JPH11304781A - Liquid chromatograph - Google Patents

Abstract

PROBLEM TO BE SOLVED: To automatically form a program for a plurality of pumps and valves, by setting at a control part a formation means for forming a gradient program including for a second pump from a gradient program for a first pump set optionally. SOLUTION: A gradient program formation initial set screen for changing a composition of eluates at a controller is displayed. A gradient program is shown at the right side in a table of a time and the composition of A, B eluates, and a gradient program formation screen graphically displaying the gradient program is displayed at the left side. In the case where the setup for a composition ratio of eluates at a gradient start point is to be changed, a column displaying the composition of the eluate B of a column 0.0 minute in the table of the composition ratio of the eluates is clicked, thereby making a reverse display and enabling inputs by numerical values. When the composition of the eluate B at the 0.0 minute is changed to 40 with the use of an input device, the screen is changed and 60 resulting from a subtraction of 40 from 100 is automatically displayed at a column of the composition ratio of the eluate A and, the graphical display is changed as well.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid chromatograph, and more particularly to a liquid chromatograph in which a plurality of columns are used to regenerate (wash and re-stabilize) the other column while analyzing one column. About.

[0002]

2. Description of the Related Art In a conventional liquid chromatograph, regeneration (washing and re-stabilization) of one column is performed during analysis of another column by using an analysis pump / regeneration pump / valve and a plurality of columns. There is a method. In a liquid chromatograph having such a configuration, the target operation (analysis, cleaning, and re-stabilization) of each pump is disassembled, a time chart is created for the operation of the pump and the operation of the valve, and further, the operation of each pump is It was necessary to make adjustments in consideration of the consistency of the time chart and create an entire gradient program.

[0003]

In the prior art, since the creation of the gradient program in consideration of the time charts of the individual pumps and valves has been performed manually by the operator, experience is required in creating the program. Was carried out by a skilled person. Therefore, there is a problem that the number of operators who can create programs is limited. In addition, there is also a problem that when developing the program into a plurality of pumps or the like, an error is likely to occur, and the analysis cannot be started until after several confirmations in advance. An object of the present invention is to provide a liquid chromatograph that automatically creates a program for a plurality of pumps and valves by inputting a series of operations (analysis, washing, and re-stabilization) on a single column.

[0004]

SUMMARY OF THE INVENTION In the above object, the present invention is characterized in that a first pump for sending an eluent for analysis and a second pump for sending an eluent for regeneration and re-stabilization of a column. A pump, a sample injection part for injecting a sample to be analyzed, at least two columns provided in parallel with the first pump for separating the sample for each component, and detection of the sample separated by the column And a control unit for controlling each of the devices, and supplies an eluent having a different composition from the second pump to the other column during sample analysis in one of the columns. In the control unit, a gradient program creating means for creating a gradient program including a second pump from an arbitrarily set gradient program for the first pump is provided. It is to be.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below with reference to examples.

FIG. 1 shows a first example of the liquid chromatograph of the present invention.
1 shows the configuration of the embodiment. The pump 1 switches the proportioning valve 2 so that the eluent 3
The eluent 4 is supplied at a constant flow rate by pressurizing the liquid while changing the composition ratio. The sample injection device 5 has a sample injection port and a sample injection high-pressure channel switching valve, and injects a sample into the channel. The injected sample is separated into a single component by the column 19 and eluted in order from the component having the smallest interaction with the column packing material. Each component in the eluate is detected as a peak by a detector 9 having a plurality of detection channels using ultraviolet light as a light source. The conditions of each unit are set by the controller 13.

FIG. 2 shows a configuration example of the controller 13.
The controller 13 includes a computing device 14, a display device 15, an input device 16, a storage device 17, and an input / output device 18. The pump / sample injection device and the valve are controlled by contact control or communication control via the input / output device 18. Is controlling.

FIG. 3 shows an example of a gradient program creation initial setting screen for changing the eluent composition in the controller 13. In this embodiment, the controller 13 uses a personal computer.

Next, an example of creating a gradient program in this embodiment will be described.

First, the time for performing the gradient, the time for re-stabilizing the column by washing the column, and the flow rate are respectively defined as “Gr”.
adient Time, Regeneration Time and Flow Rat
e "is required. The “Deley Volume (flow path stabilizing capacity)” based on the capacity of the mixer for mixing the solvent and the like indicates a value previously input at the time of system configuration, and does not need to be input here unless otherwise required.

Here, as an example, “Gradient Time” is 6
When the user inputs 6 minutes for the minutes and “Regeneration Time” and presses the OK button, the screen of FIG. 4 is displayed. In the present embodiment, as the initial display, the composition of the eluent B at the start of the gradient and at the time of column stabilization is 20%, the composition of the eluent B at the end of the gradient is 80%, and the eluent B at the time of column washing is as follows. The composition is defined as 100%, and the column washing time is defined as の of the input re-stabilization time (Regeneration Time).

The right side of the screen shown in FIG. 4 shows the set gradient program in a table of the time and the composition of the AB eluent. The left side of the screen shows the composition ratio of the eluent B in a graph with respect to the time axis. With the graphical display of the gradient program on the left side of the screen, it is possible to visually confirm what kind of gradient program is being created and easily confirm whether or not the intended program is being created.

Hereinafter, a method of creating a gradient program in the controller 13 will be described with reference to a screen example.

FIG. 5 shows an example in which the setting of the eluent composition ratio at time 0 is changed. When the user clicks on a point that intersects time 0 in the graph showing the eluent composition ratio, the point on the clicked graph is selected, and a square mark confirming that the selected point is entered. By dragging this point with a mouse, the initial eluent composition ratio of the gradient program can be set. When the point at time 0 is selected, this point moves only on the composition ratio axis of the eluent B. The current position of the pointer is displayed at the bottom of the screen as a cursor position. FIG. 6 is an example of a screen when the point indicating the eluent composition at time 0 is dropped at 40%. In accordance with the position of the pointer, the row at time 0 of the gradient program display in the table on the right side of the screen is also changed to the same numerical value, that is, “40”, for the composition ratio of the liquid B. Also, the composition ratio of the liquid B at the time of column stabilization is similarly changed to “40”.

Similarly, the initial eluent composition at the end of the gradient can be changed from the graph, and when the change is made, the numerical value of the corresponding time in the gradient program display in the table on the right side of the screen is changed.

FIG. 7 shows an example of setting the eluent composition at the time of column washing. When the user clicks on the cleaning part in the graph display, the line of the cleaning part (the line of the 100% B part in the embodiment) is selected, and the bold line indicating the selection is displayed. By dragging this line, the composition ratio of the solution B at the time of cleaning can be changed. This line moves perpendicular to the time axis by dragging. FIG. 8 shows an example in which the composition is dropped when the composition ratio of the solution B is 90%. In addition to the fact that the composition ratio of solution B was changed to 90% from the graph, the composition ratio of solution B was changed to “90” in the time lines 6.1 and 9.0 of the gradient program display in the table on the right side of the screen. Be changed.

FIG. 9 shows an example in which the ratio between the column washing time and the re-stabilization time is changed. Clicking the boundary line (vertical line at 9 minutes) between the cleaning unit and the re-stabilization unit in the graph display selects the boundary line and displays a bold line indicating that the boundary line is selected. By dragging this line, the ratio between the column washing time and the re-stabilization time can be changed. This line moves horizontally with the time axis by dragging. FIG. 10 shows an example in which a boundary line is dropped in 8 minutes. In addition to the change of the boundary line from the graph to 8 minutes, the time “9.0” and “9.1” of the gradient program display in the table on the right side of the screen are changed to “8.0” and “8.1”. Is changed to

Although the example in which the gradient program is changed by the graph has been described above, at this time, the table on the right side of the screen is not necessarily displayed, and the program can be changed even when the table is not displayed. .

FIG. 11 shows an example in which the gradient program setting is changed by displaying the gradient program in a table. FIG. 11 shows an example of changing the eluent composition at the time of 0.0 minutes, that is, the eluent composition at the gradient start point. In the table, the column displaying the composition of the eluent B at the 0.0 minutes row is clicked. Then, the column is highlighted and a numerical value can be input. When the composition of the eluent B at 0.0 minutes is input as “40” using the input device 16, the screen becomes as shown in FIG.
It is changed like 2. That is, "60", which is obtained by subtracting 40 from 100, is automatically displayed in the column for the composition ratio of the eluent A, and the graphical display on the left side of the screen is changed to the position of 40% so as to match the input in the table. At this time, 0.0
Since the minute line is the gradient start point, the composition ratio of the re-stabilization is also changed to 40%, which is the same as the composition ratio of the gradient start point.

In the present embodiment, as described above, since the gradient program can be created and edited on the graphical display screen, it is possible to intuitively recognize the program for setting the target eluent composition change. There is an effect that it can be created easily. Also in the gradient creation / editing using a table, the graphical display of the change in the composition of the eluent is simultaneously changed, which has the effect of preventing setting errors.

FIG. 13 shows the structure of a second embodiment of the liquid chromatograph of the present invention. In this embodiment, 1
A plurality of columns are provided for one analysis, and the creation of a gradient program in such a configuration is shown.

In the configuration shown in FIG. 13, two analysis pumps 1 are used.
The liquid is pressurized while the composition ratio of the eluent 3 and the eluent 4 is changed by switching the proportioning valve 2 and the liquid is sent at a constant flow rate. The sample injection device 5
A plurality of sample injection ports and a sample injection high-pressure channel switching valve are provided, and different samples are injected into the plurality of channels. The injected sample is guided to the ten-way valve 6. The ten-way valve 6 is currently set in the flow path shown by the solid line, and the sample is separated into single components by the column A of 7, and the components are eluted in the order of components having the smallest interaction with the column packing material. Each component in the eluate passes through the ten-way valve 6 again and is detected as a peak by a detector 9 having a plurality of detection channels using ultraviolet light as a light source. Each eluate flow path is connected to the fraction collector 10, and each component is collected in a container such as a test tube different for each component. During this analysis, the regeneration pump 11 changes the composition ratio of the eluent 3 and the eluent 4 by switching the proportioning valve 2, and pressurizes and sends the eluent 3 and the eluent 4 at a constant flow rate as the washing liquid and subsequently the re-stabilizing liquid. Liquid. The washing liquid and the re-stabilizing liquid are branched into two, and the column B of 8 is passed through two 10-way valves 6.
Are simultaneously washed and re-stabilized. The washing liquid and the re-stabilizing liquid are collected in the drain bottle 12.

FIG. 14 shows the vicinity of the ten-way valve 6 in detail. When the ten-way valve 6 is set to the flow path indicated by the solid line, the analysis pump 1
In addition, a regeneration pump 11 is connected to the seventh column B. At this time, the sample is analyzed in the column A of 7, and the eluate is led to the detector 9. In column B of No. 8, washing and re-stabilization are performed, and the eluate is led to the drain bottle 12. When the ten-way valve 6 is switched to the dotted line side, column B of 8
And the column A of 7 is washed and re-stabilized.

The analysis pump 1, the regeneration pump 11, the sample injection device 5 and the ten-way valve 6 are controlled by a controller 13. The configuration of the controller 13 is as follows.
FIG. 3 shows the same as the embodiment of FIG. Controller 13
Is composed of a computing device 14, a display device 15, an input device 16, a storage device 17, and an input / output device 18. The pump / sample injection device and the valve are controlled by contact control or communication control via the input / output device 18. doing.

FIG. 15 shows a gradient program created by the controller 13 in the second embodiment in the same manner as in the first embodiment. FIG. 18 shows the program in a table format. In this example, the analysis time is set to 8 minutes, the washing time is set to 2 minutes, the re-stabilization time is set to 5 minutes, and the flow rate is set to 2 mL / min. Further, the flow path stabilizing capacity mainly due to the capacity of the solvent mixing mixer provided in the flow path is 4 mL in the system of the present embodiment.

In the controller 13 of this embodiment,
Because it has two columns for analysis and regeneration,
From the gradient program set as above,
As shown in FIG. 17, A: analysis time, B: washing time,
Five parameters of C: re-stabilization time, D: flow rate, and E: flow rate stabilization capacity are obtained, each operation is performed from these parameters, and the conditions of the analysis pump and the regeneration pump are automatically calculated. In this example, A = 8 minutes, B = 2
Min, C = 5 min, D = 2 mL / min, and E = 4 mL, the calculation method shown in FIG. 17 calculates the minimum cycle of the analysis pump to be 10 minutes and the minimum cycle of the regeneration pump to be 7 minutes. The sample injection cycle is 10 minutes. From this, the flow path stabilization time of the analysis time of the analysis pump is calculated as 2 minutes, and the re-stabilization time of the regeneration pump is calculated as 8 minutes. Thus, the programs for the analysis pump / regeneration pump and the ten-way valve created based on the conditions calculated in this example are as shown in FIG. FIG. 19 shows this in a table format.

When the chromatograph of this embodiment is used, in a system having two columns for analysis and regeneration, a program for an analysis pump / regeneration pump and a valve can be programmed simply by inputting a normal gradient program. Thus, there is an effect that the throughput can be easily improved by washing and re-stabilizing the other column during analysis in one column.

[0028]

According to the present invention, in a system having a plurality of columns and two columns for analysis and regeneration in each system, an analysis pump and a pump can be obtained simply by inputting a normal gradient program. Since the programs for the regeneration pump and the valve are created, there is an effect that it is possible to easily improve the throughput by washing and re-stabilizing the other column during analysis in one column.

[Brief description of the drawings]

FIG. 1 is a configuration diagram of a first embodiment of the present invention.

FIG. 2 is a configuration diagram of a system controller of the present invention.

FIG. 3 is an example of an initial input screen of the present invention.

FIG. 4 is an example of a gradient program initial creation screen of the present invention.

FIG. 5 is an example of a gradient program creation screen of the present invention.

FIG. 6 is an example of a gradient program creation screen of the present invention.

FIG. 7 is an example of a gradient program creation screen of the present invention.

FIG. 8 is an example of a gradient program creation screen of the present invention.

FIG. 9 is an example of a gradient program creation screen of the present invention.

FIG. 10 is an example of a gradient program creation screen of the present invention.

FIG. 11 is an example of a gradient program creation screen of the present invention.

FIG. 12 is an example of a gradient program creation screen of the present invention.

FIG. 13 is a flow path configuration diagram according to a second embodiment of the present invention.

FIG. 14 is a detailed view near the ten-way valve according to the second embodiment of the present invention.

FIG. 15 is a gradient program set in the second embodiment of the present invention.

FIG. 16 shows a time program automatically created in the second embodiment of the present invention.

FIG. 17 shows an automatic program creation method according to a second embodiment of the present invention.

FIG. 18 is a gradient program set in the second embodiment of the present invention.

FIG. 19 is a time program automatically created in the second embodiment of the present invention.

[Explanation of symbols]

1 ... Analysis pump, 2 ... Proportioning valve, 3
... Eluent A, 4 ... Eluent B, 5 ... Sample injection device, 6 ... 10-way valve, 7 ... Column A, 8 ... Column B, 9 ... Detector,
10: fraction collector, 11: regeneration pump, 1
2 ... drain bottle, 13 ... system controller, 14 ...
Arithmetic unit, 15 display unit, 16 input unit, 17 storage unit, 18 input / output unit, 19 column.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kisaburo Exit 832 Nagakubo, Horiguchi, Hitachinaka-shi, Ibaraki 2 Within Hitachi Measurement Engineering Co., Ltd. (72) Inventor: Takamichi Ono, 882 Omo, Oaza-shi, Hitachinaka-shi, Ibaraki, Japan In-house measurement equipment division of Hitachi, Ltd.

Claims (2)

[Claims] A first pump for sending an eluent for analysis,
A second pump for sending an eluent for regeneration and re-stabilization of the column, a sample injecting unit for injecting a sample to be analyzed, and separating the sample for each component and in parallel with the first pump The apparatus includes at least two columns provided, a detection unit for detecting a sample separated by the column, and a control unit for controlling each of the devices. In the liquid chromatograph for supplying an eluent having a different composition from the second pump to the controller, the controller generates a gradient program including the second pump from the arbitrarily set gradient program for the first pump. A liquid chromatograph characterized by having a gradient program creating means. 2. The gradient program creating means according to claim 1, wherein the gradient program creating means of the control unit creates a gradient program including the second pump using the analysis time, the washing time, the re-stabilization time and the flow path stabilization capacity as parameters. A liquid chromatograph characterized in that: