CN218938207U - Online multi-step diluted solid phase extraction-liquid phase chromatography two-dimensional separation system - Google Patents

Abstract

The utility model discloses an online multi-step dilution solid-phase extraction-liquid chromatography two-dimensional separation system, which comprises: the device comprises a sample loading device, a solid phase extraction column, a mixer, a pump system and an analysis column; the number of mixers is not less than 2; one or more mixers are respectively connected between the sample loading device and the solid phase extraction column and between the solid phase extraction column and the analysis column, and the one or more mixers are connected with a pump system; the liquid can be injected into the mixer by a pump system such that the solution entering through the loading device or flowing into the mixer through the solid phase extraction column is diluted. The system can effectively solve the problem of solvent effect frequently encountered by a solid phase extraction column and an analysis column in a two-dimensional separation system, improve the peak type of an object to be detected and improve the sensitivity.

Description

Online multi-step diluted solid phase extraction-liquid phase chromatography two-dimensional separation system

Technical Field

The utility model relates to the technical field of high performance liquid chromatography, in particular to an online multi-step dilution solid-phase extraction-liquid chromatography two-dimensional separation system.

Background

Solid Phase Extraction (SPE) is a technique used to rapidly and selectively prepare and purify samples prior to chromatographic analysis, and is mainly used to replace sample matrix, concentrate analytes, remove interfering components and contaminants, thereby reducing sample matrix interference and improving detection sensitivity. Among the most commonly used are adsorption-elution SPEs, i.e. capturing the target analyte by means of an adsorbent, letting the matrix interfering components pass through a small column, and eluting the target by means of an eluting solution for subsequent analysis. The SPE is further divided into an off-line type and an on-line type, the on-line type SPE has high automation degree, is not dependent on manual operation, and can realize rapid, efficient and stable separation and detection of target analytes in complex matrix samples by combining with High Performance Liquid Chromatography (HPLC). A typical online SPE use process includes the steps of: activation equilibration-loading capture-desalting de-interference-elution-regeneration activation.

In a two-dimensional liquid chromatography (SPE 2 DLC) system in which SPE and HPLC are combined, a target analyte captured by an SPE column is purified and eluted to a downstream analysis column by switching a valve. Since SPE elution solutions typically contain a relatively high proportion of organic phase, such as 40% acetonitrile/methanol, etc., when eluted on-line, the target analyte does not remain well on the downstream analytical column, and the presence of solvent effects can cause the target analyte chromatographic peak to diffuse or generate multiple chromatographic peaks, thereby affecting quantitative analysis. In addition, in the pretreatment process of complex matrix samples, such as common protein precipitation treatment, the treatment solution often contains a higher proportion of organic phase, and when the sample is directly loaded, the target analyte is also not well retained on an SPE column, so that the subsequent quantitative analysis of the target analyte is influenced.

Disclosure of Invention

Aiming at the problems, the utility model provides an online multi-step diluted solid-phase extraction-liquid chromatography two-dimensional separation (ACD-SPE 2 DLC) system, which can well eliminate the solvent effect introduced by a high organic phase of a sample solution and the solvent effect introduced by SPE online elution, and solves the solvent effect problem encountered by an online SPE method.

The utility model aims at solving the problems through the following technical scheme:

the application provides an ACD-SPE2DLC system, wherein the system comprises: the device comprises a sample loading device, a solid phase extraction column, a mixer, a pump system and an analysis column;

the number of mixers is not less than 2; one or more mixers are respectively connected between the sample loading device and the solid phase extraction column and between the solid phase extraction column and the analysis column, and the one or more mixers are connected with a pump system; the liquid can be injected into the mixer by a pump system such that the solution entering the mixer between the solid phase extraction column and the analytical column through the loading device or the solution flowing into the mixer between the solid phase extraction column and the analytical column through the solid phase extraction column is diluted.

In some modes, a mixer is respectively connected between the sample loading device and the solid phase extraction column, and a mixer between the solid phase extraction column and the analysis column is denoted as a mixer a, and a mixer between the solid phase extraction column and the analysis column is denoted as a mixer b.

Further, the system also comprises a six-way valve B; the six-way valve B is sequentially provided with a first valve port B1, a second valve port B2, a third valve port B3, a fourth valve port B4, a fifth valve port B5 and a sixth valve port B6; the solid phase extraction column is connected between the first valve port B1 and the fifth valve port B5; the mixer (or mixer a) between the sample loading device and the solid phase extraction column is connected with the second valve port B2.

Preferably, a eluting ring is connected between the third valve port B3 and the fourth valve port B4; the eluting loop is used for storing the eluent.

In some aspects, the system further comprises a six-way valve C; the six-way valve C is sequentially provided with a first valve port C1, a second valve port C2, a third valve port C3, a fourth valve port C4, a fifth valve port C5 and a sixth valve port C6; the first valve port C1 is connected with a waste liquid pipeline; the second valve port C2 is connected with the sixth valve port B6; a third valve C3 is connected to the mixer (or mixer b) between the solid phase extraction column and the analytical column; the fourth valve port C4 is sealed with a plug.

Preferably, the pump system is a binary pump system; the binary pump system comprises a binary pump system P1 and a binary pump system P2; one pump of the binary pump system P1 is connected with the loading device, and the other pump is connected with a mixer (or a mixer) between the loading device and the solid-phase extraction column.

In some aspects, the system further comprises a mixer c to which both pumps of the binary pump system P2 are connected; a mixer c is connected with a mixer (or a mixer b) between the solid phase extraction column and the analysis column; the solutions pumped by the two pumps of the binary pump system P2 can be mixed in mixer c and further to the mixer between the solid phase extraction column and the analytical column (or mixer b).

In some aspects, the loading device comprises: a six-way valve A, a loading syringe and a loading ring; the six-way valve A is sequentially provided with a first valve port A1, a second valve port A2, a third valve port A3, a fourth valve port A4, a fifth valve port A5 and a sixth valve port A6; the loading injector is connected with a third valve A3; the sample loading ring is connected between the first valve port A1 and the fourth valve port A4; the second valve port A2 is connected with a waste liquid pipe; the sixth valve port A6 is connected with the mixer a; the fifth port A5 is connected to one pump of the binary pump system P1.

In some aspects, the sixth port A6 is connected to a mixer (or mixer a) between the loading device and the solid phase extraction cartridge.

In some embodiments, one pump of binary pump system P1 is connected to fifth port A5 and the other pump is connected to a mixer (or mixer a) between the loading device and the solid phase extraction column.

Downstream of the analytical column is connected a detector. The detector may be one or more of an ultraviolet detector (UV), a Diode Array Detector (DAD), an Evaporative Light Scattering Detector (ELSD), a mass spectrometry detector (MS), an electrospray detector (CAD), a fluorescence detector (FID).

The utility model has the advantages that: the utility model provides an online multi-step diluted solid-phase extraction-liquid chromatography two-dimensional separation (ACD-SPE 2 DLC) system which effectively solves the solvent effect problem encountered by an online SPE column and an analytical column while guaranteeing the online enrichment or separation of the solid-phase extraction column (SPE column) and the analytical column.

Drawings

FIG. 1 is a schematic diagram of the ACD-SPE2DLC system of example 1 of the present utility model ((1));

FIG. 2 is a schematic diagram of the ACD-SPE2DLC system of example 1 in a second step ((2));

FIG. 3 is a schematic diagram of the ACD-SPE2DLC system of example 1 when performing the third step ((3));

FIG. 4 is a schematic diagram of the ACD-SPE2DLC system of example 1 in the fourth step ((4));

FIG. 5 conditions such as gradient, flow rate, etc. for the detection of IGF-1 by the ACD-SPE2DLC system of example 1;

FIG. 6 TIC and XIC graphs of the ACD-SPE2DLC System of example 1 for IGF-1 detection

FIG. 7 is a schematic diagram of the ACD-SPE2DLC system of comparative example 1;

FIG. 8 TIC and XIC graphs of the ACD-SPE2DLC system of comparative example 1 detecting IGF-1;

FIG. 9 is a schematic diagram of the ACD-SPE2DLC system of comparative example 2;

FIG. 10 TIC and XIC graphs of the ACD-SPE2DLC system of comparative example 2 for IGF-1;

FIG. 11 is a schematic diagram of the ACD-SPE2DLC system of comparative example 3;

FIG. 12 TIC and XIC graphs of the ACD-SPE2DLC system of comparative example 3 detecting IGF-1;

FIG. 13 peak areas for IGF-1 were measured for example 1 and comparative examples 1-3, 1: examples 1,2: comparative examples 1,3: comparative examples 2,4: comparative example 3.

Detailed Description

The utility model is further described below with reference to the drawings and examples. It should be noted that the embodiments are only detailed description of the present utility model, and not intended to limit the scope of the present utility model, and all the features disclosed in the embodiments of the present utility model, or all the steps in the methods or processes disclosed, except mutually exclusive features and/or steps, can be combined in any way, and are within the scope of the present utility model. The technology not related to the utility model can be realized by the prior art.

An on-line multi-step diluted solid phase extraction-liquid chromatography two-dimensional separation (ACD-SPE 2 DLC) system, see fig. 1, comprising: a loading device 1, a solid phase extraction column (SPE column) 2, a mixer, a pump system and an analytical column 3. The mixer includes: mixer a, mixer b. The mixer a is located between the loading device 1 and the SPE column 2, when the solution, such as sample solution, entering from the loading device 1 reaches the mixer a, and the pump system supplies the diluting liquid to the mixer a, the sample solution is diluted, so that the proportion of organic phase in the sample solution can be reduced, the proportion of organic phase in the solution entering the SPE column 2 subsequently can be reduced, and the solvent effect can be reduced or eliminated. Mixer b is located between SPE column 2 and analytical column 3, and the solution likewise exiting the SPE column can be diluted in mixer b. For example, the solution flowing out of the SPE column generally contains a relatively high proportion of organic phase (e.g. 40% acetonitrile), and if the solution directly enters the downstream analysis column 3, a solvent effect is easily generated, so that the chromatographic peak of the target analyte diffuses or generates a plurality of chromatographic peaks to influence the separation or detection effect, and the proportion of the organic phase can be reduced through the mixer b, so that the solvent effect is avoided.

In some modes, the system comprises a six-way valve B, wherein a first valve port B1, a second valve port B2, a third valve port B3, a fourth valve port B4, a fifth valve port B5 and a sixth valve port B6 are sequentially arranged on the six-way valve B; the SPE column 2 is connected between the first valve port B1 and the fifth valve port B5; the mixer a is connected with the second valve port B2. The connection between adjacent valve ports of the six-way valve can be switched.

Preferably, an eluting ring 4 is connected between the third valve port B3 and the fourth valve port B4, the eluting ring 4 is used for storing an eluent to realize rapid elution of a target analyte on the SPE column, and a liquid storage process of the eluting ring 4 and a process of storing liquid in the eluting ring to elute the SPE column 2 can be realized through valve switching. The volume of the eluting ring 4 may be 100. Mu.L, or may be 50. Mu.L, 150. Mu.L, 200. Mu.L, etc., and may be specifically adjusted according to the line volume of the system and the sample to be analyzed.

In some modes, the system further comprises a six-way valve C, wherein a first valve port C1, a second valve port C2, a third valve port C3, a fourth valve port C4, a fifth valve port C5 and a sixth valve port C6 are sequentially arranged on the six-way valve C; the first valve port C1 is connected with a waste liquid pipeline; the second valve port C2 is connected with the sixth valve port B6; the third valve C3 is connected to the mixer b. The solution flowing into the six-way valve C can be made to flow to the waste liquid or to the downstream mixer b by valve switching. The fourth port C4 is sealed with a plug to ensure that there is no branching flow path for liquid from the pump system into mixer b as analysis pump P2 elutes the analytical column.

In some aspects, the pump system is a binary pump system; the binary pump system comprises a binary pump system P1 and a binary pump system P2; one pump P11 of the binary pump system P1 is connected to the loading device 1 and the other pump P12 is connected to the mixer a. The pump P11 brings the liquid into the loading device 1 and brings the sample of the loading device 1 into the mixer a downstream. Pump P12 causes liquid to enter mixer a, thereby diluting the sample solution entering mixer a.

It should be noted that, the components contained in the sample solution tend to be complex, in which components with poor water solubility may be present, and components with poor fat solubility may be present, if the pump P11 pumps directly into a high proportion of the aqueous phase or the organic phase, components with poor fat solubility (such as a high salt system) or components with poor water solubility in the sample solution may be precipitated when the aqueous phase or the organic phase is contacted with the sample solution, and the pipeline of the loading device 1 tends to be relatively fine, which may often cause clogging of the loading device 1. Therefore, it is preferable that the liquid pumped by the pump P11 into the loading device 1 has a similar composition or polarity to the sample solution to prevent precipitation problems that may exist. On this basis, the liquid pumped by pump P11 dilutes the sample solution and when reaching mixer a, the higher proportion of the aqueous or organic phase pumped by pump P12 does not lead to precipitation of components in the sample solution. Besides the primary dilution of the sample solution, the volume of the mixer a is larger, so that the liquids entering through the two channels can be fully mixed, the possibility of component precipitation is further reduced, and meanwhile, even if micro components are separated, the mixer a is not blocked. Therefore, the above-mentioned two-component pump system P1, the loading device 1, and the mixer a can effectively avoid the clogging problem while diluting the sample solution or reducing the organic phase in the sample solution.

In some aspects, the system further comprises a mixer c to which both pumps of the binary pump system P2 are connected; the mixer c is connected with the mixer b; the solutions pumped by the two pumps of the binary pump system P2 can be mixed in mixer c and further to mixer b.

In some embodiments, the loading device 1 comprises: a six-way valve A, a loading injector 11, a loading ring 12 and a loading needle 13; the six-way valve A is sequentially provided with a first valve port A1, a second valve port A2, a third valve port A3, a fourth valve port A4, a fifth valve port A5 and a sixth valve port A6; the loading injector 11 is connected with a third valve A3; the loading ring 12 is connected between the first valve port A1 and the fourth valve port A4; the front end of the sampling ring 12 is connected with a sampling needle 13; the second valve port A2 is connected with a waste liquid pipe. When the third valve port A3 is connected with the fourth valve port A4, the first valve port A1 is connected with the second valve port A2, and the fifth valve port A5 is connected with the sixth valve port A6. At this time, the sample injector 11 injects the sample solution, and the sample solution reaches the fourth port A4 from the third port A3, enters the sample loading ring 12, and is stored in the sample loading ring 12. When switching to the connection of the second valve port A2 and the third valve port A3, the connection of the fourth valve port A4 and the fifth valve port A5 and the connection of the first valve port A1 and the sixth valve port A6, the pump P11 pumps liquid to drive the sample solution in the sample loading ring 12 to sequentially reach the sample loading needle 13, the first valve port A1, the sixth valve port A6 and the mixer a.

Further, the analytical column 3 is connected to a detector 5, and the solution is separated by the analytical column and reaches the detector, so that the target analyte is detected. The detector includes: ultraviolet detector (UV), diode Array Detector (DAD), evaporative Light Scattering Detector (ELSD), mass spectrometry detector (MS), electrospray detector (CAD), fluorescence detector (FID).

The following are preferred embodiments of the utility model and related comparative studies.

Example 1 an on-line multistep dilution solid phase extraction-liquid chromatography two-dimensional separation (ACD-SPE 2 DLC) system and application

1. ACD-SPE2DLC system

FIG. 1 shows an ACD-SPE2DLC system provided by the utility model. The system comprises: the sample loading device 1, the mixer a, the six-way valve B, SPE column 2, the six-way valve C, the mixer b, the analysis column 3, the detector 5, the binary pump system P1, the binary pump system P2 and the mixer C. The loading device 1 includes: a six-way valve A, a loading injector 11, a loading ring 12 and a loading needle 13; the six-way valve A is sequentially provided with a first valve port A1, a second valve port A2, a third valve port A3, a fourth valve port A4, a fifth valve port A5 and a sixth valve port A6; the loading injector 11 is connected with a third valve A3; the loading ring 12 is connected between the first valve port A1 and the fourth valve port A4; the front end of the sampling ring 12 is connected with a sampling needle 13; the second valve port A2 is connected with a waste liquid pipe. One pump P11 of the binary pump system P1 is connected to the fifth port A5 of the six-way valve a, and the other pump P12 is connected to the mixer a. The six-way valve B is sequentially provided with a first valve port B1, a second valve port B2, a third valve port B3, a fourth valve port B4, a fifth valve port B5 and a sixth valve port B6; the SPE column 2 is connected between the first valve port B1 and the fifth valve port B5; the mixer a is connected with the second valve port B2; an eluting ring 4 is connected between the third valve port B3 and the fourth valve port B4, and the volume of the eluting ring 4 is 100 mu L. The six-way valve C is sequentially provided with a first valve port C1, a second valve port C2, a third valve port C3, a fourth valve port C4, a fifth valve port C5 and a sixth valve port C6; the first valve port C1 is connected with a waste liquid pipeline; the second valve port C2 is connected with the sixth valve port B6; the third valve C3 is connected with the mixer b; the fourth valve port C4 is sealed with a plug. Both pumps (pumps P21 and P22) of the binary pump system P2 are connected to a mixer c, downstream of which is connected to a mixer b, which is connected to an analytical column 3, downstream of which is connected to a detector 5. The detector 5 is a mass spectrometric detector.

In order to clearly clarify the working principle of the ACD-SPE2DLC system, the following description is made by dividing the specific working process into four steps:

(1) sample loading desalination (figure 1)

The loading pump uses a column head dilution (ACD) to deliver the mobile phase, pump P12 is an aqueous phase pump and pump P11 is an organic phase. When the initial gradient of the loading pump is set to 10% of the organic phase, i.e. the volume ratio of the organic phase of pump P11 to the aqueous phase of pump P12 is 1:9, 10 times of on-line aqueous phase dilution can be achieved in mixer a. If the initial gradient of the pump P11 is set to be 5% of the organic phase, 20 times of online water phase dilution can be realized, so that online dilution loading can be realized without sacrificing the absolute loading amount of a sample to be detected, and the solvent effect of loading can be eliminated for a sample with dissolved organic phase, thereby enhancing the retention of analytes to be detected on an SPE column. The SPE column 2 with lower back pressure is selected, so that the flow rate of the loading pump (such as >1.0 ml/min) is increased, the total analysis time can be shortened, and the analysis efficiency is improved. If the back pressure of SPE cartridge 2 is high, the flow rate of the loading pump is not high (e.g., <0.4 ml/min), the initial gradient setting of the loading pump and the tubing volume before the pump P11 pump head to SPE cartridge 2 are considered to set the loading period time reasonably. The time set of loading was such that the sample was guaranteed to be transferred to SPE column 2 for retention and desalted with a high water phase. At this point the initial gradient of the P1 pump was set to 5% organic phase to equilibrate the analytical column and six-way valves B and C were set to 1-2 connections (Load).

(2) SPE cartridge 2 elution on-line dilution (FIG. 2)

Six-way valves B and C are switched to 1-6 (reject), the loading pump flushes the eluting solution pre-stored on eluting loop 4 of six-way valve B onto SPE cartridge 2 at a low flow rate (e.g., 0.125 ml/min), eluting the analyte under test, and pump P2 delivers the high water phase to mixer B at a higher flow rate (e.g., 0.275 ml/min) relative to pump P1, where the eluting solution of SPE cartridge 2 is diluted in line and the analyte under test is delivered to analytical cartridge 3 for retention.

(3) Eluting with 4, replenishing, eluting with 3 (figure 3)

The six-way valve B remains connected (reject) 1-6, the six-way valve C switches back to connected (Load) 1-2, and the loading pump delivers the eluent needed for the next elution of SPE cartridge 2 to the eluting loop 4 for storage. The purpose of the elution loop 4 is to elute the target analyte from the SPE cartridge 2 as quickly as possible to reduce analysis time. At the same time, pump P2 begins gradient elution to separate the target analyte on analytical column 3.

(4) SPE cartridge 2 regeneration, analytical cartridge 3 elution, washing and activation (FIG. 4)

Six-way valve B switches back to 1-2 connection (Load), six-way valve C continues to hold 1-2 connection (Load), pump P1 runs the regeneration gradient at a high flow rate to fully elute SPE column 2, while pump P2 also runs the elution flush gradient to activate analytical column 3.

When the ACD-SPE2DLC system works, the parameters such as valve switching and a pump system can be set, so that the synchronization or coordination of the processes of retaining, eluting and separating a sample solution on the SPE column 2 and the analysis column 3, regenerating or activating the SPE column 2 and the analysis column 3 and the like can be skillfully realized on the basis of carrying out multiple on-line dilution, namely the solvent effect problem faced by the SPE column 2 and the analysis column 3 is solved, the analysis time is greatly saved, and the efficiency of the ACD-SPE2DLC system is improved.

2. Detection of IGF-1 by ACD-SPE2DLC System

IGF-1 (insulin-like growth factors-1, insulin growth factor 1) samples were tested using the ACD-SPE2DLC system of FIG. 1.

The pump flow rate and gradient and valve switching setting of the ACD-SPE2DLC system is schematically shown in FIG. 5. The conditions are obtained by the inventor through experimental optimization for a plurality of times, under the conditions, IGF-1 can achieve the best separation effect, and SPE column 2 and analytical column 3 can be regenerated or activated well.

About 200ng/ml IGF-1.1% aqueous FA solution was prepared by dissolving IGF-1 with 0.1% aqueous FA (fomic acid, formic acid), and designated as sample solution 1. About 200ng/ml IGF-1 80% acetonitrile solution was prepared by dissolving IGF-1 with 80% acetonitrile and was designated as sample solution 2. Sample solution 1 and sample solution 2 were injected into the ACD-SPE2DLC system, respectively, the sample injection amounts were 20. Mu.L, and analyzed under the conditions set in FIG. 5, and the obtained chromatograms were shown in FIG. 6. TIC (Total ion chromatogram) is the total ion flow chromatogram; XIC, EIC (Extracted ion chromatogram), is an extracted ion flow chromatogram of IGF-1.

Comparative example 1

As shown in fig. 7, the mixer a is eliminated, and the other structures are the same as in example 1; and sample solution 1 and sample solution 2 were examined under the conditions of example 1, and the obtained TIC pattern and the EIC pattern of IGF-1 were as shown in FIG. 8.

Comparative example 2

As shown in fig. 9, the mixer b is eliminated, and the other structures are the same as those of embodiment 1; and sample solution 1 and sample solution 2 were examined under the conditions of example 1, and the obtained TIC pattern and the EIC pattern of IGF-1 were as shown in FIG. 10.

Comparative example 3

As shown in fig. 11, the mixer a and the mixer b are omitted, and other structures are the same as those of embodiment 1; and sample solution 1 and sample solution 2 were examined under the conditions of example 1, and the obtained TIC pattern and the EIC pattern of IGF-1 were as shown in FIG. 12.

Peak areas of IGF-1 measured in example 1 and comparative examples 1 to 3 are shown in fig. 13.

As is clear from the above results, the ACD-SPE2DLC system of example 1 shows that the TIC pattern obtained by detecting IGF-1 and the XIC pattern of IGF-1 show the best peak pattern of IGF-1 (peak to be measured) without solvent effect, regardless of whether the solvent of the sample to be measured is an aqueous phase system or a high organic phase system. The peaks in comparative examples 1-3 were poorly formed, and particularly the IGF-1 peaks in comparative examples 2 and 3 were significantly branched and tailing, with severe solvent effects. In addition, the peak height of the IGF-1 peak of example 1 is highest, especially when IGF-1 is dissolved with 80% acetonitrile, and the peak height of the XIC pattern of example 1IGF-1 is significantly higher than that of comparative examples 1-3; meanwhile, the peak area of IGF-1 peak of example 1 is also the largest, which shows that the ACD-SPE2DLC system of example 1 has higher response value and higher sensitivity, and the system is more suitable for detecting micro samples or micro components.

The ACD-SPE2DLC system of the embodiment 1 has no solvent effect, can obviously improve the peak area of an object to be detected, effectively solves the problem that the solvent effect is caused by the existence of a high organic phase in the online solid phase extraction-high efficiency chromatography combined technology, and simultaneously improves the sensitivity.

Claims (10)

1. An on-line multi-step diluted solid-phase extraction-liquid chromatography two-dimensional separation system, comprising: the device comprises a sample loading device, a solid phase extraction column, a mixer, a pump system and an analysis column;

the number of mixers is not less than 2; one or more mixers are respectively connected between the sample loading device and the solid phase extraction column and between the solid phase extraction column and the analysis column, and the one or more mixers are connected with a pump system; the liquid can be injected into the mixer by the pump system such that the solution passing through the loading device into the mixer between the loading device and the solid phase extraction column or the solution passing through the solid phase extraction column and then into the mixer between the solid phase extraction column and the analytical column is diluted.

2. The system of claim 1, wherein a mixer is connected between the loading device and the solid phase extraction column and between the solid phase extraction column and the analytical column, respectively.

3. The system according to claim 1 or 2, characterized in that it further comprises a six-way valve B; the six-way valve B is sequentially provided with a first valve port B1, a second valve port B2, a third valve port B3, a fourth valve port B4, a fifth valve port B5 and a sixth valve port B6; the solid phase extraction column is connected between the first valve port B1 and the fifth valve port B5; the mixer between the sample loading device and the solid phase extraction column is connected with the second valve port B2.

4. The system of claim 3, wherein a elution ring is connected between the third port B3 and the fourth port B4.

5. A system according to claim 3, further comprising a six-way valve C; the six-way valve C is sequentially provided with a first valve port C1, a second valve port C2, a third valve port C3, a fourth valve port C4, a fifth valve port C5 and a sixth valve port C6; the first valve port C1 is connected with a waste liquid pipeline; the second valve port C2 is connected with the sixth valve port B6; the third valve C3 is connected with a mixer between the solid phase extraction column and the analysis column; the fourth valve port C4 is sealed with a plug.

6. The system of claim 2, wherein the pump system is a binary pump system; the binary pump system comprises a binary pump system P1 and a binary pump system P2; one pump of the binary pump system P1 is connected with a loading device, and the other pump is connected with a mixer between the loading device and the solid-phase extraction column.

7. The system of claim 6, further comprising a mixer c; both pumps of the binary pump system P2 are connected to the mixer c; the mixer c is connected with a mixer between the solid phase extraction column and the analysis column; the solutions pumped by the two pumps of the binary pump system P2 can be mixed in mixer c and further reach the mixer between the solid phase extraction column and the analytical column.

8. The system of claim 1, wherein the loading device comprises: a six-way valve A, a loading injector, a loading ring and a loading needle; the six-way valve A is sequentially provided with a first valve port A1, a second valve port A2, a third valve port A3, a fourth valve port A4, a fifth valve port A5 and a sixth valve port A6; the loading injector is connected with a third valve A3; the sample loading ring is connected between the first valve port A1 and the fourth valve port A4; the sample loading needle is positioned at the front end of the sample loading ring; the second valve port A2 is connected with a waste liquid pipe.

9. The system of claim 8, wherein a sixth port A6 and a mixer connection between the loading device and the solid phase extraction cartridge.

10. The system of claim 7, wherein the loading device comprises: a six-way valve A, a loading injector, a loading ring and a loading needle; the six-way valve A is sequentially provided with a first valve port A1, a second valve port A2, a third valve port A3, a fourth valve port A4, a fifth valve port A5 and a sixth valve port A6; the loading injector is connected with a third valve A3; the sample loading ring is connected between the first valve port A1 and the fourth valve port A4; the sample loading needle is positioned at the front end of the sample loading ring; the second valve port A2 is connected with a waste liquid pipe; the sixth valve port A6 is connected with a mixer between the sample loading device and the solid-phase extraction column; one pump of the binary pump system P1 is connected with the fifth valve port A5, and the other pump is connected with a mixer between the loading device and the solid-phase extraction column.

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