A selective detection system
Patent Information
- Application Number
- CN202521865911.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-29
- Publication Date
- 2026-09-15
- Estimated Expiration
- 2035-08-29
AI Technical Summary
[0004]由此可见,无论是采用单套检测装置还是两套或以上检测装置对样品逐个分析,在对于分离属性差异极大的目标物的分离分析上存在不足之处,难以满足现代分析科学对于高通量、高效率和高准确性的要求
[0043] Compared to existing technologies, the selective detection system of this invention sets up two or more independently operating flow paths, with each flow path sharing a single detector. It groups the target analytes based on their separation and mass spectrometric ionization properties, forming different target analyte combinations. Appropriate chromatographic columns and/or mobile phases are set in different flow paths to create optimal analytical conditions for each target analyte combination. This allows each target analyte combination to be detected under the optimal analytical conditions set in its corresponding flow path, improving detection accuracy. Ultimately, a chromatogram combining the detection results of each target analyte combination is obtained, reducing analysis time and effectively lowering equipment costs. Furthermore, by alternating injection into two or more flow paths, the waiting time for column cleaning and equilibration is reduced, improving overall detection efficiency.
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Figure CN224758476U_ABST
Abstract
Description
Technical Field
[0001] This utility model relates to the field of instrumental analysis, and in particular to a selective detection system. Background Technology
[0002] In fields such as targeted metabolomics, environmental science, and pesticide and veterinary residue analysis, samples are numerous, matrices complex, and often contain multiple target analytes. These substances often vary significantly in type and separation properties. For example, environmental samples may simultaneously contain organic pollutants, heavy metal ions, and complex natural organic matter, while targeted metabolomics studies may involve metabolites with different polarities, lipids, and small molecule compounds. In practice, researchers often need to select appropriate combinations of chromatographic columns, mobile phases, and detectors based on the properties of the target analytes to achieve optimal analytical detection results.
[0003] Currently, for the detection of large quantities of samples with complex matrices and multiple target analytes, there are two main common methods. The first method uses a single one-dimensional mass spectrometer (MS / MS) to select the most suitable detection method for each type of target analyte, analyzing each type sequentially under different separation and detection conditions. This method requires a considerable amount of time for cleaning and equilibrating the column and tubing between analyses of different target analytes, undoubtedly increasing the overall detection time. If the sample quantity is large, it may be necessary to analyze all samples using one method before switching to another, significantly extending the storage time for the second analysis and potentially causing sample deterioration or yielding quantitative results significantly different from the first analysis due to changes in instrument performance. The second method uses two or more completely independent one-dimensional MS / MS systems to simultaneously separate and detect different target analytes, with each detection system corresponding to one target analyte. This method allows for the selection of the most suitable separation conditions based on the separation properties of different target analytes, achieving better separation results. However, this method requires multiple mass spectrometers, resulting in high equipment costs. Both approaches output independent chromatograms, increasing data processing steps and time.
[0004] Therefore, it is evident that whether a single detection device or two or more detection devices are used to analyze samples one by one, there are shortcomings in the separation and analysis of target objects with extremely different separation properties, making it difficult to meet the requirements of modern analytical science for high throughput, high efficiency, and high accuracy. Utility Model Content
[0005] Based on this, the purpose of this utility model is to overcome the defects or deficiencies of the prior art and provide a selective detection system that enables the detection of two or more target substances with different properties in a sample under optimal analytical conditions. This system can improve detection accuracy, reduce analysis time, improve overall detection efficiency, and reduce equipment costs.
[0006] The selective detection system of this utility model has three implementations. In the first implementation, the selective detection system includes:
[0007] At least two parallel flow paths and one detector, each flow path including a push assembly, an injector and a chromatographic column, wherein the detector is connected to each flow path via a detection selector, wherein the detection selector is a switching valve or a selection valve having at least four ports;
[0008] The first flow path includes a first push assembly for introducing and pushing a first mobile phase, a first injector for introducing a sample, and a first chromatographic column for retaining a first combination of target substances in the sample or simultaneously retaining a first and a second combination of target substances in the sample. The outlet of the first push assembly is connected to the inlet of the first injector, the outlet of the first injector is connected to the inlet of the first chromatographic column, and the outlet of the first chromatographic column is connected to the first port of the detection selector.
[0009] The second flow path includes a second push assembly for introducing and pushing a second mobile phase, a second injector for introducing the same sample, and a second chromatographic column for retaining a second combination of target substances in the sample or simultaneously retaining a first and second combination of target substances in the sample. The outlet of the second push assembly is connected to the inlet of the second injector, the outlet of the second injector is connected to the inlet of the second chromatographic column, and the outlet of the second chromatographic column is connected to the second port of the detection selector.
[0010] The detector is connected to the third port of the detection selector, and the fourth port of the detection selector is connected to the outside of the system;
[0011] The detection selector can switch between two connection states via its different ports:
[0012] Connection State 1: The detection connector connects the outlet of the first chromatographic column to the inlet of the detector, which is used to detect the first target analyte combination flowing out of the first chromatographic column; at the same time, the detection connector connects the outlet of the second chromatographic column to the outside of the system.
[0013] Connection State 2: The detection connector connects the outlet of the second chromatographic column to the inlet of the detector, which is used to detect the second target analyte combination flowing out of the second chromatographic column; at the same time, the detection connector connects the outlet of the first chromatographic column to the outside of the system.
[0014] In the second embodiment, the selective detection system introduces samples into different flow paths via an injector and a switching valve with at least six ports. The selective detection system includes:
[0015] Two parallel flow paths and a detector, wherein the detector is connected to the two flow paths respectively via a detection selector, wherein the detection selector is a switching valve having at least four ports;
[0016] The first flow path includes a first push component for introducing and pushing a first mobile phase and a first chromatographic column for retaining a first combination of target substances in a sample, the first chromatographic column being connected to the first push component via an injection selection component;
[0017] The second flow path includes a second push assembly for introducing and pushing a second mobile phase and a second chromatographic column for retaining a second combination of target compounds in the sample, the second chromatographic column being connected to the second push assembly via an injection selection assembly;
[0018] The sample selection assembly includes a sample selection element and a sample injector for introducing the sample, wherein the sample selection element is a switching valve having at least six ports;
[0019] The inlet and outlet of the injector are respectively connected to the first port and the second port of the injection selector;
[0020] The outlet of the first push component is connected to the third port of the injection selection element, the inlet of the first chromatographic column is connected to the fourth port of the injection selection element, and the outlet of the first chromatographic column is connected to the first port of the detection selection element.
[0021] The outlet of the second push component is connected to the fifth port of the injection selection element, the inlet of the second chromatographic column is connected to the sixth port of the injection selection element, and the outlet of the second chromatographic column is connected to the second port of the detection selection element.
[0022] The detector's inlet is connected to the third port of the detection selector, and the fourth port of the detection selector is connected to the outside of the system;
[0023] The injection selector and the detection selector switch between two connection states via their respective ports:
[0024] Connection State 1: The injection selection component connects the outlet of the first push component to the inlet of the injector, and connects the outlet of the injector to the inlet of the first chromatographic column; the detection selection component connects the outlet of the first chromatographic column to the inlet of the detector, the detector being used to detect the first target analyte combination flowing out of the first chromatographic column; simultaneously, the injection selection component connects the outlet of the second push component to the inlet of the second chromatographic column, and the detection selection component connects the outlet of the second chromatographic column to the outside of the system;
[0025] Connection State 2: The injection selection component connects the outlet of the second push component to the inlet of the injector and the outlet of the injector to the inlet of the second chromatographic column. The detection selection component connects the outlet of the second chromatographic column to the inlet of the detector, which is used to detect the second target analyte combination flowing out of the second chromatographic column. At the same time, the injection selection component connects the outlet of the first push component to the inlet of the first chromatographic column, and the detection selection component connects the outlet of the first chromatographic column to the outside of the system.
[0026] In this implementation, the first and second chromatographic columns can also be used to retain combinations of first and second target analytes in the sample. Separation of different target analyte combinations is achieved by introducing first and second mobile phases with different chemical properties. The injection selector and detection selector are connected to their respective ports, switching between four connection states:
[0027] Connection State 1: The injection selection component connects the outlet of the first push component to the inlet of the injector and the outlet of the injector to the inlet of the first chromatographic column; the detection selection component connects the outlet of the first chromatographic column to the inlet of the detector; simultaneously, the injection selection component connects the outlet of the second push component to the inlet of the second chromatographic column, and the detection selection component connects the outlet of the second chromatographic column to the outside of the system.
[0028] Connection State 2: The injection selection device connects the outlet of the first push component to the inlet of the first chromatographic column, and the detection selection device connects the outlet of the first chromatographic column to the inlet of the detector, the detector being used to detect the first target analyte combination flowing out of the first chromatographic column; simultaneously, the injection selection device connects the outlet of the second push component to the inlet of the injector, and connects the outlet of the injector to the inlet of the second chromatographic column, and the detection selection device connects the outlet of the second chromatographic column to the outside of the system;
[0029] Connection State 3: The injection selection component connects the outlet of the second push component to the inlet of the injector, and connects the outlet of the injector to the inlet of the second chromatographic column; the detection selection component connects the outlet of the second chromatographic column to the inlet of the detector; simultaneously, the injection selection component connects the outlet of the first push component to the inlet of the first chromatographic column, and connects the outlet of the first chromatographic column to the outside of the system.
[0030] Connection State 4: The injection selection device connects the outlet of the second push component to the inlet of the second chromatographic column, and the detection selection device connects the outlet of the second chromatographic column to the inlet of the detector. The detector is used to detect the second target analyte combination flowing out of the second chromatographic column. At the same time, the injection selection device connects the outlet of the first push component to the inlet of the injector and connects the outlet of the injector to the inlet of the first chromatographic column. The detection selection device connects the outlet of the first chromatographic column to the outside of the system.
[0031] In the third embodiment, the selective detection system introduces samples into different flow paths through an injector and an injection detection selector, and a switching valve with at least ten ports. The selective detection system includes:
[0032] Two parallel flow paths and a detector, wherein the detector is connected to the two flow paths respectively through an injection detection selection component;
[0033] The first flow path includes a first push component for introducing and pushing a first mobile phase and a first chromatographic column for retaining a first combination of target analytes in a sample, the first chromatographic column being connected to the first push component via the injection detection selection component;
[0034] The second flow path includes a second push assembly for introducing and pushing a second mobile phase and a second chromatographic column for retaining a second combination of target compounds in the sample, the second chromatographic column being connected to the second push assembly via the injection detection selection assembly;
[0035] The sample introduction detection selection component includes a sample introduction detection selector and a sample injector for introducing the sample, wherein the sample introduction detection selector is a switching valve having at least ten ports;
[0036] The inlet and outlet of the injector are respectively connected to the first port and the second port of the injection detection selector;
[0037] The outlet of the first push component is connected to the third port of the injection detection selector, and the two ends of the first chromatographic column are connected to the fourth and fifth ports of the injection detection selector, respectively.
[0038] The outlet of the second push component is connected to the sixth port of the injection detection selector, and the two ends of the second chromatographic column are connected to the seventh and eighth ports of the injection detection selector, respectively.
[0039] The detector's inlet is connected to the ninth port of the sample injection detection selector, and the tenth port of the sample injection detection selector is connected to the outside of the system;
[0040] The sample injection detection selector can switch between two connection states by connecting to different ports:
[0041] Connection State 1: The injection detection selector connects the outlet of the first push component to the inlet of the injector, connects the outlet of the injector to one port of the first chromatographic column, and connects the other port of the first chromatographic column to the inlet of the detector, the detector being used to detect the first target analyte combination flowing out of the first chromatographic column; the injection detection selector connects the outlet of the second push component to one port of the second chromatographic column, and connects the other port of the second chromatographic column to the outside of the system;
[0042] Connection State 2: The injection detection selector connects the outlet of the second push component to the inlet of the injector, connects the outlet of the injector to one port of the second chromatographic column, and connects the other port of the second chromatographic column to the inlet of the detector, the detector being used to detect the second target analyte combination flowing out of the second chromatographic column; the injection detection selector connects the outlet of the first push component to one port of the first chromatographic column, and connects the other port of the first chromatographic column to the outside of the system.
[0043] Compared to existing technologies, the selective detection system of this invention sets up two or more independently operating flow paths, with each flow path sharing a single detector. It groups the target analytes based on their separation and mass spectrometric ionization properties, forming different target analyte combinations. Appropriate chromatographic columns and / or mobile phases are set in different flow paths to create optimal analytical conditions for each target analyte combination. This allows each target analyte combination to be detected under the optimal analytical conditions set in its corresponding flow path, improving detection accuracy. Ultimately, a chromatogram combining the detection results of each target analyte combination is obtained, reducing analysis time and effectively lowering equipment costs. Furthermore, by alternating injection into two or more flow paths, the waiting time for column cleaning and equilibration is reduced, improving overall detection efficiency.
[0044] To better understand and implement this invention, the following detailed description is provided in conjunction with the accompanying drawings. Attached Figure Description
[0045] Figure 1This is a schematic diagram illustrating the principle of the selective detection system and method of this invention for separating and detecting a combination of two target substances contained in a sample.
[0046] Figure 2 This is a schematic diagram of the structure of the first embodiment of the selective detection system of this utility model;
[0047] Figure 3 This is a schematic diagram of the selective detection system of this utility model in connection state 1 in embodiment 1;
[0048] Figure 4 This is a schematic diagram of the selective detection system of this utility model in connection state 2 in embodiment 1;
[0049] Figure 5 This is a schematic diagram of the second embodiment of the selective detection system of this utility model;
[0050] Figure 6 This is a schematic diagram of the selective detection system of this utility model in connection state 1, according to embodiment 2.
[0051] Figure 7 This is a schematic diagram of the selective detection system of this utility model in connection state 2 in embodiment 2;
[0052] Figure 8 This is a schematic diagram of the selective detection system of this utility model in connection state 3 in embodiment 2;
[0053] Figure 9 This is a schematic diagram of the selective detection system of this utility model in connection state 4 in embodiment 2;
[0054] Figure 10 This is a schematic diagram of the selective detection system of this utility model in connection state 1 in embodiment 3;
[0055] Figure 11 This is a schematic diagram of the selective detection system of this utility model in connection state 2 in embodiment 3;
[0056] Figure 12 This is a schematic diagram of the selective detection system of this utility model in connection state 3 in embodiment 3;
[0057] Figure 13 This is a schematic diagram of the selective detection system of this utility model in connection state 4 in embodiment 3;
[0058] Figure 14 This is a schematic diagram of the third embodiment of the selective detection system of this utility model;
[0059] Figure 15This is a schematic diagram of the selective detection system of this utility model in connection state 1 in embodiment 4;
[0060] Figure 16 This is a schematic diagram of the selective detection system of this utility model in connection state 2 in embodiment 4;
[0061] Figure 17 This is a schematic diagram illustrating the applicable scope of the selective detection system of this utility model, as shown in sections 1-4.
[0062] Figure 18 The chromatogram of Application Example 1 of the Selective Detection System of this Utility Model;
[0063] Figure 19 The chromatogram of Example 2 of the application of the selective detection system of this utility model;
[0064] Figure 20 This is a schematic diagram illustrating the principle of the selective detection system and method of this invention for separating and detecting two combinations of target substances contained in two samples. Detailed Implementation
[0065] Figure 1 This invention illustrates the technical concept of a selective detection system. The selective detection system uses two or more flow paths to alternately inject the same sample, so that a specific combination of target substances in one flow path is detected while the other flow paths are rinsed and balanced. Different combinations of target substances in the same sample are detected through different flow paths, and the detection results of each combination of target substances are output to the same chromatogram.
[0066] The above samples contain multiple target compounds (at least three). Based on the differences in retention behavior (separation properties) and / or mass spectrometry ionization response (mass spectrometry ionization properties) of each target compound in the chromatographic system, the target compounds are divided into at least two groups: a first target compound group and a second target compound group. The first target compound group includes at least two first target compounds, and the second target compound group includes at least one second target compound. Separation properties refer to the ability / characteristics of a target compound to be separated in the chromatographic system. When the first and second target compounds differ in hydrophobicity / polarity / charge state / molecular weight, their interaction strength with the stationary phase differs under reversed-phase, hydrophilic, ion exchange, and size exclusion modes, leading to differences in retention time, peak shape / peak width / peak height, and elution order, thus resulting in differences in physical separation within the same chromatographic column. Mass spectrometry ionization properties refer to the ability / characteristics of a target compound to be ionized during mass spectrometry detection. When the proton affinity, ionization energy, or matrix effect of the first and second target analytes differ, their ion responses in electrospray ionization or atmospheric pressure chemical ionization sources differ with the assistance of mobile phase additives. Based on this difference, and by setting the chromatographic separation conditions and the selective ion monitoring or multiple reaction monitoring mode of the detector, one set of target analytes (in which all target analytes have the optimal mass spectrometric response under the given chromatographic separation and detector detection conditions) can be exclusively selected for detection, while all target analytes in the other set can also be exclusively detected under their optimal separation and detection conditions. This allows for optimal quantitative analysis (i.e., obtaining the maximum and optimal peak integral) by separating and detecting the two sets of target analytes under the analytical conditions (including separation and detection conditions) of the first and second flow paths, respectively, based on the optimal separation and detection conditions corresponding to the first and second target analyte sets.
[0067] Based on the above approach, in practical detection applications, optimal analytical conditions can be constructed for the first and second target analyte combinations in different flow paths according to their separation and mass spectrometry ionization properties. This allows for the detection of these two target analyte combinations under optimal analytical conditions. Specifically, this includes the following two scenarios:
[0068] 1) The first and second target combinations have different separation properties;
[0069] In liquid chromatography separation, both the mobile phase and the chromatographic column have a significant impact on the separation performance of the target analytes. Therefore, based on the separation properties of the first and second target analyte combinations, the separation of the two can be achieved by selecting the appropriate chromatographic column or mobile phase.
[0070] A. When the separation properties of the first and second target analyte combinations are relatively similar, the influence of the mobile phase on the separation effect is greater than that of the chromatographic column. In this case, the first and second chromatographic columns can be configured as the same type of column (e.g., both hydrophilic columns or both reversed-phase columns) to separate the first and second target analyte combinations from other non-target substances / impurities in the same sample through the first and second chromatographic columns in the corresponding flow paths. Simultaneously, solvents with different chemical properties are used as mobile phases in different flow paths, achieving the separation of different target analyte combinations by pushing different mobile phases in different flow paths. For example, when both the first and second target analyte combinations are low to medium polar compounds, the first and second chromatographic columns are configured as reversed-phase columns, the first mobile phase is configured as an acidic mobile phase, and the second mobile phase is configured as a basic mobile phase. The first target analyte combination exhibits good retention on the first chromatographic column, thus separating it from other highly polar substances / impurities in the sample. Furthermore, each first target analyte in the combination yields a good peak shape under acidic conditions, and the acidic additives in the acidic mobile phase help each first target analyte achieve better ionization at the detector, resulting in a higher mass spectrometry response signal. Similarly, the second target analyte combination exhibits good retention on the second chromatographic column, thus separating it from other highly polar substances / impurities in the sample. Furthermore, each second target analyte in the combination exhibits a good peak shape under alkaline conditions, and the alkaline additives in the alkaline mobile phase help each second target analyte achieve better ionization at the detector, resulting in a higher mass spectrometry response signal.
[0071] B. When the separation properties of the first and second target analyte combinations differ significantly, the influence of the mobile phase on the separation effect is less than that of the chromatographic column. Therefore, different types of chromatographic columns can be used in different flow paths to achieve the separation of different target analytes. For example, when the first target analytes in the first target analyte combination are all highly polar compounds, and the second target analyte combination is all medium- to low-polarity compounds, the first chromatographic column can be configured as a hydrophilic column, and the second chromatographic column as a reversed-phase column. The highly polar first target analyte combination can be well retained in the first chromatographic column (hydrophilic column), thus achieving good separation from other medium- to low-polarity substances / impurities in the sample. In this process, the medium- to low-polarity second target analyte combination cannot be retained in the first chromatographic column and will elute without separation / retention near the dead time along with medium- to low-polarity impurities, while the first target analyte combination on the first chromatographic column is eluted and enters the detector for detection. Conversely, the low- to medium-polarity second target analyte combination can be well retained in the second chromatographic column (reversed-phase column), thus achieving good separation from other high-polarity substances / impurities in the sample. In this process, the high-polarity first target analyte combination cannot be retained in the second chromatographic column and will elute without separation / retention near the dead time along with the high-polarity impurities. The second target analyte combination on the second chromatographic column is eluted and enters the detector for detection.
[0072] 2) The first and second target analyte combinations have different mass spectrometry ionization properties;
[0073] When the first and second target analyte combinations have different mass spectrometry ionization parameters, selective / exclusive detection of only one target analyte combination is possible. In the first flow path, considering the selection of the first column and the first mobile phase, signal acquisition / detection of the first target analyte combination can be exclusively selected; similarly, in the second flow path, considering the selection of the second column and the second mobile phase, signal acquisition / detection of the second target analyte combination can be exclusively selected. This allows both the first and second target analyte combinations to achieve optimal separation and detection under optimal separation conditions constructed with the optimal mobile phase and column, aiming to obtain a relatively better mass spectrometry ionization response signal, thus achieving selective optimal separation.
[0074] Based on this, in order to achieve Figure 1The present invention provides a selective detection system by using at least two parallel chromatographic columns to form two or more independently operating flow paths, with each flow path sharing a single detector. Based on the separation properties or mass spectrometric ionization properties of different target analyte combinations in the sample, optimal separation conditions are achieved for each target analyte combination by setting appropriate chromatographic columns and / or selecting appropriate mobile phases within different flow paths. Combined with parameter adjustments at the detector end, each target analyte combination can be detected under the optimal analytical conditions (including the separation conditions composed of the chromatographic column and mobile phase, and the detector detection conditions) set within the corresponding flow path. This improves detection accuracy, reduces analysis time, increases overall detection efficiency, and lowers equipment costs.
[0075] The following describes in detail three embodiments of the selective detection system of this utility model with reference to the accompanying drawings.
[0076] Figure 2 An exemplary structure of a first embodiment of the selective detection system of this invention is shown. For example... Figure 2 As shown, the selective detection system of this embodiment includes two flow paths and a detector. The detector is connected to both flow paths via detection selectors, each having at least four ports. The first flow path includes a first push assembly, a first injector, and a first chromatographic column. The outlet of the first push assembly is connected to the inlet of the first injector, the outlet of the first injector is connected to the inlet of the first chromatographic column, and the outlet of the first chromatographic column is connected to a first port of the detection selector. The second flow path includes a second push assembly, a second injector, and a second chromatographic column. The outlet of the second push assembly is connected to the inlet of the second injector, the outlet of the second injector is connected to the inlet of the second chromatographic column, and the outlet of the second chromatographic column is connected to a second port of the detection selector. The inlet of the detector is connected to a third port.
[0077] Specifically, both the first and second push components are chromatographic pumps, the detector is a mass spectrometer, and the detection selector can be any one of a six-way switching valve, an eight-way switching valve, and a ten-way switching valve.
[0078] During detection, a first mobile phase can be introduced through a first pusher component, a second mobile phase through a second pusher component, and a sample can be introduced through a first and a second injector. The first mobile phase comprises a first aqueous phase and a first organic phase, and the second mobile phase comprises a second aqueous phase and a second organic phase. The first mobile phase introduced through the first pusher component carries the sample introduced through the first injector into the first chromatographic column; the second mobile phase introduced through the second pusher component carries the sample introduced through the second injector into the second chromatographic column.
[0079] The detection selector switches between different connection states by connecting its different ports, enabling the detector to connect to different flow paths to detect specific combinations of target substances within the corresponding flow path. When the third port of the detection selector is connected to the first port, the detector is connected to the first flow path, and the effluent from the first chromatographic column can enter the detector; when the third port of the detection selector is connected to the second port, the detector is connected to the second flow path, and the effluent from the second chromatographic column can enter the detector.
[0080] The structure and working principle of the first embodiment of the selective detection system of this utility model are described in detail below using Example 1 as an example.
[0081] Example 1
[0082] Figure 3-4 The specific structures of Embodiment 1 of the selective detection system of this utility model under different connection states are shown. For example... Figure 3-4 As shown, in this embodiment, the sample selection component 300 includes a first injector 3001 and a second injector 3002. The selection component 303 includes a detection selection element 3030, which is specifically a six-way switching valve having ports a, b, c, d, e, and f.
[0083] Specifically, in such Figure 3 In connection state 1 (initial connection state) shown, the outlet of the first push assembly 10 is connected to the inlet of the first injector 3001, the outlet of the first injector 3001 is connected to the inlet of the first chromatographic column 301, and the outlet of the first chromatographic column 301 is connected to port a of the detection selector 3030; the outlet of the second push assembly 20 is connected to the inlet of the second injector 3002, the outlet of the second injector 3002 is connected to the inlet of the second chromatographic column 302, and the outlet of the second chromatographic column 302 is connected to port e of the detection selector 3030. Port c of the detection selector 3030 is connected to the detector 40, and port f is connected to the outside of the system.
[0084] The aforementioned detection selection element 3030 can switch between two connection states by connecting its different ports through valve position switching:
[0085] Connection state 1: such as Figure 3 As shown, the detection selection element 3030 connects the first chromatographic column 301 to the detector 40 and connects the second chromatographic column 302 to the outside of the system;
[0086] Connection state 2: such as Figure 4 As shown, the detection selector 3030 connects the second chromatographic column 302 to the detector 40 and connects the second chromatographic column 302 to the outside of the system.
[0087] The detection process of the selective detection system in this embodiment is as follows:
[0088] (1) Loading and elution on the first chromatographic column 301, and cleaning and equilibration on the second chromatographic column 302;
[0089] like Figure 3 As shown, the detection selector 3030 switches to connection state 1 (initial connection state) via valve position switching. In connection state 1, ports a, b, d, and c of the detection selector 3030 are sequentially connected, enabling the first push assembly 10, the first injector 3001, the first chromatographic column 301, and the detector 40 to be sequentially connected; simultaneously, ports e and f of the detection selector 3030 are connected, enabling the second push assembly 20, the second injector 3002, and the second chromatographic column 302 to be sequentially connected to the outside of the system.
[0090] The first push component 10 introduces and pushes a first mobile phase with an initial concentration into the first injector 3001. Under the push of the first push component 10, the first mobile phase carries the sample containing the first target analyte combination and the second target analyte combination introduced through the first injector 3001 into the first chromatographic column 301. The first target analyte combination is retained at the head of the first chromatographic column 301, or both the first and second target analyte combinations are simultaneously retained at the head of the first chromatographic column 301. The eluent flowing out of the first chromatographic column 301 flows into the detector 40 via the detection selector 3030. As the proportion of the first organic phase in the first mobile phase pushed by the first push component 10 increases, gradient elution is performed on the first target analyte combination retained at the head of the first chromatographic column 301, or the simultaneously retained first and second target analyte combinations. The eluted first target analyte combination, or the simultaneously eluted first and second target analyte combinations, enters the detector 40. The detector 40 selectively detects and analyzes the first target analyte combination to obtain the first result.
[0091] While the above process is in progress, the second push component 20 introduces and pushes a second mobile phase with an initial concentration into the second chromatographic column 302 to clean and balance the second chromatographic column 302 and the corresponding pipeline, and the outflowing waste liquid is discharged out of the system.
[0092] (2) Loading and elution on the second chromatographic column 302, and cleaning and equilibration on the first chromatographic column 301;
[0093] like Figure 4As shown, the detection selector 3030 switches to connection state 2 via a valve position change. In connection state 2, ports e, d, b, and c of the detection selector 3030 are sequentially connected, connecting the second push assembly 20, the second injector 3002, the second chromatographic column 302, and the detector 40 sequentially. Simultaneously, ports a and f of the detection selector 3030 are connected, connecting the first push assembly 10, the first injector 3001, and the first chromatographic column 301 sequentially to the outside of the system, preparing for the next round of substance separation.
[0094] The second pusher component 20 introduces and pushes a second mobile phase with an initial concentration into the second injector 3002. Under the push of the second pusher component 20, the second mobile phase carries the same sample introduced through the second injector 3002 into the second chromatographic column 302. The second target analyte combination is retained at the head of the second chromatographic column 302, or both the first and second target analyte combinations are retained at the head of the second chromatographic column 302. The eluent flowing out of the second chromatographic column 302 flows into the detector 40 via the detection selector 3030. As the proportion of the second organic phase in the second mobile phase pushed by the second pusher component 20 increases, gradient elution is performed on the second target analyte combination retained at the head of the second chromatographic column 302, or the simultaneously retained first and second target analyte combinations. The eluted second target analyte combination, or the simultaneously eluted first and second target analyte combinations, enters the detector 40. The detector 40 selectively detects and analyzes the second target analyte combination to obtain the second result.
[0095] While the above process is in progress, the first push component 10 introduces and pushes the first mobile phase with an initial concentration into the first chromatographic column 301 to clean and balance the first chromatographic column 301 and the corresponding pipeline. The outflowing waste liquid is discharged out of the system to prepare for the next round of substance separation.
[0096] Since the first and second flow paths share a single detector 40, the first and second results can be output on the same chromatogram, which reduces the analysis time of the detection results and improves the overall detection efficiency.
[0097] To automate the detection process, the selective detection system of this embodiment also includes a control unit (not shown). The control unit is electrically connected to the detection selection component 3030 and controls the switching of the connection state of the detection selection component 3030 to execute the aforementioned detection process. Furthermore, the control unit is also electrically connected to the first push component 10 and the second push component 20 to simultaneously control the start and stop of the first push component 10 and the second push component 20.
[0098] Thus, by using two independently operating flow paths in parallel, it can be ensured that each of the two sets of target substances contained in the sample can achieve optimal separation and the best sensitivity at the detector end under the analytical conditions set in the corresponding flow path, thereby improving the accuracy of detection. By alternately injecting samples into the two parallel flow paths, the waiting time for cleaning and equilibration can be reduced, effectively improving the detection efficiency.
[0099] In this embodiment, the first chromatographic column 301 and the second chromatographic column 302 can be different types of chromatographic columns or the same type of chromatographic column. Here, whether the "type" of the chromatographic columns is the same depends on whether the stationary phases of the two chromatographic columns are the same.
[0100] When the first target analyte combination and the second target analyte combination have different and significantly different separation properties, the chromatographic column has a greater impact on the separation effect than the mobile phase. In this case, the first chromatographic column 301 is configured to achieve a first resolution ≥ 1.5 between any two peaks of the first target analyte in the sample; and a second resolution between any peak of the first target analyte and any peak of the second target analyte in the sample, with at least one second resolution < 1.5. Simultaneously, the second chromatographic column 302 is configured to achieve a third resolution ≥ 1.5 between any two peaks of the second target analyte in the same sample; and a fourth resolution between any peak of the second target analyte and any peak of the first target analyte in the same sample, with at least one fourth resolution < 1.5. In other words, when the first chromatographic column 301 and the second chromatographic column 302 are configured as different types of chromatographic columns, any two first target substances can be separated from each other through the first chromatographic column 301 (resolution ≥ 1.5); however, under the setting conditions of the first chromatographic column 301, the first target substance and at least one second target substance cannot be separated under the setting conditions of the first chromatographic column 301 (resolution < 1.5), so the separation of the first target substance and the second target substance needs to be achieved through the second chromatographic column 302.
[0101] Similarly, any two second target compounds can be separated from each other (resolution ≥ 1.5) using the second chromatographic column 302; however, under the setting conditions of the second chromatographic column 302, the second target compound cannot be separated from at least one first target compound (resolution < 1.5). Therefore, the second target compound needs to be separated from the first target compound using the first chromatographic column 301.
[0102] In practical detection applications, the first chromatographic column 301 better separates the first target analyte combination in the first flow path from the second target analyte combination and other non-target analytes / impurities in the sample, so that the signal of the first target analyte combination in the first flow path can be better acquired by the detector 40, and the first target analytes in the first target analyte combination can be separated from each other (resolution ≥ 1.5) and obtain good peak shapes. Similarly, the second chromatographic column 302 better separates the second target analyte combination in the second flow path from the first target analyte combination and other non-target analytes / impurities in the sample, so that the signal of the second target analyte combination in the second flow path can be better acquired by the detector 40, and the second target analytes in the second target analyte combination can be separated from each other (resolution ≥ 1.5) and obtain good peak shapes.
[0103] When the first target analyte combination and the second target analyte combination have different separation properties, but the difference in separation properties is small, the flow rate has a greater impact on the separation effect than the chromatographic column. In this case, the first chromatographic column 301 and the second chromatographic column 302 can also be configured as the same type of column.
[0104] In practical detection applications, the first and second target analyte combinations in the corresponding flow paths are separated from other non-target substances / impurities in the same sample by the first chromatographic column 301 and the second chromatographic column 302. At the same time, a first mobile phase and a second mobile phase with different chemical properties are used. The first mobile phase better separates the first target analyte combination and the second target analyte combination in the first flow path, so that the signal of the first target analyte combination in the first flow path can be better acquired by the detector 40, and the first target analytes in the first target analyte combination can be separated from each other (resolution ≥ 1.5) and obtain a good peak shape. The second mobile phase better separates the second target analyte combination and the first target analyte combination in the second flow path, so that the signal of the second target analyte combination in the second flow path can be better acquired by the detector 40, and the second target analytes in the second target analyte combination can be separated from each other (resolution ≥ 1.5) and obtain a good peak shape.
[0105] It should be noted that although the selective detection system in this embodiment only uses two chromatographic columns as separation conditions, this does not mean that only two separation conditions can be set. In practical applications, more than two separation conditions can be set depending on the number of target analytes. For example, if the sample contains three target analytes with different separation properties or mass spectrometry ionization properties, then three independently operating flow paths can be set up, each flow path including a pusher component, an injector, and a chromatographic column. It is important to note that when more than two chromatographic columns are used, the detection selection component must employ a multi-flow selection valve.
[0106] Figure 5An exemplary structure of a second embodiment of the selective detection system of this invention is shown. For example... Figure 5 As shown, the selective detection system of this embodiment differs from the first embodiment only in that: in this embodiment, the first chromatographic column in the first flow path is connected to the first push assembly via an injection selection component, and the second chromatographic column is also connected to the second push assembly via an injection selection component. Other structures and connections are the same as in the first embodiment. The injection selection component includes an injector and an injection selection element. The injection selection element has at least six ports, and by connecting its different ports, it switches between different connection states, allowing the injector to switch to different flow paths to introduce samples into the corresponding flow paths.
[0107] The structure and working principle of the first embodiment of the selective detection system of this utility model are described in detail below using Examples 2-3 as examples.
[0108] Example 2
[0109] Figure 6-9 The specific structure of Embodiment 2 of the first embodiment of the selective detection system of this utility model is shown under different connection states. For example... Figure 6-9 As shown, in this embodiment, the injection selection component 300 includes an injector 3000 and an injection selection element 3010, with other structures being the same as in Embodiment 1. The injection selection element 3010 is specifically a six-way switching valve, which has ports a', b', c', d', e', and f'.
[0110] Specifically, in such Figure 6 In the initial connection state shown, the outlet of the first push component 10 is connected to port a' of the injection selection component 3010, the inlet and outlet of the injector 3000 are connected to ports f' and c' of the injection selection component 3010, respectively, and the inlet of the first chromatographic column 301 is connected to port b' of the injection selection component 3010; the outlet of the second push component 20 is connected to port e' of the injection selection component 3010, and the inlet of the second chromatographic column 302 is connected to port d' of the injection selection component 3010. The connection method between the outlet of the first chromatographic column 301, the outlet of the second chromatographic column 302, and the inlet of the detector 40 and the port of the detection selection component 3030 is the same as the connection method in connection state 1 of Example 1.
[0111] Both the injection selection element 3010 and the detection selection element 3030 can be connected to different ports via valve position switching to switch between the following four connection states:
[0112] Connection state 1: such as Figure 6As shown, the injection selection component 3010 connects the injector 3000 to the first push assembly 10 and the first chromatographic column 301 respectively, and connects the second push assembly 20 to the second chromatographic column 302; the detection selection component 3030 connects the first chromatographic column 301 to the detector 40, and connects the second chromatographic column 302 to the outside of the system;
[0113] Connection state 2: such as Figure 7 As shown, the injection selection component 3010 connects the first push component 10 to the first chromatographic column 301, and the second push component 20 to the injector 3000, and the injector 3000 to the second chromatographic column 302; the detection selection component 3030 connects the first chromatographic column 301 to the detector 40, and connects the second chromatographic column 302 to the outside of the system.
[0114] Connection state 3: such as Figure 8 As shown, the injection selection component 3010 connects the second push component 20 to the injector 3000, connects the injector 3000 to the second chromatographic column 302, and connects the first push component 10 to the first chromatographic column 301; the detection selection component 3030 connects the second chromatographic column 302 to the detector 40, and connects the first chromatographic column 301 to the outside of the system.
[0115] Connection status 4: such as Figure 9 As shown, the injection selection component 3010 connects the second push component 20 to the second chromatographic column 302, and connects the first push component 10 to the injector 3000, and connects the injector 3000 to the first chromatographic column 301; the detection selection component 3030 connects the second chromatographic column 302 to the detector 40, and connects the first chromatographic column 301 to the outside of the system.
[0116] The detection process of the selective detection system in this embodiment is as follows:
[0117] (1) Load the sample onto the first chromatographic column 301 and clean the second chromatographic column 302;
[0118] The injection selection element 3010 and the detection selection element 3030 are switched to connection state 1 (initial connection state) via valve position switching. Figure 6 In the connection state 1 shown, port a' of injection selection component 3010 is connected to port f', and port c' is connected to port b'. Ports a, b, d, and c of detection selection component 3030 are connected in sequence, so that the first push component 10, injector 3000, first chromatographic column 301, and detector 40 are connected in sequence. At the same time, port e' of injection selection component 3010 is connected to port d', and port e and port f of detection selection component 3030 are connected, so that the second push component 20 and the second chromatographic column 302 are connected to the outside of the system in sequence.
[0119] In this connection state, the injector 3000 is located in the first flow path. The first push component 10 introduces and pushes a first mobile phase with an initial concentration into the injector 3000. Under the push of the first push component 10, the first mobile phase carries the sample containing the first target combination and the second target combination introduced from the injector 3000 into the first chromatographic column 301. The first target combination is retained at the head of the first chromatographic column 301, or the first and second target combinations are simultaneously retained at the head of the first chromatographic column 301. The eluent flowing out of the first chromatographic column 301 flows into the detector 40 through the detection selector 3030.
[0120] While the above process is in progress, the second push component 20 introduces and pushes a second mobile phase with a second organic phase ratio of 100% into the second chromatographic column 302 to clean the second chromatographic column 302 and the corresponding pipeline, and the outflowing waste liquid is discharged out of the system.
[0121] (2) Elution was performed on the first chromatographic column 301, followed by cleaning and equilibration on the second chromatographic column 302;
[0122] The injection selection element 3010 switches to connection state 2 via valve position switching, as shown in the example. Figure 7 In connection state 2 shown, port a' of injection selector 3010 is connected to port b', and the port connection of detection selector 3030 remains unchanged, so that the first push component 10, the first chromatographic column 301 and the detector 40 are connected in sequence; at the same time, port e' of injection selector 3010 is connected to port f', and port c' is connected to port d', so that the second push component 20, the injector 3000 and the second chromatographic column 302 are connected to the outside of the system in sequence.
[0123] In this connected state, as the proportion of the first organic phase introduced and pushed by the first push component 10 in the first mobile phase increases, gradient elution is performed on the first target combination retained on the head of the first chromatographic column 301 or the first and second target combinations retained at the same time. The eluted first target combination or the first and second target combinations eluted at the same time enter the detector 40. The detector 40 selectively detects the first target combination to obtain the first result.
[0124] While the above process is in progress, the second push component 20 first introduces and pushes a second mobile phase with a second organic phase ratio of 100% into the injector 3000 to rinse away the first mobile phase remaining in the injector 3000 pipeline. Then, the second push component 20 introduces and pushes a second mobile phase with an initial concentration into the injector 3000 to replace the first mobile phase in the injector 3000 with the second mobile phase.
[0125] (3) Load the sample onto the second chromatographic column 302 and clean the first chromatographic column 301;
[0126] The injection selection element 3010 and the detection selection element 3030 are switched to connection state 3 via valve position switching, as shown in the example. Figure 8 In the connection state 3 shown, port e' of injection selection component 3010 is connected to port f', port c' is connected to port d', and ports e, d, b and c of detection selection component 3030 are connected in sequence, so that the second push component 20, the second chromatographic column 302 and the detector 40 are connected in sequence; at the same time, port a' of injection selection component 3010 is connected to port b', and ports a and f of detection selection component 3030 are connected, so that the first push component 10 and the first chromatographic column 301 are connected to the outside of the system in sequence.
[0127] In this connection state, the injector 3000 is located in the second flow path. The second push component 20 introduces and pushes a second mobile phase with an initial concentration into the injector 3000. Under the push of the second push component 20, the second mobile phase carries the same sample introduced from the injector 3000 into the second chromatographic column 302. The second target analyte combination is retained at the head of the second chromatographic column 302, or the first and second target analyte combinations are simultaneously retained at the head of the second chromatographic column 302. The eluent flowing out of the second chromatographic column 302 flows into the detector 40 through the detection selector 3030.
[0128] While the above process is in progress, the first push component 10 introduces and pushes a first mobile phase with a first organic phase ratio of 100% into the first chromatographic column 301 to clean the first chromatographic column 301 and the corresponding pipeline, and the outflowing waste liquid is discharged out of the system.
[0129] (4) Elution with the second chromatographic column 302, and cleaning and equilibration with the first chromatographic column 301;
[0130] The injection selection element 3010 switches to connection state 4 via the valve position, as follows: Figure 9 In the connection state 4 shown, port e' of injection selection component 3010 is connected to port d', and the port connection mode of detection selection component 3030 remains unchanged, so that the second push component 20, the second chromatographic column 302 and the detector 40 are connected in sequence; at the same time, port a' of injection selection component 3010 is connected to port f', and port c' is connected to port b', so that the first push component 10, the injector 3000 and the first chromatographic column 301 are connected to the outside of the system in sequence.
[0131] In this connected state, as the proportion of the second organic phase introduced and pushed into the second mobile phase by the second push component 20 increases, gradient elution is performed on the second target combination retained on the head of the second chromatographic column 302, or the first and second target combinations retained simultaneously. The eluted second target combination or the first and second target combinations eluted simultaneously enter the detector 40, and the detector 40 selectively detects and analyzes the second target combination to obtain the second result.
[0132] While the above process is in progress, the first pushing component 10 first introduces and pushes a first mobile phase with a first organic phase ratio of 100% into the injector 3000 to rinse away the second mobile phase remaining in the injector 3000 pipeline. Then, the first pushing component 10 introduces and pushes a first mobile phase with an initial concentration into the injector 3000 to replace the second mobile phase in the injector 3000 with the first mobile phase.
[0133] Compared with Example 1, this example replaces an injector with a switching valve, and uses the switching valve to switch the injector between the first flow path and the second flow path, resulting in lower equipment cost.
[0134] Example 3
[0135] Figure 10-13 The specific structures of Embodiment 3 of the selective detection system of this utility model under different connection states are shown. For example... Figure 10-13 As shown, the injection selection component 300 in this embodiment also includes an injector 3000 and an injection selection element 3011. The difference between this embodiment and embodiment 2 is that in this embodiment, the injection selection element 3011 is an eight-way switching valve, which has ports a”, b”, c”, d”, e” and f”.
[0136] Specifically, in such Figure 10 In the initial connection state shown, the outlet of the first push assembly 10 is connected to port a” of the injection selection component 3011, the inlet and outlet of the injector 3000 are connected to ports e” and c” of the injection selection component 3011, respectively, the inlet of the first chromatographic column 301 is connected to port g” of the injection selection component 3011, and the outlet of the first chromatographic column 301 is connected to port a of the detection selection component 3030. The outlet of the second push assembly 20 is connected to port e’ of the injection selection component 3011, the inlet of the second chromatographic column 302 is connected to port b’ of the injection selection component 3011, and the outlet of the second chromatographic column 302 is connected to port a of the detection selection component 3030.
[0137] The aforementioned injection selection component 3011 and detection selection component 3030 together form four connection states through valve position switching. Since these four connection states are the same as those in Embodiment 2, they will not be described again here. Based on these four connection states, the detection process of the selective detection system in this embodiment is also the same as in Embodiment 2, the only difference being that the connection ports of the first push component 10, the second push component 20, the injector 3000, the first chromatographic column 301, the second chromatographic column 302, and the injection selection component 3011 in each connection state are different from those in Embodiment 2. Therefore, the following will only specifically describe the connection methods in different connection states of this embodiment:
[0138] (1) Load the sample onto the first chromatographic column 301 and clean the second chromatographic column 302;
[0139] The injection selection element 3011 and the detection selection element 3030 are switched to connection state 1 (initial connection state) via valve position switching. Figure 10 In the connection state 1 shown, ports a”, b”, f” and e” of the injection selection component 3011 are connected in sequence, and ports a”, b”, d” and c” of the detection selection component 3030 are connected in sequence, so that the first push component 10, the injector 3000, the first chromatographic column 301 and the detector 40 are connected in sequence to form the first flow path; at the same time, ports h” and d” of the injection selection component 3011 are connected, and ports e and f” of the detection selection component 3030 are connected, so that the second push component 20 and the second chromatographic column 302 are connected to the outside of the system in sequence.
[0140] In this connection state, the sample loading process of the first chromatographic column 301 and the cleaning process of the second chromatographic column 302 are the same as step (1) of the detection process in Example 2, so they will not be repeated here.
[0141] (2) Elution was performed on the first chromatographic column 301, followed by cleaning and equilibration on the second chromatographic column 302;
[0142] The injection selection element 3011 is switched to connection state 2 via the valve position, as follows: Figure 11 In connection state 2 shown, port a” of injection selection component 3011 is connected to port d”, and the connection state of detection selection component 3030 remains unchanged, so that the first push component 10, the first chromatographic column 301 and the detector 40 are connected in sequence; at the same time, port h” of injection selection component 3011 is connected to port e”, and ports c”, b”, f” and g” are connected in sequence, so that the second push component 20, the injector 3000 and the second chromatographic column 302 are connected to the outside of the system in sequence.
[0143] In this connection state, the elution process of the first chromatographic column 301 and the cleaning and equilibration process of the second chromatographic column 302 are the same as step (2) of the detection process in Example 2, so they will not be described again here.
[0144] (3) Load the sample onto the second chromatographic column 302 and clean the first chromatographic column 301;
[0145] The injection selection element 3011 and the detection selection element 3030 are switched to connection state 3 via valve position switching, as shown in the example. Figure 12 In the connection state 3 shown, port a” of injection selector 3011 is connected to port d”, and port h” is connected to port e”, while ports c”, b”, f” and g” are connected in sequence; at the same time, the detection selector 3030 switches its valve position so that ports a, b, d and d are connected in sequence, and ports e and f are connected, so that the second push assembly 20, the second chromatographic column 302 and the detector 40 are connected in sequence to form a second flow path; at the same time, the first push assembly 10 is connected to the first chromatographic column 301 and connected to the outside of the system.
[0146] In this connection state, the sample loading process of the second chromatographic column 302 and the cleaning process of the first chromatographic column 301 are the same as step (3) of the detection process in Example 2, so they will not be described again here.
[0147] (4) Elution with the second chromatographic column 302, and cleaning and equilibration with the first chromatographic column 301;
[0148] The injection selection element 3011 and the detection selection element 3030 are switched to connection state 4 via the valve position, as shown in the example. Figure 13 In the connection state 1 shown, port b” is connected to port g”, and ports a”, b”, f” and e” are connected in sequence, and port c” is connected to port d”. At the same time, the detection selection element 3030 switches its position through the valve, and its ports a, b, d and c are connected in sequence, and port e is connected to port f, so that the second push assembly 20, the second chromatographic column 302 and the detector 40 are connected in sequence. At the same time, the first push assembly 10, the injector 3000 and the first chromatographic column 301 are connected in sequence and connected to the outside of the system.
[0149] In this connection state, the elution process of the second chromatographic column 302 and the cleaning and equilibration process of the first chromatographic column 301 are the same as step (4) of the detection process in Example 2, so they will not be repeated here.
[0150] Similar to the first embodiment, in this embodiment, the first chromatographic column 301 and the second chromatographic column 302 can be configured as different types of columns or as the same type of column. When the first chromatographic column 301 and the second chromatographic column 302 are different types, the first chromatographic column 301 is configured to retain the first target analyte combination in the sample, and the second chromatographic column 302 is configured to retain the second target analyte combination in the sample. The first target analyte combination and the second target analyte combination, as well as other non-target substances / impurities in the sample, are separated in the first flow path by the first chromatographic column 301. Similarly, the second target analyte combination and the first target analyte combination, as well as other non-target substances / impurities in the sample, are separated in the second flow path by the second chromatographic column 302. When the first chromatographic column 301 and the second chromatographic column 302 are of the same type, both the first chromatographic column 301 and the second chromatographic column 302 can retain the first and second target analyte combinations in the sample. The first chromatographic column 301 and the second chromatographic column 302 separate the first and second target analyte combinations in the corresponding flow paths from other non-target substances / impurities in the same sample. Simultaneously, a first mobile phase and a second mobile phase with different chemical properties are used. The first mobile phase better separates the first target analyte combination from the second target analyte combination in the first flow path, and the second mobile phase better separates the second target analyte combination from the first target analyte combination in the second flow path. Since the configuration basis of the first chromatographic column 301 and the corresponding detection principle are the same as in the first embodiment, they will not be repeated here.
[0151] In this embodiment, since the first and second flow paths share a single injector, if the first and second mobile phases have different chemical properties (e.g., the first mobile phase is acidic and the second mobile phase is alkaline), the residual first mobile phase in the injector after separating and detecting the first target analyte combination through the first flow path will affect the separation and detection of the second target analyte combination, and vice versa. Therefore, when the first and second mobile phases have different chemical properties, the selective detection system needs to rinse the injector through connection states 2 and 4. However, if the first and second mobile phases have the same or similar chemical properties, after separating and detecting the first target analyte combination, even if the injector retains the first mobile phase, its impact on the detection results of the second target analyte combination is minimal, and vice versa. In this case, the selective detection system only needs to switch to connection states 1 and 3, and does not need to switch to connection states 2 and 4. In other words, the selective detection system of this embodiment is applicable to both cases where the first and second mobile phases have the same or similar chemical properties and cases where the first and second mobile phases have different chemical properties.
[0152] To automate the detection process, the selective detection system of this embodiment also includes a control unit (not shown). The control unit is electrically connected to the sample selection components 3010, 3011 and the detection selection component 3030, respectively. The control unit controls the switching of the connection states of the sample selection components 3010, 3011 and the detection selection component 3030 to achieve the above-mentioned detection process. Furthermore, the control unit is also electrically connected to the first push component 10 and the second push component 20 to simultaneously control the start and stop of the first push component 10 and the second push component 20.
[0153] Figure 14 An exemplary structure of a third embodiment of the selective detection system of this utility model is shown. For example... Figure 14 As shown, the difference between this embodiment and the second embodiment is that the selective detection system in this embodiment combines the sample injection selection component and the detection selection component in the second embodiment into a single functional unit, namely the sample injection detection selection component. The sample injection detection selection component includes a sample injector and a sample injection detection selector. The sample injection detection selector has at least ten ports. By connecting its different ports, it switches between different connection states, allowing the sample injector to switch to different flow paths to introduce samples into the corresponding flow paths, and enabling the detector to connect to different flow paths to detect specific target combinations within the corresponding flow paths.
[0154] The structure and working principle of the third embodiment of the selective detection system of this utility model are described in detail below using Example 4 as an example.
[0155] Example 4
[0156] Figure 15-16 The specific structure of the selective detection system of this utility model under different connection states is shown in Embodiment 4. In this embodiment, the sample injection detection selection component 310 includes a sampler 3000 and a sample injection detection selection element 3102. The sample injection detection selection element 3102 is specifically a ten-way switching valve, which has ports a1, b1, c1, d1, e1, f1, g1, h1, i1 and j1.
[0157] Specifically, such as Figure 15In the initial connection state shown, the outlet of the first push component 10 is connected to port a1 of the injection detection selector 3102, the inlet and outlet of the injector 3000 are connected to ports j1 and c1 of the injection detection selector 3102, the two ports of the first chromatographic column 301 are connected to ports b1 and f1 of the injection detection selector 3102, and the inlet of the detector 40 is connected to port g1 of the injection detection selector 3102. At the same time, the outlet of the second push component 20 is connected to port i1 of the injection detection selector 3102, the two ports of the second chromatographic column 302 are connected to ports d1 and h1 of the injection detection selector 3102, and port e1 of the injection detection selector 3102 is connected to the outside of the system.
[0158] The aforementioned sample injection detection selector 3102 can be connected to different ports via valve position switching, switching between the following two connection states:
[0159] Connection state 1: such as Figure 15 As shown, the injection detection selection element 3102 connects the injector 3000 to the first push assembly 10 and the first chromatographic column 301 respectively, connects the first chromatographic column 301 to the detector 40, and connects the second chromatographic column 302 to the outside of the system.
[0160] Connection state 2: such as Figure 16 As shown, the injection detection selector 3102 connects the injector 3000 to the second push assembly 20 and the second chromatographic column 302 respectively, connects the second chromatographic column 302 to the detector 40, and connects the first chromatographic column 301 to the outside of the system.
[0161] The detection process of the selective detection system in this embodiment is as follows:
[0162] (1) Loading and elution on the first chromatographic column 301, and cleaning and equilibration on the second chromatographic column 302;
[0163] The sample injection detection selector 3102 switches to the position via a valve position switch, as shown below. Figure 14 The connection state 1 (initial connection state) is shown. In connection state 1, port a1 of the injection detection selector 3102 is connected to port j1, port b1 is connected to port c1, and port f1 is connected to port g1, so that the first push component 10, the injector 3000, the first chromatographic column 301 and the detector 40 are connected in sequence to form the first flow path; at the same time, port i1 of the injection detection selector 3102 is connected to port h1, and port d1 is connected to port e1, so that the second push component 20 and the second chromatographic column 302 are connected to the outside of the system in sequence.
[0164] In this connection state, the injector 3000 is located in the first flow path. The first push component 10 introduces and pushes a first mobile phase with an initial concentration into the injector 3000. Under the push of the first push component 10, the first mobile phase carries the sample containing the first target analyte combination and the second target analyte combination introduced by the injector 3000 into the first chromatographic column 301. The first target analyte combination is retained at the head of the first chromatographic column 301, while the eluent flowing out of the first chromatographic column 301 flows into the detector 40 via the injection detection selector 3102. As the proportion of the first organic phase in the first mobile phase introduced and pushed by the first push component 10 increases, the first target analyte combination retained at the head of the first chromatographic column 301 undergoes gradient elution. The eluted first target analyte combination enters the detector 40, which selectively detects and analyzes the first target analyte combination to obtain the first result.
[0165] While the above process is in progress, the second push component 20 introduces and pushes a second mobile phase with an initial concentration into the second chromatographic column 302 to clean and balance the second chromatographic column 302 and the corresponding pipeline, and the outflowing waste liquid is discharged out of the system.
[0166] (2) Loading and elution on the second chromatographic column 302, and cleaning and equilibration on the first chromatographic column 301;
[0167] The sample injection detection selector 3102 switches to the position via a valve position switch, as shown below. Figure 16 The connection state 2 is shown. In connection state 2, port i1 of the injection detection selector 3102 is connected to port j1, port c1 is connected to port d1, and port h1 is connected to port g1, so that the second push component 20, the injector 3000, the second chromatographic column 302 and the detector 40 are connected in sequence to form a second flow path; at the same time, port a1 of the injection detection selector 3102 is connected to port b1, and port e1 is connected to port f1, so that the first push component 10 and the first chromatographic column 301 are connected to the outside of the system in sequence.
[0168] In this connection state, the injector 3000 is located in the second flow path. The second pusher assembly 20 introduces and pushes a second mobile phase with an initial concentration into the injector 3000. Under the push of the second pusher assembly 20, the second mobile phase carries the same sample introduced by the injector 3000 into the second chromatographic column 302. The second target analyte combination is retained at the head of the second chromatographic column 302, while the eluent flowing out of the second chromatographic column 302 flows into the detector 40 via the injection detection selector 3102. As the proportion of the second organic phase in the second mobile phase introduced and pushed by the second pusher assembly 20 increases, the second target analyte combination retained at the head of the second chromatographic column 302 undergoes gradient elution. The eluted second target analyte combination enters the detector 40, which selectively detects and analyzes the second target analyte combination to obtain the second result.
[0169] While the above process is in progress, the first push component 10 introduces and pushes the first mobile phase with an initial concentration into the first chromatographic column 301 to clean and balance the first chromatographic column 301 and the corresponding pipeline, and the outflowing waste liquid is discharged out of the system.
[0170] Compared to the second embodiment, although the selective detection system of this embodiment combines the functions of the injection component and the selection component into one, further reducing equipment costs, it cannot switch to connection states 2 and 4 of the second embodiment. Therefore, it cannot clean the injector 3000 in the injection detection selection component 310. Thus, the selective detection system of this embodiment is only suitable for detection using a first mobile phase and a second mobile phase with the same or similar chemical properties as separation solvents. Therefore, the first chromatographic column 301 and the second chromatographic column 302 of this embodiment are configured as different types of chromatographic columns. The first chromatographic column 301 and the second chromatographic column 302 separate the first target analyte combination in the first flow path and the second target analyte combination in the second flow path, respectively. Since the detection principles of the first chromatographic column 301 and the second chromatographic column 302 and the detection through different types of chromatographic columns have been explained in the first embodiment, they will not be repeated here.
[0171] To automate the detection process, the selective detection system of this embodiment also includes a control unit (not shown). The control unit is electrically connected to the sample injection detection selector 3102 and controls the switching of the connection state of the sample injection detection selector 3102 to achieve the above-mentioned detection process. Furthermore, the control unit is also electrically connected to the first push component 10 and the second push component 20 to simultaneously control the start and stop of the first push component 10 and the second push component 20.
[0172] Figure 17 The applicable scope of Examples 1-4 is shown. For example... Figure 17As shown, the flow path design with two injectors and one switching valve in Example 1 has the widest applicability, followed by the flow path design with one injector and two switching valves in Examples 2-3. The flow path design with one injector and one switching valve in Example 4 has the smallest applicability. The appropriate flow path design can be selected according to the actual separation needs to detect combinations of target substances with different properties.
[0173] The technical effects of the selective detection system of this utility model are illustrated below through two application examples based on Embodiment 3 and Embodiment 4, respectively.
[0174] Application Example 1
[0175] This application example is based on the selective detection system of Example 3. It separates and detects 742 compounds (as shown in Table 1) in a sample based on the acidic and basic properties of each compound. The separation conditions are shown in Table 2 below:
[0176] Table 1
[0177]
[0178]
[0179]
[0180]
[0181] Table 2
[0182]
[0183] The specific detection and analysis process based on the selective detection system of Example 3 has been described in detail above, and therefore will not be repeated here.
[0184] In this application example, among the 742 compounds shown in Table 1, acidic compounds numbered 1-613 constitute the first target analyte combination, and basic compounds numbered 614-742 constitute the second target analyte combination. Since both the first and second target analyte combinations are of low to medium polarity, meaning their separation properties are relatively similar, both the first column 301 and the second column 302 in this application example are configured as reversed-phase columns. The first column 301 separates the first and second target analyte combinations in the first flow path from other highly polar substances / impurities in the sample, and the second column 302 separates the first and second target analyte combinations in the second flow path from other highly polar substances / impurities in the sample. To separate the first and second target analyte combinations in each flow path, the first mobile phase in this application example uses an acidic mobile phase, and the second mobile phase uses a basic mobile phase. The acidic additive in the first mobile phase helps the first target compound combination in the first flow path to achieve better ionization at detector 40, thereby obtaining a higher mass spectrometry response signal. Therefore, selectively detecting only the first target compound combination (acidic compounds numbered 1-613) using detector 40 can better acquire the signals of each acidic compound in the first target compound combination, allowing each acidic compound to be separated from each other (resolution ≥ 1.5) and obtain good peak shapes, resulting in the first result. The basic additive in the second mobile phase helps the second target compound combination in the second flow path to achieve better ionization at detector 40, thereby obtaining a higher mass spectrometry response signal. Therefore, selectively detecting the second target compound combination (basic compounds numbered 614-742) using detector 40 can better acquire the signals of each basic compound in the second target compound combination, allowing each basic compound to be separated from each other (resolution ≥ 1.5) and obtain good peak shapes, resulting in the second result. Finally, the first and second results are output as follows: Figure 18 The chromatogram shown illustrates this. Thus, by selecting an appropriate mobile phase as the analytical conditions, the detection of different combinations of target analytes can be achieved.
[0185] Because the acidic first mobile phase and the basic second mobile phase have vastly different chemical properties, traditional methods using a single one-dimensional mass spectrometer to sequentially employ both mobile phases require a considerable amount of time for cleaning and equilibration of residual mobile phase from the previous separation. However, the selective detection system in this application features two parallel flow paths that do not interfere with each other. This ensures that both acidic and basic compounds in the sample are separated and detected under optimal analytical conditions, improving detection accuracy. Furthermore, the detection results can be output to the same chromatogram, reducing analysis time. In addition, alternating injections and flow path operation significantly reduce cleaning and equilibration waiting time, improving overall detection efficiency.
[0186] Application Example 2
[0187] This application example is based on the selective detection system of Example 4. It separates and detects 268 compounds (as shown in Table 3) in a sample based on the polarity of each compound. The separation conditions are shown in Table 4 below:
[0188] Table 3
[0189]
[0190]
[0191]
[0192] Table 4
[0193]
[0194] The specific detection and analysis process based on the selective detection system of Example 4 has been described in detail above, and therefore will not be repeated here.
[0195] Of the 268 compounds shown in Table 3, the highly polar compounds numbered 1-206 constitute the first target analyte combination, while the medium-to-low polar compounds numbered 207-268 constitute the second target analyte combination. Since the first and second target analyte combinations have different polarities, their separation properties differ significantly. Therefore, in this application example, the first chromatographic column 301 is configured as a hydrophilic column, and the second chromatographic column 302 is configured as a reversed-phase column. After loading and eluting the first chromatographic column 301, the highly polar first target analyte combination is retained at the column head, while the second target analyte combination, along with various medium-to-low polar impurities, is eluted near the dead time. Thus, in the first flow path, the first target compound combination is separated from the second target compound combination and other low- to medium-polarity impurities by the first chromatographic column 301. The detector 40 then selectively detects the eluted first target compound combination. Isocratic / gradient elution ensures that the high-polarity compounds in each first target compound combination are separated (resolution ≥ 1.5) with good peak shapes, yielding the first result. Similarly, after loading and eluting the second chromatographic column 302, the low- to medium-polarity second target compound combination is retained at the column head of the second chromatographic column 302, while the first target compound combination and various high-polarity impurities are eluted near the dead time. Thus, in the second flow path, the second target compound combination is separated from the first target compound combination and other highly polar impurities by the second chromatographic column 302. The detector 40 then selectively detects the eluted second target compound combination. Isocratic / gradient elution ensures that the low- and medium-polarity compounds in each second target compound combination are separated (resolution ≥ 1.5) and all have good peak shapes, yielding the second result. Finally, the first and second results are output as follows: Figure 19 The chromatogram shown illustrates this. Thus, by selecting appropriate chromatographic columns as analytical conditions, the detection of different target analytes can be achieved.
[0196] The selective detection systems described in the three embodiments above are all suitable for the continuous detection of two or more different samples. The following will use... Figure 20 The first and second samples shown are used as examples to illustrate the detection process of the selective detection system of this invention for multiple samples.
[0197] It is known that both the first and second samples contain multiple identical target analytes. Based on the separation properties or mass spectrometric ionization properties of these target analytes, they are classified into a first target analyte combination and a second target analyte combination. When the separation properties of the first and second target analyte combinations differ significantly, the separation and detection of the first and second target analyte combinations in each sample can be achieved by setting different types of chromatographic columns (such as hydrophilic columns and reverse-phase columns).
[0198] like Figure 20As shown, during the test, the first sample is first introduced into the first flow path, and the first target analyte combination is separated by the first chromatographic column. After detection by the detector, the first result of the first sample is obtained. Simultaneously, the second chromatographic column in the second flow path is flushed and equilibrated. Next, the same first sample is introduced into the second flow path, and the second target analyte combination is separated by the second chromatographic column. After detection by the detector, the second result of the first sample is obtained. Simultaneously, the first flow path is flushed and equilibrated. After the detection of the first sample is completed, the second sample is introduced into the first flow path, and its first target analyte combination is detected to obtain the first result of the second sample. Simultaneously, the second flow path is flushed and equilibrated. Then, the same second sample is introduced into the second flow path, and its second target analyte combination is detected to obtain the second result of the second sample. Simultaneously, the first flow path is flushed and equilibrated. After the detection is completed, the first and second results of the first sample are combined and output on one chromatogram, and the first and second results of the second sample are combined and output on another chromatogram. Thus, based on the two independent flow paths set up in parallel in the selective detection system of this utility model, continuous and quantitative testing of multiple samples can be achieved by sequentially and alternately injecting samples into the two independent flow paths. Furthermore, the detection results of each target analyte combination in each sample can be output to the same chromatogram. In contrast, the traditional detection method, using a single one-dimensional mass spectrometer to detect multiple samples, requires first detecting the first target analyte combination in the first sample using a first chromatographic column (e.g., a hydrophilic column), followed by cleaning and equilibration of the first column, and then injecting the second sample to detect the second target analyte combination. After completing the detection of the first target analyte combinations in the first and second samples, the second column (e.g., a reversed-phase column) is used, and after cleaning and equilibration of the tubing and the second column, the above steps are repeated to sequentially detect the second target analyte combinations in the first and second samples. Compared to the selective detection system of this utility model, the traditional one-dimensional mass spectrometry system for detecting multiple samples can only first focus on detecting the first target analyte combinations of all samples, and then focus on detecting the second target analyte combinations of all samples. As the number of samples to be tested increases, the waiting time for the same sample to be detected also increases. When there are hundreds or thousands of samples to be tested, for some special samples (such as blood samples), the sample may have already deteriorated while waiting for the detection of its second target analyte combination. Although using two sets of one-dimensional mass spectrometers to detect multiple samples can simultaneously detect the first and second target analyte combinations of the same sample, reducing cleaning and waiting time, the first and second results of the same sample are output on two different chromatograms, requiring complex data processing and increasing the analysis time.Therefore, compared with the traditional one-dimensional mass spectrometry detection system and two one-dimensional mass spectrometry detection systems, the selective detection system of this invention can perform continuous and quantitative high-throughput detection on a large number of samples with complex matrices and numerous target substances, shortening the overall detection cycle, improving the overall detection efficiency, and significantly reducing the subsequent data analysis time.
[0199] Compared with existing technologies, the selective detection system of this invention can achieve the following beneficial effects:
[0200] (1) For a large number of target substances in a sample, which are of different types and have different separation properties or mass spectrometry ionization properties, the target substances can be grouped according to their separation properties or mass spectrometry ionization properties to form different target substance combinations. By setting up independent flow paths corresponding to different target substance combinations and flexibly combining chromatographic columns and mobile phases, the optimal separation of each target substance combination can be achieved. With the selective acquisition of signals at the detector end, the optimal quantitative detection results can be obtained, thereby improving the accuracy of detection.
[0201] (2) By alternating the injection of different flow paths, the cleaning and equilibration time of the chromatographic column and the dead time of ineffective separation are reduced, which greatly improves the detection efficiency.
[0202] (3) Although the same sample is injected repeatedly, only one chromatogram is output in the end, and the target compound in the sample is collected only once. There is no redundant data collection, which makes data analysis easier, reduces analysis time, and helps improve the overall detection efficiency.
[0203] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to limit the embodiments of this application. The singular forms “a,” “the,” and “the” used in the embodiments and claims of this application are also intended to include the plural forms, unless the context clearly indicates otherwise. It should also be understood that, unless otherwise stated, “a plurality” means two or more; the terms “first,” “second,” “third,” etc., are used only to distinguish and not to describe a particular order or sequence, nor should they be construed as indicating or implying relative importance. The term “and / or” as used herein refers to and includes any or all possible combinations of one or more associated listed items. When the above description relates to drawings, unless otherwise indicated, the same numbers in different drawings represent the same or similar elements. In the description of this application, those skilled in the art can understand the specific meaning of the above terms in this application according to the specific circumstances.
[0204] The embodiments described above are merely examples of several implementations of this utility model, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the utility model patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this utility model, and these modifications and improvements all fall within the protection scope of this utility model.
Claims
1. A selective detection system, characterized in that: include: At least two parallel flow paths and one detector, each flow path including a push assembly, an injector and a chromatographic column, wherein the detector is connected to each flow path via a detection selector, wherein the detection selector is a switching valve or a selection valve having at least four ports; The first flow path includes a first push assembly for introducing and pushing a first mobile phase, a first injector for introducing a sample, and a first chromatographic column for retaining a first combination of target substances in the sample or simultaneously retaining a first and a second combination of target substances in the sample. The outlet of the first push assembly is connected to the inlet of the first injector, the outlet of the first injector is connected to the inlet of the first chromatographic column, and the outlet of the first chromatographic column is connected to the first port of the detection selector. The second flow path includes a second push assembly for introducing and pushing a second mobile phase, a second injector for introducing the same sample, and a second chromatographic column for retaining a second combination of target substances in the sample or simultaneously retaining a first and second combination of target substances in the sample. The outlet of the second push assembly is connected to the inlet of the second injector, the outlet of the second injector is connected to the inlet of the second chromatographic column, and the outlet of the second chromatographic column is connected to the second port of the detection selector. The detector is connected to the third port of the detection selector, and the fourth port of the detection selector is connected to the outside of the system; The detection selector can switch between two connection states via its different ports: Connection State 1: The detection connector connects the outlet of the first chromatographic column to the inlet of the detector, which is used to detect the first target analyte combination flowing out of the first chromatographic column; at the same time, the detection connector connects the outlet of the second chromatographic column to the outside of the system. Connection State 2: The detection connector connects the outlet of the second chromatographic column to the inlet of the detector, which is used to detect the second target analyte combination flowing out of the second chromatographic column; at the same time, the detection connector connects the outlet of the first chromatographic column to the outside of the system.
2. The selective detection system according to claim 1, characterized in that: The stationary phase of the first chromatographic column is different from that of the second chromatographic column; When the first target combination includes at least two first target compounds and the second target combination includes at least one second target compound, the first chromatographic column is configured such that the resolution between any two chromatographic peaks of the first target compounds in the sample is a first resolution, and the first resolution is ≥1.5; the resolution between any chromatographic peak of any first target compound and any chromatographic peak of any second target compound in the sample is a second resolution, and at least one second resolution is <1.
5. The second chromatographic column is configured to achieve a third resolution between any two chromatographic peaks of the second target analyte in the same sample, wherein the third resolution is ≥1.5; the second chromatographic column is configured to achieve a fourth resolution between any chromatographic peak of the second target analyte and any chromatographic peak of the first target analyte in the same sample, wherein at least one of the fourth resolutions is <1.
5.
3. The selective detection system according to claim 1, characterized in that: The stationary phase of the first chromatographic column is the same as that of the second chromatographic column.
4. A selective detection system, characterized in that: include: Two parallel flow paths and a detector, wherein the detector is connected to the two flow paths respectively via a detection selector, wherein the detection selector is a switching valve having at least four ports; The first flow path includes a first push component for introducing and pushing a first mobile phase and a first chromatographic column for retaining a first combination of target substances in a sample, the first chromatographic column being connected to the first push component via an injection selection component; The second flow path includes a second push assembly for introducing and pushing a second mobile phase and a second chromatographic column for retaining a second combination of target compounds in the sample, the second chromatographic column being connected to the second push assembly via an injection selection assembly; The sample selection assembly includes a sample selection element and a sample injector for introducing the sample, wherein the sample selection element is a switching valve having at least six ports; The inlet and outlet of the injector are respectively connected to the first port and the second port of the injection selector; The outlet of the first push component is connected to the third port of the injection selection element, the inlet of the first chromatographic column is connected to the fourth port of the injection selection element, and the outlet of the first chromatographic column is connected to the first port of the detection selection element. The outlet of the second push component is connected to the fifth port of the injection selection element, the inlet of the second chromatographic column is connected to the sixth port of the injection selection element, and the outlet of the second chromatographic column is connected to the second port of the detection selection element. The detector's inlet is connected to the third port of the detection selector, and the fourth port of the detection selector is connected to the outside of the system; The injection selector and the detection selector switch between two connection states via their respective ports: Connection State 1: The injection selection component connects the outlet of the first push component to the inlet of the injector, and connects the outlet of the injector to the inlet of the first chromatographic column; the detection selection component connects the outlet of the first chromatographic column to the inlet of the detector, the detector being used to detect the first target analyte combination flowing out of the first chromatographic column; simultaneously, the injection selection component connects the outlet of the second push component to the inlet of the second chromatographic column, and the detection selection component connects the outlet of the second chromatographic column to the outside of the system; Connection State 2: The injection selection component connects the outlet of the second push component to the inlet of the injector and the outlet of the injector to the inlet of the second chromatographic column. The detection selection component connects the outlet of the second chromatographic column to the inlet of the detector, which is used to detect the second target analyte combination flowing out of the second chromatographic column. At the same time, the injection selection component connects the outlet of the first push component to the inlet of the first chromatographic column, and the detection selection component connects the outlet of the first chromatographic column to the outside of the system.
5. The selective detection system according to claim 4, characterized in that: The stationary phase of the first chromatographic column is different from that of the second chromatographic column; When the first target combination includes at least two first target compounds and the second target combination includes at least one second target compound, the first chromatographic column is configured such that the resolution between any two chromatographic peaks of the first target compounds in the sample is a first resolution, and the first resolution is ≥1.5; the resolution between any chromatographic peak of any first target compound and any chromatographic peak of any second target compound in the sample is a second resolution, and at least one second resolution is <1.
5. The second chromatographic column is configured to achieve a third resolution between any two chromatographic peaks of the second target analyte in the same sample, wherein the third resolution is ≥1.5; the second chromatographic column is configured to achieve a fourth resolution between any chromatographic peak of the second target analyte and any chromatographic peak of the first target analyte in the same sample, wherein at least one of the fourth resolutions is <1.
5.
6. A selective detection system, characterized in that: include: Two parallel flow paths and a detector, wherein the detector is connected to the two flow paths respectively via a detection selector, wherein the detection selector is a switching valve having at least four ports; The first flow path includes a first push assembly for introducing and pushing a first mobile phase, and a first chromatographic column for retaining a combination of first and second target analytes in the sample, the first chromatographic column being connected to the first push assembly via an injection selection assembly; The second flow path includes a second push assembly for introducing and pushing a second mobile phase, and a second chromatographic column for retaining the combination of the first and second target analytes in the sample, the second chromatographic column being connected to the second push assembly via an injection selection assembly; The sample selection assembly includes a sample selection element and a sample injector for introducing the sample, wherein the sample selection element is a switching valve having at least six ports; The inlet and outlet of the injector are respectively connected to the first port and the second port of the injection selector; The outlet of the first push component is connected to the third port of the injection selection element, the inlet of the first chromatographic column is connected to the fourth port of the injection selection element, and the outlet of the first chromatographic column is connected to the first port of the detection selection element. The outlet of the second push component is connected to the fifth port of the injection selection element, the inlet of the second chromatographic column is connected to the sixth port of the injection selection element, and the outlet of the second chromatographic column is connected to the second port of the detection selection element. The detector's inlet is connected to the third port of the detection selector, and the fourth port of the detection selector is connected to the outside of the system; The sample injection selector and the detection selector are connected to their respective ports, allowing switching between the following four connection states: Connection State 1: The injection selection component connects the outlet of the first push component to the inlet of the injector and the outlet of the injector to the inlet of the first chromatographic column; the detection selection component connects the outlet of the first chromatographic column to the inlet of the detector; simultaneously, the injection selection component connects the outlet of the second push component to the inlet of the second chromatographic column, and the detection selection component connects the outlet of the second chromatographic column to the outside of the system. Connection State 2: The injection selection device connects the outlet of the first push component to the inlet of the first chromatographic column, and the detection selection device connects the outlet of the first chromatographic column to the inlet of the detector, the detector being used to detect the first target analyte combination flowing out of the first chromatographic column; simultaneously, the injection selection device connects the outlet of the second push component to the inlet of the injector, and connects the outlet of the injector to the inlet of the second chromatographic column, and the detection selection device connects the outlet of the second chromatographic column to the outside of the system; Connection State 3: The injection selection component connects the outlet of the second push component to the inlet of the injector, and connects the outlet of the injector to the inlet of the second chromatographic column; the detection selection component connects the outlet of the second chromatographic column to the inlet of the detector; simultaneously, the injection selection component connects the outlet of the first push component to the inlet of the first chromatographic column, and connects the outlet of the first chromatographic column to the outside of the system. Connection State 4: The injection selection device connects the outlet of the second push component to the inlet of the second chromatographic column, and the detection selection device connects the outlet of the second chromatographic column to the inlet of the detector. The detector is used to detect the second target analyte combination flowing out of the second chromatographic column. At the same time, the injection selection device connects the outlet of the first push component to the inlet of the injector and connects the outlet of the injector to the inlet of the first chromatographic column. The detection selection device connects the outlet of the first chromatographic column to the outside of the system.
7. The selective detection system according to claim 6, characterized in that: The stationary phase of the first chromatographic column is the same as that of the second chromatographic column.
8. A selective detection system, characterized in that: include: Two parallel flow paths and a detector, wherein the detector is connected to the two flow paths respectively through an injection detection selection component; The first flow path includes a first push component for introducing and pushing a first mobile phase and a first chromatographic column for retaining a first combination of target analytes in a sample, the first chromatographic column being connected to the first push component via the injection detection selection component; The second flow path includes a second push assembly for introducing and pushing a second mobile phase and a second chromatographic column for retaining a second combination of target compounds in the sample, the second chromatographic column being connected to the second push assembly via the injection detection selection assembly; The sample introduction detection selection component includes a sample introduction detection selector and a sample injector for introducing the sample, wherein the sample introduction detection selector is a switching valve having at least ten ports; The inlet and outlet of the injector are respectively connected to the first port and the second port of the injection detection selector; The outlet of the first push component is connected to the third port of the injection detection selector, and the two ends of the first chromatographic column are connected to the fourth and fifth ports of the injection detection selector, respectively. The outlet of the second push component is connected to the sixth port of the injection detection selector, and the two ends of the second chromatographic column are connected to the seventh and eighth ports of the injection detection selector, respectively. The detector's inlet is connected to the ninth port of the sample injection detection selector, and the tenth port of the sample injection detection selector is connected to the outside of the system; The sample injection detection selector can switch between two connection states by connecting to different ports: Connection State 1: The injection detection selector connects the outlet of the first push component to the inlet of the injector, connects the outlet of the injector to one port of the first chromatographic column, and connects the other port of the first chromatographic column to the inlet of the detector, the detector being used to detect the first target analyte combination flowing out of the first chromatographic column; the injection detection selector connects the outlet of the second push component to one port of the second chromatographic column, and connects the other port of the second chromatographic column to the outside of the system; Connection State 2: The injection detection selector connects the outlet of the second push component to the inlet of the injector, connects the outlet of the injector to one port of the second chromatographic column, and connects the other port of the second chromatographic column to the inlet of the detector, the detector being used to detect the second target analyte combination flowing out of the second chromatographic column; the injection detection selector connects the outlet of the first push component to one port of the first chromatographic column, and connects the other port of the first chromatographic column to the outside of the system.
9. The selective detection system according to claim 8, characterized in that: The stationary phase of the first chromatographic column is different from that of the second chromatographic column; When the first target combination includes at least two first target compounds and the second target combination includes at least one second target compound, the first chromatographic column is configured such that the resolution between any two chromatographic peaks of the first target compounds in the sample is a first resolution, and the first resolution is ≥1.5; the resolution between any chromatographic peak of any first target compound and any chromatographic peak of any second target compound in the sample is a second resolution, and at least one second resolution is <1.
5. The second chromatographic column is configured to achieve a third resolution between any two chromatographic peaks of the second target analyte in the same sample, wherein the third resolution is ≥1.5; the second chromatographic column is configured to achieve a fourth resolution between any chromatographic peak of the second target analyte and any chromatographic peak of the first target analyte in the same sample, wherein at least one of the fourth resolutions is <1.
5.
10. The selective detection system according to claim 8 or 9, characterized in that: The sample injection detection selector is a ten-way switching valve.