Analysis system
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-06
- Publication Date
- 2026-07-10
Smart Images
Figure CN122374642A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to an analytical system comprising a solid-phase separation column. Background Technology
[0002] Previously, a technique was known in which samples containing a large number of impurities were pretreated using a solid phase extraction (SPE) column before being analyzed by an analytical unit. For example, "Automated Online SPE for LC / MS / MS Analysis of Trace Organic Contaminants in Water Using the Agilent 1290 Infinity Flexible Cube Module" (https: / / www.agilent.com / cs / library / applications / 5991-6115EN.pdf, Non-Patent Document 1) discloses a technique for pretreating samples using an SPE column and then analyzing them using a liquid chromatography-tandem mass spectrometry (LC / MS / MS) device to resolve trace organic pollutants.
[0003] Existing technical documents Non-patent literature Non-patent literature 1: "Automated Online SPE for LC / MS / MS Analysis of Trace Organic Contaminants in Water Using the Agilent 1290 Infinity Flexible Cube Module", https: / / www.agilent.com / cs / library / applications / 5991-6115EN.pdf Summary of the Invention The technical problem that the invention aims to solve Pretreatment using chromatographic columns such as SPE columns requires a considerable amount of time. Furthermore, the analysis of the analytical unit itself, particularly in the so-called "method construction"—that is, the establishment of the analytical conditions—also requires a significant amount of time. Therefore, in analytical systems that utilize SPE columns for sample pretreatment before analysis, there is a strong demand for minimizing the time required for analysis.
[0004] The present invention was conceived in view of the above-mentioned actual situation, and its purpose is to provide a technique for shortening the operation time of method construction for analysis while pretreating the sample with an SPE column before analysis in the analytical unit.
[0005] Solution to the above technical problems According to one aspect of this disclosure, the analytical system includes: an analytical unit; an injector; a switching valve; a first flow path disposed between the injector and the switching valve, and including one or more solid-phase separation columns; a second flow path disposed parallel to the first flow path between the injector and the switching valve; and a controller configured to control the injector to supply a sample to the first flow path or the second flow path, the controller further configured to: when controlling the injector to supply a sample to the first flow path, perform sample purification in the first flow path using one or more solid-phase separation columns; and when controlling the injector to supply a sample to the second flow path, not perform sample purification in the second flow path.
[0006] Invention Effects According to one aspect of this disclosure, a technique is provided that reduces the operation time for method construction for analysis while pretreating the sample using an SPE column before analysis in the analytical unit. Attached Figure Description
[0007] 【 Figure 1 The diagram shown is a summary of the structure of analysis system 1.
[0008] 【 Figure 2 The diagram shows the specific configuration related to the sample flow path within the analysis system 1.
[0009] 【 Figure 3 The diagram is an example of the operation flow of the analysis system 1 when it is transported to the analysis unit via the first flow path 21.
[0010] 【 Figure 4 The diagram is an example of the operation flow of the analysis system 1 when it is transported to the analysis unit via the first flow path 21.
[0011] 【 Figure 5 The diagram is an example of the operation flow of the analysis system 1 when it is transported to the analysis unit via the first flow path 21.
[0012] 【 Figure 6The diagram is an example of the operation flow of the analysis system 1 when it is transported to the analysis unit via the first flow path 21.
[0013] 【 Figure 7 The diagram is an example of the operation flow of the analysis system 1 when it is transported to the analysis unit via the second flow path 22.
[0014] 【 Figure 8 The diagram is an example of the operation flow of the analysis system 1 when it is transported to the analysis unit via the second flow path 22.
[0015] 【 Figure 9 The diagram shows the configuration of a variant of the analysis system 1. Detailed Implementation
[0016] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Furthermore, identical or equivalent parts in the drawings are labeled with the same symbols and will not be described again.
[0017] [Overview of the Analysis System] Figure 1 This is a diagram showing the general structure of analysis system 1. For example... Figure 1 As shown, the analysis system 1 includes an autosampler 10, a first flow path 21, a second flow path 22, a switching valve 30, a column oven 40, a detector 50, and a controller 60. The column oven 40 contains an analytical column (analytical column 41), which will be referred to later. Figure 2 Please provide an explanation.
[0018] In the analysis system 1, the autosampler 10 injects a sample into either the first flow path 21 or the second flow path 22. The autosampler 10 includes a pump for delivering the solution to deliver the sample to the first flow path 21 or the second flow path 22.
[0019] The sample injected into the first flow path 21 or the second flow path 22 is introduced into the detector 50 via the switching valve 30 and the analytical column in the column oven 40. In the analysis system 1, the analytical column and the detector 50 constitute an example of an analytical unit. The detector 50 is, for example, a liquid chromatography-mass spectrometry (LC-MS) analyzer. Furthermore, in the analysis system 1, the analytical unit is not limited in its specific components as long as it contains elements of the analytical sample.
[0020] The controller 60 includes a processor 61, a storage device 62, an input device 63, and a display 64. The processor 61 performs calculations to control the actions of various elements within the analysis system 1 and outputs instructions to each element based on the calculation results. The storage device 62 stores the programs and data used for the aforementioned calculations. The controller 60 obtains instructions from the user based on operations on the input device 63 and displays the calculation results on the display 64.
[0021] [Specific configuration related to the sample flow path within the analytical system] Figure 2 This is a diagram showing the specific configuration related to the sample flow path within the analysis system 1.
[0022] The autosampler 10 includes a syringe 11, inlets 12A and 12B, and a valve 13. The syringe 11 injects a sample contained in a container (not shown) into inlet 12A or inlet 12B. The sample injected into inlet 12A, along with a solution dispensed from a pump (not shown), is sent to valve 213 (described later). The sample injected into inlet 12B, along with a solution dispensed from a pump (not shown), is sent to valve 13.
[0023] Valve 13 is a six-way valve. Within valve 13, a... Figure 2 The connection status shown and described later Figure 7 The connection state is shown. Valve 13 has a metering ring 13A.
[0024] The first flow path 21 includes a first SPE column 211, a second SPE column 212, a valve 213, and a valve 214. The first flow path 21 is configured to deliver a sample from the autosampler 10 to the switching valve 30 via the first SPE column 211 or the second SPE column 212.
[0025] Valve 213 is a six-way valve. Within valve 213, a... Figure 2 The connection status shown and described later Figure 3 The connection state is shown. Valve 213 has a metering ring 213A.
[0026] Valve 214 is an eight-way valve. Within valve 214, a... Figure 2 The connection status shown and described later Figure 3 The connection status is shown.
[0027] The second flow path 22 includes two tubes connecting the valve 13 of the autosampler 10 and the switching valve 30.
[0028] Switching valve 30 is a six-way valve. Within switching valve 30, a process is formed... Figure 2 The connection status shown and described later Figure 8 The connection status is shown.
[0029] The analysis system 1 also includes a first pump 71 and second pumps 72 and 73. When a sample from the autosampler 10 is sent to the switching valve 30 via the first flow path 21, the sample is pretreated in the first SPE column 211 or the second SPE column 212 before being sent to the analysis unit (analytical column 41 and detector 50). Thus, the analysis system 1 can process samples such as blood or sewer water that require pretreatment before being sent to the analysis unit.
[0030] On the other hand, when a sample from the autosampler 10 is sent to the switching valve 30 via the second flow path 22, the sample is sent to the analytical unit (analytical column 41 and detector 50) without purification by the SPE column. In the method construction of the analytical unit, if a sample that does not require purification is used, the analytical system 1 can send it to the analytical unit without purification, thereby shortening the time required for method construction. Furthermore, as a method, for example, the flow rate and / or composition of the mobile phase used in sample separation using the analytical column 41 can be set.
[0031] In recent years, in particular, there has been an increasing demand for quantitative analysis of pharmaceuticals and other substances present in sewage water, leading to a growing need for liquid chromatography-mass spectrometry (LC-MS) systems capable of simultaneously analyzing multiple target components. However, due to the numerous impurities present in sewage water, it is difficult to directly analyze collected sewage water using LC-MS. At least a purification or pretreatment step is required before analysis. Currently, this is done manually by operators, resulting in very poor throughput. Analysis System 1 integrates SPE column purification and analysis into a single process, which helps improve throughput for operators.
[0032] Here, to analyze more than one target component in a sample containing a large number of impurities, analytical system 1 needs to construct a method capable of simultaneously analyzing more than one target component. The sample required for method construction is a solution containing more than one target component, or a solution containing several components including the target component. Therefore, purification using an SPE column is not required during method construction. If method construction includes purification, it would take an extremely long time until the method is optimized. Analytical system 1 can deliver samples to the analytical unit without purification using an SPE column. Thus, analytical system 1 can shorten the time required for method construction.
[0033] In other words, if analytical system 1 is used, even if the sample contains a large amount of impurities, such as sewer water, operators do not need to perform pretreatment operations, including purification. Furthermore, if analytical system 1 is used, a different flow path can be used in method construction compared to the time-consuming purification process using SPE columns, thereby shortening the time required for method construction.
[0034] To construct the method, the operator repeatedly feeds the sample for method construction into the analysis unit via the second flow path 22 and repeatedly obtains the analysis results. While observing the analysis results, the operator adjusts the analysis conditions and constructs the analytical method. Then, the operator feeds the analyte sample into the analysis unit via the first flow path 21 and performs the analysis according to the constructed method.
[0035] In one implementation example, the sample used for method construction is prepared as a solution containing the component of interest from the analyte sample (e.g., sewer water or blood).
[0036] Furthermore, the analysis system 1 can process only the analyte sample in the first flow path 21, and only the sample adjusted for method construction in the second flow path 22. That is, the analyte sample can be avoided in the second flow path 22 of the analysis system 1. The analyte sample may introduce contamination into the flow path that cannot be completely cleaned. Therefore, in the analysis system 1, the second flow path 22 is protected from such contamination that cannot be completely cleaned, thus allowing it to be used for a variety of purposes.
[0037] [Sample transport via the first flow path] Figures 3-6 This is a diagram illustrating an example of the operational flow of the analysis system 1 when data is transported to the analysis unit via the first flow path 21. Figures 3-6 In the diagram, the liquid flowing through the pipes connecting the elements is represented by the shading applied within those pipes. (See reference...) Figures 3-6 This describes the action in analysis system 1 where the sample from autosampler 10 is purified using an SPE column and then fed into the analysis unit.
[0038] First, the analysis system 1 is controlled to be in a state of Figure 3 The state shown. In Figure 3 In the indicated state, the sample from the autosampler 10 is delivered to the first flow path 21. More specifically, the injection needle 11 injects the sample into the injection port 12A. The sample is then conveyed from the injection port 12A to the valve 213 via liquid from a pump (not shown), as indicated by arrow A1, and accumulates in the metering loop 213A.
[0039] Next, analysis system 1 is controlled to be in a state of... Figure 4 The state shown. In Figure 4 In the indicated state, the sample accumulated in the metering loop 213A is fed to the first SPE column 211 via liquid from the first pump 71, as indicated by arrow A3. More than one component contained in the sample is retained in the stationary phase of the first SPE column 211.
[0040] Next, analysis system 1 is controlled to be in a state of... Figure 5 The state shown. In Figure 5 In the indicated state, the sample (one or more components) retained in the stationary phase of the first SPE column 211 is fed to the analytical column 41 via switching valve 30 through liquid from the second pumps 72 and 73, as indicated by arrows A5 and A6. After passing through the analytical column 41, the sample is sent to the detector 50.
[0041] exist Figure 3In the example, sample elution to the first SPE column 211 is represented as isocranial elution using the first pump 71, and sample elution to the analytical column 41 is represented as gradient elution using the second pumps 72 and 73. Furthermore, whether isocranial elution or gradient elution is used can be appropriately changed depending on the usage of the analytical system 1.
[0042] exist Figure 3 The sample accumulated in the quantitative loop 213A under the shown condition can also be accumulated in the second SPE column 212. In this case, the analytical system 1 is controlled to be in a state where... Figure 6 The state shown. In Figure 6 In the indicated state, the sample accumulated in the metering loop 213A is fed to the second SPE column 212 via liquid from the first pump 71, as indicated by arrows A7 and A8. More than one component contained in the sample is retained in the stationary phase of the second SPE column 212. Subsequently, the analytical system 1 is controlled to operate in... Figure 3 or Figure 4 As shown in the diagram, the sample (one or more components) retained in the second SPE column 212, as indicated by arrow A2, is fed to the analytical column 41 via switching valve 30 through liquid from the second pumps 72 and 73. After passing through the analytical column 41, the sample is sent to detector 50.
[0043] The above is as follows (refer to) Figures 3-6 As explained, by supplying a sample from the autosampler 10 to the first flow path 21, the analysis system 1 retains one or more components contained in the sample in the SPE column and supplies the retained one or more components to the analysis unit.
[0044] In analytical system 1, as an example of sample purification: the liquid and sample flow towards the SPE column in a first direction to allow the SPE column to retain more than one component of the sample, and the liquid and sample flow towards the SPE column in a second direction opposite to the first direction to deliver the retained sample component to the analytical unit. Furthermore, the method of changing the direction of liquid flow through the column is not limited to changing the positions of valves 213 and 214, but may also include other methods such as rotating the column itself.
[0045] Analysis system 1 includes a first SPE column 211 and a second SPE column 212. In analysis system 1, as... Figure 3 and Figure 4 As shown, when a sample is supplied to the first SPE column 211, a sample (more than one component) that is retained in the second SPE column 212 is supplied to the analytical unit. Figure 3 and Figure 4 The state shown is an example of the "first state". On the other hand, as... Figure 5 and Figure 6 As shown, when a sample is supplied to the second SPE column 212, the sample (more than one component) retained in the first SPE column 211 is supplied to the analytical unit. Figure 5 and Figure 6 The state shown is an example of the "second state".
[0046] In other words, the analysis system 1, by having multiple SPE columns, can perform sample retention and sample delivery to the analysis unit in parallel. Therefore, the analysis system 1 can analyze more samples per unit time. In this case, the first SPE column 211 and the second SPE column 212 are preferably filled with the same type of packing agent (or with similar or identical properties of the trapped components) as the stationary phase.
[0047] [Sample transport via the second flow path] Figure 7 and Figure 8 This is a diagram illustrating an example of the operational flow of the analysis system 1 when data is transported to the analysis unit via the second flow path 22. Figure 7 and Figure 8 In the diagram, the liquid flowing through the pipes connecting the elements is represented by the shading applied within those pipes. (See reference...) Figure 7 and Figure 8 This describes the action of introducing samples from the autosampler 10 into the analysis unit in the analysis system 1 without purification by the SPE column.
[0048] First, the analysis system 1 is controlled to be in a state of Figure 7 The state shown. In Figure 7 In the indicated state, the injection needle 11 injects the sample into the injection port 12B. The sample is then conveyed to valve 13 by liquid from a pump (not shown) and accumulates in the metering loop 13A.
[0049] Next, analysis system 1 is controlled to be in a state of... Figure 8 The state shown. In Figure 8 In the state shown, the sample accumulated in the quantitative loop 13A is sent to the second flow path 21 by liquid from the second pumps 72 and 73, and then sent to the analytical column 41 and detector 50 via the switching valve 30.
[0050] In reference Figure 7 and Figure 8 During the delivery process, the sample is introduced into the analytical unit without being purified by an SPE column.
[0051] [Variation Example] As described above, in analytical system 1, the sample is purified by an SPE column when it is introduced into the analytical unit via the first flow path 21, but is not purified by an SPE column when it is introduced into the analytical unit via the second flow path 22. By using the first flow path 21 in the analysis, analytical system 1 can purify the sample before analysis. Furthermore, by using the second flow path in the method construction of the analytical unit, analytical system 1 can deliver the sample to the analytical unit without performing unnecessary and time-consuming purification.
[0052] Figure 9 This is a diagram showing the configuration of a modified example of analysis system 1. In Figure 9 In the example, a trapping column 221 is added to the second flow path 22. The trapping column 221 is filled with the same type of filler as the first SPE column 211 or the second SPE column 212.
[0053] In the analysis system 1, the first flow path 21 is used for sample analysis using the analysis unit, and the second flow path 22 is used for method construction within the analysis unit. When introducing a sample into the analysis unit for method construction, it is preferable to perform the process under conditions close to those in actual analysis. In actual analysis, the sample is introduced into the analysis unit from either the first SPE column 211 or the second SPE column 212. To ensure that the sample introduction conditions for method construction closely approximate those in actual analysis, a trapping column 221 is provided on the second flow path 22.
[0054] [plan] Those skilled in the art should understand that the above-described exemplary embodiments are specific examples of the following solutions.
[0055] (Item 1) An analytical system comprising: an analytical unit; an injector; a switching valve; a first flow path disposed between the injector and the switching valve, and including one or more solid-phase separation columns; a second flow path disposed parallel to the first flow path between the injector and the switching valve; and a controller configured to control the injector to supply a sample to the first flow path or the second flow path, the controller further configured to: when controlling the injector to supply a sample to the first flow path, perform purification of the sample in the first flow path using the one or more solid-phase separation columns; and when controlling the injector to supply a sample to the second flow path, not perform purification of the sample in the second flow path.
[0056] According to the analytical system in item 1, a technique is provided that shortens the operation time for method construction for analysis while pretreating the sample using an SPE column before analysis in the analytical unit.
[0057] (Item 2) In the analytical system described in Item 1, the first flow path includes a first valve disposed between the injector and the one or more solid-phase separation columns, the first valve having a metering loop, and the controller being configured to control the first valve to a state in which the sample from the injector is accumulated in the metering loop, and to a state in which the sample accumulated in the metering loop is supplied to the one or more solid-phase separation columns.
[0058] According to the analysis system in item 2, the sample can be stored in the first valve.
[0059] (Item 3) The analytical system described in Item 2 may further include: a first pump that supplies liquid to the metering loop to deliver the sample to one or more solid-phase separation columns.
[0060] According to the analytical system in item 3, the sample accumulated in the first valve is sent to one or more solid-phase separation columns.
[0061] (Item 4) In the analytical system of any one of Items 1 to 3, the more than one solid-phase separation column includes a first solid-phase separation column and a second solid-phase separation column, and the controller is configured to control the first flow path to a first state and a second state, wherein in the first state the sample from the injector is loaded onto the first solid-phase separation column and the sample to be loaded onto the second solid-phase separation column is sent to the switching valve, and in the second state the sample from the injector is loaded onto the second solid-phase separation column and the sample to be loaded onto the first solid-phase separation column is sent to the switching valve.
[0062] According to the analytical system described in item 4, multiple solid-phase separation columns can be used for sample purification in the first flow path.
[0063] (Item 5) In the analysis system described in Item 4, the first flow path includes a second valve for switching the first flow path between the first state and the second state.
[0064] According to the analysis system in item 5, the switching of the first flow path between the first state and the second state can be easily realized.
[0065] (6) The analytical system of any one of the items 1 to 5 further includes a second pump connected to the switching valve, the controller being configured to control the switching valve to switch its state between: a state in which liquid from the second pump delivers the sample in the first flow path to the analytical unit; and a state in which liquid from the second pump delivers the sample in the second flow path to the analytical unit.
[0066] According to the analysis system in item 6, the second pump can be used for both the transport of samples in the first flow path and the transport of samples in the second flow path.
[0067] (Item 7) In any one of items 1 to 6, the analysis unit includes a detector and an analysis column disposed between the detector and the switching valve.
[0068] According to the analysis system in item 7, the time required to construct analysis-related methods utilizing detectors and analysis columns can be reduced.
[0069] (Item 8) The analytical system of any one of items 1 to 7 may further include a trapping column in the second flow path, the trapping column having the same packing material as at least one of the more than one solid phase separation columns.
[0070] According to the analysis system in item 8, in the construction using the second flow path, the analysis unit can be driven under analysis conditions close to those of the sample being analyzed using the first flow path.
[0071] The embodiments disclosed herein should be considered illustrative rather than restrictive in all respects. The scope of this disclosure is defined not by the description of the above embodiments but by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims. Furthermore, the techniques in the embodiments are intended to be implementable individually or, where necessary, in combination with other techniques in the embodiments.
[0072] Explanation of reference numerals in the attached figures 1 Analytical system, 10 Autosampler, 11 Injection needle, 12A, 12B Injection ports, 13, 213, 214 Valves, 13A, 213A Quantitative loop, 21 First flow path, 22 Second flow path, 30 Switching valve, 40 Column oven, 41 Analytical column, 50 Detector, 60 Controller, 61 Processor, 71 First pump, 72, 73 Second pump, 211 First solid-phase separation column, 212 Second solid-phase separation column, 221 Trapping column.
Claims
1. An analysis system, characterized in that, include: Analysis unit; Injector; Switching valve; The first flow path is located between the injector and the switching valve, and includes one or more solid-phase separation columns; The second flow path is arranged in parallel with the first flow path between the injector and the switching valve; as well as A controller configured to control the injector to supply sample to either the first or second flow path. The controller is also configured to: While controlling the injector to supply the sample to the first flow path, the purification of the sample using one or more solid-phase separation columns is carried out in the first flow path; While controlling the injector to supply the sample to the second flow path, the purification of the sample is not performed in the second flow path.
2. The analysis system as described in claim 1, characterized in that, The first flow path includes a first valve disposed between the injector and the one or more solid-phase separation columns. The first valve has a metering ring. The controller is configured to control the first valve to either accumulate the sample from the injector in the quantitative loop or to supply the sample accumulated in the quantitative loop to one or more solid-phase separation columns.
3. The analysis system as described in claim 2, characterized in that, Also includes: A first pump supplies liquid to the metering loop to deliver the sample to one or more solid-phase separation columns.
4. The analysis system as described in claim 1 or 2, characterized in that, The one or more solid-phase separation columns include a first solid-phase separation column and a second solid-phase separation column. The controller is configured to control the first flow path to enter a first state and a second state. In the first state, the sample from the injector is loaded onto the first solid-phase separation column, and the sample to be loaded onto the second solid-phase separation column is sent to the switching valve. In the second state, the sample from the injector is loaded onto the second solid-phase separation column, and the sample to be loaded onto the first solid-phase separation column is sent to the switching valve.
5. The analysis system as described in claim 4, characterized in that, The first flow path includes a second valve for switching the first flow path between the first state and the second state.
6. The analysis system as described in claim 1 or 2, characterized in that, Also includes: The second pump connected to the switching valve, The controller controls the switching valve to switch its state between the following states: the state in which liquid from the second pump delivers the sample in the first flow path to the analysis unit; And the state in which the liquid from the second pump delivers the sample in the second flow path to the analysis unit.
7. The analysis system as described in claim 1 or 2, characterized in that, The analysis unit includes a detector and an analysis column disposed between the detector and the switching valve.
8. The analysis system as described in claim 1 or 2, characterized in that, The second flow path also includes a trapping column having the same packing as at least one of the more than one solid phase separation columns.