CN109225171B - Preparation method and application of surface ion imprinted polymer modified organic-inorganic hybrid monolithic column - Google Patents

Preparation method and application of surface ion imprinted polymer modified organic-inorganic hybrid monolithic column Download PDF

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CN109225171B
CN109225171B CN201811144884.2A CN201811144884A CN109225171B CN 109225171 B CN109225171 B CN 109225171B CN 201811144884 A CN201811144884 A CN 201811144884A CN 109225171 B CN109225171 B CN 109225171B
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胡斌
欧孝笑
陈贝贝
何蔓
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Wuhan University WHU
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Abstract

The invention discloses a preparation method and application of a surface ion imprinted polymer modified organic-inorganic hybrid monolithic column. Preparing a polymethyl trimethoxy silane organic-inorganic hybrid monolithic column by adopting an in-situ polymerization mode, and then synthesizing Gd on the surface of the monolithic column in situ by modifying a double-bond functional group on the siloxy surface of the monolithic column3+The polymer is imprinted on the surface and embedded into a microfluidic chip channel, an integrated column capillary micro-extraction array chip is prepared by combining the design of an array gas valve, the chip is used for separating and enriching Gd elements in complex samples, the online analysis of the Gd elements in human urine and serum can be realized, the adsorption capacity (3.5 times), selectivity and sample flux of the chip on the Gd elements are obviously improved, and the integrated column capillary micro-extraction array chip has the advantages of high sensitivity, high automation, low sample consumption, strong matrix interference resistance, high analysis speed and the like.

Description

Preparation method and application of surface ion imprinted polymer modified organic-inorganic hybrid monolithic column
Technical Field
The invention belongs to the technical field of separation and analysis detection, and particularly relates to a preparation method of a surface ion imprinted polymer modified organic-inorganic hybrid monolithic column, and the column is used for carrying out online analysis and detection on trace Gd by being combined with inductively coupled plasma mass spectrometry.
Background
Gadolinium (Gd), which is a rare earth element, is widely used in the fields of magnetic resonance imaging, drug therapy, steel production, petroleum refining, etc. by virtue of its excellent optical, electrical, magnetic properties, etc., Gd is widely used, so that it inevitably accumulates in the environment and enters the human body through drinking water and food chain. Studies have shown that Gd accumulation in humans may cause damage to brain nerves, decreased mental capacity, organ failure, etc., especially in patients with renal dysfunction. Therefore, the method has important significance for detecting trace Gd in human bodies.
Inductively coupled plasma mass spectrometry (ICP-MS) is considered as a powerful means for element analysis due to the characteristics of high sensitivity, wide linear range, capability of simultaneously detecting multiple elements and the like. However, when ICP-MS is used for direct analysis of trace amounts of Gd in biological samples, there is still an elemental concentration (sub ng. L) in the sample-1Level) is lower than the detection limit of the instrument, and the sample matrix is too complex, thereby affecting the accuracy of the detection result. Therefore, it is often necessary to supplement the assay with appropriate sample pretreatment techniques to remove the matrix, isolate and enrich for the analyte of interest. The sample pretreatment technologies which are used for Gd separation and enrichment at present comprise liquid phase extraction, solid phase extraction, capillary micro-extraction and the like. Wherein, the liquid phase extraction usually needs to consume organic reagents and has complex operation; the solid phase extraction can avoid using organic reagents, but also has the defects of large sample consumption, transfer loss and the like; the capillary micro-extraction has the advantages of low sample and solvent consumption, high mass transfer speed, easiness in automation and the like, and is combined with a highly-integrated micro-fluidic chip capable of accurately controlling trace liquid, so that the method is favorable for establishing an analysis method which is simple to operate, green, environment-friendly, rapid and accurate.
According to the difference of extraction materials, capillary micro-extraction can be divided into a packed column, an open tubular column and an integral column, wherein the integral column is beneficial to a through hole for liquid circulation and micropores for increasing the fixed ratio surface area due to the unique double-hole structure, so that the extraction efficiency can be effectively improved. The monolithic column micro-extraction can be divided into inorganic monolithic columns, organic polymer monolithic columns and organic-inorganic hybrid monolithic columns according to different column bed materials. The organic polymer monolithic column is relatively simple to prepare, has good biocompatibility and chemical stability, but has the defects of poor mechanical strength, easy swelling in an organic solvent, easy deformation under heating and the like compared with an inorganic monolithic column. The inorganic monolithic column has the characteristics of high porosity, good permeability, uniform skeleton distribution, high mechanical strength and the like, but the preparation of the inorganic monolithic column is difficult, the period is long, the process is complex, and the subsequent derivatization steps are complicated. The organic-inorganic hybrid monolithic column can combine the advantages of the inorganic monolithic column and the organic polymer monolithic column, overcomes the defects of the inorganic monolithic column and the organic polymer monolithic column, and has better development prospect.
The surface molecule/ion imprinted polymer has the characteristics of specific recognition capability on target ions, high mass transfer rate, good stability, good solvent resistance, large specific surface area and the like, and has great application potential in the aspect of capillary monolithic column modification. The surface molecule/ion imprinted polymer modified monolithic column has the advantages of increasing recognition sites on the surface, improving the selectivity of the column to target analytes, enhancing the tolerance of the column to interfering ions, increasing the adsorption capacity, expanding the application range of the monolithic column and the like. The surface imprinting monolithic column can be prepared by polymerizing a pre-polymerization solution containing a template (namely a target analyte) and double bonds on the surface of the monolithic column, and imprinting sites with the same structure with the target analyte are left after the template is eluted, so that the specific recognition and extraction of the target analyte are realized. At present, surface molecularly imprinted polymer modified monolithic columns (including organic polymer monolithic columns, inorganic monolithic columns and organic-inorganic hybrid monolithic columns) have been used for capillary electrophoresis and HPLC (high performance liquid chromatography) on-line analysis of small organic molecules, polypeptides, proteins and other biological macromolecules in biological samples, but surface molecularly imprinted polymer modified organic-inorganic hybrid monolithic columns and application thereof in separation and detection of inorganic ions are not reported.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a preparation method of a surface ion imprinted polymer modified organic-inorganic hybrid monolithic column for separation and enrichment of Gd element. The second purpose of the invention is that the organic-inorganic hybrid monolithic column modified by the surface ion imprinted polymer is applied to detecting Gd element in a sample, and is embedded into a microfluidic Chip channel to establish a surface ion imprinted polymer modified organic-inorganic hybrid monolithic column capillary micro-extraction array Chip (Chip-based atomic capillary micro-extraction) and inductively coupled plasma mass spectrometry (ICP-MS) online combined analysis, so that online analysis of Gd element in human serum and urine can be realized, and the adsorption capacity, interference resistance and analysis speed of Gd element are obviously improved; the method has the advantages of high automation, high sensitivity, high sample flux, low sample consumption, strong matrix interference resistance and the like, and is suitable for analyzing trace/ultra-trace Gd elements in trace complex matrix samples.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a surface ion imprinted polymer modified organic-inorganic hybrid monolithic column comprises the following steps:
(1) pre-activation process of capillary: selecting fused quartz capillary (20cm is multiplied by 530 μm), washing with ethanol for 10min, washing with ultrapure water for 10min, and washing with 1.0 mol.L-1Washing with NaOH solution for 2h, washing with ultrapure water for 30min, and washing with 1.0 mol. L- 1Washing with HCl solution for 2h, washing with ultrapure water for 30min to neutrality, and blowing with argon; flushing a mixed solution of 3- (trimethoxysilyl) propyl methacrylate (gamma-MAPS) and ethanol with a volume ratio of 1:1 into a capillary, sealing two ends of the capillary with silica gel, placing the capillary in a 70 ℃ oven for reaction for 12 hours, flushing unreacted reagents in the capillary with ethanol, and blowing the capillary for later use with argon;
(2) preparation of poly (γ -MAPS) monolithic column: synthesizing a monolithic column by adopting a thermal initiation in-situ polymerization method, taking 575 mu L of gamma-MAPS into a 2mL EP tube, adding 100 mu L of 0.12 mol.L-1The reaction solution was stirred at room temperature for 30min while 30mg of Azobisisobutyronitrile (AI) was addedBN) is added into 420 mu L of toluene, stirring reaction is carried out for 30min, 180 mu L of gamma-MAPS mixed solution is added into the toluene mixed solution, ultrasonic treatment is carried out for 3min after uniform mixing, and N is carried out2Degassing for 10s, injecting the mixture into the capillary activated in the step (1) by using an injector, sealing two ends of the capillary by using a silica gel gasket, heating and polymerizing the mixture in a water bath kettle at the temperature of 80 ℃ for 2.5h, and washing the mixture by using ethanol to remove a pore-forming agent and unreacted reagents to obtain an organic-inorganic hybrid monolithic column poly (gamma-MAPS);
(3) performing surface ethylenic bond functional modification on the monolithic column in the step (2): washing with an ethanol solution (1:1, v/v) of gamma-MAPS for 30min, sealing two ends, heating in a constant-temperature drying oven at 60 ℃ for 12h, taking out, and washing with ethanol and water in sequence to remove unreacted solvent to obtain an organic-inorganic hybrid monolithic column with surface ethylenic bond functionalization;
(4)poly(γ-MAPS@Gd3+SIIP) preparation of capillary monolithic column: 340 mu L of functional monomer GMA-IDA-2Na+、150μL 4mol·L-1HNO3Solution, 102.3mg false template ion Eu (NO)3)3·6H2Mixing O, 157.2mg of cross-linking agent Bis, 1mL of pore-forming agent DMSO and 6.0mg of initiator AIBN uniformly to obtain clear pre-polymerization liquid, performing ultrasonic treatment for 20min, injecting the clear pre-polymerization liquid into the capillary integral column functionalized by the olefinic bond in the step (3), sealing two ends after the integral column is filled with the pre-polymerization liquid, heating the capillary integral column in a constant-temperature drying box at 60 ℃ for 1h, and performing ultrasonic treatment on the capillary integral column by using 0.5 mol.L-1HNO3Flushing the solution until Eu in effluent3+Close to the blank value (about 12 hours), use 0.1 mol. L-1Ammonium acetate is balanced to be neutral to obtain a surface ion imprinted organic-inorganic hybrid monolithic column, namely poly (gamma-MAPS @ Gd)3+SIIP) monolithic column.
The invention provides a surface ion imprinted polymer modified organic-inorganic hybrid monolithic column, which is prepared by the preparation method.
The third aspect of the invention provides an application of the organic-inorganic hybrid monolithic column modified by the surface ion imprinted polymer in enriching and detecting Gd element in a sample, the Gd element is embedded into a microfluidic Chip channel, a surface ion imprinted monolithic column capillary micro-extraction array Chip (Chip-based organic capillary micro-extraction) is established, and the Gd element in human serum and urine is analyzed by inductively coupled plasma mass spectrometry (ICP-MS) in an online combined manner, so that online analysis of Gd element in human serum and urine is realized.
The principle of the invention is as follows: gd is prepared by modifying surface ion imprinted polymer3+Surface imprinted polymer modified poly (gamma-MAPS @ Gd)3+SIIP) organic-inorganic hybrid monolithic column, and embedding the hybrid monolithic column into a poly-trimethoxysilane (PDMS) chip channel to prepare the monolithic column capillary micro-extraction array chip. In the construction process of surface ion imprinting sites, in order to solve the problem of inaccurate analysis result caused by template leakage in the subsequent analysis process due to incomplete template ion cleaning in the template cleaning process, a method of false template imprinting is selected, namely Gd and target ions are adopted3+Eu of similar structural properties3+Takes part in the synthesis of surface ion imprinted polymer as a template, and then uses nitric acid to make Eu3+After elution, the Eu remains in the polymer3+Sterically complementary cavities due to Gd3+Structure and properties of and Eu3+Quite similarly, the surface ion imprinting organic-inorganic hybrid monolithic column can specifically identify target Gd3+Meanwhile, the adsorption sites on the surface of the monolithic column are obviously increased, so that the anti-interference capability and the adsorption capacity of the monolithic column are improved, and weak Eu is used3+The residue and release will not affect the subsequent Gd3+The analysis and detection of (2). As shown in particular in figure 1.
Compared with the prior art, the invention has the following advantages and effects:
based on the good selective adsorption capacity of the organic-inorganic hybrid capillary monolithic column microextraction array chip modified by the surface ion imprinted polymer prepared by the invention on Gd element, a novel method for analyzing Gd element in a complex matrix sample by combining microextraction of the organic-inorganic hybrid capillary monolithic column array chip modified by the surface ion imprinted polymer and inductively coupled plasma mass spectrometry is provided, and the method can realize online analysis of Gd element in human urine and serum (after digestion). The organic-inorganic hybrid monolithic column adopted by the method has the advantages of both organic polymer monolithic column and inorganic monolithic column, and has the advantages of simple preparation and strong solubilityThe agent and the acid-base resistance, stronger mechanical stability and the like. For the selective adsorption effect of the surface ion imprinting technology, the selection and the composition of a functional monomer, a cross-linking agent and a pore-foaming agent in the pre-polymerization liquid play a decisive role, and the optimal imprinting conditions of the invention are that the monomer: template: crosslinker 6:2: 3. Compared with the imprinted monolithic column synthesized under the condition and a non-ionic imprinted polymer modified poly (gamma-MAPS @ NIP) monolithic column, the prepared ionic imprinted polymer monolithic column has the adsorption capacity improved by 3.5 times, and has higher relative selectivity compared with rare earth ions La and Ce with similar structures. The established method has the advantages of high automation, high flux, low sample solvent consumption, strong anti-matrix interference capability, high sensitivity, high sample flux, simple operation, good preparation reproducibility, long service life and the like, and is suitable for trace/ultra-trace Gd element (the detection limit is 1.27 ng.L) in trace complex matrix samples-1) The rapid and accurate analysis.
Drawings
Fig. 1 is a schematic diagram of the technical solution of the present invention.
FIG. 2 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) Scanning Electron Microscopy (SEM) image (500 μm) of monolithic column.
FIG. 3 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) Scanning Electron Microscopy (SEM) image (100 μm) of monolithic column.
FIG. 4 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) Scanning Electron Microscopy (SEM) image (20 μm) of monolithic column.
FIG. 5 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) Scanning Electron Microscopy (SEM) image (20 μm) of the monolith embedded chip.
FIG. 6 is a graph of the infrared spectrum (IR) of the associated monolith prepared in example 1; wherein A, B, C, D respectively represents poly (gamma-MAPS) monolithic column, ethylene bond functional modified poly (gamma-MAPS) monolithic column, poly (gamma-MAPS @ Gd)3+SIIP) and poly (gamma-MAPS @ NIP) monoliths.
FIG. 7 is a schematic diagram of the channel design and structure of the capillary monolithic column micro-extraction array of example 1.
FIG. 8 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) optimization of the pH of the monolith sample solution.
FIG. 9 is poly (γ -MAPS @ Gd) prepared in example 13+SIIP) optimization plot of the flow rate of the monolith sample solution.
FIG. 10 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) optimization plot of nitric acid concentration of the monolithic column eluent.
FIG. 11 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) optimization plot of the flow rate of the monolithic column eluate.
FIG. 12 is the poly (γ -MAPS @ Gd) prepared in example 13+SIIP) optimization plot of monolith injection volume.
Detailed Description
The features and advantages of the present invention will be further understood from the following detailed description taken in conjunction with the accompanying drawings. The examples provided are merely illustrative of the method of the present invention and do not limit the remainder of the disclosure in any way.
Example 1 preparation of capillary monolithic column micro-extraction array chip modified by surface ion imprinted polymer
(1) Pre-activation process of capillary: selecting fused quartz capillary (20cm is multiplied by 530 μm), washing with ethanol for 10min, washing with ultrapure water for 10min, and washing with 1.0 mol.L-1Washing with NaOH solution for 2h, washing with ultrapure water for 30min, and washing with 1.0 mol. L- 1And (3) washing with HCl solution for 2h, washing with ultrapure water for 30min to neutrality, and then blowing with nitrogen. The method comprises the following steps of flushing a mixed solution (volume ratio is 1:1) of gamma-MAPS and ethanol into a capillary, sealing two ends of the capillary by using a silica gel pad, placing the capillary in an oven at 70 ℃ for reaction for 12 hours, flushing out unreacted reagents in the capillary by using ethanol, and blowing the inside of the capillary by using argon for later use.
(2) preparation of poly (γ -MAPS) monolithic column: synthesizing a monolithic column by adopting a thermal initiation in-situ polymerization method, taking 575 mu L of gamma-MAPS into a 2mL EP tube, adding 100 mu L of 0.12 mol.L-1Stirring hydrochloric acid solution at room temperature for 30min while adding 30mg AIBN into 420 μ L toluene, stirring for 30min, adding 180 μ L gamma-MAPS mixed solution into toluene mixed solution, mixing wellUltrasonic 3min, N2Degassing for 10s, injecting the mixture into the capillary tube activated in the step (1) by using an injector, sealing two ends of the capillary tube by using a silica gel gasket, placing the capillary tube in a water bath kettle at the temperature of 80 ℃, heating and polymerizing for 2.5h, washing by using ethanol to remove a pore-forming agent and an unreacted reagent, and then carrying out surface ethylenic bond functional modification: washing with gamma-MAPS ethanol solution (1/1, v/v) for 30min, sealing both ends, heating in a constant temperature drying oven at 60 deg.C for 12 hr, and washing with ethanol and water to remove unreacted solvent.
(3)poly(γ-MAPS@Gd3+SIIP) preparation of capillary monolithic column: 340 mu L of functional monomer GMA-IDA-2Na+、150μL 4mol·L-1HNO3Solution, 102.3mg false template ion Eu (NO)3)3·6H2Mixing O, 157.2mg of cross-linking agent Bis, 1mL of pore-forming agent DMSO and 6.0mg of initiator AIBN uniformly to obtain clear pre-polymerization liquid, performing ultrasonic treatment for 20min, injecting into the capillary monolithic column functionalized by the olefinic bond in the step (2), filling the pre-polymerization liquid into the monolithic column, sealing two ends of the capillary monolithic column, heating in a constant-temperature drying oven at 60 ℃ for 1h, and performing ultrasonic treatment at a concentration of 0.5 mol/L-1HNO3Flushing the solution until Eu in effluent3+Close to the blank value (about 12 hours), use 0.1 mol. L-1And balancing ammonium acetate to be neutral to obtain the surface ion imprinting capillary monolithic column.
The preparation of the nonionic blotting capillary monolithic column is the same as the preparation process of the blotting monolithic column except that dummy template ions are not added.
(4) Designing a capillary monolithic column micro-extraction array chip: the chip design comprises 8 capillary monolithic column extraction channels (M1-M8), 8 sample inlets (I1-I8), 8 waste discharge outlets (W1-W8), 12 gas valve channels (V1-V12) and a connector CN connected with an ICP-MS micro concentric atomizer, wherein a quartz capillary tube with the inner diameter of 75 mu M is inserted at the position during analysis, and the quartz capillary tube is connected with the ICP-MS micro concentric atomizer through a capillary tube connecting tube for online detection. Wherein, the height of the micro-extraction channel is 50 μm, the width is 500 μm, the integral column part channel of the capillary is a square column channel with the height of 650 μm and the width of 650 μm, the height of the air valve channel is 50 μm, the width of the air valve channel is 800 μm, the width of the air valve channel is increased to 1000 μm at the part where the air valve channel and the extraction channel are crossed, so as to strengthen the air valve strength. When the sample solution is analyzed, 8 extraction channels are adopted for simultaneously loading samples, and then online desorption is carried out in sequence, so that the sample flux is improved, and the analysis speed is accelerated.
(5) Preparing a capillary monolithic column micro-extraction array chip: referring to the preparation method of the capillary monolithic column microextraction array chip mentioned in the article published by analytical chemistry in 2017, 5, 25, the structure of the array chip of the invention is a three-layer sandwich structure, firstly, a square quartz capillary tube with the length of 1cm and the width and the height of 650 mu m is introduced into a fluid channel of a PDMS chip as a template of a capillary imprinting monolithic column, and then PDMS (10/1, m) is poured onA/mB) And (3) degassing, heating and curing at 75 ℃ for more than 3 hours, and taking out the square quartz capillary tube to obtain the fluid channel.
Preparing a gas valve channel: mixing the component A and the component B of PDMS at 15/1(m/m), degassing, pouring onto the smooth surface of the silicon wafer, homogenizing at 600rpm for 15s and 1200rpm for 30s to obtain a PDMS film, and heating and curing at 75 deg.C for more than 30 min.
Chip array capillary monolithic column integration: firstly, cutting the capillary monolithic column synthesized in the step (3) into a length of 1cm, embedding the capillary monolithic column into a template channel of PDMS, and coating a proper amount of uncured PDMS (10/1, m) glue around the capillary monolithic columnA/mB) Filling the gap between the capillary monolithic column and the channel, curing at 75 deg.C for 6min, taking out, and punching at corresponding position with a puncher with diameter of 0.7 mm. And (3) putting the processed PDMS containing the fluid channel and the control channel into a plasma cleaner for cleaning for 1min, taking out the PDMS and bonding the PDMS and the fluid channel, and paying attention to ensure that the fluid channel and the control channel are vertically corresponding. And then placing the glass slide and the glass slide in a plasma cleaner for cleaning for 1min, taking out the glass slide and then quickly bonding the glass slide to increase the mechanical strength of the chip array, and placing the chip array in a constant-temperature drying oven at 60 ℃ for aging for 6h to finish the preparation of the chip array monolithic column.
Prepared poly (gamma-MAPS @ Gd)3+SIIP) scanning electron micrographs of monolithic columns as shown in FIGS. 2 to 4, it can be seen that the monolithic columns have a uniform morphology and are composed of microspheres crosslinked with one another, and that the porous bed is bonded to the inner wall of the capillaryThe method is good, and the phenomenon of bed separation is avoided; FIG. 5 is a cross-sectional view of an integral column embedded in a chip, which shows that there is no obvious gap between the outer wall of a capillary and the wall of a PDMS chip channel, and the microstructure of the integral column of the capillary is not changed, so that the loose and porous structure is well maintained, and the successful preparation of the capillary micro-extraction array chip is illustrated.
Prepared poly (gamma-MAPS @ Gd)3+SIIP) monolith was characterized by Fourier-IR spectroscopy (FIG. 6), poly (γ -MAPS @ Gd) relative to an unmodified poly (γ -MAPS) monolith3+-SIIP) monolithic column at 1384cm-1And strong absorption exists, namely C-N stretching vibration, and the successful coating of the imprinted coating on the surface of the poly (gamma-MAPS) monolithic column is indicated.
The imprinting sites of the prepared ion imprinting coating pass through N2The adsorption experiment (table 1) and the competitive adsorption experiment (table 2) are characterized, and as can be seen from table 1, the specific surface area and the pore volume of the ion imprinting and non-ion imprinting modified monolithic column are smaller than those of the unmodified monolithic column, which indicates the successful coating of the imprinting coating and the non-imprinting coating. As can be seen from Table 2, the surface ion imprinted polymer modified monolithic column is comparable to La with similar structure3+、Ce3+And Zn2+For Gd3+Has higher adsorption capacity, and indicates the successful preparation of the imprinting sites on the surface of the monolithic column.
TABLE 1N2Pore structure parameter of capillary monolithic column measured by adsorption experiment
Figure BDA0001816578170000081
TABLE 2 selective adsorption results of surface imprinted monolithic columns and non-imprinted monolithic columns on structurally similar ions and target ions
Figure BDA0001816578170000082
Example 2 Effect of different compositions of prepolymerization solution on Selective adsorption Capacity of monolith column
Surface ion imprinted polymer modified organic inorganicThe organic hybrid capillary monolithic column plays a decisive role in the selection and composition of functional monomers, cross-linking agents and pore-forming agents in the pre-polymerization liquid for the selective adsorption effect of the surface ion imprinting technology. For optimal selective adsorption of Gd3+The effect of selecting GMA-IDA-2Na having strong interaction with rare earth ions+The functional monomer is used as a functional monomer, Bis is used as a cross-linking agent, a mixed solution of DMSO and water is used as a pore-foaming agent, and the influence of the proportion of different components of the pre-polymerization solution on the selectivity of the whole column is researched. The monolithic column pair Gd of the imprinting synthesis was investigated in the ranges of monomer-template molecule molar ratios of 7:1, 5:1 and 3:13+、La3+、Ce3+、Zn2+Selective adsorption behavior of (see table 3). According to the relative selectivity factor Sr in the competitive adsorption experiment, the selectivity of the imprinted monolithic column is better along with the increase of the dosage of the template molecules, the ratio of the monomer to the template molecules is finally selected to be 3:1, and the ratio of the monomer to the cross-linking agent is considered to be 1:1, 2:1 and 4:1 on the basis3+、La3+、Ce3+、Zn2+The adsorption behavior of (1). The result shows that the selectivity of the imprinted monolithic column is better with the increase of the content of the cross-linking agent, but the permeability of the monolithic column is poorer, the ratio of the monomer to the cross-linking agent is selected to be 2:1 by comprehensively considering the permeability and the specificity, and the optimal imprinting condition is that the monomer: template: crosslinker 6:2: 3.
TABLE 3 Effect of different compositions of prepolymerization liquid on the Selective adsorption Capacity of the monolith column
Figure BDA0001816578170000091
Figure BDA0001816578170000101
[ example 3 ] Poly (γ -MAPS @ Gd)3+Application of-SIIP) monolithic column micro-extraction array chip in Gd element detection
Poly (gamma-MAPS @ Gd) prepared in example 1 was added3+SIIP) monolithic column micro-extraction array chip for chip micro-extractionThe method for detecting Gd elements by using Chip-based array MCME-ICP-MS is established by combining extraction and ICP-MS:
the method comprises the following steps:
(1) fixing the injector with sample solution on the multi-flow path injection pump, opening air valves V5 and V10 of the microfluidic chip, closing other air valves, and injecting sample solution with volume of 500 μ L at 40 μ L.min-1Simultaneously loading sample from inlet ends I1-I8 of extraction channels, discharging raffinate from waste discharge outlets W1-W8 respectively, introducing the raffinate into a waste liquid bottle via a connecting pipe, closing V5 after 750s, opening V1, desorbing the first extraction channel, and introducing the desorbed liquid at 25 μ L/min-1Flows through the monolithic column M1 from the I1 end and enters ICP-MS for analysis through the outlet end CN; closing V1 after 35s, opening V11, and injecting 0.5 mol.L from I11 and I12 ends-1After the nitric acid solution is used for cleaning the pipeline for 60s, the V11 is closed, the V12 is opened, and 0.1 L.min is introduced from the ends I9 and I10-1N of (A)2The gas flow separates the liquid on the channel, and the extraction process of the first sample is completed after 10 s; the remaining channels were then sequentially analyzed for desorption as described above. The above processes are all controlled by using Matlab program, and the specific operation program is shown in table 4.
TABLE 4 control program for array air valves
Figure BDA0001816578170000111
Figure BDA0001816578170000121
(2) And (3) operating the high-purity water without the element to be detected according to the step (1), and measuring by using ICP-MS (inductively coupled plasma-mass spectrometry), wherein the obtained signal value is used as a blank value.
Example 4 for poly (γ -MAPS @ Gd)3+SIIP) optimization of extraction conditions of monolithic column micro-extraction array chip
(1) Poly (gamma-MAPS @ Gd)3+SIIP) optimization of extraction conditions of monolithic column micro-extraction array chip, as shown in FIGS. 8-12, the extraction conditions were optimized one by a single-variable method, and the optimum conditions were finally determined asThe pH value of the sample solution is 5, and the sample flow rate is 40 mu L/min-1The volume of the sample is 0.5mL, and the eluent is HNO3Eluent concentration and volume are respectively 0.2 mol.L -115 uL, eluent flow rate 25 uL min-1。
(2) The influence of common interfering ions (shown in table 5) on the enrichment and detection of rare earth elements is investigated under the optimal conditions, and the result shows that the method has stronger matrix interference resistance and matrix separation capacity when the actual sample is analyzed, and can be used for analyzing trace/ultra-trace Gd elements in human urine and serum.
TABLE 5 Poly (γ -MAPS @ Gd)3+SIIP) tolerant concentration of coexisting ions for chip micro-extraction experiments
Figure BDA0001816578170000122
Figure BDA0001816578170000131
(3) For poly (gamma-MAPS @ Gd)3+SIIP) preparation reproducibility and service life of monolithic column microextraction array chip were examined. The preparation reproducibility of the chip was examined, the extraction recovery rate of the target Gd element by the single chip monolithic columns prepared in the same batch (n-7) and different batches (n-7) was examined under the optimal experimental conditions, and the relative standard deviation was calculated. The RSD (n ═ 9) in the same batch was 6.2%, and the RSD (n ═ 7) in different batches was 6.9%. Furthermore, 20. mu.L, 0.1 mol. L was used-1Ammonium acetate at 40. mu.L/min-1The regeneration of the chip can be realized by flushing the chip at the flow rate. Under the optimal condition, the chip can be repeatedly used for more than 15 times without obvious reduction of extraction efficiency.
(4) To investigate poly (gamma-MAPS @ Gd)3+Whether the adsorption capacity of the SIIP) monolithic column to Gd element is obviously improved or not is compared with that of a non-ionic imprinting monolithic column poly (gamma-MAPS @ Gd)3+SNIP) and ion-imprinted monolithic column poly (gamma-MAPS @ Gd)3+SIIP) adsorption capacity of monolithic columns, respectively 1584μg·m-1And 459. mu.g.m-1The adsorption capacity is improved by 3.5 times.
(5) In order to investigate whether the introduction of the chip array obviously improves the analysis speed of the method, the sample fluxes of the capillary monolithic column outside the chip and the capillary monolithic column array chip are compared under the optimal condition and are respectively 4h-1And 18h-1The analysis speed of the sample is improved by 4.5 times.
(6) The method was used for analysis of urine and serum from healthy persons, and the average of the three measurements is shown in table 6. Respectively carrying out a standard addition recovery experiment on the samples, wherein the standard addition recovery rate is 88.1-96.7%, which indicates that the method can be used for analyzing trace/ultra-trace Gd elements in complex biological samples.
TABLE 6 detection results and standard recovery results of Gd element in urine and serum of healthy people
Figure BDA0001816578170000132
Figure BDA0001816578170000141
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (3)

1. A preparation method of a surface ion imprinted polymer modified organic-inorganic hybrid monolithic column is characterized by comprising the following steps:
(1) pre-activation process of capillary: selecting fused quartz capillary with length of 20cm × diameter of 530 μm, sequentially washing with ethanol for 10min, ultrapure water for 10min, and washing with 1.0mol · L-1Washing with NaOH solution for 2h, washing with ultrapure water for 30min, and washing with 1.0 mol. L-1Washing with HCl solution for 2h, washing with ultrapure water for 30min to neutrality, and blowing with argon; will be provided withFlushing a mixed solution of 3- (trimethoxysilyl) propyl methacrylate (gamma-MAPS) and ethanol with a volume ratio of 1:1 into a capillary, sealing two ends of the capillary by using silica gel, placing the capillary in a 70 ℃ drying oven for reaction for 12 hours, flushing unreacted reagents in the capillary out by using ethanol, and drying the capillary for later use by using argon;
(2) preparation of poly (γ -MAPS) monolithic column: synthesizing a monolithic column by adopting a thermal initiation in-situ polymerization method, taking 575 mu L of gamma-MAPS into a 2mL EP tube, adding 100 mu L of 0.12 mol.L-1Stirring hydrochloric acid solution at room temperature for 30min while adding 30mg of Azobisisobutyronitrile (AIBN) into 420 μ L of toluene, stirring for 30min, adding 180 μ L of the above gamma-MAPS mixed solution into the toluene mixed solution, mixing well, and performing ultrasonic treatment for 3min, wherein N is N2Degassing for 10s, injecting the mixture into the capillary activated in the step (1) by using an injector, sealing two ends of the capillary by using a silica gel gasket, heating and polymerizing the mixture in a water bath kettle at the temperature of 80 ℃ for 2.5h, and washing the mixture by using ethanol to remove a pore-forming agent and unreacted reagents to obtain an organic-inorganic hybrid monolithic column poly (gamma-MAPS);
(3) performing surface ethylenic bond functional modification on the monolithic column in the step (2): ethanol solution with γ -MAPS, i.e., γ -MAPS: washing with ethanol at a volume ratio of 1:1 for 30min, sealing two ends, heating in a constant-temperature drying oven at 60 deg.C for 12h, taking out, washing with ethanol and water in sequence to remove unreacted solvent to obtain organic-inorganic hybrid monolithic column with surface ethylenic bond functionalized;
(4)poly(γ-MAPS@Gd3+SIIP) preparation of capillary monolithic column: 340 mu L of functional monomer GMA-IDA-2Na+、150μL 4mol·L-1HNO3Solution, 102.3mg false template ion Eu (NO)3)3·6H2Mixing O, 157.2mg of cross-linking agent Bis, 1mL of pore-forming agent DMSO and 6.0mg of initiator AIBN uniformly to obtain clear pre-polymerization liquid, performing ultrasonic treatment for 20min, injecting the clear pre-polymerization liquid into the capillary integral column functionalized by the olefinic bond in the step (3), sealing two ends after the integral column is filled with the pre-polymerization liquid, heating the capillary integral column in a constant-temperature drying box at 60 ℃ for 1h, and performing ultrasonic treatment on the capillary integral column by using 0.5 mol.L-1HNO3Flushing the solution until Eu in effluent3+Close to blank value, use 0.1 mol.L-1Balancing ammonium acetate to be neutral to obtain the surface ion imprinted polymerModified organic-inorganic hybrid monolithic column namely poly (gamma-MAPS @ Gd)3+SIIP) monolithic column.
2. A surface ion imprinted polymer modified organic-inorganic hybrid monolithic column obtained by the preparation method of claim 1.
3. The application of the surface ion imprinted polymer modified organic-inorganic hybrid monolithic column of claim 2 in enriching and detecting Gd element in a sample is characterized in that the surface ion imprinted polymer modified organic-inorganic hybrid monolithic column is embedded into a microfluidic chip channel, a surface ion imprinted monolithic column capillary micro-extraction array chip is established, and the surface ion imprinted polymer modified organic-inorganic hybrid monolithic column is in online coupled analysis with inductively coupled plasma mass spectrometry to realize analysis of Gd element in human serum and urine.
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