromatograph mass spectrometer as described above is analyzed and processed by a data processing apparatus equipped with dedicated data processing software, and is displayed on the monitor screen and presented to the user. During execution of the above various measurement events, mass scanning and channel switching are repeatedly performed at short time intervals in the MS unit, and a mass spectrum representing the ion intensity of each mass is acquired each time. Further, a mass chromatogram representing the time change of the intensity of a predetermined ion in the mass spectrum and a total ion chromatogram representing the time change of the total ion intensity on the mass spectrum are generated. For this reason, depending on the measurement conditions, a large number of chromatograms may be acquired by one sample analysis using a chromatographic mass spectrometer (that is, a measurement operation accompanying one sample introduction into the LC unit or GC unit). is there.

  However, in the conventional data processing device, when displaying the chromatogram obtained by one sample analysis using the chromatograph mass spectrometer on the monitor, two types of display, “all segment display” and “segment display”, are displayed. Only the method could be selected. Here, the segment indicates a time range in which one or more measurement events are executed in a time range from the start to the end of analysis of a certain sample by the chromatograph mass spectrometer. Note that measurement events belonging to the same segment must have the same execution start time and end time. Moreover, different segments may partially overlap in time. That is, for example, if the execution start time and the execution end time of two measurement events are the same, they belong to the same segment, while, for example, the execution start times of two measurement events are the same and the execution end time Are different, these measurement events belong to different segments.

  When “All Segment Display” is selected in the above conventional data processing device, all of the chromatograms acquired from the start to the end of the analysis of one sample by the chromatograph mass spectrometer are displayed on the monitor screen. The On the other hand, when “display by segment” is selected, only the chromatogram obtained in the segment specified by the user is displayed.

  FIG. 6 shows an example of a setting screen for setting the display method of the chromatogram in the segment display. In this example, “segment # 104” and “event # 109” are displayed in the segment selection area 91 at the upper left of the screen. This indicates that the display setting of “Segment # 104” is currently set on this setting screen, and that this segment includes one measurement event “Event # 109”. Note that the segment to be displayed can be changed as appropriate by pressing the arrow button 92 in the segment selection area 91. Radio buttons 93, 94, 95, and 96 are used to select the type of chromatogram to be displayed in addition to the mass chromatogram for the measurement event checked by the user in the adjacent event selection area 97. . Here, “TIC” means a total ion chromatogram, “BPC” means a base peak chromatogram (a chromatogram created using only the intensity of the highest intensity peak on each spectrum), and “MIC”. Means a mixed ion chromatogram (a sum of a plurality of mass chromatograms). When the “None” radio button 96 is selected, TIC, BPC, or MIC is not displayed, and only the mass chromatogram is displayed. The transition selection field 98 allows the user to select which transition to display a mass chromatogram when the event is MRM measurement.

Japanese Unexamined Patent Publication No. 7-201304

"Triple quadrupole LC / MS / MS system LCMS-8030", [online], Shimadzu Corporation, [October 28, 2013 search], Internet <URL: http: //www.an.shimadzu .co.jp / lcms / lcms8030 / 8030-1.htm>

  Such a method of displaying a chromatogram does not cause a problem particularly when the number of chromatograms generated by one sample analysis by a chromatograph mass spectrometer is small. However, in recent years, the number of measurement events that can be set in one analysis method file (that is, the number of measurement events executed in one sample analysis) has increased, and the multi-channeling of the MS section has progressed. An enormous number of chromatograms have been generated. Therefore, when all segments are displayed, a large number of chromatograms are displayed as shown in FIG. 7, and it is difficult to visually recognize individual chromatograms. On the other hand, in the segment display, as shown in FIG. 8, only the chromatogram relating to the selected segment is displayed, so the number of chromatograms displayed at a time is relatively small (two in the example in the figure). Individual chromatograms can be easily visually recognized. On the other hand, when a plurality of chromatograms that the user wants to check spans different segments, they cannot be displayed properly.

  The present invention has been made in view of the above points, and the object of the present invention is to appropriately display even when a plurality of chromatograms that the user wants to confirm belong to different segments. It is an object of the present invention to provide a data processing device for a chromatograph mass spectrometer that can be presented to a user in a state where a chromatogram can be easily visually recognized.

A data processing apparatus for a chromatograph mass spectrometer according to the present invention, which has been made to solve the above-mentioned problems, is a chromatograph mass spectrometer that analyzes each component in a sample temporally separated by a chromatograph using a mass spectrometer. A data processing apparatus for chromatographic mass spectrometry that processes data obtained by an apparatus,
a) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by analysis using the chromatograph mass spectrometer and representing a time change of ion intensity at one or a plurality of masses;
b) grouping means for creating a plurality of chromatogram groups by grouping the plurality of chromatograms according to their acquisition times;
c) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
It is characterized by having.

Further, the data processing device for a chromatograph mass spectrometer according to the present invention processes data obtained by a chromatograph mass spectrometer that analyzes each component in a sample temporally separated by a chromatograph using a mass spectrometer. A data processing apparatus for chromatographic mass spectrometry,
a) mass spectrum acquisition means for acquiring a mass spectrum for each component in the sample obtained by analysis using the mass spectrometer;
b) a compound identification means for identifying the compound corresponding to the mass spectrum by collating the mass spectrum with a compound library describing mass spectrum patterns for a plurality of compounds;
c) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by the analysis by the chromatograph mass spectrometer and representing the time change of the ionic strength at one or a plurality of masses;
d) Among the plurality of chromatograms, one or a plurality of chromatograms relating to the mass derived from each compound identified by the compound identification means are grouped as a chromatogram relating to the compound, thereby obtaining a plurality of chromatogram groups. Grouping means to create,
e) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
It is good also as what is characterized by having.

Further, the data processing device for a chromatograph mass spectrometer according to the present invention processes data obtained by a chromatograph mass spectrometer that analyzes each component in a sample temporally separated by a chromatograph using a mass spectrometer. A data processing apparatus for chromatographic mass spectrometry,
a) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by analysis using the chromatograph mass spectrometer and representing a time change of ion intensity at one or a plurality of masses;
b) grouping means for creating a plurality of chromatogram groups by dividing the plurality of chromatograms into a plurality of groups;
c) a user instruction receiving means for allowing a user to select a chromatogram to be included in each of the plurality of chromatogram groups created by the grouping means from the plurality of chromatograms;
d) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
It is good also as what is characterized by having.

  According to the data processing apparatus for a chromatograph mass spectrometer according to the present invention configured as described above, a plurality of chromatograms obtained by analyzing a sample by the chromatograph mass spectrometer are displayed across the segments. be able to. As a result, even if multiple chromatograms that the user wants to confirm belong to different segments, they can be displayed properly and each chromatogram can be presented to the user in a state where they can be easily viewed. It becomes.

1 is a block diagram showing a schematic configuration of a sample analysis system including a data processing apparatus according to an embodiment of the present invention. The figure which shows an example of the measurement condition setting screen in the data processor which concerns on the same embodiment. The figure which shows an example of the display setting screen in the data processor which concerns on the same embodiment. The figure which shows an example of the screen display at the time of carrying out group display of the chromatogram in the data processor which concerns on the same embodiment. The figure which shows an example of the highlight display setting screen in the data processor which concerns on the same embodiment. The figure which shows an example of the display setting screen in the conventional data processor. The figure which shows an example of all the segment display in the conventional data processor. The figure which shows an example of the display according to segment in the conventional data processor.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of a sample analysis system including a data processing device for a chromatograph mass spectrometer according to the present embodiment, and FIGS. 2 to 5 are diagrams showing examples of screen display in the data processing device according to the present embodiment. is there.

  The sample analysis system according to the present embodiment controls the operation of the liquid chromatograph mass spectrometer (LC / MS) 10 and the LC / MS 10, acquires measurement data from the LC / MS 10, and analyzes and processes the data. The control / data processing device 20 is included.

  The LC / MS 10 includes an LC unit 11 that temporally separates a sample by a column (not shown) and sequentially elutes, and an MS unit 12 for detecting sample components that are sequentially eluted from the LC unit 11. The MS unit 12 includes an A / D converter (not shown), and sends a digitized detection signal to the control / data processing device 20 through a communication line.

  The actual state of the control / data processing apparatus 20 is a computer such as a workstation or a personal computer, a CPU (Central Processing Unit) 22 which is a central processing unit, a memory 23, a LCD (Liquid Crystal Display) and the like (display). Part) 24, an input part 25 comprising a keyboard, a mouse, etc., and a storage part 30 comprising a mass storage device such as a hard disk or SSD (Solid State Drive). The storage unit 30 stores an OS (Operating System) 37, an LC / MS control program 31, a data processing / display program 32, and a compound library 33, and a compound table storage unit 34, a setting storage unit 35, and measurement data. A storage unit 36 is provided. In the compound library 33, structural formulas, mass spectra, and the like are recorded as information necessary for qualitative analysis of various compounds. The control / data processing apparatus 20 further includes an interface (I / F) 21 for direct connection with an external apparatus or connection with a network such as a LAN (Local Area Network) with the external apparatus. The I / F 21 is connected to the LC / MS 10 via a USB cable. In this example, the LC / MS control program 31 and the data processing / display program 32 are mounted on the same computer, and the computer functions as the control / data processing apparatus 20, but these programs are stored in another computer. It is possible to mount the LC / MS control device and the data processing device separately.

  In FIG. 1, as in the data processing / display program 32, a spectrum creation unit 41 (corresponding to mass spectrum acquisition means in the present invention), a chromatogram creation unit 42 (corresponding to chromatogram acquisition means in the present invention), a group A conversion unit 43, a compound identification unit 44, a display control unit 45, a base shift unit 46, a waveform enhancement unit 47, and an all segment TIC display switching unit 48 are shown. These are basically functional means realized by software by the CPU 22 executing the data processing / display program 32.

  When analyzing a sample by the sample analysis system according to the present embodiment, first, the user appropriately operates the input unit 25 to instruct execution of the LC / MS control program 31 and monitor various setting screens. 24, the measurement conditions of the LC unit 11 and the MS unit 12 are set, and stored in the setting storage unit 35 as an analysis method.

  The MS unit 12 does not perform the same measurement for the entire sample introduced after being separated from the LC unit 11 in time, but changes in the chromatogram such as where a peak exists. It is usual to carry out a predetermined measurement for only the places that are seen, i.e. only for one or more time ranges. Therefore, in order to execute a desired analysis, a past chromatogram for the same sample is prepared as a reference chromatogram, and a user executes which measurement at which time while referring to this reference chromatogram. It is necessary to set this. FIG. 2 shows an example of a measurement condition setting screen for performing such setting work. The measurement condition setting screen includes an event addition button area 51, a chromatogram display area 52, a measurement condition name display area 53, and a measurement condition setting area 54. In the chromatogram display area 52, a reference chromatogram designated by the user is displayed. Then, for example, when the user designates an event to be executed by pressing a button arranged in the event addition button area 51 and inputs measurement conditions for the measurement event in the measurement condition setting area 54, the chromatogram is displayed each time. A range bar that visually indicates the execution time range of each event is displayed superimposed on the reference chromatogram displayed in the gram display area 52.

  In the example of FIG. 2, a total of five events 1 to 5 are set, the “product ion scan” of event 1 is a time range of 39 to 42 minutes, and the “MRM” of event 2 is 31 to 34 minutes. Time range, “precursor ion scan” of event 3 is 27-33 minutes, event 4 “product ion scan” is also 27-33 minutes, and event 5 “neutral loss scan” is 4-10 Set to run in minutes. Correspondingly, in the chromatogram display area 52, range bars B1 to B5 relating to the respective events 1 to 5 are displayed superimposed on the reference chromatogram in terms of time. Each range bar B1 to B5 has a horizontal axis direction corresponding to the length of time each measurement is performed at a position corresponding to each time range described above on the time axis (horizontal axis) of the reference chromatogram. Shown with length. In this example, since the start time and end time of event 3 and event 4 coincide with each other, they belong to the same segment (segment 3 in the figure). On the other hand, since event 1, event 2, and event 5 do not have the same start time and end time as other events, they belong to different segments (segment 1, segment 2, and segment 4 in the figure). It becomes.

  When the user performs a predetermined operation from the input unit 25 to instruct the start of sample analysis, the measurement time set on the measurement condition setting screen is set to 0 minutes when the sample is injected into the mobile phase in the LC unit 11. It is sequentially executed by the MS unit 12. When each event is executed, ion detection of a predetermined mass or mass range is repeatedly executed in the MS unit 12, and a detection signal is sent to the control / data processing device 20 accordingly. Thus, three-dimensional data having three dimensions of time, mass (m / z), and signal intensity (ion intensity) is stored in the measurement data storage unit 36 for each measurement event.

  The data processing / display program 32 executes various processes on the collected data. For example, the spectrum creation unit 41 creates a mass spectrum representing the mass and intensity of ions detected at a predetermined time based on the three-dimensional data. Further, the chromatogram creation unit 42 is a mass chromatogram representing the time change of the ion intensity of a predetermined mass, or a total ion chromatogram representing the time change of the total ion intensity detected by the MS unit 12 at each time. And so on. The mass spectrum and chromatogram created as described above are also stored in the measurement data storage unit 36.

  The control / data processing apparatus 20 according to the present embodiment is characterized by a display method when displaying the chromatogram created by the chromatogram creation unit 42 on the monitor 24. Hereinafter, this point will be described.

  First, the grouping unit 43 of the data processing / display program 32 groups a number of chromatograms created by the chromatogram creation unit 42 according to a predetermined standard (described later). Thereby, a plurality of groups each containing one or a plurality of chromatograms (hereinafter referred to as “chromatogram groups”) are created. Information about which chromatogram group each chromatogram belongs to is stored in the setting storage unit 35. Then, the display control unit 45 displays all the chromatograms belonging to the predetermined chromatogram group side by side on the screen of the monitor 24. Here, the chromatogram group to be displayed can be appropriately changed by the user performing a predetermined operation with the input unit 25. For example, when the user clicks a button displayed on the screen of the monitor 24 using the input unit 25, the chromatogram belonging to the chromatogram group immediately before or after it is replaced with the chromatogram group currently displayed. Can be displayed, or the user can input a chromatogram group identifier (for example, group name or number) from the input unit 25 to display a desired chromatogram group on the monitor 24. In addition to displaying only one chromatogram group, the monitor 24 can simultaneously display two or more chromatogram groups.

  Examples of the grouping standard in the grouping unit 43 include (1) acquisition time of each chromatogram, (2) user instruction, (3) a compound corresponding to each chromatogram, and the like.

  In the grouping method based on the “acquisition time of each chromatogram” in the above (1), for example, the grouping unit 43 obtains a large number of mass chromatograms created by the chromatogram creation unit 42 by the acquisition time ( A predetermined number of groups are grouped in the order of the time of the start point or end point of the mass chromatogram. Alternatively, grouping can be done by setting multiple time zones in the time range from the start to the end of the analysis of one sample by LC / MS10 and grouping the mass chromatograms belonging to the same time zone with the same acquisition time. You may make it perform. In any case, the number of chromatograms included in one chromatogram group and the time zone to be grouped may be automatically set by the apparatus, or may be set by the user via the input unit 25. Good. By appropriately setting the number or the time zone, even when a plurality of target chromatograms straddle different segments, the chromatograms can be appropriately displayed. FIG. 3 shows an example of a setting screen for performing such setting. In this example, in the grouping condition setting area 61, the user can specify the number of chromatogram groups displayed on the screen at a time and the number of chromatograms included in one chromatogram group.

  The all segment TIC display setting area 62 below it is provided with a check box 63 for selecting whether or not the display / non-display setting of the total ion chromatogram is the same for all segments. When the check box 63 is checked, the two radio buttons below it can be selected. When the “TIC” radio button 64 is selected, both the mass chromatogram and the total ion chromatogram are displayed on the monitor 24 for all segments by the all segment TIC display switching unit 48, and when the “none” radio button 65 is selected. Only the mass chromatogram is displayed on the monitor 24 for all segments by the all segment TIC display switching unit 48, and the total ion chromatogram is not displayed. In this way, the display / non-display of the total ion chromatogram can be set for all the segments at once, so that each segment can be individually displayed / non-displayed as in the conventional data processing apparatus described with reference to FIG. As compared with the case of setting, the setting operation by the user can be saved.

Here, for example, it is assumed that sample analysis by the LC / MS 10 is performed using a method file having the following contents.
Number of events: 1000, measurement mode of each event: MRM measurement (two types of transitions are set for each event), number of segments: 1000 (set by shifting the analysis start time of each event).
As a result, two mass chromatograms corresponding to the two types of transitions and a total ion chromatogram obtained by adding their ion intensities are obtained for one measurement event, so a series of measurements according to this method file. As a result, a total of 3000 chromatograms are obtained. Now, suppose that the user wants to confirm the chromatogram of the first transition of the 301st event and the second transition of the 315th event. All the total ion chromatograms are not displayed. In this case, the following settings are performed on the setting screen of FIG.
Number of groups: 1, Number of chromatograms per group: 30, Check box 63 of “Set all segments to the same setting”, and select “None” radio button 75.
As a result, the two chromatograms are assigned to the same chromatogram group and are simultaneously displayed on the screen of the monitor 24 as shown in FIG. The figure shows a state in which the 21st chromatogram group is displayed among 67 chromatogram groups created based on the above settings, and the first transition of the 301st event is shown. The chromatogram is displayed at the top of the screen, and the chromatogram of the second transition of the 315th event is displayed at the bottom of the screen.

  In such a group display (segment cross-sectional display) of the chromatogram, the base shift unit 46 sets the baseline of each chromatogram included in the chromatogram group to be displayed in the vertical axis direction as shown in FIG. Can be shifted. Thereby, since the overlap between chromatograms decreases, visual confirmation of each chromatogram by a user becomes easy. Such a shift of the baseline is appropriately turned on / off by checking or unchecking the “perform base shift” check box 66 on the setting screen of FIG. 3, for example. can do. When the base shift is turned off, since the baselines of the chromatograms are displayed in a matched state, the peak heights can be easily compared.

  In the group display, the waveform emphasizing unit 47 can highlight any chromatogram included in the display target chromatogram group. For example, in the example of FIG. 4, the chromatograms displayed at the top and bottom of the screen are drawn with thicker lines and different colors. For the chromatogram to be highlighted, for example, when the user performs a right click operation or the like on the chromatogram display screen of FIG. 4, the highlight setting screen as shown in FIG. 5 is displayed, and the same setting screen is used. Can be arbitrarily set by the user. In the highlight setting screen shown in the figure, a list of mass chromatograms included in the chromatogram group to be displayed is displayed, and a check box for specifying whether to highlight each chromatogram. 71 and a color designation field 72 for designating the color of the chromatogram.

  In the case of the grouping method based on the “user instruction” in (2) above, the user can arbitrarily enter the number and name of the chromatogram groups to be created, the chromatograms to be included in each chromatogram group, etc. using the input unit 25. The grouping unit 43 groups the plurality of chromatograms generated by the chromatogram creation unit 42 based on the instructions of these users. The chromatograms to be included in each chromatogram group are, for example, the display control unit 45 displaying a list of chromatograms obtained by sample analysis by the LC / MS 10 on the monitor 24, and an arbitrary chromatogram from among them is input to the input unit The user may be allowed to select via 25, or a list of measurement events executed in the sample analysis by the LC / MS 10 is displayed on the monitor 24, and an arbitrary measurement event is selected from the list. It may be. In the latter case, all the mass chromatograms obtained by the selected measurement event are distributed to a predetermined chromatogram group.

  In the case of the grouping method based on the “compound corresponding to each chromatogram” in (3) above, the compound identification unit 44 identifies each component in the sample based on the result of the sample analysis by the LC / MS 10, and the The grouping unit 43 groups chromatograms based on the identification result. Specifically, the compound identification unit 44 first acquires a total ion chromatogram created for each measurement event from the measurement data storage unit 36 and detects a peak on the total ion chromatogram. In the measurement event (for example, MRM measurement) that does not involve mass scanning in the MS unit 12, qualitative information other than the holding time cannot be obtained. Therefore, here, measurement events that involve mass scanning (for example, precursor ion scan, product ion scan) Use the TIC created for measurement etc.). Then, the mass spectrum obtained at the time near the top of each peak is acquired from the measurement data storage unit 36, and the pattern of each mass spectrum is collated with the mass spectrum pattern recorded in the compound library 33 to determine the similarity of the patterns. By extracting a compound having a high value, a compound corresponding to each peak on the total ion chromatogram is identified. Subsequently, mass chromatograms relating to one or more masses characteristic of each identified compound are acquired from the measurement data storage unit 36, and those mass chromatograms are grouped as chromatograms relating to the compounds. The information on the “mass characteristic of the compound” may be acquired from the compound library 33, or the mass satisfying a predetermined condition on the mass spectrum used for identification of the compound (for example, the signal intensity is It is good also considering the mass more than a predetermined value as a characteristic mass for this compound.

  The chromatograms grouped for each corresponding compound in this way are displayed on the monitor 24 under the control of the display control unit 45, for example, in the order of the retention time of each compound. For example, when the user instructs the chromatogram group display from the input unit 25, one or a plurality of mass chromatograms belonging to the chromatogram group corresponding to the compound having the shortest retention time among the compounds contained in the sample are monitored. 24 screens are displayed at once. Thereafter, when the user instructs to display the next chromatogram group, instead of the chromatogram group corresponding to the compound having the shortest retention time, the one belonging to the chromatogram group corresponding to the compound having the second shortest retention time. One or more mass chromatograms are displayed.

  In addition to the display according to the retention time order of the compounds, a compound table, that is, a table in which identification information (typically compound names) of a plurality of compounds is described in a predetermined order is stored in the compound table storage unit 34. In addition, the chromatogram groups may be displayed according to the description order on the compound table. In this case, the description order of each compound on the compound table is changed, or a plurality of compound tables having different compound description orders are stored in the compound table storage unit 34, and the compound table used for determining the display order is switched. By doing so, the display order of the chromatogram groups can be appropriately changed.

  It should be noted that it is preferable that the user can appropriately select via the input unit 25 on which criteria the grouping unit 43 performs chromatogram grouping.

  As mentioned above, although the form for implementing this invention was demonstrated, this invention is not limited to the said embodiment, A change is accept | permitted suitably in the range of the meaning of this invention. For example, in the above embodiment, the case where the data processing apparatus for a chromatogram mass spectrometer according to the present invention is used as a data processing apparatus for LC / MS has been described as an example. However, for the chromatogram mass spectrometer according to the present invention, The data processing device may be a data processing device for GC / MS. Moreover, in the said embodiment, although the spectrum creation part 41 and the chromatogram creation part 42 correspond to the mass spectrum acquisition means and chromatogram acquisition means in this invention, respectively, the mass spectrum acquisition means and chromatogram acquisition in this invention exist. The means may acquire a mass spectrum and a chromatogram created by a computer configured separately from the chromatograph mass spectrometry data processing apparatus according to the present invention via a network or the like.

10 ... LC / MS
DESCRIPTION OF SYMBOLS 20 ... Control / data processing device 24 ... Monitor 25 ... Input part 30 ... Storage part 32 ... Data processing / display program 33 ... Compound library 34 ... Compound table storage part 35 ... Setting storage part 36 ... Measurement data storage part 41 ... Spectrum creation Unit 42 ... Chromatogram creation unit 43 ... Grouping unit 44 ... Compound identification unit 45 ... Display control unit 46 ... Base shift unit 47 ... Waveform emphasis unit 48 ... All segment TIC display switching unit

Claims (8)

A data processing apparatus for chromatographic mass spectrometry that processes data obtained by a chromatographic mass spectrometer that analyzes each component in a sample temporally separated by a chromatograph by a mass spectrometer,
a) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by analysis using the chromatograph mass spectrometer and representing a time change of ion intensity at one or a plurality of masses;
b) grouping means for creating a plurality of chromatogram groups by grouping the plurality of chromatograms according to their acquisition times;
c) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
A data processing apparatus for chromatographic mass spectrometry, comprising: A data processing apparatus for chromatographic mass spectrometry that processes data obtained by a chromatographic mass spectrometer that analyzes each component in a sample temporally separated by a chromatograph by a mass spectrometer,
a) mass spectrum acquisition means for acquiring a mass spectrum for each component in the sample obtained by analysis using the mass spectrometer;
b) a compound identification means for identifying the compound corresponding to the mass spectrum by collating the mass spectrum with a compound library describing mass spectrum patterns for a plurality of compounds;
c) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by the analysis by the chromatograph mass spectrometer and representing the time change of the ionic strength at one or a plurality of masses;
d) Among the plurality of chromatograms, one or a plurality of chromatograms relating to the mass derived from each compound identified by the compound identification means are grouped as a chromatogram relating to the compound, thereby obtaining a plurality of chromatogram groups. Grouping means to create,
e) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
A data processing apparatus for chromatographic mass spectrometry, comprising: Furthermore,
f) Compound table storage means for storing a compound table describing a plurality of compounds in a predetermined order;
The chromatogram mass according to claim 2, wherein the chromatogram rendering means renders a chromatogram in units of the chromatogram groups in accordance with a description order of the compounds on the compound table. Data processing device for analysis.   3. The chromatogram mass spectrometric analysis according to claim 2, wherein the chromatogram rendering means renders chromatograms in units of the chromatogram groups in the order of retention times of the compounds corresponding to the chromatogram groups. Data processing device. A data processing apparatus for chromatographic mass spectrometry that processes data obtained by a chromatographic mass spectrometer that analyzes each component in a sample temporally separated by a chromatograph by a mass spectrometer,
a) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by analysis using the chromatograph mass spectrometer and representing a time change of ion intensity at one or a plurality of masses;
b) grouping means for creating a plurality of chromatogram groups by dividing the plurality of chromatograms into a plurality of groups;
c) a user instruction receiving means for allowing a user to select a chromatogram to be included in each of the plurality of chromatogram groups created by the grouping means from the plurality of chromatograms;
d) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
A data processing apparatus for chromatographic mass spectrometry, comprising: A data processing program for chromatograph mass spectrometry for processing data obtained by a chromatograph mass spectrometer that analyzes each component in a sample separated in time by a chromatograph by a mass spectrometer, comprising:
a) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by analysis using the chromatograph mass spectrometer and representing a time change of ion intensity at one or a plurality of masses;
b) grouping means for creating a plurality of chromatogram groups by grouping the plurality of chromatograms according to their acquisition times;
c) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
A data processing program for chromatographic mass spectrometry, characterized in that it functions as: A data processing program for chromatograph mass spectrometry for processing data obtained by a chromatograph mass spectrometer that analyzes each component in a sample separated in time by a chromatograph by a mass spectrometer, comprising:
a) mass spectrum acquisition means for acquiring a mass spectrum for each component in the sample obtained by analysis using the mass spectrometer;
b) a compound identification means for identifying the compound corresponding to the mass spectrum by collating the mass spectrum with a compound library describing mass spectrum patterns for a plurality of compounds;
c) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by the analysis by the chromatograph mass spectrometer and representing the time change of the ionic strength at one or a plurality of masses;
d) Among the plurality of chromatograms, one or a plurality of chromatograms relating to the mass derived from each compound identified by the compound identification means are grouped as a chromatogram relating to the compound, thereby obtaining a plurality of chromatogram groups. Grouping means to create,
e) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
A data processing program for chromatographic mass spectrometry, characterized in that it functions as: A data processing program for chromatograph mass spectrometry for processing data obtained by a chromatograph mass spectrometer that analyzes each component in a sample separated in time by a chromatograph by a mass spectrometer, comprising:
a) a chromatogram acquisition means for acquiring a plurality of chromatograms obtained by analysis using the chromatograph mass spectrometer and representing a time change of ion intensity at one or a plurality of masses;
b) grouping means for creating a plurality of chromatogram groups by dividing the plurality of chromatograms into a plurality of groups;
c) a user instruction receiving means for allowing a user to select a chromatogram to be included in each of the plurality of chromatogram groups created by the grouping means from the plurality of chromatograms;
d) a chromatogram rendering means for rendering the plurality of chromatograms on a display screen in units of the chromatogram groups;
A data processing program for chromatographic mass spectrometry, characterized in that it functions as:

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