JP2013024603A - Control device for liquid chromatograph and program - Google Patents

Abstract

PROBLEM TO BE SOLVED: To shorten the time required for a series of analyses when gradient analyses in various conditions are continuously conducted.SOLUTION: In a control device for a liquid chromatograph, the liquid chromatograph is controlled before a sample is analyzed (actual analysis) so as to perform preparatory liquid feeding (empty analysis) with the same gradient conditions as those during analysis of the sample. When the analyses of the sample are conducted for a plurality of time, the preparatory liquid feeding between two sample analyses sequentially conducted is omitted if kinds of columns, kinds of solvents, and mixture ratios of the solvents at the start of a gradient process that are applied to the two sample analyses are compared with each other and they are identical.

Description

  The present invention relates to a control device for controlling the operation of a liquid chromatograph, and a program used in the control device.

  The liquid chromatograph is composed of a plurality of units such as an autosampler, a pump, and a column oven, and the operation of each unit is controlled according to a control signal from a control device.

  In recent years, in such a liquid chromatograph, a control device in which a predetermined control / processing program is installed in a personal computer has been widely used to control each analysis unit in an integrated manner or to process collected data. Yes. In such a control device, a continuous analysis of multiple samples can be automatically performed by creating a schedule table prior to the start of analysis (see, for example, Patent Document 1).

  FIG. 11 is an example of a schedule table in the liquid chromatograph analysis. In this table, one row corresponds to one analysis, and the sample number, sample injection amount, method file name, and analysis result are included as information necessary to execute the analysis in one row. Describes the data file name, etc. when saving. A method file is a file that defines the operating conditions (hereinafter referred to as “analysis method”) of each unit constituting the liquid chromatograph. For example, the method file includes the mobile phase used during analysis, the type of column, Various parameters such as pump flow rate and column oven temperature are described.

  When the start of analysis is instructed after the schedule table as described above is created, samples are sequentially selected according to the schedule, analysis conditions are set, and analysis of a large number of samples is automatically executed.

  In such a liquid chromatograph, an analysis under various conditions may be performed on one sample to search for an optimal analysis condition for the sample. This is called method scouting. In such method scouting, a user creates a plurality of types of method files in which various parameters described above are combined in advance, and further specifies a different method file for each row of the schedule table as shown in FIG. The start of analysis is instructed with the same sample injection amount. Thereby, the analysis under various conditions according to the description of the method file of each line is sequentially executed. The chromatogram data as the analysis result is stored in one data file for each analysis and stored in a storage device such as a hard disk drive. The user refers to the chromatogram data stored in the storage device, and determines the analysis condition when the optimum analysis result is obtained as an analysis method to be applied to the analysis of the sample.

  By the way, there is a gradient liquid feeding method as one of analysis methods of a liquid chromatograph. In this method, for example, a plurality of solvents having different properties such as water and an organic solvent are mixed, and a mobile phase whose mixing ratio is changed over time is sent to a column. It is particularly useful for good separation.

  When performing analysis by the gradient liquid feeding method (hereinafter referred to as “gradient analysis”), the user sets a gradient profile as shown in FIG. 10, for example, as one of analysis parameters included in the method file. The gradient profile indicates the target value of the mobile phase composition with the passage of time from the start of analysis. The example of FIG. 10 is a gradient analysis profile using a mixed solution of solvent A and solvent B as a mobile phase, and the mobile phase composition is represented by the ratio of solvent B in the mixed solution. As the solvent A, a solvent having a relatively weak dissolution power (for example, a solvent having a higher polarity in the case of the reverse phase mode) is used, and as the solvent B, a solvent having a stronger dissolution power than the solvent A (for example, a reverse phase). In the case of the mode, a solvent having a low polarity is used. First, during a period from when the sample is injected at time t0 until a predetermined time elapses (time t0 to t1), the ratio of the solvent B is kept low, whereby each component in the sample is temporarily put into the column. Adsorbed. Thereafter, the ratio of the solvent B increases in proportion to the passage of time (time t1 to t2), whereby each of the components is sequentially eluted from the column according to its characteristics (for example, polarity). Subsequently, after the component remaining in the column was discharged from the column while maintaining a high ratio of the solvent B over a certain period of time (time t2 to t3), it was returned to the initial mobile phase composition again. The state is further maintained for a certain time (time t3 to t4), and the inside of the column is equilibrated.

  Hereinafter, the process corresponding to the time t0 to t1 is referred to as a sample introduction process, the process corresponding to the time t1 to t2 is equivalent to the gradient process, the process corresponding to the time t2 to t3 is equivalent to the cleaning process, and the time t3 to t4. The process is called an equilibration process. In some cases, the above-described sample introduction step is omitted, and the gradient step is started simultaneously with the sample injection.

JP 2005-127814 A

  As described above, in the gradient analysis, a washing step is executed after the gradient step to wash the inside of the column, and further, the inside of the column is equilibrated by the equilibration step. However, when gradient analysis under the same conditions is continuously performed on the same sample a plurality of times, there is a difference in the retention time of each component between the first analysis and the second and subsequent analyses. For example, FIG. 12 superimposes the results of three consecutive gradient analyzes on the same sample under the same conditions, and the chromatograms (thick lines) obtained by the second and third analyzes are completely one. However, the peak appearance time (retention time) is different between the chromatogram (thin line) obtained in the first analysis and the other chromatograms.

  Such a shift in retention time is caused by the difference in the equilibrium state of the column at the start of analysis between the first analysis and the second and subsequent analyses. Therefore, in order to obtain an appropriate analysis result in the gradient analysis, it is necessary to perform the gradient analysis a plurality of times continuously under the same conditions and adopt the second and subsequent data. In such a case, the second and subsequent gradient analyzes are called actual analysis, and the first gradient analysis is called empty analysis.

  Therefore, when performing multiple analyzes with various gradient profiles in the method scouting described above, an empty analysis using the same gradient profile as the actual analysis is performed before each actual analysis with each gradient profile. There is a problem that it takes a long time to complete a series of analyzes because it is necessary to perform the analysis.

  In addition, since method scouting considers various analysis conditions, the number of analyzes generally tends to increase. For this reason, since a large number of data files are generated as analysis results, there is a problem in that it is impossible to determine under which conditions each file has an analysis result unless the data file is opened.

  The present invention has been made to solve the above problems, and a first object of the present invention is to take a time required for a series of analyzes in a case where a plurality of gradient analyzes using various gradient profiles are continuously performed. It is an object of the present invention to provide a control apparatus for a liquid chromatograph capable of shortening the time. The second object is to provide a liquid chromatograph control device that allows a user to easily determine under what conditions each data file is an analysis result even when a large number of data files are generated. Is to provide.

In order to solve the above problems, a liquid chromatograph control device according to the present invention has a gradient analysis function for performing chromatographic analysis while temporally changing the mixing ratio of a plurality of solvents constituting a mobile phase. A liquid chromatograph control device for controlling the operation of the liquid chromatograph,
a) During the analysis of the sample, the mixing ratio of the solvent is from the first mixing ratio at which the dissolution power of the mobile phase is minimized during the analysis to the second mixing at which the dissolution power of the mobile phase is maximized during the analysis. An analysis control means for controlling the liquid chromatograph so as to return to the first mixing ratio again through the ratio;
b) Before the analysis of the sample, the mixing ratio of the solvent is changed from the same first mixing ratio as the analysis of the sample to the first mixing ratio again through the second mixing ratio same as the analysis of the sample. Preliminary liquid feeding control means for controlling the liquid chromatograph so as to execute the preliminary liquid feeding back to
And when the preliminary liquid feeding control means performs sample analysis a plurality of times, the column type, the solvent type, the first mixing ratio applied to two sample analyzes executed before and after, When the second mixing ratio is the same, preliminary liquid feeding between the two sample analyzes is omitted.

  Here, the “analysis of the sample” corresponds to the actual analysis described above, and the “preliminary liquid feeding” corresponds to the empty analysis described above. In general, the dissolution power of the mobile phase in one gradient analysis is minimized at the start of the gradient process and is maximized in the cleaning process. Therefore, typically, the mixing ratio of the solvent at the start of the gradient process is the first mixing ratio in the present invention, and the mixing ratio of the solvent in the cleaning process is the second mixing ratio in the present invention. When the mobile phase has a sufficiently high dissolved power at the end of the gradient process, the cleaning process may be omitted. In such a case, the mixing ratio of the solvent at the end of the gradient process becomes the second mixing ratio in the present invention.

  As described above, when the column type, the solvent type, the first mixing ratio, and the second mixing ratio applied to two consecutive sample analyzes are the same, the sample analysis performed first is performed. It will play the same role as the empty analysis for the sample analysis to be performed later. Therefore, even if the empty analysis is not performed before the sample analysis to be performed later, the above-described shift in the retention time does not occur in the sample analysis. Thus, according to the control apparatus for a liquid chromatograph according to the present invention having the above-described configuration, it is possible to omit the empty analysis within a range that does not affect the analysis result.

Furthermore, the liquid chromatograph control device according to the present invention comprises:
c) analysis result storage means for storing the results of multiple gradient analyzes in one data file for each analysis;
d) The name of the column and solvent used in each gradient analysis, and the solvent mixing ratio at the beginning of the step of continuously changing the solvent mixing ratio in each gradient analysis and the mixing ratio at the end of the step Data file name automatic assigning means for assigning a file name including at least one of the data name to the data file in which the analysis result is stored;
It is desirable to have.

  Here, the “step of continuously changing the mixing ratio of the solvents” corresponds to the above-described gradient step.

  As described above, according to the liquid chromatograph control device according to the present invention having the above-described configuration, it is possible to omit the empty analysis (preliminary liquid feeding) within a range that does not affect the analysis result. Therefore, in the case where the gradient analysis is continuously performed a plurality of times as in the method scouting described above, it is possible to shorten the time required for a series of analyzes without reducing the analysis accuracy.

  Further, if the data file name automatic assigning unit is provided, it is possible for the user to easily determine under which conditions each data file is an analysis result without opening the file.

The schematic block diagram of the liquid chromatograph provided with the control apparatus which concerns on one Example of this invention. The flowchart which shows operation | movement of the control apparatus which concerns on the same Example. The flowchart which shows operation | movement of the schedule table preparation part in the Example. The figure which shows the example of the gradient profile in a present Example. It is a time chart which shows the example of a mobile phase composition change at the time of execution of an empty analysis and real analysis, (a) is based on the conventional apparatus, (b) is based on the apparatus of a present Example. The figure which shows another example of the gradient profile in a present Example. The time chart which shows another example of the mobile phase composition change at the time of execution of an empty analysis and a real analysis. It is a figure which shows an example of the schedule table in method scouting, Comprising: (a) is based on the conventional apparatus, (b) is based on the apparatus of a present Example. The schematic diagram for demonstrating the effect by the apparatus of a present Example. The figure which shows an example of a gradient profile. The figure which shows the conventional schedule table. The chromatogram which shows the result of having performed gradient analysis on the same sample on the same conditions 3 times continuously.

  An embodiment of a liquid chromatograph control apparatus according to the present invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of a liquid chromatograph provided with a control device according to the present embodiment.

  This liquid chromatograph is obtained by the detection unit 40 through the liquid feeding unit 10, the autosampler 20, the column oven 30, the detection unit 40, the system controller 50 that controls these units, and the system controller 50. A control device 60 that analyzes and processes data, an operation unit 71 including a keyboard and a mouse connected to the control device 60, a display unit 72 including a display, and the like are provided.

Feeding unit 10 is for delivering a solvent A which is sucked by the liquid feed pump P _A, and a solvent B which has been sucked by the liquid feed pump P _B to the column on which is mixed by a gradient mixer 17, further The solvent pumps P _A and P _B are connected to four solvent containers via solvent switching valves 15 and 16 and degassing units 13 and 14, respectively. Among them, connected to the solvent container 11a~11d the liquid feed pump P _A is accommodated eg aqueous solvents (i.e., solvents mainly composed of water), by switching the solvent selection valve 15, the four one of the solvents container 11a~11d but solvent in the selected container is sucked by the liquid feed pump P _a as the solvent a. On the other hand, the solvent containers 12 a to 12 d connected to the liquid feed pump P _B contain, for example, an organic solvent (that is, a solvent containing an organic solvent as a main component), and four solvents are selected by switching the solvent switching valve 16. one of the container 12a~12d but solvent in the selected container is sucked by the liquid feed pump P _B as the solvent B. These liquid feed pump P _A, the flow rate of P _B is can be controlled to vary respectively with time, whereby the solvent A, feeding the gradient method mixing ratio of B is changed temporally It can be performed. The column oven 30 includes six columns 32a to 32f and flow path switching units 31 and 33 for selectively connecting any one of these columns to the flow path of the mobile phase. The detector 40 is provided with a detector 41 such as a PDA detector. In the liquid chromatograph of this example, columns for reverse phase chromatography are used as the columns 32a to 32f, and a solvent B having a lower polarity than the solvent A is used. Therefore, the higher the ratio of the solvent B in the mobile phase, the stronger the elution power of the mobile phase (the power to elute the sample components from the column).

  The control device 60 includes a storage unit 61, an analysis condition setting unit 62, a schedule table creation unit 63, an analysis control unit 64, and a data processing unit 65 as functional blocks. The substance of the control device 60 is a personal computer, and various functions as described below are achieved by executing dedicated control / processing software installed in the personal computer. The schedule table creation unit 63 and the analysis control unit 64 cooperate to function as an analysis control unit and a preliminary liquid feeding control unit in the present invention. The data processing unit 65 corresponds to the analysis result storage means and the data file name automatic assignment means in the present invention.

A standard analysis operation in one gradient analysis using the above liquid chromatograph is as follows. That is, under the control of the system controller 50 receives an instruction from the analysis control unit 64 of the control device 60, the solvent selector valve 15, 16 selects one solvent container, respectively, the liquid feed pump P _A, the P _B wherein The solvent is sucked from the solvent container at a predetermined flow rate. The solvent is sucked by the aspirated solvent A and the liquid feed pump P _B in the liquid feed pump P _A B is homogeneously mixed with a gradient mixer 17, the mobile phase after mixing, to the column via the autosampler 20 Inflow. A rack in which one or more sample bottles (vials) are mounted is set in the autosampler 20, and a predetermined sample is selected and collected under the control of the system controller 50. The sample is injected into the mobile phase. This sample rides on the mobile phase and is introduced into any of the columns 32a to 32f.

At this time, as shown in the gradient profile of FIG. 10, the liquid feed pump P is set so that the ratio of the solvent B is low and the ratio of the solvent A is high until a predetermined time elapses from the injection of the sample. The flow rates of _A and P _B are controlled (time t0 to t1: sample introduction step). As the solvent A, a solvent having a weak dissolution power is used, so that each component in the sample is once adsorbed on the column. Subsequently, the ratio of the solvent B is increased by changing the flow rates of the liquid feed pumps P _A and P _B over time (time t1 to t2: gradient process). As the solvent B, a solvent having a strong dissolution power is used, so that each component adsorbed on the column is sequentially eluted from the column according to its polarity and introduced into the detection unit 40.

  Then, each component is sequentially detected by a detector 41 provided in the detection unit 40, and data obtained by digitizing a detection signal corresponding to the concentration is sent to the control device 60 via the system controller 50. The control device 60 stores the received data in a storage unit 61 provided on a storage device such as a hard disk, and creates a chromatogram by performing predetermined processing in the data processing unit 65 and displays it on the screen of the display unit 72. To do. Thereafter, the column is washed by feeding solvent B at a high concentration for a certain time (time t2 to t3: washing step), and returned to the initial mobile phase composition to equilibrate the column for a certain time (time t3 to t4). : Equilibration step).

  Next, as a characteristic operation in the liquid chromatograph control apparatus of the present embodiment, an operation at the time of creating a method file and a schedule table will be described with reference to the flowchart of FIG.

  First, the user operates the operation unit 71 to input to the analysis condition setting unit 62 that method scouting is performed by gradient analysis. Thereby, since a predetermined setting screen (not shown) is displayed on the screen of the display unit 72, the sample name to be analyzed and its injection amount, the type of solvent used as the solvent A, and the solvent used as the solvent B The user selects the column type, column type, and the like on the setting screen (step S11).

  When the setting on the setting screen is completed, a gradient condition input screen (not shown) is displayed on the screen of the display unit 72, so that the user sets a gradient condition to be applied to one gradient analysis. Here, the gradient conditions are the above-described sample introduction process, gradient process, cleaning process, and equilibration process execution time, mobile phase composition at the start of the gradient process, mobile phase composition at the end of the gradient process, When the user inputs these values, the analysis condition setting unit 62 creates a gradient profile as shown in FIG. 10 (step S12). The composition of the mobile phase can be specified, for example, by the ratio of the solvent B in the mixed mobile phase (ie, solvent A + solvent B).

  Since the mobile phase composition in the sample introduction step and the equilibration step is the same as the mobile phase composition at the start of the gradient analysis, these steps can be performed if the user sets the mobile phase composition at the start of the gradient step. The mobile phase composition at is also automatically determined. In addition, the mobile phase composition in the washing process is set so that the mobile power of the mobile phase in the cleaning process is equal to or higher than the mobile power of the mobile phase at the end of the gradient process. Therefore, in one gradient analysis, the mobile phase solution power is minimized at the start of the gradient process (and the sample introduction step and the equilibration step), and the mobile phase solution power is maximized in the washing step. Therefore, the mobile phase composition at the start of the gradient process corresponds to the first mixing ratio in the present invention, and the mobile phase composition in the cleaning process corresponds to the second mixing ratio in the present invention.

  Thereafter, when the user instructs creation of a method file from the operation unit 71, one method file is generated based on the contents set above and stored in the storage unit 61 (step S13). In this method file, parameters such as the types of the solvents A and B and the column type input in step S11 and the gradient profile created in step S12 are described.

  Thereafter, by repeatedly executing the above steps S11 and S13, a gradient profile and a method file are created for each of a plurality of gradient analyzes to be executed in the method scouting. Thereby, a plurality of method files having different analysis conditions are generated and stored in the storage unit 61. Hereinafter, each method file is referred to as method 1, method 2,.

  Here, the user inputs and sets the gradient profiles in each analysis one by one, but the present invention is not limited to this. For example, the user can determine the basic gradient conditions, the number of steps of the mobile phase composition at the start and end of the gradient process, and how much the mobile phase composition is changed at each step of the change. The analysis condition setting unit 62 creates a plurality of types of gradient profiles in which the mobile phase composition at the start and end of the gradient process is changed stepwise from the basic gradient conditions. A plurality of method files including a gradient profile may be automatically created and stored in the storage unit 61.

  When the creation of all method files to be executed in the method scouting is completed (that is, Yes in step S14), the schedule table creation unit 63 creates a schedule table by the user performing a predetermined operation with the operation unit 71. Instruct. Thereby, the empty analysis and the actual analysis using each method file are registered in the schedule table (step S15).

  The operation of the schedule table creation unit 63 at this time will be described below with reference to the flowchart of FIG. First, the schedule table creation unit 63 sets a variable n representing a method file number to 1 (step S21), and the first method file (that is, the method file) among the plurality of method files created in step S13. The empty analysis using 1) is registered in the first row of the schedule table (step S22). As described above, since the sample is not introduced in the empty analysis, the sample name and the sample injection amount are not entered in the first row of the schedule table. Subsequently, the schedule table creation unit 63 registers the actual analysis using the first method file in the second row of the schedule table (step S23). At this time, the values set by the user in step S11 are described in the column of sample name and sample injection amount.

  Thereafter, the schedule table creation unit 63 determines whether or not all the method files created in step S13 described above are registered in the schedule table (step S24), and determines that they are not registered (No in step S24). In step S25, the variable n is incremented.

  Subsequently, the schedule table creation unit 63 compares the description content of the second method file (that is, method 2) with the description content of the method file (that is, method 1) used in the immediately preceding actual analysis, and both Whether the type of column described in the method file is the same (step S26), whether the types of solvents A and B are the same (step S27), the mobile phase composition at the start of the gradient process in the gradient profile Are the same (step S28). And when all are the same (namely, step S26-S28 are all Yes), the real analysis using the said 2nd method file is registered into the 3rd line of a schedule table (step S30), and the said The process returns to step S24 (that is, the empty analysis using the method 2 is not registered in the schedule table).

  On the other hand, if any of the steps S26 to S28 is No, the empty analysis using the second method file is registered in the third row of the schedule table (step S29), and the same method file is further registered. The actual analysis used is registered in the fourth row of the schedule table (step S30), and the process returns to step S24. Also at this time, the sample name and the sample injection amount are not described in the blank analysis line, and the sample name and injection amount set by the user in step S11 are described in the actual analysis line.

  Thereafter, the processing in steps S24 to S30 is repeatedly executed until the answer in step S24 becomes Yes (that is, until all the method files are registered in the schedule table).

  Since the mobile phase composition in the washing process is often set to the same value in all method files, in the above example, whether the mobile phase composition in the washing process is the same between the two method files. Judgment is not performed. However, if there is a possibility that the mobile phase composition of the washing process may be set to a different value between the method files, whether the mobile phase composition at the start of the column, solvent, and gradient process is the same. In addition to the determination (steps S26 to S28), it is desirable to further determine whether or not the mobile phase composition in the washing step is the same. If even one of them is different, both empty analysis and actual analysis are registered in the schedule table for the method file (steps S29 and S30), and if all are the same, registration of empty analysis is omitted. The actual analysis is registered (step S30).

  As described above, the control device 60 according to the present embodiment determines whether or not the column type, the solvent type, and the mobile phase composition at the start of the gradient process are the same in two actual analyzes that are performed before and after. However, if they are the same, an empty analysis between the two analyzes is omitted. Hereinafter, this point will be described with a specific example.

  For example, a gradient profile (profile 1) as indicated by a solid line in FIG. 4 is described in the above method 1, and a gradient profile (hereinafter referred to as “profile 2”) as indicated by a dotted line in FIG. Call). Note that the column type and the solvent type are the same in the methods 1 and 2, respectively.

  As shown in FIG. 4, profile 1 and profile 2 differ only in the mobile phase composition at the end of the gradient process, and other conditions, that is, the execution time of the sample introduction process, the gradient process, the cleaning process, and the equilibration process. In addition, the mobile phase composition at the start of the gradient process and the mobile phase composition in the cleaning process are the same.

  When the method 1 describing the profile 1 and the method 2 describing the profile 2 are registered in the schedule table, in the conventional apparatus, an empty analysis using the method 1 (empty analysis 1) and an actual analysis using the method 1 ( Actual analysis 1), empty analysis using method 2 (empty analysis 2), and actual analysis using method 2 (actual analysis 2) are registered in this order. The time chart of the mobile phase composition change at this time is shown in FIG. This corresponds to two profiles 1 and 2 shown in FIG.

As described above, in profile 1 and profile 2, the mobile phase composition at the start of the gradient process is the same (concentration of solvent B: 5%), and the mobile phase composition in the washing process is also the same (concentration of solvent B: 95%). Therefore, as shown in FIG. 5A, in the time chart, the process in which the mixing ratio of the solvent B returns from 5% to 95% and then back to 5% is repeated four times. At this time, the equilibrium state of the column at the start time t _A , t _B , t _C of the second, third, and fourth steps, that is, the actual analysis 1, the empty analysis 2, and the actual analysis 2 is almost the same. Conceivable. Therefore, even if the sample is introduced at the start time t _B of the empty analysis 2 in FIG. 5A, the analysis is almost the same as when the sample is introduced at the start time t _C of the actual analysis 2. The result is considered to be obtained.

  Therefore, in the control device 60 of the present embodiment, the empty analysis 2 is omitted, and the empty analysis 1, the actual analysis 1, and the actual analysis 2 are registered in the schedule table in this order. A time chart of the mobile phase composition change at this time is shown in FIG. This corresponds to the arrangement of two profiles 1 and one profile 2 shown in FIG. Thereby, the time required from the start of the empty analysis 1 to the end of the actual analysis 2 can be shortened compared to the conventional case.

  On the other hand, for example, as shown in FIG. 6, when the mobile phase composition at the start of the gradient process in profile 1 and profile 2 is different, in the apparatus of this example, as in the prior art, empty analysis 1 and actual analysis are performed. 1, empty analysis 2, and actual analysis 2 are registered in the schedule table in this order. A time chart of the mobile phase composition change at this time is shown in FIG. This is equivalent to two profiles 1 and 2 shown in FIG.

As described above, since the mobile phase composition at the start of the gradient process is different between profile 1 and profile 2 in FIG. 6, starting time t _A of actual analysis 1, empty analysis 2, and actual analysis 2 in the time chart of FIG. 7. , T _B , t _C are considered to be different from each other. Therefore, in such a case, the empty analysis 2 cannot be omitted.

  An example of the schedule table created by the liquid chromatograph control device of this embodiment is shown in FIG. On the table, one line corresponds to one gradient analysis, and the sample name, sample injection amount, method file name, data file name, etc. are included in one line as information necessary to execute the analysis. Described. In addition, since it is not necessary to introduce the sample in the empty analysis, the sample name and the sample injection amount are not described in the line corresponding to the empty analysis.

  Here, the schedule table in the case where the mobile phase composition at the start of the gradient process is different between the methods 1 and 3 and the methods 1 and 2 and the methods 3 and 4 are the same is shown. Even in such a case, in the conventional apparatus, the actual analysis and the empty analysis are registered for all the method files as shown in FIG. 8A, but in the apparatus of the present embodiment, the actual analysis is performed as shown in FIG. Empty analysis between 1 and 2 and between actual analyzes 3 and 4 (ie empty analysis 2 and 4) is omitted. Therefore, in the schedule table of FIG. 8B, the analysis using the methods 1 and 3 is registered for each two lines, but the analysis using the methods 2 and 4 is registered for only one line each.

  As described above, according to this embodiment, it is possible to omit the empty analysis within a range that does not affect the analysis result, so that the time required for a series of analyzes can be shortened without reducing the analysis accuracy in method scouting or the like. Will be able to.

  Further, as described above, each line of the schedule table describes the data file name when the analysis result is stored. In the conventional apparatus, a serial number or the like is described as a data file name. However, in the apparatus of this embodiment, a file name representing an analysis condition as shown in FIG. 8B is automatically described. In the case of FIG. 8B, the data file name is (prefix) _ (column name) _ (solvent A name) _ (solvent B name) _ (composition ratio of solvent B at the start of the gradient process). _ (Composition ratio of solvent B at the end of the gradient process). Among these, the prefix is common to each line, and an arbitrary character string set in advance by the user is input. In addition to the prefix, an appropriate character string is input based on the description of the method file described in the line.

  Thereafter, when the user performs a predetermined operation to instruct the start of analysis, automatic analysis according to the schedule table is started, and gradient analysis using various gradient profiles is sequentially executed.

  The chromatogram data obtained as a result of each analysis is stored in one data file for each analysis, and each data file is given the data file name described in the corresponding row of the schedule table. This makes it possible for the user to easily determine under which conditions each data file is an analysis result without opening the file.

  In the example of FIG. 8B, since the same data file name is described in the actual analysis line and the corresponding empty analysis line, the data file generated by executing the empty analysis is This is overwritten by the data file of the actual analysis performed immediately after. However, there is no particular problem because the user is unlikely to refer to the result of the empty analysis. Also, for example, a character string indicating the distinction between empty analysis and actual analysis is added to the end of the file name so that the result of empty analysis and the result of actual analysis are saved with different data file names. Also good. Alternatively, a serial number or the like may be assigned to the data file name of the empty analysis as usual so that the user can easily distinguish the data file of the empty analysis from the data file of the actual analysis. Further, the storage location of the empty analysis data file and the actual analysis data file may be separated.

  As mentioned above, although the form for implementing this invention using an Example was demonstrated, this invention is not limited to the said Example, A change is accept | permitted suitably in the range of the meaning of this invention. It is. For example, in the above example, it is determined whether the mobile phase composition at the start of the gradient process is the same between the column type, the solvent type, and the gradient process in the two actual analyzes performed before and after. In this case, the empty analysis between the two actual analyzes is omitted, but at least one of the sample introduction process, the gradient process, the washing process, and the equilibration process in each actual analysis is omitted. It may be determined whether the execution time of one process is the same between the two actual analyses. In this case, in the two actual analyses, if the column type, the solvent type, the mobile phase composition at the start of the gradient process, and the execution time are the same, the empty analysis between the two actual analyses. If there is one that is not the same, empty analysis is not omitted.

  In the above embodiment, method files related to the previous and subsequent analysis are sequentially registered in the schedule table while comparing them one by one. However, after all the method files are registered in the schedule table, the method files that are moved back and forth in a batch You may make it perform comparison of. In this case, first, the actual analysis line and the empty analysis line are registered in the schedule table for all method files, and then the comparison is performed. As a result, only the empty analysis line determined to be omissible is deleted. Alternatively, first, only the actual analysis rows for all method files are registered in the schedule table, and then the comparison is performed. As a result, only the method files for which it is determined that the empty analysis cannot be omitted. An empty analysis line using the method file may be inserted before. In addition, after registering each method file in the schedule table, it is determined whether or not there are a plurality of completely identical analyzes in the table, and if they exist, one of them is left and deleted. You may do it. As a result, the time required for method scouting can be further shortened.

10 ... liquid supply unit 11 a to 11 d, 12 a to 12 d ... solvent container _{P A,} P B _... feeding pump 15, 16 ... solvent selector valve 17 ... gradient mixer 20 ... automatic sampler 30 ... Column Oven 32a-32f ... column 40 ... Detection unit 41 ... Detector 50 ... System controller 60 ... Control device 61 ... Storage unit 62 ... Analysis condition setting unit 63 ... Schedule table creation unit 64 ... Analysis control unit 65 ... Data processing unit 71 ... Operation unit 72 ... Display unit

Claims (3)

A control device for a liquid chromatograph that controls the operation of a liquid chromatograph having a gradient analysis function for performing chromatographic analysis while temporally changing a mixing ratio of a plurality of solvents constituting a mobile phase,
a) During the analysis of the sample, the mixing ratio of the solvent is from the first mixing ratio at which the dissolution power of the mobile phase is minimized during the analysis to the second mixing at which the dissolution power of the mobile phase is maximized during the analysis. An analysis control means for controlling the liquid chromatograph so as to return to the first mixing ratio again through the ratio;
b) Before the analysis of the sample, the mixing ratio of the solvent is changed from the same first mixing ratio as the analysis of the sample to the first mixing ratio again through the second mixing ratio same as the analysis of the sample. Preliminary liquid feeding control means for controlling the liquid chromatograph so as to execute the preliminary liquid feeding back to
Have
When the preliminary liquid feeding control means performs analysis of the sample a plurality of times, the column type, the solvent type, the first mixing ratio, and the second type applied to two sample analyzes executed before and after. A liquid chromatograph control device characterized in that, when the mixing ratio is the same, preliminary liquid feeding between the two sample analyzes is omitted. c) analysis result storage means for storing the results of multiple gradient analyzes in one data file for each analysis;
d) The name of the column and solvent used in each gradient analysis, and the solvent mixing ratio at the beginning of the step of continuously changing the solvent mixing ratio in each gradient analysis and the mixing ratio at the end of the step Data file name automatic assigning means for assigning a file name including at least one of the data name to the data file in which the analysis result is stored;
The liquid chromatograph control device according to claim 1, further comprising:   A program for causing a computer to function as the analysis control means and the preliminary liquid feeding control means according to claim 1.

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