JP2006317176A - Liquid chromatograph system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid chromatograph system capable of ensuring measurement of high precision by preventing not only analysis using a deteriorated solution but also analysis performed when precise measurement can not be performed because peak intensity is not stabilized when a column is not sufficiently aged, etc. <P>SOLUTION: In the liquid chromatograph system, it is measured whether a reaction liquid 8 is deteriorated using a detector 11 before a solution such as the eluting solution 1 sent from a liquid sending pump 2, the first reaction liquid 8 sent from a liquid sending pump 6, the second reaction liquid 9 sent from a liquid sending pump 7, etc. is introduced from an injector 3. It is determined whether the solution is within a predetermined prescribed value using a control device and test measurement performing the ageing of a separation column 5 is further executed. After it is determined that the solution is within the predetermined prescribed value by the control device, the sample is analyzed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid chromatograph apparatus in which a sample is introduced into an eluent and separated by a separation column, then a reaction liquid is mixed and reacted, and then detection is performed by a detector.

  In recent years, highly sensitive and highly selective analysis of various harmful substances has been demanded. Among liquid chromatographs, reaction liquid chromatographs measure normal liquid chromatographs in order to detect a sample that has been introduced into the eluent and separated by a separation column and then mixed and reacted. Analysis with higher sensitivity and selectivity. The following non-patent document 1 can be cited as an example of a method for analyzing harmful substances using a reaction liquid chromatograph.

  Patent Document 1 discloses a technique for diagnosing a device used for analysis during a long-term analysis period, checking the usage time of consumable parts, and automatically verifying the validity of the analysis. Has been.

Japanese Patent Laid-Open No. 10-318803 Notice from the Director of the Water Bureau, Health Bureau, Ministry of Health, Labor and Welfare, October 10, 2003

  A reaction liquid chromatograph uses a plurality of solutions. Specifically, it is an eluent that introduces a sample and is separated by a separation column, and one or more kinds of reaction solutions that are mixed and reacted after being separated. In the above method, even if one solution is defective, it cannot be measured with high accuracy.

  According to the technique disclosed in Patent Document 1, it is possible to diagnose an apparatus used for analysis, but no consideration is given to defects or deterioration of the eluent or the like.

  In addition, the reason why high-precision measurement cannot be performed is that the peak intensity is increased when the column is not sufficiently aged (equilibrium) or when the flow path including the device is not completely replaced by the solution. May not stabilize.

  An object of the present invention is to detect a defect or deterioration of a solution such as an eluent or a reaction solution, and to prevent analysis when the peak intensity of a sample component is not stable, and to perform highly accurate measurement. It is to realize a liquid chromatograph apparatus.

  In order to solve the problem of increasing the accuracy of the liquid chromatograph apparatus, in the present invention, a solution check is performed before the analysis of the sample is started. Specifically, each solution is measured with a detector, and test or sample measurement is performed after it is confirmed by the data processing of the control device that the user is within the prescribed range determined in advance by the user. To do. When it is out of the specified range, the user is notified with an error message and automatically replaced with a new solution to continue the measurement.

  In the test measurement, a sample serving as an index is measured a plurality of times, and the sample is measured after it is confirmed by the data processing of the control device that the user is within the predetermined rules. If it is out of the specified range, test measurement will continue until it falls within the specified range.

  According to the present invention, it is possible to prevent the use of a solution such as a poor or deteriorated eluent or reaction solution. In addition, since the analysis can be prevented even when the column is not sufficiently aged, the sample can be measured with high accuracy.

  Hereinafter, the above and other embodiments of the present invention will be described with reference to the drawings.

  A first embodiment of the present invention will be described with reference to FIGS.

  FIG. 1 is a schematic configuration diagram of a bromate analysis system to which a liquid chromatograph apparatus according to a first embodiment of the present invention is applied.

  In FIG. 1, the bromate analysis system includes a liquid feed pump 2 for feeding an eluent 1, an injector 3 for introducing a sample, a liquid feed pump 6 for feeding a first reaction liquid 8, and a second A liquid feed pump 7 for feeding the reaction liquid 9, a column oven 4, a detector 11, and a control device (not shown) are provided.

  The column oven 4 includes a separation column 5 and a reaction coil 10 therein.

  The liquid feed pump 2 is connected to a separation column 5 provided inside the column oven 4 via an injector 3, and an eluent 1 made of 4 mmol / L sodium carbonate solution is supplied to the separation column 5 at 1.0 ml / min. Pump at the flow rate.

  The injector 3 introduces a sample into the eluent 1 sent from the liquid feed pump 2.

  The column oven 4 controls the temperature by heating or cooling the separation column 5 installed inside and the reaction coil 10. The separation column 5 guides the eluent 1 into which the sample is introduced at the controlled temperature to the inside of the column and separates the sample.

  The reaction coil 10 is connected to the separation column 5, mixes a sample separated by the separation column 5, a first reaction liquid 8 and a second reaction liquid 9 described later, and is controlled at a temperature controlled by the column oven 4. React in.

  The liquid feed pump 6 is connected to a path connecting the separation column 5 and the reaction coil 10, and feeds the first reaction liquid 8 to the sample separated in the separation column 5 at a flow rate of 0.4 mL / min. To do. The first reaction solution 8 is obtained by dissolving 1.5 mol / L potassium bromide in 1 mol / L sulfuric acid.

  The liquid feed pump 7 is connected to a path connecting the separation column 5 and the reaction coil 10, and feeds the second reaction liquid 9 to the sample separated in the separation column 5 at a flow rate of 0.2 mL / min. To do. The second reaction liquid 9 is a 1.2 mmol / L sodium nitrate solution.

  The detector 11 is connected to the reaction coil 10, the first reaction liquid 8 and the second reaction liquid 9 are mixed in the reaction coil 10, and the sample subjected to the reaction is fed. As the detector 11, a UV-VIS detector is used, but a detector based on another detection method capable of performing the same measurement may be used.

  The control device is connected to the liquid feed pumps 2, 6, 7, the injector 3, the column oven 4, and the detector 11, and controls the liquid feed of each solution, the control of sample introduction, and the temperature of the column oven 4. Control, control of the detector 11 and input of the detection result are performed.

  Next, the control operation in the first embodiment of the present invention will be described.

  FIG. 2 is a control operation flowchart in the embodiment of the present invention.

  In step S201 in FIG. 2, a solution check described later is performed. In step S201, if there is no problem in checking the solution, the process proceeds to step S204, and if not, the process proceeds to step S202.

  In step S202, an error message is displayed to inform the user of the solution failure and record the solution failure history. Next, it progresses to step S203, solution automatic exchange is performed, and it returns to step S201. Automatic solution replacement can be realized by using a low pressure gradient unit, preparing a plurality of solutions in advance, and switching the solutions.

  If there is no problem in the solution check in step 201, the process proceeds to step S204, and it is determined whether or not to perform a test measurement described later. In step S204, if the test measurement is performed, the process proceeds to step S205, and if not, the process proceeds to step S206. In step S205, a test measurement is performed. If the test measurement falls within a specified value described later, the process proceeds to step S206. Otherwise, the test measurement is continued until it falls within the specified value.

  Next, in step S206, sample measurement is started, and the process proceeds to step S207. In step S207, it is determined whether or not a certain time has elapsed since the start of sample measurement. If the certain time has elapsed, the process proceeds to step S208, and if not, the process proceeds to step S211.

  In step S208, a solution check is performed. If there is no problem in the solution check, the process proceeds to step S211. Otherwise, the process proceeds to step S209. In step S209, an error message similar to that in step S202 is displayed, the process proceeds to step S210, the solution automatic exchange similar to that in step S203 is performed, the process proceeds to step S208, and the solution check is performed again.

  Next, in step S211, it is determined whether or not the measurement is finished. If the measurement is not finished, the process proceeds to step S207, and the process is repeated. If the measurement is finished, the process is finished.

  Next, the solution check in steps S201 and S208 and the test measurement in step S205 will be specifically described.

  FIG. 3 is a data processing screen when the solution check and test measurement are performed by the detector 11 such as a UV-VIS detector.

  In FIG. 3, a solution check item 1-10 is displayed at the top, and a test measurement item 11-20 is displayed at the bottom.

  Before starting the measurement, the user inputs an arbitrary numerical value to the solution check item on the data processing screen shown in FIG. 3 to perform a solution check on an arbitrary solution.

  For example, when the user inputs an arbitrary value in item 7, the first reaction liquid 8 is fed by the liquid feeding pump 6 before the start of the main measurement, and the inside of the cell of the detector 11 is The first reaction liquid 8 is filled, and the absorbance at an arbitrary wavelength is measured. By comparing this measurement result with an arbitrary numerical value input by the user, it is determined whether or not the first reaction liquid 8 is defective.

  In addition, when the user inputs an arbitrary value to the item 6, the spectrum similarity of the first reaction liquid 8 is measured before the start of the main measurement, and the first reaction liquid 8 is defective. It is determined whether or not.

  Similarly, the solution check of the eluent 1 is performed by inputting arbitrary numerical values in the items 3 and 4 in FIG. 3, and the second reaction liquid 9 is input by inputting arbitrary numerical values in the items 9 and 10. The solution is checked to determine whether the eluent 1 and the second reaction liquid 9 are deteriorated. When performing this solution check, each solution is measured in turn, and a small amount of solution is fed from a solution pump that feeds a solution that has not been measured during this measurement, and the solution check is performed. Prevents backflow of solution.

  Thus, by performing a solution check of the solution used before the main measurement, finding a deteriorated solution, and replacing it with a new solution, a highly accurate measurement can be performed.

  In addition, since the measurement of a normal sample takes a long time, the solution may be deteriorated during the measurement. For this reason, it is determined whether or not the measurement of the sample takes a certain time or more as in step S207, and if so, the solution is checked again after a certain time has elapsed, and if a defective solution is found. By performing the automatic solution exchange, it is possible to prevent the case where the solution deteriorates during the long-time measurement and the high-precision measurement is not performed.

  Next, before starting the measurement, the user inputs an arbitrary numerical value to the test measurement item on the data processing screen shown in FIG. 3 and performs the test measurement.

  Specifically, the user performs a test measurement by inputting a parameter related to the index in the item 12-15 of the data processing screen shown in FIG. 3 and inputting a parameter related to the stability in the item 16-20. The user can input an arbitrary numerical value up to the item 1-10 of the solution check shown in FIG. 3 and perform test measurement after performing the solution check.

  In test measurement, a sample to be used as an index is measured multiple times, it is determined whether the measurement result is within a specified value, and if the measurement result is not within the specified value, the measurement result is within the specified value. By repeating this measurement until it enters, it is possible to prevent cases where the separation column is not aged (equilibrium) or when the solution is not sufficiently distributed in the flow path including the device section. Is not stable and accurate measurement cannot be performed.

  Next, an embodiment of the present invention will be described by showing specific data.

  In the bromate analysis system, an arbitrary numerical value is input to the item of the first reaction liquid 8 in the data processing screen shown in FIG. 3, and measurement is performed according to the control flow shown in FIG.

  FIG. 4 is a diagram showing spectra when adjusting normal potassium bromide and adjusting deteriorated potassium bromide as the first reaction liquid 8.

  In FIG. 4, when the first reaction liquid 8 is prepared with potassium bromide that has not been properly stored, the first reaction liquid 8 itself has an absorption near 268 nm.

  For this reason, in the bromic acid analysis, if the absorbance at 268 nm is measured by the detector 11 such as the UV-VIS detector and the solution check is performed, the deteriorated potassium bromide can be detected.

  FIG. 5 is a diagram showing chromatograms when normal potassium bromide is adjusted as the first reaction liquid 8 and when deteriorated potassium bromide is adjusted.

  In FIG. 5, the peak at 5-6 min is bromate ion. The chromatogram using the first reaction solution 8 prepared with deteriorated potassium bromide has a larger noise and higher accuracy than the chromatogram using the first reaction solution 8 adjusted with ordinary potassium bromide. It can be seen that measurement cannot be performed.

  According to the first embodiment of the present invention configured as described above, it is possible to prevent the use of a defective or deteriorated reaction solution before starting measurement of a sample, and to perform highly accurate measurement. Can do.

  In the first embodiment of the present invention, the solution check is performed only for the first reaction solution 8, but the solution check of other solutions, that is, the eluent 1 and the second reaction solution 9 is performed, Alternatively, test measurement may be performed after the solution check, and the separation column 5 may be aged to perform measurement with higher accuracy.

  In addition, when performing a solution check of one solution, for example, the first reaction liquid 8, if the pumps 2 and 7 are completely stopped, the first reaction liquid 8 is put into the separation column 5 or the second reaction liquid 9. There is a possibility of backflow. For this reason, even when the solution check of the first reaction liquid 8 is performed, the liquid feed pumps 2 and 7 do not completely stop, and a very small amount of eluent or the like that does not affect the solution check. Deliver liquid.

  Next, a second embodiment of the present invention will be described with reference to FIGS.

  FIG. 6 is a schematic configuration diagram of a cyan analysis system to which the liquid chromatograph apparatus according to the second embodiment of the present invention is applied.

  In FIG. 6, the cyan analysis system includes a liquid feed pump 2 for feeding an eluent 12, an injector 3 for introducing a sample, a liquid feed pump 6 for feeding a first reaction liquid 14, and a second reaction. A liquid feed pump 7 for feeding the liquid 15, a column oven 4, a thermostatic chamber 18, a detector 11, and a control device (not shown) are provided.

  The column oven 4 includes a separation column 13 and a reaction coil 16 therein, and the thermostatic chamber 18 includes a reaction coil 17 therein.

  The liquid feed pump 2 is connected to a separation column 13 provided inside the column oven 4 via an injector 3, and an eluent 12 made of a 1 mmol / L sulfuric acid solution is supplied to the separation column 13 at a flow rate of 0.5 mL / min. Pump the liquid.

  The injector 3 introduces a sample into the eluent 12 sent from the liquid feed pump 2.

  The column oven 4 controls the temperature by heating or cooling the separation column 13 installed inside and the reaction coil 16. In the controlled temperature, the separation column 13 guides the eluent 12 into which the sample has been introduced into the column, and separates the sample.

  The reaction coil 16 is connected to the separation column 13, and a sample separated by the separation column 13 and a first reaction liquid 14 described later are mixed and reacted in a temperature controlled by the column oven 4.

  The liquid feed pump 6 is connected to a path connecting the separation column 13 and the reaction coil 16, and feeds the first reaction liquid 14 to the sample separated in the separation column 13 at a flow rate of 0.5 mL / min. To do. The first reaction solution 14 is 0.1% chloramine T (p-toluenesulfone chloroamide sodium trihydrate), 20 mmol / L sodium dihydrogen phosphate, 80 mmol / L disodium hydrogen phosphate. It was prepared.

  The reaction coil 17 is connected to the reaction coil 16, mixes the sample that has been mixed with the first reaction solution 14 and reacted in the reaction coil 16, and the second reaction solution 15 described later, and is heated by a constant temperature bath 18. The reaction is carried out while heated to ° C.

  The liquid feed pump 7 is connected to a path connecting the reaction coil 16 and the reaction coil 17, and the second reaction liquid 15 is applied to the sample that has been mixed with the first reaction liquid 14 and reacted in the reaction coil 16. At a flow rate of 0.5 mL / min. The second reaction solution 15 is prepared by dissolving 2.5 g of 1-phenyl-3-methyl-5-pyrazolone in 150 mL of N, N-dimethylformamide and separately dissolving 7.0 g of sodium 4-pyridinecarboxylate in about 300 mL of purified water. Both solutions were combined and purified water was added to make 500 mL.

  The detector 11 is connected to the reaction coil 17, the second reaction liquid 15 is mixed in the reaction coil 17, and the sample subjected to the reaction is fed. As the detector 11, a UV-VIS detector is used, but a detector based on another detection method capable of performing the same measurement may be used.

  The control device is connected to the liquid feed pumps 2, 6, 7, the injector 3, the column oven 4, the high-temperature tank 18, and the detector 11, and controls the liquid feed of each solution, the control of sample introduction, the column Control of the temperature of the oven 4, control of the temperature of the high-temperature tank 18, control of the detector 11, and input of detection results are performed.

  The control device in the second embodiment of the present invention performs the same control as the control flow shown in FIG. 2 of the first embodiment, and the data processing screen for performing the solution check and the test measurement is the first control screen. The same data processing screen as that shown in FIG. 3 of the embodiment is used.

  Next, the operation of the second embodiment of the present invention will be described.

  In the cyan analysis system, an arbitrary numerical value is input to the item of the second reaction liquid 15 in the data processing screen shown in FIG. 3, and measurement is performed according to the control flow shown in FIG.

  FIG. 7 is a diagram showing a case where the spectrum of the second reaction liquid 15 is measured every time.

  In FIG. 7, it can be seen that the second reaction liquid 15 itself has an absorption around 638 nm as time elapses.

  For this reason, it is understood that the second reaction liquid 15 that has progressed over time can be detected by measuring the absorbance at 638 nm by the detector 11 such as the UV-VIS detector in the cyan analysis and performing the solution check.

  FIG. 8 is a chromatogram when the second reaction solution 15 is used every time.

  In FIG. 8, the peak at 3-4 min is cyanide ion. The chromatogram using the second reaction liquid 15 that has passed 6 days after preparation is noisier than the chromatogram using the second reaction liquid 15 immediately after preparation, and the measurement should be performed with high accuracy. I can't understand.

  According to the second embodiment of the present invention configured as described above, it is possible to prevent the use of a reaction solution that has deteriorated due to the passage of time after the adjustment of the solution, and perform highly accurate measurement. be able to.

  In the second embodiment of the present invention, the solution check is performed only for the second reaction solution 15, but the solution check of other solutions, that is, the eluent 12 and the first reaction solution 14, is performed. Alternatively, test measurement may be performed after the solution check, the separation column 13 may be aged, and more accurate measurement may be performed.

  Next, a third embodiment of the present invention will be described with reference to FIGS.

  FIG. 9 is a schematic configuration diagram of an iminotadine analysis system to which the liquid chromatogram apparatus according to the third embodiment of the present invention is applied.

  In FIG. 9, the iminotadine analysis system includes a liquid feed pump 2 for feeding an eluent 19, an injector 3 for introducing a sample, a liquid feed pump 6 for feeding a first reaction liquid 21, and a second reaction. A liquid feed pump 7 for feeding the liquid 22, a column oven 4, a thermostat 18, a detector 25, and a control device (not shown) are provided.

  The column oven 4 includes a separation column 20 therein, and the thermostatic chamber 18 includes a reaction coil 23 and a reaction coil 24 therein.

  The liquid feed pump 2 is connected to the separation column 20 provided inside the column oven 4 via the injector 3, and sends the eluent 19 to the separation column 20 at a flow rate of 0.8 mL / min. As an eluent 19, 14.1 g of sodium perchlorate monohydrate, 400 mg of sodium hydroxide and 1.8 mL of lactic acid were dissolved in purified water to 1000 mL, and acetonitrile was mixed at a volume ratio of 17: 5. Is.

  The injector 3 introduces a sample into the eluent 19 sent from the liquid feed pump 2.

  The column oven 4 controls the temperature by heating or cooling the separation column 20 installed inside. The separation column 20 guides the eluent 19 into which the sample has been introduced into the column at the controlled temperature to separate the sample.

  The reaction coil 23 is connected to the separation column 20, and a sample separated by the separation column 20 and a first reaction liquid 21 described later are mixed and reacted while being heated to 100 ° C. by the high-temperature bath 18.

  The liquid feed pump 6 is connected to a path connecting the separation column 20 and the reaction coil 23, and feeds the first reaction liquid 21 at a flow rate of 0.2 mL / min to the sample separated in the separation column 20. To do. The first reaction liquid 21 is a 0.5 mol / L sodium hydroxide solution.

  The reaction coil 24 is connected to the reaction coil 23, mixes the sample that has been mixed with the first reaction solution 21 and reacted in the reaction coil 23, and a second reaction solution 22 that will be described later. The reaction is carried out while heated to ° C.

  The liquid feed pump 7 is connected to a path connecting the reaction coil 23 and the reaction coil 24, and the second reaction liquid 22 is applied to the sample that has been mixed with the first reaction liquid 21 and reacted in the reaction coil 23. At a flow rate of 0.1 mL / min. The second reaction liquid 22 is a 3 g / L ninhydrin solution.

  The detector 25 is connected to the reaction coil 24, the second reaction liquid 22 is mixed in the reaction coil 24, and the sample subjected to the reaction is fed. In iminotadine analysis, a fluorescence detector is used as the detector 25 for measurement at an excitation wavelength of 395 nm and a fluorescence wavelength of 500 nm. However, a detector based on another detection method capable of performing the same measurement may be used. .

  The control device is connected to the liquid feed pumps 2, 6, 7, the injector 3, the column oven 4, the high-temperature tank 18, and the detector 25, and controls the liquid feed of each solution, the control of sample introduction, the column Control of the temperature of the oven 4, control of the temperature of the high-temperature tank 18, control of the detector 25, and input of detection results are performed.

  FIG. 10 is a data processing screen when the solution check and test measurement are performed by the detector 25 such as a fluorescence detector.

  The control device in the third embodiment of the present invention performs the same control as the control flow shown in FIG. 2 of the first embodiment, and the data processing screen for performing the solution check and the test measurement is shown in FIG. Use the data processing screen shown.

  Next, the operation of the third embodiment of the present invention will be described.

  In the iminotadine analysis system, an arbitrary numerical value is input to the test measurement item in the data processing screen shown in FIG. 10, and the measurement is performed according to the control flow shown in FIG.

  FIG. 11 is a diagram showing the chromatogram of the iminotadine analysis system as time passes from the start of measurement.

  In FIG. 11, a phenomenon is observed in which the peak intensity of iminotazine of 10-12 min increases with time after the measurement is started.

  For this reason, if the detector 23 such as a fluorescence detector is used for iminotazine analysis with an excitation wavelength of 395 nm and a fluorescence wavelength of 500 nm and a test measurement is performed, the aging (equilibration) progress of the separation column 20 can be detected. Can do.

  FIG. 12 is a diagram showing the relationship between the aging (equilibration) time of the separation column 20 and the peak intensity.

  In FIG. 12, it can be seen that the phenomenon in which the peak intensity increases continues up to 1000 min, and thereafter a constant peak intensity can be obtained.

  The cause is considered that the separation column 20 is not sufficiently aged (equilibrated) in the eluent 19, and unless the separation column 20 sufficiently aged (equilibrated) until the peak intensity is stabilized is used. It can be seen that high-precision measurement cannot be performed.

  According to the third embodiment of the present invention configured as described above, the test measurement is performed before starting the measurement of the sample, and the peak intensity is stable when the column is not sufficiently aged (equilibrated). Measurement can be prevented when it is not realized, and highly accurate measurement can be performed.

  In the third embodiment of the present invention, only the test measurement is performed. However, before the test measurement is performed, a solution check of an arbitrary solution is performed, and then the test measurement is performed continuously. It is good also as what performs a highly accurate measurement.

  Next, a fourth embodiment of the present invention will be described with reference to FIGS.

  FIG. 13 is a schematic configuration diagram of a cyanogen bromide combined analysis system to which a liquid chromatogram apparatus according to the fourth embodiment of the present invention is applied.

  In FIG. 13, the cyanogen bromide combined analysis system separately measures the bromate analysis system shown in the first embodiment and the cyanate analysis system shown in the second embodiment. , 6, 7, the injector 3, the column oven 4, and the detector 11 such as a UV-VIS detector are shared, and the liquid feed pumps 2, 6, 7 use the eluent, the first reaction liquid, the second This is realized by switching the reaction solution, flow path, separation column, and reaction coil.

  The control device is connected to the liquid feed pumps 2, 6, 7, the injector 3, the column oven 4, the high-temperature tank 18, and the detector 11, and controls the liquid feed of each solution, the control of sample introduction, the column Control of the temperature of the oven 4, control of the temperature of the high-temperature tank 18, control of the detector 11, and input of detection results are performed.

  The control device in the fourth embodiment of the present invention performs the same control as the control flow shown in FIG. 2 of the first embodiment, and the data processing screen for performing the solution check and the test measurement is the first control screen. The same data processing screen as that shown in FIG. 3 of the embodiment is used.

  Next, the operation of the fourth embodiment of the present invention will be described.

  In the cyanogen bromide combined analysis system according to the fourth embodiment of the present invention, an arbitrary numerical value is input to the test measurement item in the data processing screen shown in FIG. 3, and the measurement is performed according to the control flow shown in FIG. .

  FIG. 14 is a diagram showing a chromatogram for each passage of time when switching from bromic acid analysis to cyan analysis in the cyanogen bromate acid analysis system.

  In FIG. 14, a phenomenon is observed where the peak of 3-4 min cyanide ion gradually increases with time. The eluent and reaction liquid for bromic acid analysis remain slightly in the shared devices such as the liquid feed pumps 2, 6, 7, the injector 3, and the detector 11 such as the UV-VIS detector, This is probably because the eluent and reaction solution for cyan analysis gradually wash them out over time.

  Therefore, by setting a specified value to detect chromatogram noise in the cyanogen bromate acid analysis system and performing test measurements, it is possible to detect when the inside of the flow path including the device section has not been completely replaced with a new solution. I understand.

  According to the fourth embodiment of the present invention configured as described above, the test measurement is performed before starting the measurement of the sample, and the inside of the flow path including the device unit is not completely replaced by the solution, and the peak intensity It is possible to prevent the measurement from being performed when it is not stabilized, and to perform a highly accurate measurement.

  In the fourth embodiment of the present invention, only the test measurement is performed. However, before performing the test measurement, a solution check of an arbitrary solution is performed, and then the test measurement is performed continuously. It is good also as what performs a highly accurate measurement.

1 is a schematic configuration diagram of a bromate analysis system to which a liquid chromatograph apparatus according to a first embodiment of the present invention is applied. It is a control operation | movement flowchart of this invention. It is a figure which shows the data processing screen in the case of performing a solution check and test measurement with detectors, such as a UV-VIS detector. It is a figure which shows the spectrum at the time of adjusting the normal potassium bromide as a 1st reaction liquid of the bromic acid analysis system by the 1st Embodiment of this invention, and adjusting the deteriorated potassium bromide. It is a figure which shows the chromatogram at the time of adjusting the normal potassium bromide as a 1st reaction liquid of the bromic acid analysis system by the 1st Embodiment of this invention, and adjusting the deteriorated potassium bromide. It is a schematic block diagram of the cyan analysis system to which the liquid chromatograph apparatus by the 2nd Embodiment of this invention is applied. It is a figure which shows the case where the spectrum of the 2nd reaction liquid of the cyan | cyanogen analysis system by the 2nd Embodiment of this invention is measured for every time. It is a figure which shows the chromatogram at the time of using the 2nd reaction liquid of the cyanide analysis system by the 2nd Embodiment of this invention for every time passage. It is a schematic block diagram of the iminoctazine analysis system to which the liquid chromatogram apparatus by the 3rd Embodiment of this invention is applied. It is a figure which shows the data processing screen in the case of performing a solution check and test measurement with detectors, such as a fluorescence detector. It is a figure which shows the chromatogram of the iminoctazine analysis system by the 3rd Embodiment of this invention for every time progress from a measurement start. It is a figure which shows the relationship between the aging (equilibration) time and peak intensity of the separation column of the iminoctazine analysis system by the 3rd Embodiment of this invention. It is a schematic block diagram of the cyanogen bromic acid combined analysis system to which the liquid chromatogram apparatus by the 4th Embodiment of this invention is applied. It is a figure which shows the chromatogram for every time passage at the time of switching from a bromic acid analysis to a cyan analysis in the cyanogen bromic acid combined analysis system by the 4th Embodiment of this invention.

Explanation of symbols

1,12,19 Eluent 2,6,7 Liquid feed pump 3 Injector 4 Column oven 5,13,20 Separation column 8,9,14,15,21,22 Reaction liquid 10, 16, 17, 23, 24 Reaction Coil 11,25 detector

Claims (5)

A first liquid feed pump for feeding an eluent, a sample introduction part for introducing a sample into the eluent, a separation column to which the eluent into which the sample is introduced is supplied, and a sample eluted from the separation column A second liquid-feeding pump that feeds the reaction liquid, a reaction means that mixes and reacts the sample to which the reaction liquid has been sent, a detector that measures the sample that has been mixed and reacted by the reaction means, and In a liquid chromatograph apparatus comprising a control means for controlling the operation of the first liquid feed pump, the second liquid feed pump, the sample introduction means and the reaction means,
Before starting the analysis of the sample, the control means includes the eluent sent from the first liquid feed pump or the solution containing the reaction liquid sent from the second liquid feed pump. Any or all of the liquid chromatographs are measured by the above-mentioned detector and analysis of the sample is started after it is determined whether or not the measurement result is within a predetermined specified value. apparatus. In the liquid chromatograph device according to claim 1,
The liquid chromatograph apparatus characterized in that there are a plurality of the second liquid feeding pumps, and the determination of the solution by the control means is performed for a plurality of reaction liquids. The liquid chromatograph apparatus according to claim 1,
The control means measures the specific sample after it is determined that the solution is within the specified value, and repeats the measurement of the specific sample until the measurement result is within a predetermined specified value. The liquid chromatograph is characterized in that the analysis of the sample is started after it is determined that the measurement result is within the specified value. The liquid chromatograph apparatus according to claim 1,
In the liquid chromatograph apparatus, the control device automatically replaces the solution when it is determined in the determination of the solution that the solution is not within a predetermined value. The liquid chromatograph apparatus according to claim 1,
A liquid chromatograph characterized by determining whether or not the solution is again within a predetermined specified value after a certain period of time has elapsed after the analysis of the sample has started. apparatus.

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