CN112552470B - Teicoplanin-modified silica gel surface molecularly imprinted polymer, and aqueous phase preparation method and application thereof - Google Patents

Teicoplanin-modified silica gel surface molecularly imprinted polymer, and aqueous phase preparation method and application thereof Download PDF

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CN112552470B
CN112552470B CN202011134293.4A CN202011134293A CN112552470B CN 112552470 B CN112552470 B CN 112552470B CN 202011134293 A CN202011134293 A CN 202011134293A CN 112552470 B CN112552470 B CN 112552470B
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teicoplanin
silica gel
imprinted polymer
modified silica
molecularly imprinted
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CN112552470A (en
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贺利民
周豪
刘戎
彭侃霖
陈倩倩
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South China Agricultural University
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Abstract

The invention belongs to the fields of analytical chemistry and pollutant analysis and detection, and discloses a water phase preparation method and application of a teicoplanin-modified silica gel surface molecularly imprinted polymer. Adding aminated modified silica gel, teicoplanin and a functional monomer into water, and carrying out prepolymerization at 4-10 ℃; and then adding a cross-linking agent and an initiator, stirring and polymerizing at 40-90 ℃ under a protective atmosphere, centrifuging the obtained product, eluting to remove a teicoplanin template, further washing, and drying in vacuum to obtain the teicoplanin-modified silica gel surface molecularly imprinted polymer. The method has the advantages of simple process, low cost, green and pollution-free solvent, uniform particle size of the prepared molecularly imprinted polymer, large adsorption capacity, high mass transfer speed, good selectivity and adsorption effect on teicoplanin, and application of selectively separating and enriching trace (0.01-100 mu gmL) in complex samples‑1) The analysis and detection of teicoplanin has wide application prospect.

Description

Teicoplanin-modified silica gel surface molecularly imprinted polymer, and aqueous phase preparation method and application thereof
Technical Field
The invention belongs to the technical field of analytical chemistry and pollutant analysis and detection, and particularly relates to a teicoplanin-modified silica gel surface molecularly imprinted polymer, and a water phase preparation method and application thereof.
Background
Teicoplanin is a glycopeptide antibiotic produced by fermentation of Actinoplanes, and mainly comprises 5 compounds (A2-1, A2-2, A2-3, A2-4 and A2-5) with similar structures, wherein A2-2 is used as the main component. Teicoplanin is a new generation glycopeptide antibiotic developed after vancomycin and is clinically used for treating various serious gram-positive bacterial infections, especially vancomycin-resistant bacterial infections. Glycopeptide antibiotics have been banned from food animals in the european union, usa, japan and australia. Vancomycin, salts, esters and preparations thereof are forbidden to be used for all food animals in GB 31650 and 2019 standards of rural agricultural ministry, and other glycopeptide antibiotics are not limited. With the use of antibiotics in large quantities, the environmental residue has attracted attention. It is known that trace residues of antibiotics in complex environmental media can cause great harm to the ecosystem and human health. Therefore, analytical detection of trace amounts of antibiotics in environmental samples has become a focus of attention for researchers. However, because glycopeptide antibiotics are usually formed by condensing a plurality of amino acids, the glycopeptide antibiotics have large molecular weight, strong polarity and high detection difficulty, and thus, the reports on the analysis of teicoplanin residues are few.
The molecular imprinting technology is a high-selectivity and specific separation and analysis technology, and the idea of the technology is derived from antigen-antibody specific recognition. The polymer material based on molecular recognition-molecularly imprinted polymer has the outstanding characteristics of having a memory function on target molecules, being capable of selectively recognizing target objects in complex matrixes and realizing selective separation and enrichment of low-concentration target objects under the interference of the complex matrixes in actual environmental samples. However, most of the existing molecularly imprinted polymers are prepared in nonpolar organic solvents such as acetonitrile, chloroform, toluene and the like, which can bring secondary pollution to the environment on one hand, and on the other hand, the polymers often show poor adsorption performance in polar solvents in which pollutants are widely present. Therefore, how to realize the preparation of the molecularly imprinted polymer in green polar medium water becomes a hot point of research. In addition, the polymer prepared by the traditional molecular imprinting technology has the defects of slow mass transfer, low adsorption capacity, low particle strength and the like. The invention adopts the carrier silica gel modification firstly, and the preparation of the molecular imprinting polymer membrane high molecular material on the surface of the carrier silica gel is not reported in related documents.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a method for preparing a teicoplanin-modified silica gel surface molecularly imprinted polymer, wherein the teicoplanin-modified silica gel surface molecularly imprinted polymer prepared in a green medium aqueous solution has better selective adsorption performance on a target object.
The invention also aims to provide the teicoplanin-modified silica gel surface molecularly imprinted polymer prepared by the method.
The invention further aims to provide application of the teicoplanin-modified silica gel surface molecularly imprinted polymer.
The purpose of the invention is realized by the following technical scheme:
a water phase preparation method of teicoplanin-modified silica gel surface molecularly imprinted polymer comprises the following specific steps:
s1, mixing toluene, silica gel and a modifier, reacting at 100-120 ℃ in a protective atmosphere, washing an obtained product, and drying in vacuum to obtain aminated modified silica gel;
s2, adding the aminated modified silica gel into an aqueous solution system of teicoplanin and a functional monomer, and carrying out prepolymerization at 4-10 ℃; and then adding a cross-linking agent and an initiator, stirring and polymerizing at 40-90 ℃ under a protective atmosphere, centrifuging the obtained product, eluting to remove a teicoplanin template, washing, and drying in vacuum to obtain the spherical particle teicoplanin-modified silica gel surface molecularly imprinted polymer.
Preferably, the modifier in step S1 is one or more selected from 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrihydroxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (butylamino) propyltriethoxysilane, and 3- (4-ureidoamino) propyltriethoxysilane.
Preferably, the initiator in step S2 is azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, benzoyl peroxide, potassium persulfate, or ammonium persulfate.
Preferably, the protective atmosphere in steps S1 and S2 is argon or nitrogen.
Preferably, the functional monomer in step S2 is a double bond-containing compound, and is 2-hydroxyethyl methacrylate, methacrylic acid (MAA), methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, acrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 3-propyl methacrylate potassium salt, 4-vinylpyridine (4-VP), 2-vinylpyridine (2-VP), itaconic acid, Acrylamide (AM), 2-hydroxyethyl methacrylate (HEMA).
Preferably, the dosage ratio of the toluene, the silica gel and the modifier in the step S1 is 50mL to 1g (0.5-2) mL; in the step S2, the molar ratio of teicoplanin to the functional monomer to the cross-linking agent is 1 (5-10) to (20-60); the mass ratio of the amination modified silica gel to the teicoplanin is (0.3-0.6) to (0.1-0.3); the volume ratio of the total molar amount of the aminated modified silica gel, the teicoplanin and the functional monomer to the water in the aqueous solution system is 1 (30-60).
Preferably, the crosslinking agent in step S2 is one or any two of Glycidyl Methacrylate (GMA), Ethylene Glycol Diglycidyl Ester (EGDE), N-Methylene Bisacrylamide (MBA), or Ethylene Glycol Dimethacrylate (EGDMA).
Preferably, the reaction time in the step S1 is 6-18 h; the prepolymerization time in the step S3 is 4-12 h; the polymerization reaction time is 12-24 h.
A teicoplanin-modified silica gel surface molecularly imprinted polymer is prepared by the method.
The obtained teicoplanin-modified silica gel surface molecularly imprinted polymer is applied to the field of selective recognition or detection of teicoplanin.
The teicoplanin-modified silica gel surface molecularly imprinted polymer can selectively identify teicoplanin template molecules and structural analogues thereof; the teicoplanin-modified silica gel surface molecularly imprinted polymer has uniform particle size, high pressure resistance, large adsorption capacity and high mass transfer speed, has three-dimensional holes matched with teicoplanin template molecules and specifically combined active sites on the surface, can be used for selective separation and enrichment of trace teicoplanin in a complex sample, and can be recycled after regeneration.
Compared with the prior art, the invention has the following beneficial effects:
1. the water phase preparation method of the teicoplanin-modified silica gel surface molecularly imprinted polymer has the advantages of simple process, low cost and green and pollution-free solvent, and the prepared teicoplanin-modified silica gel surface molecularly imprinted polymer has the advantages of uniform particle size (5-12 mu m), high strength (pressure resistance of 200-400 bar) and large adsorption capacity (30-50 mg. g)-1) And high mass transfer rate (1-20 min).
2. Compared with the prior non-polar organic solvents such as acetonitrile, chloroform and the like, the preparation method of the invention adopts pure water as the preparation solvent, greatly reduces the pollution of the solvent to the environment, simultaneously improves the adsorption capacity of the imprinted polymer in a polar medium, and lays a foundation for the synthesis of the molecularly imprinted polymer in polar media such as a water phase and the like.
3. According to the invention, the teicoplanin imprinted polymer is prepared on the surface of the silica gel particles through the combined action of the cross-linking agent and the initiator, and the imprinted polymer has an action site with specific recognition performance on teicoplanin and has good selectivity and adsorption effect on teicoplanin. The method can be used for selectively separating and enriching trace (0.01-100 mu g/mL) in complex samples by combining with a high performance liquid chromatography technology-1) The analysis and detection of teicoplanin has wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of a molecularly imprinted polymer on the surface of aminated modified silica gel and teicoplanin-modified silica gel in example 1;
FIG. 2 is an SEM photograph of the molecularly imprinted polymer on the surface of teicoplanin-modified silica gel of example 1;
FIG. 3 is a graph showing the adsorption effect of imprinted polymers and non-imprinted polymers prepared from different monomers in examples 1-5;
FIG. 4 shows the adsorption effect of imprinted polymers and non-imprinted polymers prepared with different cross-linkers in example 1;
FIG. 5 shows the evaluation results of the specific adsorption of the teicoplanin-modified silica gel surface molecularly imprinted polymer in example 1;
FIG. 6 is a liquid chromatogram of the desorption of teicoplanin from imprinted polymer and non-imprinted polymer in example 1.
FIG. 7 is a schematic diagram of the synthesis route of the molecularly imprinted polymer according to the present invention.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
1. Respectively adding 100mL of toluene, 5g of silica gel and 5mL of modifier 3-aminopropyltriethoxysilane into a reaction container, reacting for 12h at 100-120 ℃ under the atmosphere of argon, washing the obtained product, and drying in vacuum to obtain aminated modified silica gel;
2. 30mL of water and 0.24g of teicoplanin template molecule are added into a 50mL round bottom flask, mixed evenly by vortex and ultrasound, and stirred at room temperature until all the teicoplanin template molecule is dissolved. Then, 0.5g of the aminated modified silica gel and 0.15mL of 2-hydroxyethyl methacrylate monomer were added, and prepolymerized at 4 ℃ for 6 hours. And then adding 0.47mL of ethylene glycol dimethacrylate and 0.39mL of glycidyl methacrylate double cross-linking agent, then adding 10mg of azodiisobutyronitrile, uniformly mixing, introducing argon gas for protection, stirring and polymerizing at 60 ℃ for 24 hours, eluting the obtained product with 10-50% acetic acid/methanol or ammoniated methanol (1:4, v/v), removing teicoplanin template molecules, washing with methanol and water to be neutral, and performing vacuum drying at 50-70 ℃ to obtain the teicoplanin-modified silica gel surface molecularly imprinted polymer.
Comparative example 1
The difference from example 1 is that: in step 2, a non-molecularly imprinted polymer is prepared without adding teicoplanin template molecules.
The adsorption capacity of the teicoplanin-modified silica gel surface molecularly imprinted polymer and the non-imprinted polymer prepared in example 1 and comparative example 1 respectively to teicoplanin under the same conditions is as follows: 46.5mg g-1And 21.9mg g-1The imprinting factor was 2.12.
FIG. 1 is the infrared absorption spectrum of the aminated modified silica gel (A) and the teicoplanin-modified silica gel surface molecularly imprinted polymer (B) in example 1. As can be seen from FIG. 1, at 464cm-1、805cm-1And 1085cm-1Nearby absorption peaks belonging to the stretching vibration characteristic absorption peaks of Si-O and Si-O-Si; at 1639cm-1Absorption peak at (a), which is attributed to N-H deformation vibration of amino group; at 2957cm-1Absorption peak, which is attributed to C-H stretching vibration of alkane; 3460cm-1And 3490cm-1The absorption peak is attributed to the N-H stretching vibration peak of amide; at 1723cm-1And a newly appeared absorption peak is attributed to the C ═ O stretching vibration of acyl, and is the C ═ O stretching vibration characteristic peak of 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate and glycidyl methacrylate, which indicates that the surface of the silica gel particles is successfully coated with the molecularly imprinted polymer layer, namely the teicoplanin-modified silica gel surface molecularly imprinted polymer.
FIG. 2 is a scanning electron micrograph of a molecularly imprinted polymer on the surface of teicoplanin-modified silica gel prepared in example 1. As can be seen from FIG. 2, the molecularly imprinted polymer is coated with a polymer film, the polymer film is compact and compact, and the surface is rough. The polymer layer is located on the surface of the carrier, which facilitates rapid mass transfer during template binding and removal.
Example 2
The difference from example 1 is that: replacing 0.15mL of 2-hydroxyethyl methacrylate with 0.07mL of methacrylic acid monomer in step 2; the resulting product was eluted with acetic acid/methanol (1:1, v/v).
Comparative example 2
The difference from example 2 is that: in step 2, a non-molecularly imprinted polymer is prepared without adding teicoplanin template molecules.
The adsorption capacity of the teicoplanin-modified silica gel surface molecularly imprinted polymer and the non-molecularly imprinted polymer prepared in example 2 and comparative example 2 respectively to teicoplanin under the same conditions are respectively as follows: 38.9mg g-1And 27.0mg g-1The imprinting factor was 1.44.
Example 3
The difference from example 1 is that: 0.13mL 2-vinylpyridine was used in place of 0.15mL 2-hydroxyethyl methacrylate. The resulting product was eluted with acetic acid/methanol (1:1, v/v).
Comparative example 3
The difference from example 3 is that: in step 2, a non-molecularly imprinted polymer is prepared without adding teicoplanin template molecules.
The adsorption capacity of the teicoplanin-modified silica gel surface molecularly imprinted polymer and the non-molecularly imprinted polymer prepared in example 3 and comparative example 3 respectively to teicoplanin under the same conditions are respectively as follows: 40.1mg g-1And 32.3mg g-1The imprinting factor was 1.24.
Example 4
The difference from example 1 is that: 888.5mg acrylamide was substituted for 0.15mL 2-hydroxyethyl methacrylate and the resulting product was eluted with acetic acid/methanol (1:1, v/v).
Comparative example 4
The difference from example 4 is that: in the step, teicoplanin template molecules are not added, and a non-molecularly imprinted polymer is prepared.
The adsorption capacity of the teicoplanin-modified silica gel surface molecularly imprinted polymer and the non-molecularly imprinted polymer prepared in example 4 and comparative example 4 respectively to teicoplanin under the same conditions is as follows: 36.7mg g-1And 31.7mg g-1The imprinting factor was 1.1.
Example 5
The difference from example 1 is that: the crosslinker used was ethylene glycol dimethacrylate.
Comparative example 5
The difference from example 5 is that: in the step, teicoplanin template molecules are not added, and a non-molecularly imprinted polymer is prepared.
The adsorption amounts of the teicoplanin-modified silica gel surface molecularly imprinted polymer and the non-molecularly imprinted polymer prepared in example 5 and comparative example 5 respectively to teicoplanin under the same conditions were: 42.7mg g-1And 22.0mg g-1The imprinting factor was 1.94.
Example 6
The difference from example 1 is that: replace 0.47mL ethylene glycol dimethacrylate and 0.39mL glycidyl methacrylate with 0.78mL glycidyl methacrylate; replace 0.15mL of 2-hydroxyethyl methacrylate with 0.14mL of 2-vinylpyridine; the resulting product was eluted with acetic acid/methanol (1:1, v/v).
Comparative example 6
The difference from example 6 is that: in the step, teicoplanin template molecules are not added, and a non-molecularly imprinted polymer is prepared.
The adsorption amounts of the teicoplanin-modified silica gel surface molecularly imprinted polymer and the non-molecularly imprinted polymer prepared in example 6 and comparative example 6, respectively, to teicoplanin under the same conditions were: 39.5mg g-1And 26.8mg g-1The imprinting factor was 1.47.
FIG. 3 is a graph showing the adsorption effect of imprinted polymers and non-imprinted polymers prepared from different monomers in examples 1-5. As can be seen from FIG. 3, the adsorption amount and selectivity of the imprinted polymer prepared in example 1 are the highest when 2-hydroxyethyl methacrylate is used as a monomer. 16 compounds were selected for comparison from the monomer screen, including MAA, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, acrylic acid, methyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 3-sulfopropyl methacrylate potassium salt, 2-vinylpyridine (2-VP), 4-vinylpyridine (4-VP), itaconic acid, Acrylamide (AM), 2-hydroxyethyl methacrylate (HEMA); wherein, the imprinted polymer prepared by taking HEMA as a monomer has the best adsorption performance.
FIG. 4 shows the adsorption effect of imprinted polymers and non-imprinted polymers prepared with different cross-linkers in example 1. As can be seen from fig. 4, in example 1, when ethylene glycol dimethacrylate and glycidyl methacrylate are used as the composite cross-linking agent, the adsorption performance of the prepared imprinted polymer is the best. 4 compounds and compounds are selected for screening the cross-linking agent for comparison, wherein the compounds comprise one or any two of Glycidyl Methacrylate (GMA), Ethylene Glycol Diglycidyl Ester (EGDE), N' -Methylene Bisacrylamide (MBA) or Ethylene Glycol Dimethacrylate (EGDMA); the adsorption amount of the imprinted polymer is the highest when MBA is used as a cross-linking agent, but the selectivity is poor. When EGDMA is used as a cross-linking agent, the selectivity of the imprinted polymer is highest, but the adsorption amount is slightly lower than GMA; EGDMA and GMA are preferably used in combination.
Fig. 5 shows the results of evaluating the specific adsorption of teicoplanin-modified silica gel surface molecularly imprinted polymer in methanol-water (v/v ═ 1: 1) solution in example 1. Wherein the used teicoplanin standard solution is: 5mL of methanol aqueous solution (1:1, v/v), and the concentration of teicoplanin is 200 mug mL-1. As can be seen from FIG. 5, the imprinted polymer has low adsorption amount and poor specificity to vancomycin which is a teicoplanin structural analogue, and the imprinting factor is 0.59. The imprinted polymer has poor adsorption specificity to virginiamycin, and the imprinting factor is 0.98. Therefore, the absorption efficiency of the imprinted polymer to teicoplanin is obviously higher than that of other medicines, which proves that the imprinted material of teicoplanin has a specific recognition function. Wherein, the imprinted polymer has no adsorption on teicoplanin structural analogue bacitracin, polymyxin B, polymyxin E, small molecular drugs of spiramycin, tilmicosin, enrofloxacin and sulfadimidine. The specific recognition cavity and action site on the surface of the synthesized molecular imprinting material are only matched with the shape, size and spatial arrangement of groups of teicoplanin molecules, but not matched with other compounds with different structures, so that the adsorption capacity is low. FIG. 6 is a liquid chromatogram of teicoplanin desorption from imprinted polymer and non-imprinted polymer in example 1; from FIG. 6As can be seen, the imprinted polymer has larger adsorption capacity to teicoplanin, and the concentration of teicoplanin in the desorption solution is obviously higher than that of the non-imprinted polymer.
FIG. 7 is a schematic diagram of the synthetic route of the teicoplanin-modified silica gel surface molecularly imprinted polymer of the present invention; wherein, the carrier is amination modified silica gel; the template is teicoplanin. As can be seen from fig. 7, the silica gel is first aminated and modified by APTES, then the modified silica gel is used as a carrier, the template and the monomer are self-assembled in the aqueous medium system, and the formed prepolymer is polymerized by the initiation of free radicals in the presence of the cross-linking agent and the initiator to form a polymer imprinted polymer film layer with a network structure on the surface of the aminated silica gel. And further washing the template teicoplanin and other residual substances in the reaction system by using 10% acetic acid methanol to prepare the teicoplanin-modified silica gel surface molecularly imprinted polymer. The teicoplanin-imprinted polymer membrane on the surface of the modified silica gel has high specificity, and can be used for selective adsorption of teicoplanin and structural analogues thereof in a complex medium system.
The teicoplanin-modified silica gel surface molecularly imprinted polymer is prepared by taking a surface porous silica microsphere as a carrier for imprinting polymerization after amination modification; the obtained teicoplanin-modified silica gel surface molecularly imprinted polymer has excellent performances of uniform particle size (5-12 mu m), high strength (withstand voltage of 200-400 bar), large adsorption capacity (30-50 mg/g) and the like, and the imprinted material can specifically identify teicoplanin within a short time (1-20 min) and has a high mass transfer rate. The high specific surface area provided by the imprinted polymer coated on the surface of the silica gel core increases the number of specific binding sites of the imprinted material; the distribution of the imprinting layer on the surface layer of the carrier also enables imprinting sites to be easily accessed, and the effect of rapidly recognizing template molecules and structural analogues thereof is achieved. The teicoplanin-modified silica gel surface molecularly imprinted polymer has good specific selectivity. The method can be used for trace (0.01-100 mu g mL) in practical samples by combining with the high performance liquid chromatography technology-1) The analysis and detection of teicoplanin enable the imprinted polymer to be expected to realize identification of teicoplanin in complex matrix in practical applicationAnd detecting.
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 (8)

1. A water phase preparation method of teicoplanin-modified silica gel surface molecularly imprinted polymer is characterized by comprising the following specific steps:
s1, mixing toluene, silica gel and a modifier, reacting at 100-120 ℃ in a protective atmosphere, washing the obtained product, and drying in vacuum to obtain aminated modified silica gel;
s2, adding the aminated modified silica gel into an aqueous solution system of teicoplanin and a functional monomer methacrylic acid-2-hydroxyethyl ester, and carrying out prepolymerization at 4-10 ℃; then adding a cross-linking agent and an initiator, wherein the cross-linking agent is ethylene glycol dimethacrylate and glycidyl methacrylate; stirring and polymerizing at 40-90 ℃ under a protective atmosphere, centrifuging the obtained product, eluting to remove a teicoplanin template, washing, and drying in vacuum to obtain the teicoplanin-modified silica gel surface molecularly imprinted polymer with spherical particles.
2. The method for preparing the teicoplanin-modified silica gel surface molecularly imprinted polymer in the water phase according to claim 1, wherein the modifier in step S1 is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrihydroxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (butylamino) propyltriethoxysilane, or 3- (4-ureidoamino) propyltriethoxysilane.
3. The method for preparing the teicoplanin-modified silica gel surface molecularly imprinted polymer in the water phase according to claim 1, wherein the initiator in the step S2 is azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, benzoyl peroxide, potassium persulfate or ammonium persulfate.
4. The aqueous phase preparation method of teicoplanin-modified silica gel surface molecularly imprinted polymer according to claim 1, wherein the protective atmosphere in steps S1 and S2 is argon or nitrogen.
5. The aqueous phase preparation method of teicoplanin-modified silica gel surface molecularly imprinted polymer according to claim 1, wherein the dosage ratio of the toluene, the silica gel and the modifier in step S1 is 50mL:1g (0.5-2) mL; in the step S2, the molar ratio of teicoplanin to the functional monomer to the cross-linking agent is 1 (5-10) to (20-60); the mass ratio of the amination modified silica gel to the teicoplanin is (0.3-0.6) to (0.1-0.3); the volume ratio of the total molar amount of the aminated modified silica gel, the teicoplanin and the functional monomer to the water in the aqueous solution system is 1 (30-60).
6. The aqueous phase preparation method of teicoplanin-modified silica gel surface molecularly imprinted polymer according to claim 1, wherein the reaction time in step S1 is 6-18 h; the prepolymerization time in the step S2 is 4-12 h; the polymerization reaction time is 12-24 h.
7. A teicoplanin-modified silica gel surface molecularly imprinted polymer, characterized in that the molecularly imprinted polymer is prepared by the method of any one of claims 1 to 6.
8. The use of the teicoplanin-modified silica gel surface molecularly imprinted polymer of claim 7 in the field of selective recognition or detection of teicoplanin.
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CN101757896A (en) * 2009-11-13 2010-06-30 南京医科大学 Preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides
CN101845127A (en) * 2010-05-10 2010-09-29 南京医科大学 Method for preparing core-shell structured composite nano surface molecular imprinting polymer of tanshinone compound
US20120270964A1 (en) * 2009-12-01 2012-10-25 Cranfield University Preparation of molecularly imprinted polymers
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US5587273A (en) * 1993-01-21 1996-12-24 Advanced Microbotics Corporation Molecularly imprinted materials, method for their preparation and devices employing such materials
CN101757896A (en) * 2009-11-13 2010-06-30 南京医科大学 Preparation method of molecularly imprinted polymer on nano-silica gel surfaces of sulfonylurea herbicides
US20120270964A1 (en) * 2009-12-01 2012-10-25 Cranfield University Preparation of molecularly imprinted polymers
CN101845127A (en) * 2010-05-10 2010-09-29 南京医科大学 Method for preparing core-shell structured composite nano surface molecular imprinting polymer of tanshinone compound
CN108659159A (en) * 2018-04-19 2018-10-16 广州市疾病预防控制中心 A kind of molecular engram microsphere and its preparation and application for detecting teicoplanin

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