JP4682682B2 - Chromatographic data processor - Google Patents

Description

The present invention relates to a chromatograph mass spectrometer combining a chromatograph such as a gas chromatograph (GC) or a liquid chromatograph (LC) and a mass spectrometer, or a liquid chromatograph using a photodiode array detector as a detector. such as, time, data for addition to mass can be acquired three-dimensional chromatogram data having a third dimension, such as and the wavelength (exact mass-to-charge ratio m / z is) chromatographic signal strength The present invention relates to a processing apparatus.

GC / MS has a configuration in which a sample component temporally separated by column GC, detected each of the separated components were separated according to mass various ions after ionization, respectively. Thus based on the detected data, on the horizontal axis mass, mass spectrum is created by taking the detected ionic strength on the vertical axis. The time elapsed by focusing on a particular one quality amount (i.e. separation direction of the sample components) on the horizontal axis, mass chromatogram (MC) is created by taking the ionic strength on the vertical axis. Also, the horizontal axis the time elapsed by focusing on a plurality of specific mass or mass range, mixed ion chromatogram (MIC) is created by taking the ionic strength on the vertical axis. Furthermore, regardless of the mass, the horizontal axis the time course, the total ion chromatogram (TIC) is created by taking the ionic strength on the vertical axis.

  Since chromatograms such as TIC, MIC, and MC are often compared with each other, a plurality of chromatograms can be simultaneously displayed on the same display screen (see Patent Document 1, etc.), or a plurality of chromatograms can be displayed along the same time axis. In many cases, the chromatogram is overlaid and displayed while gradually shifting the baseline in the signal intensity direction.

  By the way, in general, in such a chromatogram, peak detection is automatically performed based on the slope of the chromatogram curve. For example, when a plurality of peaks are overlapped as shown in FIG. Even if a plurality of peaks can be discriminated if confirmed, the automatic peak detection process often detects a single peak. In such cases, the operator manually divides the overlapping peaks by performing operations such as determining the start and end points of each peak, but multiple chromatograms are overlaid and displayed as described above. If so, the peak is divided at the same dividing point designated for all chromatograms.

  However, in actuality, the time position where the peak should be divided for each chromatogram is slightly different or there is a chromatogram that does not require peak division, so in a mode where multiple chromatograms are overlaid and displayed. The peak splitting process as described above is not very appropriate.

Japanese Patent Laid-Open No. 5-164751 (paragraph [0002])

  The present invention has been made to solve such a problem, and an object of the present invention is to appropriately divide a desired peak of a desired chromatogram in a state where a plurality of chromatograms are overlaid and displayed. It is an object of the present invention to provide a chromatographic data processing apparatus capable of performing the above.

In order to solve the above problems, the first aspect of the present invention provides a plurality of chromatograms created based on three-dimensional chromatogram data having a third dimension in addition to time and signal intensity. In the chromatograph data processing apparatus having a function of drawing along the display screen and drawing on the display screen,
a) an input means for an operator to specify an arbitrary position on a display screen on which a plurality of chromatograms are overlaid and displayed;
b) identification means for identifying a chromatogram closest to the designated point on a time corresponding to the designated point from the input means among a plurality of chromatograms displayed in an overlaid manner;
c) division processing means for dividing the peak appearing in the chromatogram identified by the identification means at a time position corresponding to the designated point;
Each of the peaks divided into two by the division processing means when calculating peak information including peak area and / or peak height, each of the division processing means, Determining means for determining whether or not there is a peak to be divided at a time position corresponding to the specified point, and when the determining means determines that there is no peak to be divided by the determining means, Identifying a chromatogram next to the designated point next to the designated point or a time closest to the designated point from a plurality of chromatograms displayed in an overlaid manner, and the identified chromatogram The peak division processing by the division processing means is executed for the above.
According to the second aspect of the present invention, a plurality of chromatograms created based on three-dimensional chromatogram data having a third dimension in addition to time and signal intensity are shifted along the same time axis and in the intensity axis direction. In the chromatograph data processing device having the function of overdrawing and drawing on the display screen,
a) an input means for an operator to specify an arbitrary position on a display screen in which a plurality of chromatograms are overlaid and displayed with the same time axis shifted in the intensity axis direction;
b) an identification means for identifying a chromatogram closest to the designated point on the time corresponding to the designated point by the input means from among the plurality of chromatograms displayed in an overlaid manner;
c) division processing means for dividing the peak appearing in the chromatogram identified by the identification means at a time position corresponding to the designated point;
When the peak information including the peak area and / or the peak height is calculated, each of the peaks divided into two by the division processing unit is handled as a separate peak.

  In the chromatograph data processing apparatus according to the present invention, when a peak appearing in a certain chromatogram among a plurality of chromatograms displayed in an overlapping manner is to be divided into two, A position close to the chromatogram (relative to other chromatograms) on the time position to be divided on the chromatogram is designated by the input means. The discriminating means is a chromatogram closest to the designated point or on the time corresponding to the designated point (generally, on the line including the designated point and parallel to the signal intensity axis and perpendicular to the time axis). The chromatogram closest to the designated point, that is, the desired chromatogram, is identified, and the dividing means vertically divides the peak appearing in the chromatogram vertically in time at the time position corresponding to the designated point.

However, in some cases, an operator may mistakenly or unintentionally specify a position that is not a peak by using the input means. Accordingly, in a first aspect, the division processing unit including determining means for determining whether the peak should be divided into a time position corresponding to the designated point exists. Determine the constant unit may determine whether there is a peak depending on whether e.g. dividing point become to the time position is sandwiched between the starting point and the end point of the peak of the peak.

  When the division processing unit divides the peak vertically, for example, the position is determined as the end point of the immediately preceding peak and the start point of the immediately following peak. Of course, if the end point and start point of a new peak are determined in this way, the graph display may be updated so that the graph display control means adds such display. Further, by executing calculations of the peak area, peak height, holding time, concentration, etc. with the peak end point and start point updated, peak information corresponding to the divided peaks can be obtained. Along with peak splitting instructions, automate the recalculation of peak information after such splitting, and reflect the peak information obtained by recalculation in the numerical values displayed on the display screen or other screens. You may do it.

  As described above, according to the chromatographic data processing apparatus of the present invention, only the peak appearing in any one chromatogram among the plurality of chromatograms displayed in an overlaid manner is included in the other chromatograms. It can be divided by a simple operation without any influence. Therefore, peak splitting can be performed efficiently and accurate peak information can be obtained for each chromatogram.

In addition , according to the first aspect , the input means designates a chromatogram that is not the target chromatogram that is originally intended to be split by mistake or carelessly at a position where there is a relatively close chromatogram. However, if there is no peak at the time position corresponding to the specified point in the chromatogram that is not the purpose, the next closest chromatogram is identified and the chromatogram is divided. Will be tried. Therefore, even if there is an error or inappropriateness in the operator's operation regarding the designation of the division position, the possibility of performing desired peak division increases.

Further, according to the first aspect , when it is known that no peak exists in a chromatogram relatively closer to the target chromatogram at the desired time position, the target chromatogram is dared. It is not necessary to specify by the input means at the nearest position. This improves the workability when the operator designates the time position at which peak division is desired by the input means.

  In this configuration, a configuration further includes notification means for alerting the operator when there is no peak to be divided at a time position corresponding to the specified point for all of the plurality of chromatograms displayed in an overlaid manner. It is good to do.

  Hereinafter, an example (Example 1) of a chromatographic data processing apparatus according to the present invention will be described with reference to FIGS. FIG. 1 is an overall configuration diagram of a gas chromatograph mass spectrometer equipped with a data processing apparatus according to this embodiment.

The GC unit 1 includes a column, and temporally separates components contained in the sample to be analyzed and sends the components to the MS unit 2. MS unit 2 ionizes sample components provided sequentially over time, separating and detecting the ions mass to (strictly mass-to-charge ratio m / z) each. For example, in scan measurement, mass analysis is sequentially performed in a predetermined mass step in a predetermined mass range, and ion intensity data in the predetermined mass range is obtained at each time by repeating this continuously. Each component in the original sample is after being separated in the time axis direction by GC unit 1, since further separated on mass axis in the MS unit 2, the data processing unit 3, time, signal strength (ionic strength) and 3-D chromatogram data to mass and dimensions is obtained. The chromatogram data is stored in the storage unit 5 and a predetermined calculation process is executed. The control unit 4 has a function of controlling the operations of the GC unit 1 and the MS unit 2, and is substantially embodied by a personal computer (PC) 6 together with the data processing unit 3 and the storage unit 5. A pointing device such as a keyboard and a mouse is connected to the PC 6 as the operation unit 7, and a monitor is connected as the display unit 8.

  The data processing unit 3 includes a peak division processing unit 11 as a characteristic function of the present embodiment, and the processing result of the peak division processing unit 11 is input to the peak information calculation unit 12, and the peak area, peak height, etc. The peak information is configured to be recalculated.

  Next, the peak splitting process performed with the peak splitting processing unit 11 as the center will be described with reference to FIGS. FIG. 2 is a control flowchart of peak division processing, FIG. 3 is an example of an overlaid chromatogram displayed on the display screen of the display unit 8, and FIG. 4 is a peak waveform diagram showing a state of peak division.

  As shown in FIG. 3A, a plurality of chromatograms (which may be any of TIC, MIC, and MC) G1, G2, and G3 are along the same time axis (horizontal axis) and each baseline is a signal intensity axis. When the operator performs a predetermined operation with the operation unit 7 in a state of being overlaid and displayed in a state shifted in the (vertical axis) direction, the mode shifts to the peak division mode (step S1). 3A and 3B, the upward arrow display 31 indicates the peak start point, and the downward arrow display 32 indicates the peak end point.

  When shifting to the peak division mode, the data processing unit 3 changes the mouse cursor displayed in the display screen 30 to a cross shape (indicated by reference numeral 33 in FIG. 3A) (step S2). The operator operates the mouse which is a part of the operation unit 7 and moves the cross-shaped mouse cursor 33 to the time position of the peak where the desired chromatogram is to be divided (it is not necessarily placed on the chromatogram curve). The position is specified by executing a click operation (step S3), as long as the position is relatively close to the other chromatograms on the vertical line including at least the time position.

  The peak division processing unit 11 of the data processing unit 3 detects the click position by acquiring the coordinate position information where the click operation is performed in the display screen 30 (step S4), and at the same time as the click position, That is, the closest chromatogram is identified on the vertical line that includes the click position and is parallel to the signal intensity axis and perpendicular to the time axis (step S5). As shown in FIG. 3A, when the click operation is performed when the cross-shaped mouse cursor 33 is positioned, the chromatogram G2 is identified as the latest chromatogram. This process is why it is not always necessary to place the cross-shaped mouse cursor 33 on the chromatogram curve as described above.

  Next, the peak division processing unit 11 determines whether or not the time position corresponding to the click position on the chromatogram G2 is between the peak start point and the peak end point (step S6). In the case of the example of FIG. 3A, since it is between the peak start point and end point, the process proceeds to step S7. For example, the operator mistakenly performs a click operation at a position where no peak exists. If it has, the process proceeds from step S6 to step S10, a predetermined warning message is displayed in the display screen 30, and the operator is informed that the click operation is not appropriate.

  In step S7, the peak division processing unit 11 vertically divides the peak appearing in the identified chromatogram G2 back and forth at the time position corresponding to the click position. Thereby, the division point becomes the end point of the immediately preceding peak and the start point of the immediately following peak. Therefore, after the vertical division, as shown in FIGS. 3B and 3C, an upward arrow display 31 and a downward arrow display 32 are displayed at the division points, and a peak division boundary line 34 parallel to the signal intensity axis is displayed. The screen is updated so as to be drawn (step S8).

  As shown in FIG. 4, by the vertical division, the peak division boundary 34 is ahead of the peak division boundary 34 to the peak P <b> 1 having the peak end point, and the peak division boundary 34 is behind the peak division boundary 34. The line 34 is handled as being divided into two peaks P2 having a peak start point. Therefore, the peak information calculation unit 12 receiving the processing result of the peak division processing unit 11 recalculates the peak information such as the peak area, peak height, holding time, and concentration value of each of the peaks P1 and P2, and displays the display screen. The numerical value of the peak information displayed in 30 is updated (step S9). Of course, the peak information may be displayed in a screen different from the display screen 30.

  In addition, what is necessary is just to perform operation from said step S3 continuously, when it is desired to divide the peak of the same or another chromatogram.

  Further, the peak division as described above moves as it is even when the chromatogram is translated. Even if the baseline is inclined rather than horizontal, the division itself is vertical, that is, a line parallel to the signal intensity axis, and the peak information of each peak is recalculated while the baseline is inclined. It will be.

  Next, a chromatographic data processing apparatus according to another embodiment (Example 2) of the present invention will be described. Since the overall configuration of the gas chromatograph mass spectrometer equipped with the data processing apparatus according to the second embodiment is the same as that of the first embodiment, the description thereof is omitted. In the second embodiment, the content of the peak division processing executed mainly by the peak division processing unit 11 is slightly different from the first embodiment. This difference will be described with reference to FIGS. 6 and 7 corresponding to FIGS. 2 and 3 in the first embodiment. FIG. 6 is a control flowchart of the peak division process, and FIG. 7 is an example of an overlaid chromatogram displayed on the display screen of the display unit 8.

  In FIG. 6, steps having the same processing contents as those in the flowchart in FIG. When the operator performs a predetermined operation on the operation unit 7 (step S1) and shifts to the peak split mode, the data processing unit 3 changes the mouse cursor displayed in the display screen 30 to a cross shape (step S2). ). The operator operates the mouse to move the cross-shaped mouse cursor 33 to the time position of the peak desired to be divided in the desired chromatogram, and designates the position by executing a click operation (step S3). Here, it is assumed that a click operation is performed in a state where the cross-shaped mouse cursor 33 is moved to the position indicated by reference numeral 33 in FIG.

  The peak division processing unit 11 detects the click position by acquiring the coordinate position information where the click operation is performed in the display screen 30 (step S4), and the chromatograph located at the closest position on the same time as the click position. The gram is identified (step S5). If a click operation is performed when the cross-shaped mouse cursor 33 is positioned as shown in FIG. 7A, the chromatogram G1 is identified as the most recent chromatogram.

  Next, the peak division processing unit 11 determines whether or not the time position corresponding to the click position on the chromatogram G1 is between the peak start point and the peak end point (step S6). The processing so far is the same as in the first embodiment. In the case of the example of FIG. 7A, since the time position is not between the peak start point and the end point, the process proceeds from step S6 to step S11. In step S11, it is determined whether or not there is a chromatogram that is overlaid in addition to the previously identified chromatogram, and if there is another chromatogram, the next click position is the same time as the previous click position. A chromatogram at a close position is identified (step S12), and the process returns to step S6.

  For example, in the case of the example of FIG. 7A, YES is determined in step S11, and the chromatogram G2 in the next closest position is identified in step S12. Then, returning to step S6, it is determined whether or not the time position corresponding to the click position is between the peak start point and the peak end point on the chromatogram G2. Accordingly, since the time position corresponding to the click position is between the peak start point and the end point at this time, the process proceeds from step S6 to S7, and the process of steps S7 to S9, that is, the peak division process is executed as described above. Is done. As a result, as shown in FIGS. 7B and 7C, with respect to the chromatogram G2, an upward arrow display 31 and a downward arrow display 32 are displayed at the division points, and the peak division boundary line is parallel to the signal intensity axis. The screen is updated so that 34 is rendered.

  Although not so in the example of FIG. 7, if the time position corresponding to the click position is not between the peak start point and the peak end point even on the chromatogram G2, whether there is another chromatogram in step S11 again. If there is no other chromatogram, the process proceeds to step S10, where a predetermined warning message is displayed in the display screen 30 to notify the operator that the click operation was not appropriate.

  Therefore, according to the second embodiment, the operator mistakenly or inadvertently clicks with the cross-shaped mouse cursor 33 moved to a position closest to another chromatogram that is not the chromatogram to be divided. Even if the position is not within the peak range of the latest chromatogram, the next closest chromatogram is automatically selected and the peak splitting process is executed. As a result, it is possible to compensate for the operator's mistakes and carelessness and to increase the possibility of performing peak division of the target chromatogram (of course, appropriate peak division is not necessarily performed).

  In both the first and second embodiments, the position is the same as the position designated by the operator clicking with the mouse, that is, on the vertical line that includes the click position and is parallel to the signal intensity axis and perpendicular to the time axis. The chromatogram near the click position was identified, but the chromatogram is not necessarily identified at the same time as the click position. For example, the chromatogram near the distance in the diagonal direction in the graph is identified. Also good. For example, when a click operation is performed in FIG. 7A in Example 2 above, the chromatogram G1 is identified as the most recent chromatogram on the same time as the position of the cross-shaped mouse cursor 33. If there is no limitation that the click position is on the same time, the closest chromatogram G2 from the position to the lower right is identified as the closest chromatogram to the position of the cross-shaped mouse cursor 33. Of course, considering the workability of the operator, it may be possible to select the chromatogram close to the click position in either the range on the same time as the click position or the range not limited to the same time.

  Moreover, the said Example is only an example of this invention, and it is clear that a deformation | transformation and correction can be performed suitably in the range in line with the meaning of this invention. For example, all of the above embodiments are those in which the present invention is applied to a gas chromatograph mass spectrometer, but it is naturally applicable to a liquid chromatograph mass spectrometer. Further, even in a liquid chromatograph apparatus using a PDA detector as a detector, a plurality of chromatograms having different wavelengths can be overlaid and displayed as shown in FIGS. 3 (a) and 7 (a). It can be easily conceived that peak splitting of a specific chromatogram is useful in the same manner as in the above example.

BRIEF DESCRIPTION OF THE DRAWINGS The whole block diagram of the gas chromatograph mass spectrometer provided with the data processor by one Example (Example 1) of this invention. 5 is a control flowchart of peak division processing in the data processing apparatus according to the first embodiment. The figure which shows an example of the overlay chromatogram displayed on the display screen of a display part in the data processor of Example 1. FIG. FIG. 3 is a waveform diagram illustrating a peak division state in the data processing apparatus according to the first embodiment. The figure which shows an example of the chromatogram curve when two peaks overlap. The control flowchart of the peak division | segmentation process in the data processor of the other Example (Example 2) of this invention. The figure which shows an example of the overlay chromatogram displayed on the display screen of a display part in the data processor of Example 2. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... GC part 2 ... MS part 3 ... Data processing part 4 ... Control part 5 ... Storage part 6 ... Personal computer (PC)
DESCRIPTION OF SYMBOLS 7 ... Operation part 8 ... Display part 11 ... Peak division | segmentation process part 12 ... Peak information calculating part 30 ... Display screen 31 ... Up arrow display 32 ... Down arrow display 33 ... Cross-shaped mouse cursor 34 ... Peak division | segmentation boundary line

Claims (3)

A chromatograph having a function of overlaying a plurality of chromatograms created based on three-dimensional chromatogram data having a third dimension in addition to time and signal intensity along the same time axis and drawing on the display screen. In the data processing device for
a) an input means for an operator to specify an arbitrary position on a display screen on which a plurality of chromatograms are overlaid and displayed;
b) identification means for identifying a chromatogram closest to the designated point on a time corresponding to the designated point from the input means among a plurality of chromatograms displayed in an overlaid manner;
c) division processing means for dividing the peak appearing in the chromatogram identified by the identification means at a time position corresponding to the designated point;
Each of the peaks divided into two by the division processing means when calculating peak information including peak area and / or peak height, each of the division processing means, Determining means for determining whether or not there is a peak to be divided at a time position corresponding to the specified point, and when the determining means determines that there is no peak to be divided by the determining means, Identifying a chromatogram next to the designated point next to the designated point or a time closest to the designated point from a plurality of chromatograms displayed in an overlaid manner, and the identified chromatogram A chromatograph data processing apparatus , wherein peak split processing by the split processing means is performed on the chromatogram. Claim 1, further comprising a reminder notification unit to workers when the peak to be divided into a time position corresponding to the designated point is not present for all of the plurality of chromatograms are displayed overlaid 2. A chromatographic data processing apparatus according to 1. Time displayed overlaid in addition to a state of shifting to the third three-dimensional chromatogram data along had and intensity axis direction a plurality of chromatograms is created in the same time axis on the basis of having a dimension of the signal intensity screen In the chromatograph data processing device having the function of drawing on the top,
a) an input means for an operator to specify an arbitrary position on a display screen in which a plurality of chromatograms are overlaid and displayed with the same time axis shifted in the intensity axis direction ;
b) identification means for identifying a nearest chromatogram finger fixed point in time corresponding to the closest or finger fixed point to the specified point by the input means from a plurality of chromatograms is the overlaid display,
c) division processing means for dividing the peak appearing in the chromatogram identified by the identification means at a time position corresponding to the designated point;
A chromatograph data processing apparatus, wherein when the peak information including the peak area and / or peak height is calculated, the peak divided into two by the division processing means is treated as a separate peak. .

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