JP2023113415A - Analysis system - Google Patents

Abstract

To provide an analysis system that can measure a sample in a proper condition.SOLUTION: In the analysis system: a detector detects a sample supplied from a sample supply unit; a calibration curve acquisition unit 3 acquires a calibration curve indicative of a relationship between concentration of a reference sample and detection intensity of the reference sample; a determination unit 5 determines whether or not detection intensity of the sample outputted by the detector is larger than a set threshold; when the detection intensity of the sample is larger than the threshold, a determination unit 6 determines a dilution rate of the sample on the basis of the detection intensity and the threshold; when the detection intensity of the sample is equal to or less than the threshold, a processing unit quantifies concentration of the sample on the basis of the detection intensity and the calibration curve acquired by the calibration curve acquisition unit 3; and the sample supply unit dilutes the sample at the dilution rate determined by the determination unit 6, and then supplies the diluted sample.SELECTED DRAWING: Figure 2

Description

The present invention relates to analytical systems.

In the measurement of a sample using an analyzer such as a chromatograph, a plurality of samples (standard samples) with known concentrations are detected to show the relationship between the concentration of the standard sample and the detection intensity of the standard sample. A standard curve is generated. Also, samples with unknown concentrations (unknown samples) are detected. The concentration of the unknown sample is quantified based on the calibration curve generated using the standard sample and the detection intensity of the unknown sample (see Patent Document 1, for example).

Japanese Patent Application Laid-Open No. 2021-012170

Since it takes a relatively long working time to measure a sample in an analyzer, the burden on the person in charge of measurement is heavy. For this reason, in recent years, in the analysis industry, unskilled workers such as part-time workers are increasingly in charge of measurement. In this case, the administrator of the analyzer can analyze the sample by reviewing the measurement results obtained by the analyst without operating the analyzer.

However, since the person in charge of measurement does not have sufficient knowledge about the analyzer, it is often impossible to judge whether the sample was measured under appropriate conditions in the analyzer. If the sample is not measured under proper conditions, the sample cannot be analyzed accurately. Therefore, it is required to develop an analysis system that can measure samples under appropriate conditions.

An object of the present invention is to provide an analysis system capable of measuring samples under appropriate conditions.

One aspect of the present invention includes a sample supply unit that supplies a sample, a detection unit that detects the sample supplied by the sample supply unit and outputs the detection intensity of the sample, the concentration of the standard sample, and the detection intensity of the standard sample. A calibration curve acquisition unit that acquires a calibration curve showing the relationship between, a determination unit that determines whether the detection intensity of the sample output by the detection unit is greater than a set threshold value, and the detection intensity of the sample is greater than the threshold, a determination unit that determines a dilution ratio of the sample based on the detected intensity and the threshold; and if the detected intensity of the sample is equal to or less than the threshold, a processing unit that quantifies the concentration of the sample based on the calibration curve acquired by the calibration curve acquisition unit, and the sample supply unit dilutes and supplies the sample at the dilution ratio determined by the determination unit. for analytical systems.

According to the present invention, samples can be measured under appropriate conditions.

It is a figure showing composition of an analysis system concerning an embodiment of the invention. 2 is a diagram showing the configuration of an analysis control unit in FIG. 1; FIG. It is a figure which shows an example of a calibration curve. FIG. 4 is a flow chart showing an example of an algorithm for quantitative processing of a sample in a reference example; FIG. FIG. 3 is a flow chart showing an example of sample quantification processing by the analysis control unit of FIG. 2 ; FIG. FIG. 3 is a flow chart showing an example of sample quantification processing by the analysis control unit of FIG. 2 ; FIG. It is a figure which shows the structure of the analysis control part in a modification. 10 is a flow chart showing an example of sample quantitative processing in a modified example. 10 is a flow chart showing an example of sample quantitative processing in a modified example.

(1) Configuration of Analysis System Hereinafter, an analysis system according to an embodiment of the present invention will be described in detail with reference to the drawings. FIG. 1 is a diagram showing the configuration of an analysis system according to an embodiment of the present invention. As shown in FIG. 1, analysis system 300 includes control device 100 and analysis device 200 .

The control device 100 is, for example, a personal computer, and includes a CPU (central processing unit) 110, a RAM (random access memory) 120, a ROM (read only memory) 130, a storage unit 140, an operation unit 150, a display unit 160, and an input/output unit. It is composed of an I/F (interface) 170 and a bus 180 . CPU 110 , RAM 120 , ROM 130 , storage unit 140 , operation unit 150 , display unit 160 and input/output I/F 170 are connected to bus 180 .

The RAM 120 consists of, for example, a volatile memory and is used as a work area for the CPU 110 . The ROM 130 is composed of, for example, non-volatile memory. A system program is stored in the ROM 130 . Analysis control unit 10 is configured by CPU 110 , RAM 120 and ROM 130 . Details of the analysis control unit 10 will be described later.

Storage unit 140 includes a storage medium such as a hard disk or a semiconductor memory. The storage unit 140 stores a batch file indicating a sample analysis sequence, a control program for the analysis device 200, and the like. A batch file, a control program, or the like may be stored in a storage medium different from storage unit 140 . The CPU 110 executes the control program stored in the storage unit 140 or the like on the RAM 120 to perform quantitative processing of the sample according to the batch file.

The operation unit 150 is an input device such as a keyboard, mouse or touch panel. The display unit 160 is a display device such as a liquid crystal display unit. A user of the analysis system 300 can make various designations to the control device 100 by operating the operation unit 150 . The display unit 160 can display analysis results such as a calibration curve or a chromatogram obtained by measuring the sample. Input/output I/F 170 is connected to analysis device 200 .

In this example, analytical device 200 is a liquid chromatograph and includes mobile phase supply 210 , sample supply 220 , separation column 230 and detector 240 . The mobile phase supply unit 210 includes, for example, a liquid feed pump, and pressure-feeds a mobile phase such as an aqueous solution or an organic solvent. The mobile phase supply section 210 may include a plurality of liquid transfer pumps and gradient mixers to perform gradient liquid transfer of the mobile phase.

The sample supply unit 220 is, for example, an autosampler, and supplies the sample to the separation column 230 together with the mobile phase supplied by the mobile phase supply unit 210 . The samples include standard samples with known concentrations and unknown samples with unknown concentrations. Further, when the dilution rate of the sample is set in the sample supply unit 220, the sample supply unit 220 uses a diluent having the same components as the mobile phase when supplying the sample. Dilute the sample by the dilution factor.

The separation column 230 is housed inside a column constant temperature bath (not shown) and adjusted to a predetermined constant temperature. Separation column 230 separates the introduced sample into components based on differences in chemical properties or composition. Detector 240 is, for example, a PDA (photodiode array) or UV (ultraviolet) detector. Detector 240 may be a mass spectrometer. Detector 240 detects the components of the sample separated by separation column 230 and outputs the detected intensity.

(2) Configuration of Control Device FIG. 2 is a diagram showing the configuration of the analysis control unit 10 in FIG. As shown in FIG. 2, the analysis control unit 10 includes a batch acquisition unit 1, a measurement execution unit 2, a calibration curve acquisition unit 3, a setting unit 4, a determination unit 5, a determination unit 6, and a processing unit 7 as functional units. . The functional units of the analysis control unit 10 are implemented by the CPU 110 of FIG. 1 executing the control program stored in the storage unit 140 or the like. A part or all of the functional units of the analysis control unit 10 may be realized by hardware such as an electronic circuit.

The batch acquisition unit 1 acquires a batch file stored in the storage unit 140 or the like based on an instruction from the operation unit 150 . A user can specify a desired batch file to be used for sample measurement to the batch acquisition unit 1 by operating the operation unit 150 . The measurement execution unit 2 controls the operations of the mobile phase supply unit 210, the sample supply unit 220, the separation column 230 (column constant temperature bath), and the detector 240 of the analysis device 200 according to the batch file acquired by the batch acquisition unit 1. .

The calibration curve acquisition unit 3 acquires a calibration curve showing the relationship between the concentration of the standard sample and the detected intensity of the standard sample. FIG. 3 is a diagram showing an example of a calibration curve. In FIG. 3, the horizontal axis indicates the concentration of the standard sample, and the vertical axis indicates the detected intensity of the standard sample. In this example, in the analyzer 200, a plurality of standard samples are sequentially detected by the detector 240 according to the analysis sequence indicated by the batch file. The calibration curve acquisition unit 3 generates the calibration curve shown in FIG. 3 based on the detected intensity of each standard sample output from the detector 240 and the concentration of each standard sample.

The setting unit 4 sets a threshold for the detected intensity of the sample. In this example, the setting unit 4 sets the threshold based on the maximum detected intensity of the standard sample in the calibration curve of FIG. 3 acquired by the calibration curve acquisition unit 3 . In this case, the threshold value for properly diluting the sample can be easily set. For example, the threshold value may be the maximum value of the detection intensity of the standard sample, a value smaller than the maximum value of the detection intensity of the standard sample by a predetermined amount, or the threshold value of the detection intensity of the standard sample. It may be a value that is a predetermined percentage of the maximum value.

Alternatively, the setting unit 4 may receive designation of a threshold value to be set from the operation unit 150, as indicated by a dashed line in FIG. In this case, the user can designate any threshold value to the setting unit 4 by operating the operation unit 150 . In this configuration, it is preferable that a value equal to or more than the minimum value and equal to or less than the maximum value of the detected intensity of the standard sample in the calibration curve of FIG.

In the analyzer 200, unknown samples are detected by the detector 240 according to the analysis sequence indicated by the batch file. The determination unit 5 acquires the detection intensity of the unknown sample output by the detector 240 . The determination unit 5 also determines whether or not the acquired detection intensity of the unknown sample is greater than the threshold value set by the setting unit 4 .

If the determining unit 5 determines that the detected intensity of the unknown sample is greater than the threshold, the determining unit 6 determines the dilution ratio of the unknown sample based on the detected intensity and the threshold. In this example, the ratio of the threshold to the detection intensity of the unknown sample is determined as the dilution factor. In this case, unknown samples can be diluted easily and appropriately. The determination unit 6 sets the determined dilution rate in the sample supply unit 220 of the analyzer 200 . As a result, the sample supply unit 220 dilutes the unknown sample at the set dilution rate and supplies it.

When the determining unit 5 determines that the detected intensity of the unknown sample is equal to or less than the threshold value, the processing unit 7 determines the unknown sample based on the detected intensity and the calibration curve obtained by the calibration curve obtaining unit 3. Quantify the concentration. The processing unit 7 may further generate a chromatogram based on the retention time of the unknown sample in the separation column 230 of the analyzer 200 and the detection intensity of the unknown sample.

(3) Reference Example FIG. 4 is a flow chart showing an example of a sample quantitative processing algorithm in a reference example. An example of sample quantitative processing in the reference example will be described below using the analysis system 300 in FIG. 1, the analysis control unit 10 in FIG. 2, and the flowchart in FIG.

First, the batch acquisition unit 1 determines whether or not a batch file has been specified (step S1). If no batch file is specified, the batch acquisition unit 1 waits until a batch file is specified. When the batch file is specified, the batch acquisition unit 1 acquires the specified batch file from the storage unit 140 or the like (step S2). After that, the analysis sequence of steps S3 to S15 indicated by the batch file obtained in step S2 is sequentially executed.

Specifically, the measurement executing section 2 controls the operation of the analyzer 200 to measure the first standard sample having the first concentration (step S3). Accordingly, in the analyzer 200 , the mobile phase supply unit 210 supplies the mobile phase, and the sample supply unit 220 supplies the first standard sample to the separation column 230 together with the mobile phase supplied by the mobile phase supply unit 210 . Detector 240 detects the first standard sample that has passed through separation column 230 and outputs the detected intensity.

Similarly, measurement execution unit 2 controls the operation of analyzer 200 to measure a second standard sample having a second concentration (step S4). The measurement executing section 2 controls the operation of the analyzer 200 to measure the third standard sample having the third concentration (step S5). The measurement executing section 2 controls the operation of the analyzer 200 to measure the fourth standard sample having the fourth concentration (step S6). The calibration curve acquisition unit 3 obtains the calibration curve of FIG. (step S7).

Next, the measurement executing section 2 controls the operation of the analyzer 200 to measure the first unknown sample (step S8). In this case, in the analyzer 200 , the mobile phase supply unit 210 supplies the mobile phase, and the sample supply unit 220 supplies the first unknown sample to the separation column 230 together with the mobile phase supplied by the mobile phase supply unit 210 . Detector 240 detects the first unknown sample that has passed through separation column 230 and outputs the detected intensity. Subsequently, the processing unit 7 quantifies the concentration of the first unknown sample based on the calibration curve obtained in step S7 and the detection intensity of the first unknown sample output by the detector 240 in step S8. (step S9).

Similarly, measurement execution unit 2 controls the operation of analyzer 200 to measure the second unknown sample (step S10). The processing unit 7 quantifies the concentration of the second unknown sample based on the calibration curve and the detected intensity of the second unknown sample output in step S10 (step S11).

Further, the measurement execution unit 2 controls the operation of the analysis device 200 so as to measure the third unknown sample (step S12). The processing unit 7 quantifies the concentration of the third unknown sample based on the calibration curve and the detected intensity of the third unknown sample output in step S12 (step S13).

Furthermore, the measurement executing section 2 controls the operation of the analyzer 200 to measure the fourth unknown sample (step S14). The processing unit 7 quantifies the concentration of the fourth unknown sample based on the calibration curve and the detected intensity of the fourth unknown sample output in step S14 (step S15), and ends the sample quantification process. .

According to the quantitative processing described above, the concentrations of the first to fourth unknown samples can be quantified. However, the detected intensities of the first to fourth unknown samples output in steps S8, S10, S12, and S14 are the minimum and maximum values of the detected intensities of the standard samples in the calibration curve of FIG. not necessarily between If the detected intensities of the first to fourth unknown samples are greater than the maximum value of the detected intensities of the standard samples, the linearity of the calibration curve is not ensured. Therefore, the concentrations of the first to fourth unknown samples cannot be accurately quantified in steps S9, S11, S13, and S15.

(4) Quantitative Processing FIGS. 5 and 6 are flowcharts showing an example of sample quantitative processing by the analysis control unit 10 of FIG. The quantitative processing in FIG. 5 is performed by CPU 110 in FIG. 1 executing a control program stored in storage unit 140 or the like on RAM 120 . An example of sample quantitative processing according to the present embodiment will be described below with reference to the analysis system 300 of FIG. 1, the analysis control unit 10 of FIG. 2, and the flow charts of FIGS.

In the quantitative processing in this embodiment, first, steps S1 and S2 similar to steps S1 and S2 in FIG. 4 are executed. As a result, the analysis sequence of steps S3 to S15 indicated by the batch file acquired in step S2 is executed. Here, in the present embodiment, the following steps S7a, steps S8a and 8b, steps S10a and 10b, steps S12a and 12b, and steps S14a and 14b are appropriately executed during the analysis sequence indicated by the batch file.

Specifically, after step S2, steps S3 to S7 similar to steps S3 to S7 in FIG. 4 are sequentially executed. After step S7, the setting unit 4 sets the threshold for the detected intensity of the sample based on the maximum value of the detected intensity of the standard sample on the calibration curve obtained in step S7 (step S7a). Note that the setting unit 4 may set a value designated by the user through the operation unit 150 as the threshold for the sample detection intensity. In this case, step S7a may be performed before step S7.

Next, the measurement executing section 2 controls the operation of the analyzer 200 to measure the first unknown sample (step S8), as in step S8 of FIG. The determination unit 5 determines whether or not the detection intensity of the first unknown sample output by the detector 240 in step S8 is greater than the threshold set in step S7a (step S8a).

If the detection intensity of the first unknown sample is greater than the threshold, the determination unit 6 determines the dilution ratio of the first unknown sample based on the detection intensity and the threshold (step S8b), and the process proceeds to step S8. return. As a result, the dilution rate determined in step S8b is set in the sample supply section 220 of the analyzer 200. FIG. Also, in step S8, the diluted first unknown sample is measured again. The amount of sample measured at this time is the same as the amount of sample measured before dilution. Steps S8-S8b are repeated until the detected intensity of the first unknown sample falls below the threshold.

In step S8a, if the detected intensity of the first unknown sample is equal to or less than the threshold value, the processing unit 7, similarly to step S9 in FIG. Based on the detected intensity of the first unknown sample output by 240, the concentration of the first unknown sample is quantified (step S9).

Similarly, measurement execution unit 2 controls the operation of analyzer 200 to measure the second unknown sample (step S10). The determination unit 5 determines whether or not the detection intensity of the second unknown sample output by the detector 240 in step S10 is greater than the threshold set in step S7a (step S10a).

If the detection intensity of the second unknown sample is greater than the threshold, the determination unit 6 determines the dilution ratio of the second unknown sample based on the detection intensity and the threshold (step S10b), and the process proceeds to step S10. return. If the detected intensity of the second unknown sample is equal to or less than the threshold, the processing unit 7 combines the calibration curve obtained in step S7 with the detected intensity of the second unknown sample output by the detector 240 in step S10. and quantify the concentration of the second unknown sample (step S11).

The measurement execution unit 2 controls the operation of the analysis device 200 to measure the third unknown sample (step S12). The determination unit 5 determines whether or not the detection intensity of the third unknown sample output by the detector 240 in step S12 is greater than the threshold set in step S7a (step S12a).

If the detection intensity of the third unknown sample is greater than the threshold, the determination unit 6 determines the dilution ratio of the third unknown sample based on the detection intensity and the threshold (step S12b), and the process proceeds to step S12. return. If the detected intensity of the third unknown sample is equal to or less than the threshold, the processing unit 7 combines the calibration curve obtained in step S7 with the detected intensity of the third unknown sample output by the detector 240 in step S12. and the concentration of the third unknown sample is quantified (step S13).

The measurement executing unit 2 controls the operation of the analyzer 200 to measure the fourth unknown sample (step S14). The determination unit 5 determines whether or not the detected intensity of the fourth unknown sample output by the detector 240 in step S14 is greater than the threshold value set in step S7a (step S14a).

If the detection intensity of the fourth unknown sample is greater than the threshold, the determination unit 6 determines the dilution ratio of the fourth unknown sample based on the detection intensity and the threshold (step S14b), and the process proceeds to step S14. return. If the detected intensity of the fourth unknown sample is equal to or less than the threshold, the processing unit 7 combines the calibration curve obtained in step S7 with the detected intensity of the fourth unknown sample output by the detector 240 in step S14. , the concentration of the fourth unknown sample is quantified (step S15), and the sample quantification process is terminated.

(5) Modification FIG. 7 is a diagram showing the configuration of the analysis control unit 10 in a modification. As shown in FIG. 7, the analysis control section 10 further includes a batch generation section 8 as a functional section. If the determination unit 5 determines that the detection intensity of any unknown sample is greater than the threshold value in the analysis sequence indicated by the batch file, the batch generation unit 8 generates a new batch indicating the analysis sequence of the unknown sample. Generate files. The batch file newly generated by the batch generation unit 8 is linked to the batch file acquired by the batch acquisition unit 1 .

The measurement execution unit 2 controls the operation of the analysis device 200 according to the analysis sequence indicated by the batch file acquired by the batch acquisition unit 1 . After the analysis sequence ends, when a new batch file is generated by the batch generation unit 8, the measurement execution unit 2 controls the operation of the analysis device 200 according to the newly generated batch file.

8 and 9 are flowcharts showing an example of sample quantitative processing in the modified example. An example of sample quantification processing in the modification will be described below with reference to the analysis system 300 in FIG. 1, the analysis control unit 10 in FIG. 7, and the flow charts in FIGS.

In the quantitative processing in the modified example, first, steps S1 and S2 similar to steps S1 and S2 in FIG. 4 are executed. As a result, the analysis sequence of steps S3 to S15 indicated by the batch file acquired in step S2 is executed. Here, in the modified example, after the analysis sequence indicated by the batch file obtained in step S2 is finished, the following processes after step S16 are executed.

Specifically, after step S15, the setting unit 4 sets the threshold for the detected intensity of the sample based on the maximum value of the detected intensity of the standard sample in the calibration curve obtained in step S7 (step S16). Step S16 may be performed before step S15. The setting unit 4 may also set a value specified by the user through the operation unit 150 as the threshold for the sample detection intensity. In this case, step S16 may be performed before step S7.

Next, the determination unit 5 determines whether or not the detected intensity of any unknown sample output by the detector 240 in steps S8, S10, S12, and S14 is greater than the threshold value set in step S16. (Step S17). If the detected intensities of all unknown samples are equal to or less than the threshold value, the determination unit 5 terminates the quantitative processing of the samples. If the detection intensity of any unknown sample is greater than the threshold, the batch generator 8 creates a new batch file indicating the analysis sequence of the unknown sample (step S18). The new batch file generated in step S18 is associated with the batch file obtained in step S2.

In this example, it is assumed that the detection intensities of the first and fourth unknown samples are determined to be greater than the threshold. In this case, the determination unit 6 determines the dilution ratio of the first unknown sample based on the detection intensity of the first unknown sample output in step S8 and the threshold value (step S19). As a result, the dilution rate determined in step S19 is set in the sample supply unit 220 of the analyzer 200. FIG. Subsequently, the measurement executing section 2 controls the operation of the analyzer 200 to measure the first unknown sample according to the analysis sequence indicated by the new batch file generated in step S18 (step S20).

In this case, in the analyzer 200, the mobile phase supply unit 210 supplies the mobile phase, and the sample supply unit 220 dilutes the first unknown sample together with the mobile phase supplied by the mobile phase supply unit 210 at the set dilution ratio. and supplied to the separation column 230 . Detector 240 detects the first unknown sample that has passed through separation column 230 and outputs the detected intensity. After that, the processing unit 7 quantifies the concentration of the first unknown sample based on the calibration curve obtained in step S7 and the detection intensity of the first unknown sample output by the detector 240 in step S20. (Step S21).

Similarly, the determination unit 6 determines the dilution ratio of the fourth unknown sample based on the detection intensity and threshold of the fourth unknown sample output in step S14 (step S22). Subsequently, the measurement executing section 2 controls the operation of the analyzer 200 to measure the fourth unknown sample according to the analysis sequence indicated by the new batch file generated in step S18 (step S23). Thereafter, the processing unit 7 quantifies the concentration of the fourth unknown sample based on the calibration curve and the detected intensity of the fourth unknown sample output in step S23 (step S24).

Next, the determination unit 5 determines whether or not the detected intensity of any unknown sample output by the detector 240 in steps S20 and S23 is greater than the threshold value set in step S16 (step S25). . If the detected intensities of all unknown samples are equal to or less than the threshold value, the determination unit 5 terminates the quantitative processing of the samples. If the detected intensity of any unknown sample is greater than the threshold value, the batch generator 8 generates a new batch file indicating the analysis sequence of the unknown sample (step S26), as in step S18. After that, the same processing as steps S19 to S25 is repeated until the detected intensities of all unknown samples become equal to or less than the threshold value.

(6) Effect When the concentration of the unknown sample supplied by the sample supply unit 220 is relatively high, the detection intensity of the unknown sample output by the detector 240 may become excessively high. In analysis system 300 according to the present embodiment, in such a case, determination unit 6 determines the dilution ratio of the unknown sample based on the detection intensity and the threshold value. Also, the unknown sample is diluted by the sample supply unit 220 at the determined dilution ratio and supplied.

This configuration reduces the detection intensity of the unknown sample output by the detector 240 . Therefore, it becomes easy to quantify the concentration of the sample using the detection intensity within the range in which the linearity of the calibration curve acquired by the calibration curve acquisition unit 3 is ensured. As a result, even if the person in charge of measurement does not have sufficient knowledge of the analyzer 200, the unknown sample can be measured under appropriate conditions.

Further, in the present embodiment, the batch acquisition unit 1 acquires a batch file indicating the sample analysis sequence, and the measurement execution unit 2 controls the operation of the analysis device 200 according to the analysis sequence. In this case, the samples can be easily measured based on the batch file.

Here, in the quantitative processing of FIGS. 5 and 6, the determination unit 6 determines the unknown sample each time the determination unit 5 determines that the detection intensity of the unknown sample is greater than the threshold value during the analysis sequence. The sample supply unit 220 is controlled so as to dilute and supply the sample with the dilution ratio. Further, the detector 240 is controlled to detect the unknown sample diluted and supplied by the sample supply unit 220 .

According to this quantitative processing, when the detection intensity of any unknown sample becomes excessively large during the analysis sequence, the unknown sample is diluted during the analysis sequence. This allows each unknown sample to be measured under appropriate conditions during the analysis sequence.

On the other hand, in the quantitative processing of FIGS. 8 and 9, when the determination unit 5 determines that the detection intensity of any unknown sample is greater than the threshold value in the analysis sequence, a new A batch file is generated by the batch generator 8 . After the previous analysis sequence is finished, according to the analysis sequence indicated by the new batch file, the sample whose detection intensity is determined to be greater than the threshold value is diluted by the dilution ratio determined by the determination unit 6 and supplied. A sample supply unit 220 is controlled. Further, the detector 240 is controlled to detect the sample diluted and supplied by the sample supply unit 220 .

According to this quantitative processing, when the detection intensity of any sample becomes excessively large during the previous analysis sequence, the sample is diluted after the previous analysis sequence ends. As a result, a sample whose detection intensity was excessively increased in the previous analysis sequence can be measured under appropriate conditions during the analysis sequence indicated by the new batch file.

(7) Other Embodiments (a) In the above embodiment, the calibration curve acquisition unit 3 acquires the calibration curve based on the measurement of the standard sample according to the analysis sequence indicated by the batch file. is not limited to If the calibration curve is stored in the storage unit 140 or the like, the calibration curve acquisition unit 3 may acquire the calibration curve from the storage unit 140 or the like.

(b) In the above embodiment, the analysis control unit 10 includes the setting unit 4, but the embodiment is not limited to this. The analysis control unit 10 does not need to include the setting unit 4 when a threshold for the sample detection intensity is set in advance.

(c) In the above embodiment, the determination unit 6 determines the ratio of the threshold value to the detection intensity of the unknown sample as the dilution ratio of the sample, but the embodiment is not limited to this. The determination unit 6 may determine the sample dilution ratio by performing other calculations based on the detected intensity and the threshold value.

(8) Aspects It will be appreciated by those skilled in the art that the multiple exemplary embodiments described above are specific examples of the following aspects.

(Section 1) An analysis system according to one aspect includes:
a sample supply unit for supplying a sample;
a detection unit that detects the sample supplied by the sample supply unit and outputs the detected intensity of the sample;
a calibration curve acquisition unit that acquires a calibration curve showing the relationship between the concentration of the standard sample and the detection intensity of the standard sample;
a determination unit that determines whether the detected intensity of the sample output by the detection unit is greater than a set threshold;
a determining unit that, if the detected intensity of the sample is greater than the threshold, determines a dilution ratio of the sample based on the detected intensity and the threshold;
a processing unit that quantifies the concentration of the sample based on the detected intensity and the calibration curve acquired by the calibration curve acquisition unit when the detected intensity of the sample is equal to or less than the threshold;
The sample supply section may dilute and supply the sample at the dilution ratio determined by the determination section.

In this analysis system, when the detection intensity of the sample output by the detector becomes excessively high due to the relatively high concentration of the sample supplied by the sample supply unit, the detection intensity and the threshold Then, the dilution ratio of the sample is determined by the determination unit. Also, the sample is supplied after being diluted by the sample supply unit at the determined dilution ratio. Therefore, the detected intensity of the sample output by the detector is reduced. Therefore, it becomes easy to quantify the concentration of the sample using the detection intensity within the range in which the linearity of the calibration curve obtained by the calibration curve obtaining unit is ensured. As a result, the sample can be measured under appropriate conditions.

(Section 2) The analysis system described in Section 1,
A setting unit may be further provided for setting the threshold value based on the maximum value of the detected intensity of the standard sample in the calibration curve acquired by the calibration curve acquisition unit.

In this case, the threshold value for properly diluting the sample can be easily set.

(Section 3) The analysis system described in Section 1,
A setting unit may be further provided which accepts designation of the threshold and sets the accepted threshold.

In this case, any threshold can be set.

(Section 4) In the analysis system according to any one of Sections 1 to 3,
The determination unit may determine a ratio of the threshold value to the detection intensity of the sample as the dilution ratio.

In this case, the sample can be diluted easily and appropriately.

(Section 5) The analysis system according to any one of Sections 1 to 4,
a batch acquisition unit for acquiring a first batch file indicating a first analysis sequence of the sample;
It may further include a measurement execution section that controls operations of the sample supply section and the detection section according to the first analysis sequence.

In this case, the samples can be easily measured based on the first batch file.

(Section 6) In the analysis system described in Section 5,
During the first analysis sequence, the measurement execution unit adjusts the sample to the dilution ratio determined by the determination unit each time the determination unit determines that the detection intensity of the sample is greater than the threshold value. and the detection unit may be controlled to detect the sample diluted and supplied by the sample supply unit.

According to this configuration, when the detection intensity of any sample becomes excessively large during the first analysis sequence, the sample is diluted during the first analysis sequence. This allows each sample to be measured under appropriate conditions during the first analysis sequence.

(Section 7) The analysis system according to Section 5,
A batch for generating a second batch file indicating a second analysis sequence of a sample when the determination unit determines that the detection intensity of any sample is greater than a threshold value in the first analysis sequence further comprising a generator,
After the end of the first analysis sequence, the measurement execution unit divides the sample determined to have a detection intensity greater than the threshold value according to the second analysis sequence by the dilution ratio determined by the determination unit. and the detection unit may be controlled to detect the sample diluted and supplied by the sample supply unit.

According to this configuration, when the detected intensity of any sample becomes excessively large during the first analysis sequence, the sample is diluted after the first analysis sequence is completed. As a result, a sample whose detection intensity has become excessively large in the first analysis sequence can be measured under appropriate conditions during the second analysis sequence.

DESCRIPTION OF SYMBOLS 1... Batch acquisition part, 2... Measurement execution part, 3... Calibration curve acquisition part, 4... Setting part, 5... Judgment part, 6... Determination part, 7... Processing part, 8... Batch generation part, 10... Analysis control part , 100...control device, 110...CPU, 120...RAM, 130...ROM, 140...storage unit, 150...operation unit, 160...display unit, 170...input/output I/F, 180...bus, 200...analyzer, 210... Mobile phase supply unit, 220... Sample supply unit, 230... Separation column, 240... Detector, 300... Analysis system

Claims (7)

a sample supply unit for supplying a sample;
a detection unit that detects the sample supplied by the sample supply unit and outputs the detected intensity of the sample;
a calibration curve acquisition unit that acquires a calibration curve showing the relationship between the concentration of the standard sample and the detection intensity of the standard sample;
a determination unit that determines whether the detected intensity of the sample output by the detection unit is greater than a set threshold;
a determining unit that, if the detected intensity of the sample is greater than the threshold, determines a dilution ratio of the sample based on the detected intensity and the threshold;
a processing unit that quantifies the concentration of the sample based on the detected intensity and the calibration curve acquired by the calibration curve acquisition unit when the detected intensity of the sample is equal to or less than the threshold;
The analysis system, wherein the sample supply unit dilutes and supplies the sample at the dilution ratio determined by the determination unit. 2. The analysis system according to claim 1, further comprising a setting unit that sets said threshold value based on the maximum value of the detected intensity of the standard sample in the calibration curve acquired by said calibration curve acquisition unit. 2. The analysis system according to claim 1, further comprising a setting unit that receives designation of said threshold value and sets said received threshold value. 4. The analysis system according to any one of claims 1 to 3, wherein said determination unit determines a ratio of said threshold value to sample detection intensity as said dilution rate. a batch acquisition unit for acquiring a first batch file indicating a first analysis sequence of the sample;
The analysis system according to any one of claims 1 to 4, further comprising a measurement execution section that controls operations of said sample supply section and said detection section according to said first analysis sequence. During the first analysis sequence, the measurement execution unit adjusts the sample to the dilution ratio determined by the determination unit each time the determination unit determines that the detection intensity of the sample is greater than the threshold value. 6. The analysis system according to claim 5, wherein the sample supply unit is controlled to supply the sample diluted with , and the detection unit is controlled to detect the sample diluted and supplied by the sample supply unit. A batch for generating a second batch file indicating a second analysis sequence of a sample when the determination unit determines that the detection intensity of any sample is greater than a threshold value in the first analysis sequence further comprising a generator,
After the end of the first analysis sequence, the measurement execution unit divides the sample determined to have a detection intensity greater than the threshold value according to the second analysis sequence by the dilution ratio determined by the determination unit. 6. The analysis system according to claim 5, wherein the sample supply unit is controlled to supply the sample diluted with , and the detection unit is controlled to detect the sample diluted and supplied by the sample supply unit.

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