JP3798158B2 - Liquid chromatograph - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid chromatograph device, and more particularly, to a liquid chromatograph device including a data processing device that displays a signal detected by a detector as a chromatogram and performs waveform processing and the like.
[0002]
[Prior art]
In a conventional liquid chromatograph device, a chromatogram or spectrum is displayed on a display device using a data processing device. Since the display device displays a chromatogram that includes all detected peaks, the peak in the displayed chromatogram is either a separate peak or an unseparated peak. It is difficult to determine if there is any. Therefore, conventionally, when the operator designates an arbitrary area in the displayed chromatogram, the data processing apparatus is configured to enlarge and display the designated area. The operator checks whether the peak is a separated peak or a non-separated peak from the enlarged chromatogram, and changes the waveform processing method for obtaining the area of each peak according to the type of each peak.
[0003]
Here, in a conventional liquid chromatograph device, on the display device such as a CRT on which a chromatogram is displayed, the upper left portion of the region to be enlarged is left-clicked with a mouse or the like and then dragged to the lower right corner. By doing so, the area was specified. When an area is specified, the inside of the area is enlarged and displayed, so the waveform processing method was selected while viewing the enlarged chromatogram.
[0004]
[Problems to be solved by the invention]
However, in the conventional liquid chromatograph device, if the number of peaks of the chromatogram displayed on the display device is large, it is necessary to repeat the left click and drag mouse operation each time an enlarged region is designated. There was a problem that operation took time and operability was poor.
[0005]
An object of the present invention is to provide a liquid chromatograph apparatus with improved operability.
[0006]
[Means for Solving the Problems]
(1) To achieve the above object, the present invention provides a liquid chromatograph having data processing means for detecting each component separated by a column with a detector and displaying the detected peak of each component as a chromatogram. In the apparatus, the data processing means recognizes and recognizes the peaks before and after the designated retention time position with reference to the designated retention time position with respect to the displayed chromatogram . The peak itself is enlarged and displayed. According to such a configuration, the chromatogram is enlarged and displayed only by designating the position of the holding time, so that the operability of the enlarged display operation can be improved.
[0007]
(2) In the above (1), preferably, the number of peaks within a predetermined range to be enlarged and displayed by the data processing means can be designated.
[0008]
( 3 ) Further , in order to achieve the above object, the present invention provides a liquid having data processing means for detecting each component separated by a column with a detector and displaying a peak of each detected component as a chromatogram. In the chromatographic apparatus, the data processing means recognizes non-separated peaks before and after the designated retention time position with reference to the designated retention time position for the displayed chromatogram. The recognized non-separated peak itself is enlarged and displayed. According to such a configuration, the chromatogram is enlarged and displayed only by designating the position of the holding time, so that the operability of the enlarged display operation can be improved.
[0009]
(4) In the above (3), preferably, the data processing means is configured to move the separation peak to the rear side of the separation peak enlarged and displayed after the separation peak is enlarged and displayed.
( 5 ) In the above (1) or (3) , preferably, the data processing means displays an enlarged display when the number of data points of the displayed chromatogram is larger than the number of pixels in the lateral direction of the chromatogram display area. It is a thing. With this configuration, when the number of data points of the displayed chromatogram is larger than the number of pixels in the horizontal direction of the chromatogram display area, the displayed chromatogram may not be displayed correctly, and the waveform processing conditions may be set by operating errors. It can prevent mistakes.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the configuration of a liquid chromatograph apparatus according to an embodiment of the present invention will be described with reference to FIGS.
First, the overall configuration of the liquid chromatograph apparatus according to the present embodiment will be described with reference to FIG.
[0011]
The pump 10 switches the proportioning valve 20, pressurizes the liquid while changing the composition ratio of the eluents 30 and 32, and sends the liquid to the sample injection device 40 and the column 50 at a constant flow rate. The sample injection device 40 has a sample injection port and a high-pressure channel switching valve for sample injection, and injects the sample into the channel. The injected sample is introduced into the column 50 by the eluent sent by the pump 50, separated into single components by the column 50, and eluted in ascending order of interaction with the column packing material. Each component in the eluate is detected as a peak by a detector 60 that uses ultraviolet light as a light source and includes a plurality of detection channels.
[0012]
The data processing device 70 performs switching control of the proportioning valve 20, control of the liquid feeding amount of the pump 10, control of sample injection of the sample injection device 40, and the like, and takes in the peak detected by the detector 60. The chromatogram is displayed on a display device 80 such as a CRT display or a liquid crystal display. The data processing device 70 is constituted by a personal computer, for example. The input device 90 is configured by a keyboard, a mouse, and the like, and is used for setting input of zoom conditions, specifying input of an enlarged area, and the like, as will be described later.
[0013]
Next, processing contents using the data processing apparatus for zoom display according to the present embodiment will be described with reference to the flowchart of FIG.
The processing content of the zoom display according to the present embodiment includes a zoom condition setting process 100 and a zoom display process 110. The zoom condition setting process 100 is a process in which the data processing device 70 sets a condition using the input device 90 using a zoom condition setting screen displayed on the display device 80. The set zoom condition is the data processing device. 70. Details of the zoom condition setting processing 100 will be described later with reference to FIG.
[0014]
The zoom display process 110 is a process in which when the data processing device 70 satisfies the stored zoom condition, the peak of the chromatogram is enlarged and displayed on the display device 80 with the designated position as a reference. Details of the zoom display processing 110 will be described later with reference to FIG.
[0015]
Next, the contents of the zoom condition setting process according to the present embodiment will be described using the display example of FIG.
FIG. 3 shows a case where a zoom condition setting screen 80A is displayed as the display screen of the display device 80 shown in FIG.
[0016]
The zoom condition setting screen 80A is roughly divided into “zoom condition 1” and “zoom condition 2”. "Zoom condition 1"
(1-a) “number of data points> number of pixels in the horizontal direction of the display area”;
(1-b) “Number of peaks:“ 100 ”or more”
These two zoom processing execution conditions can be set.
[0017]
The “data score” is determined by the sampling period that the data processing device 70 captures while detecting the signal detected by the detector 60 shown in FIG. 1 and the holding time that is the total time of the detected signal. is there. For example, if the sampling period is 600 ms (= 0.6 s) and the holding time is 32 minutes (= 1920 s), the number of data points is 3200 points (= 1920 / 0.6). The sampling period can be arbitrarily changed in various measurements, and the minimum sampling period is, for example, 12.5 ms. In addition, the retention time varies depending on the type of specimen, and for example, it is about 2 hours in amino acid analysis. In this case, the number of data points is 576,000.
[0018]
On the other hand, the “number of pixels in the horizontal direction of the display area” varies depending on the image display size of the display device 80. For example, when the number is 1024 pixels × 768 pixels, the “display area of the display area” can be used to display the chromatogram. The “number of pixels in the horizontal direction” is, for example, 700 pixels.
[0019]
In other words, “1-a)“ number of data> number of pixels in the horizontal direction of the display area ”of“ zoom condition 1 ”indicates that the number of data points of the chromatogram detected by the detector 60 is the chromatogram display of the display device 80. A condition for zooming (enlarging) when the number of pixels in the horizontal direction of the area is larger is shown.
[0020]
If the number of data points is larger than the number of pixels in the horizontal direction of the display area, all data cannot be displayed, so the horizontal direction (retention time of chromatogram) on the display device is thinned out and displayed. As a result, an accurate chromatogram is not displayed. For example, as described above, when the number of data points is 3200 points and the number of pixels in the horizontal direction of the display area is 700 pixels, the horizontal direction of the displayed chromatogram is thinned out to about 1/5. Will be. Therefore, there is a possibility that the peak shape of the displayed chromatogram may select the wrong waveform processing method because the information that the user wants to see may not be accurately displayed due to the resolution of the display device. Therefore, it is necessary to enlarge the necessary area and determine whether it is a separated peak or a non-separated peak.
[0021]
“Number of peaks:“ 100 ”or more” in (1-b) of “Zoom condition 1” indicates a condition for zooming (enlarging) when the number of peaks included in the displayed chromatogram is 100 or more. Yes. When the number of peaks included in the chromatogram is small, it is rare that the peaks are close to each other, so that it may not be necessary to determine whether the peak is a separated peak or a non-separated peak. Therefore, by determining the number of peaks as a zoom processing execution condition in advance, it is possible to determine whether zoom processing is necessary or not based on the number of peaks.
[0022]
Here, “100” in the zoom processing execution condition can be arbitrarily changed. By selecting the rectangular frame of “100” shown in FIG. 3, it can be changed by inputting a number as text. For example, when “the number of peaks:“ 30 ”or more”, zooming (enlargement) may be performed.
[0023]
The black circle (●) shown on the left side of (1-a) and (1-b) in “Zoom condition 1” indicates that the condition is selected, and the white circle (◯) Indicates that no condition has been selected. In the state shown in the figure, “1-a)“ number of data> number of pixels in the horizontal direction of the display area ”of“ zoom condition 1 ”is selected, and (1-b)“ number of peaks: “100” or more ”. Indicates a state that is not selected. Selection / non-selection is switched by left-clicking the black and white circles shown in the figure to change from the selected state (black circle) to the non-selected state (white circle), and vice versa. To the selected state (black circle).
[0024]
As “Zoom condition 2” on the zoom condition setting screen 80A,
(2-a) “Peak before and after”,
(2-b) “Non-separated peak”
These two zoom processing execution conditions can be set.
[0025]
“Peak before and after” is the position where the right-click at any position in the display area with the chromatogram displayed is based on the horizontal position (holding time direction) of the clicked position. Only the peaks within a predetermined range before and after are enlarged and displayed.
[0026]
“Non-resolved peak” is the position when the right side of the display area is right-clicked with the chromatogram displayed and the horizontal position (holding time direction) of the clicked position is used as a reference. The non-separation peak in the backward direction is automatically detected, and the non-separation peak is enlarged and displayed.
[0027]
In the illustrated state, (2-a) “Peak before and after” in “Zoom condition 1” is selected, and (2-b) “Non-separated peak” is not selected. When both (2-a) and (2-b) of “Zoom condition 1” are set, only (2-a) of “Zoom condition 1” is made effective. .
[0028]
Next, the contents of the zoom display process according to the present embodiment will be described with reference to FIGS.
FIG. 4 is a flowchart showing the processing contents of the zoom display processing in the liquid chromatograph apparatus according to the present embodiment, and FIG. 5 is a chromatogram display example for explaining the zoom display processing according to the present embodiment.
[0029]
First, as shown in FIG. 5, a chromatogram is displayed on the display screen 80B of the display device 80, the horizontal axis indicates the retention time (min), and the vertical axis indicates the signal intensity (mV). Show. The chromatogram display area is an area where a chromatogram can be displayed. In this area, as shown in the figure, a chromatogram between retention times 0 min and 32 min is displayed. The chromatogram display area is 700 pixels, for example. If the data sampling period is 600 ms, the retention time is 32 minutes, and the number of data points is 3200 points (= 1920 / 0.6). When the “number of data points” is 3200 points and the “number of pixels in the horizontal direction of the display area” is 700 pixels, the horizontal direction of the displayed chromatogram is thinned out to about 1/5. Therefore, since the shape of the peak is not accurately displayed, for example, whether the peaks are separated from each other, such as the peaks of “ Cys ” and “Val”, or non-separated peaks that are not separated. The determination may occur when it is difficult to determine from the display screen.
[0030]
Therefore, in the present embodiment, by right-clicking the mouse at an arbitrary position on the display screen, the enlarged display is performed based on that position. For example, when the mouse is right-clicked at an arbitrary position on the cursor line KL indicated at the position where the holding time is 17 minutes, the enlarged display is performed based on the holding time of 17 minutes.
[0031]
Here, the processing contents of the display processing 110 executed by the data processing device 70 will be described with reference to FIG.
In step 111, the data processing device 70 determines whether or not a right click of the mouse has been performed, and waits until the right click is performed. When the right button of the mouse is pressed, the process proceeds to step 112.
[0032]
Next, in step 112, it is determined whether or not the currently displayed chromatogram is after execution of zoom processing. If zoom display is in progress, that is, after execution of zoom processing, the process proceeds to step 113, and if before zoom execution, the process proceeds to step 114.
If the zoom is being displayed, in step 113, the original size of the chromatogram, that is, the display before zooming is returned to and the process is terminated.
[0033]
If it is before zoom execution, in step 114, it is determined whether or not the current chromatogram display satisfies the condition set in “zoom condition 1” shown in FIG. For example, in the example shown in FIG. 3, only (1-a) “number of data points> number of pixels in the horizontal direction of the display area” is set as “zoom condition 1”, so the chromatogram shown in FIG. It is determined whether or not the graph satisfies this condition (1-a). If it is satisfied, the process is terminated; otherwise, the process proceeds to step 115.
For example, if the “number of data points” in the chromatogram shown in FIG. 5 is 3200 and the “number of pixels in the horizontal direction of the display area” is 700 pixels, “zoom condition 1” shown in FIG. 3 is set. Since the current chromatogram display satisfies the condition, the process proceeds to step 115.
[0034]
In step 115, it is determined whether (2-a) of the zoom condition shown in FIG. 3 is set. If it is set, the process proceeds to step 116, and if it is not set, the process proceeds to step 117.
[0035]
If the zoom condition (2-a) is set, in step 116, the peaks before and after the mouse cursor (pointer) position are zoomed and displayed on the chromatogram display screen.
For example, if the right button of the mouse is clicked at the position on the cursor line KL in the figure on the chromatogram display screen before zoom display shown in FIG. Zoom display as shown in
[0036]
In the example shown in FIG. 6, the specification is such that three peaks before and after the position of the mouse cursor (pointer) are zoomed. Here, as a method for recognizing a peak, for example, “D-7500 chromatographic data processing apparatus instruction manual, (issued in 1995), p.3-1 to 3-3, (“ 3.1 Peak Detection Method ”). "," D-2510 GC integrator manual (issued in 1991), p. 3-1 to 3-3, (see “3.1 Peak Detection Method”), Japanese Patent Laid-Open No. 6-230001 (paragraph numbers <0003>, <0008> to <0011>, <FIG. 2>) <See FIG. 3>), Japanese Patent Laid-Open No. 6-201673 (see paragraph numbers <0002>, <0006> to <0013>, and <FIG. 1> to <FIG. 3>), Japanese Patent Laid-Open No. 5-281221 ( (See paragraph numbers <0002>, <0006> to <0008>, <FIG. 1>, and <FIG. 3>) The zoom display conditions can be specified by the user . For example, zoom display of two peaks before and after the mouse cursor position is possible, and further, before and after the mouse cursor position, “the number of data points ≦ the number of pixels in the horizontal direction of the display area”. Day that meets the conditions It is also possible to make up the number of zoom (enlarge) display. Since the number of pixels in the horizontal direction of the display area is 700 pixels in the example shown in FIG. 5, when the data sampling period is 600 ms, the holding time is zoomed in a range of 7 minutes (= 700 × 0.6 s). Can be displayed.
[0037]
If the zoom condition (2-a) is not set, it is determined in step 117 whether or not the zoom condition (2-b) shown in FIG. 3 is set. If it is set, the process proceeds to step 118, and if it is not set, the process proceeds to step 119.
[0038]
If the zoom condition (2-b) is set, in step 118, a non-separation peak after the current position of the mouse pointer is searched, and the non-separation peak is zoomed as shown in FIG. . Here, as a method for recognizing the non-separation peak, for example, Japanese Patent Laid-Open No. 2-120662 (first page, right line 46, second page, left line 12, second page right line 46, third page, right line 7) , And <FIG. 3>), JP-A-6-94696 (paragraph numbers <0002>, <0003>, <0020> to <0073>, <FIG. 1>, <FIG. 3>, <FIG. 7> and <Refer to <FIG. 8>), JP-A-9-304370 (see paragraph numbers <0005> to <0007>, <0009> to <0011>, <FIG. 1>, <FIG. 2> and <FIG. 4>). The known methods described can be used. Note that FIG. 7 shows “Cys” and “Val” that are not separated in the vicinity of 14.5 minutes when the position on the left side of the retention time of 14 minutes is indicated by the mouse pointer in the example shown in FIG. The peak is zoomed. At this time, the reference position of the zoom display (the origin of the horizontal axis in FIG. 7) is the non-separated peak (“Cys” and “Val” in FIG. 7) of the peak with the shorter retention time (“Cys”). Furthermore, it is a left point. Thereafter, when the right button of the mouse is clicked again, the display returns to the chromatogram display before zoom display in step 113, and at the same time, the cursor line moves to the position after the searched non-separated peak. Therefore, when the user right-clicks again at that position, the next non-separated peak can be searched and zoomed in.
[0039]
If the zoom condition (2-b) is not set, the peaks before and after the mouse cursor (pointer) position are zoomed and displayed on the chromatogram display screen in step 119 as in step 116.
[0040]
In addition, about the waveform processing method for calculating | requiring a peak area, arbitrary methods can be selected. For example, as shown in FIG. 7, the “Cys” and “Val” non-separated peaks are divided into a “Cys” peak and a “Val” peak by a dividing line DL as shown by a one-dot chain line in the figure. It can isolate | separate and can obtain | require the area of each peak. As another method, as shown in FIG. 7, for the non-separated peaks of “Cys” and “Val”, baselines BL1 and BL2 as shown by two-dot chain lines in the figure are assumed. The area of the peak of “Cys” can be obtained from the portion above the base line BL1, and the area of the peak of “Val” can also be obtained from the portion above the base line BL2.
[0041]
In the above description, the zoom display is performed by clicking the right button of the mouse. However, when only the keyboard is used as the input device 90, the cursor movement button (right It is also possible to perform zoom display by operating the enter key after the cursor is moved to a desired position by an arrow or a left arrow).
[0042]
As described above, in the past, the range to be enlarged was specified by left-clicking the upper left corner of the enlarged area and then dragging it to the lower right corner as it was. The display position is simply specified, and the non-separated peaks before and after the specified position are displayed as a zoom with reference to the specified position. Will improve. Therefore, it is possible to prevent an error in setting the waveform processing conditions due to the false recognition of the peak shape.
[0043]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the operativity of the zoom display in a liquid chromatograph apparatus can be improved.
[Brief description of the drawings]
FIG. 1 is a block diagram showing an overall configuration of a liquid chromatograph apparatus according to an embodiment of the present invention.
FIG. 2 is a flowchart showing the processing contents of zoom display using the data processing apparatus in the liquid chromatograph apparatus according to one embodiment of the present invention.
FIG. 3 is an explanatory diagram of a display example of a zoom condition setting screen in the liquid chromatograph apparatus according to the embodiment of the present invention.
FIG. 4 is a flowchart showing the processing contents of zoom display processing in the liquid chromatograph apparatus according to the embodiment of the present invention.
FIG. 5 is an explanatory diagram of a display example of a chromatogram for explaining zoom display processing in the liquid chromatograph apparatus according to the embodiment of the present invention.
FIG. 6 is an explanatory diagram of a zoom display example in the liquid chromatograph apparatus according to the embodiment of the present invention.
FIG. 7 is an explanatory diagram of another zoom display example in the liquid chromatograph apparatus according to the embodiment of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 ... Pump 20 ... Proportioning valve 30, 32 ... Eluent 40 ... Sample injection apparatus 50 ... Column 60 ... Detector 70 ... Data processing apparatus 80 ... Display apparatus 90 ... Input device

Claims (5)

In a liquid chromatograph apparatus having data processing means for detecting each component separated by a column with a detector and displaying the peak of each detected component as a chromatogram,
The data processing means is
A liquid chromatograph apparatus , wherein a peak within a predetermined range before and after the position is enlarged and displayed with reference to the position of the retention time designated for the displayed chromatogram. The liquid chromatograph apparatus according to claim 1,
A liquid chromatograph apparatus characterized in that the number of peaks within a predetermined range to be enlarged and displayed by the data processing means can be designated. In a liquid chromatograph apparatus having data processing means for detecting each component separated by a column with a detector and displaying the peak of each detected component as a chromatogram,
The data processing means is
Based on the specified retention time position for the displayed chromatogram,
A liquid chromatograph characterized by enlarging and displaying a non-separation peak behind the position . The liquid chromatograph apparatus according to claim 3,
The data processing means moves to the rear side of the separated peak in which the reference position is enlarged and displayed after the separated peak is enlarged and displayed. In the liquid chromatograph apparatus in any one of Claim 1 or Claim 3 ,
The liquid chromatograph apparatus, wherein the data processing means displays an enlarged display when the number of data points of the displayed chromatogram is larger than the number of pixels in the lateral direction of the chromatogram display area.

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