CN111440265A - Suspension polymerization preparation method and application of mixed eight-template imprinted polymer - Google Patents

Suspension polymerization preparation method and application of mixed eight-template imprinted polymer Download PDF

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CN111440265A
CN111440265A CN202010279723.5A CN202010279723A CN111440265A CN 111440265 A CN111440265 A CN 111440265A CN 202010279723 A CN202010279723 A CN 202010279723A CN 111440265 A CN111440265 A CN 111440265A
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CN111440265B (en
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高文惠
张凯杰
田景升
张展展
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Hebei University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
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    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
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    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
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    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents

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Abstract

The invention discloses a suspension polymerization preparation method of a mixed eight-template imprinted polymer, which comprises the steps of selection of a dispersion medium and a functional monomer, dissolution, prepolymerization, polymerization, template molecule elution, drying and the like. Eight substances are used as template substances, and a molecularly imprinted polymer capable of specifically recognizing triazole substances, pyrethroid substances, triazine substances, carbamate substances, phenylurea substances, benzimidazole substances, sulfonylurea substances and neonicotinoid substances is synthesized by a suspension polymerization method. The preparation process is simple, the conditions are easy to control, the prepared polymer has good stability, acid and alkali resistance and good dispersibility, does not need grinding, can specifically adsorb triazole, pyrethroid, triazine, carbamate, phenylurea, benzimidazole, sulfonylurea and neonicotinoid substances at the same time, and has high adsorption efficiency.

Description

Suspension polymerization preparation method and application of mixed eight-template imprinted polymer
Technical Field
The invention belongs to the technical field of chemical synthesis, analytical chemistry, supramolecular chemistry and food safety, and relates to a suspension polymerization preparation method and application of a mixed eight-template imprinted polymer.
Background
In China, the yield and the use amount of the eight pesticides including triazoles, pyrethrins, triazines, carbamates, phenylureas, benzimidazoles, sulfonylureas and neonicotinoids are large, and meanwhile, the eight pesticides also cause great harm to the ecological environment and the food safety. In order to ensure the ecological environment and food safety of China, the establishment of a rapid, efficient and accurate detection method for the eight types of pesticides is an urgent task for environment and food safety analysis workers. However, since these substances have low residual concentrations in natural environments and various interfering substances exist, it is difficult for conventional detection and analysis methods to effectively measure them. In addition, matrix effect brought by the complex matrix also provides a challenge influence on the analysis of the eight types of pesticides, and a great challenge for researchers is how to reduce the influence of the matrix effect on the analysis effect during sample processing. Therefore, it is very important to explore an enrichment method with strong identification and small interference.
Molecular Imprinting Technology (MIT) is a technology for preparing molecularly imprinted polymers, also called template technology, and is a novel technology developed on the basis of simulating the interaction between antigens and antibodies in organisms. The receptor with a three-dimensional space structure is synthesized through the interaction of the template molecule, the functional monomer and the cross-linking agent, has a specific memory function on the template molecule, and embodies high selectivity, special affinity and excellent molecular recognition capability. Molecularly Imprinted Polymers (MIPs) are prepared by copolymerizing template molecules with functional monomers, crosslinkers, initiators, and the like in a specific dispersion system to produce highly crosslinked rigid Polymers. And then removing template molecules in the MIPs by a physical or chemical method to obtain a polymer with a cavity with a determined spatial configuration and with accurately arranged functional groups in the cavity. Therefore, the MIPs have the capability of selectively extracting target molecules or certain compounds with similar structures from complex samples, are suitable for being used as solid-phase extraction fillers, solid-phase microextraction coatings and molecularly imprinted membranes to separate and enrich trace analytes in the complex samples, overcome the disadvantages of complex sample systems, complex pretreatment and the like, and achieve the purpose of separating and purifying the samples.
The suspension polymerization is a polymerization method for dispersing organic matters such as template molecules, functional monomers, cross-linking agents and the like into small droplets for polymerization in an aqueous system and then preparing the molecularly imprinted polymer microspheres. The suspension polymerization method is simple and convenient to operate, and the prepared imprinted polymer has the advantages of controllable particle size, large specific surface area, uniform appearance, strong adsorption capacity and easy functionalization, so that the molecularly imprinted polymer can be widely applied.
The MIPs prepared by the mixed template molecules can shorten the detection time and reduce the detection cost, and various substances can be simultaneously detected by one-time polymerization, so that the MIPs are expected to be better applied. However, in the preparation of MIPs by mixing a plurality of template molecules, the more the template molecules, the greater the difficulty of preparation, because of the competitive relationship and self-polymerization between different template molecules, and to control the above factors, not only is a suitable raw material selected according to the overall reaction between the respective substances, but also the amount of each substance is precisely controlled during the preparation process to synthesize a desired polymerization product. The more the template molecules are, the more the species are, and the more difficult it becomes to select each material for judgment.
Disclosure of Invention
In order to solve the above defects in the prior art, the invention aims to provide a suspension polymerization preparation method of a mixed eight-template imprinted polymer, so as to synthesize a molecularly imprinted polymer which can specifically recognize triazole substances, pyrethroid substances, triazine substances, carbamate substances, phenylurea substances, benzimidazole substances, sulfonylurea substances and neonicotinoid substances at the same time, thereby achieving the purpose of detecting and analyzing residual pesticides in food, feed and other samples with high flux.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a suspension polymerization preparation method of a mixed eight-template imprinted polymer comprises the following steps of:
s1 selection of functional monomer and dispersion medium
Respectively selecting proper functional monomers and dispersion media aiming at the mixed eight-template substances by utilizing a mode of constructing a model by software; wherein the mixed octatemplate substance consists of triazole compounds, pyrethroid compounds, triazine compounds, carbamate compounds, phenylurea compounds, benzimidazole compounds, sulfonylurea compounds and neonicotinoid compounds;
s2, dissolving
Dissolving a polyvinyl alcohol dispersant and a mixed octatemplate substance into a dispersion medium, and then adding a functional monomer to obtain a solution B;
the molar ratio of the triazole compound, the pyrethroid compound, the triazine compound, the carbamate compound, the phenylurea compound, the benzimidazole compound, the sulfonylurea compound and the neonicotinoid compound in the mixed octatemplate substance is 1-1.3: 1-2: 1-1.3: 1-1.5;
the molar ratio of the mixed octatemplate substance to the functional monomer is 1: 0.5-10;
the molar volume ratio of the mixed octatemplate substance to the dispersion medium is 1mmol: 1-15 m L;
s3 prepolymerization
Performing ultrasonic treatment on the solution B at the frequency of 200Hz for 30-60 min, and then standing at the temperature of 4 ℃ for 8-16 h to obtain a product C;
s4 polymerization
Adding a crosslinking agent ethylene glycol dimethacrylate and an initiator azobisisobutyronitrile into the product C, performing ultrasonic treatment at the frequency of 200Hz for 10-30 min to obtain a mixture, dropwise adding the mixture into a water phase, and mixing to obtain a product D;
placing the product D in a constant-temperature water bath oscillator at 50-70 ℃, and carrying out oscillation reaction for 12-24 h to obtain a product E;
s5 elution of template molecules
Standing the product E to obtain a polymer product F, removing mixed octatemplate substances by using a methanol-acetic acid mixed solution, and then soaking by using methanol to remove excessive acetic acid to obtain a product G;
s6, drying
And drying the product G for 6H at the temperature of 45 ℃ and the vacuum degree of 0.04MPa to obtain a final product H, namely the mixed eight-template imprinted polymer.
As a limitation of the present invention, in step S1, the functional monomers are selected by using a Hyperchem software simulation method, and the steps are as follows:
a1, constructing a model by using Hyperchem software, and respectively optimizing a functional monomer, a template molecule and a functional monomer-template molecule compound structure by using an Amber force field to search the energy minimum conformation of the molecular model;
a2, after convergence, namely when RMS is 0.01, further fitting by adopting a semi-empirical quantification method, wherein the convergence standard is RMS 0.01, and obtaining single-point energy of the template molecule and the functional monomer;
a3, calculating the binding energy between the functional monomer and the template molecule, and the formula is as follows:
ΔE＝Epolymer-Efunction-Etemplate
wherein Δ E is binding energy, EpolymerIs a functional monomer-template molecule complex single-point energy, EfunctionAs a functional monomer with a single point of energy, EtemplateIs template molecule single point energy;
a4, comparing the binding energy between various functional monomers and template molecules, and selecting the functional monomers with the binding energy of the template molecules within the range of 1.9-12.0 kcal/mol.
As another limitation of the present invention, in step S1, the dispersion medium is selected by using Gaussian View software simulation, and the steps are as follows:
b1, constructing a model by using Gaussian View software, and performing structural optimization on the template molecules;
b2, and then calculating the solvation energy of the template molecule by adopting an IEFPCM polarized continuous medium model, wherein the calculation formula is as follows: | Δ E*|＝ES-EV；
Wherein, Delta E*Is the solvation energy of the template molecule in the dispersing medium, ESIs the interaction energy of the functional monomer and the template molecule in the solvent environment, EVIs the interaction energy of the functional monomer and the template molecule under the gas phase condition;
b3, selecting a dispersion medium having a small solvation energy as a criterion for the solvation energy.
As a third limitation of the present invention, in step S2, the polyvinyl alcohol dispersant accounts for 1.51% of the total mass of solution B; adding 5.23ml of dispersion medium into every 1mmol of mixed eight-template substance; the dissolving process of the product A and the mixed eight-template substance is carried out under the stirring condition, wherein the stirring speed is 350 r/min.
As still another limitation of the present invention, the triazole-based compound is bitertanol;
the pyrethroid compound is cyhalothrin;
the triazine compound is atrazine;
the carbamate compound is carbofuran;
the phenylurea compound is buthiuron;
the benzimidazole compound is probenazole;
the sulfonylurea compound is bensulfuron-methyl;
the neonicotinoid compound is imidacloprid;
the functional monomer is α -methacrylic acid;
the dispersion medium is chloroform.
As a further limitation of the present invention, the molar ratio of said bitertanol, cyhalothrin, atrazine, carbofuran, thifensulfuron-methyl, probenazole, bensulfuron-methyl, imidacloprid is 1.3:1: 2:1.3:1.3: 2: 1: 1.3.
in still another embodiment of the present invention, the molar ratio of the molar amount of the crosslinking agent to the total amount of the mixed octatemplate material is 15 to 40: 1;
when the dosage of the cross-linking agent is low, the prepared polymer has too low cross-linking degree, does not have certain rigidity, is difficult to form stable recognition cavities, and causes the reduction of adsorption capacity; on the contrary, the crosslinking degree is too high, the channel entering the hole is too hard and has no certain elasticity, so that the template molecules are difficult to enter the hole and the elution of the template molecules is not facilitated;
the molar ratio of the molar amount of the initiator to the total amount of the mixed octatemplate substances is 0.4-1.2: 1.
If the amount of the initiator is too large, the reagent is wasted, and if the amount of the initiator is too small, the polymerization cannot be initiated.
As a further limitation of the present invention, the volume ratio of methanol to acetic acid in the methanol-acetic acid mixed solution is 9: 1.
The invention also provides application of the mixed eight-template imprinted polymer, which is used for specifically adsorbing any one or more of triazole substances, pyrethroid substances, triazine substances, carbamate substances, phenylurea substances, benzimidazole substances, sulfonylurea substances and neonicotinoid substances.
As a limitation of the invention, the method is used for purifying any one or more of triazole compounds, pyrethroid compounds, triazine compounds, carbamate compounds, phenylurea compounds, benzimidazole compounds, sulfonylurea compounds and neonicotinoid compounds in a sample; or used for enriching and extracting any one or more of triazole compounds, pyrethroid compounds, triazine compounds, carbamate compounds, phenylurea compounds, benzimidazole compounds, sulfonylurea compounds and neonicotinoid compounds which are residual in the sample.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the mixed eight-template imprinted polymer prepared by the method has good stability and acid and alkali resistance, has multiple specific spatial sites, can simultaneously realize specific adsorption on eight compounds, namely triazoles, pyrethrins, triazines, carbamates, phenylureas, benzimidazoles, sulfonylureas and neonicotinoids, and has high adsorption efficiency and large adsorption capacity, so that the high flux problem in pesticide residue analysis is effectively solved, the detection efficiency is improved, and the detection cost is reduced.
(2) In the invention, when the functional monomer and the dispersion medium are selected, the selection is realized by adopting a software simulation mode, so that the times of operation experiments of researchers are reduced, the result deviation caused by the fact that the experiment conditions of each time are not ensured to be completely consistent and some errors of the researchers in the experiments can be avoided, and the waste of experiment raw materials is reduced (the selection experiment generally needs to carry out a plurality of different experiments and carry out contrastive analysis on the results). On the premise of reducing cost and ensuring reliability, corresponding functional monomers and dispersion media can be accurately selected according to different adopted template molecules, so that simple operability of a preparation process is ensured, and a good foundation is laid for preparing stable and efficient polymers.
(3) The mixed eight-template imprinted polymer prepared by the method has good dispersibility during use, and does not need complicated processes such as grinding, sieving and the like.
In conclusion, the preparation method provided by the invention is taken as a whole, the preparation process is simple, the conditions are easy to control, the prepared polymer is good in stability, acid and alkali resistance and dispersibility, grinding is not required, the triazole substances, the pyrethroid substances, the triazine substances, the carbamate substances, the phenylurea substances, the benzimidazole substances, the sulfonylurea substances and the neonicotinoid substances can be specifically adsorbed at the same time, and the preparation method is high in adsorption efficiency, strong in selectivity, good in stability and simple and convenient to operate.
The method is suitable for preparing the mixed eight-template imprinted polymer, and the prepared product can be further applied to separation and enrichment of samples during residue analysis of triazole, pyrethroid, triazine, carbamate, phenylurea, benzimidazole, sulfonylurea and neonicotinoid substances in food, feed, environmental samples and other samples.
Drawings
The invention is described in further detail below with reference to the figures and the embodiments.
FIG. 1 is a chemical structural formula of bitertanol;
FIG. 2 is a chemical structural formula of cyhalothrin;
FIG. 3 is the chemical structural formula of atrazine;
FIG. 4 is a chemical structural formula of carbofuran;
FIG. 5 is the chemical structural formula of buthiuron;
FIG. 6 shows the chemical structure of thiabendazole;
FIG. 7 is a chemical structural formula of bensulfuron methyl;
FIG. 8 is the chemical structural formula of imidacloprid;
FIG. 9 is a graph showing the effect of different proportions of functional monomers and mixed octatemplate materials on the UV spectrum of a preassembled system;
FIG. 10 is a perspective view and an isometric view of the effect of rotational speed and mass concentration of polyvinyl alcohol on the specific surface area of MIP;
FIG. 11 is a diagram of competitive adsorption performance of a mixed eight-template molecularly imprinted solid phase extraction column;
FIG. 12 is a scanning electron micrograph of a molecularly imprinted microsphere;
FIG. 13 mixed standard solution chromatography separation profile;
FIG. 14 is a chromatogram of an extract from a corn sample;
FIG. 15 is a graph of chromatographic separation of an eluate from a sample extract after MIP treatment;
FIG. 16 is a graph of chromatographic separation of an MIP-treated eluate of a sample spiked extract;
in fig. 11, 13 and 16: 1. 2-aminobenzimidazole, 2, thiabendazole, 3, methomyl, 4, simazine, 5, imidacloprid, 6, acetamiprid, 7, buthiuron, 8, metosulfuron, 9, carbofuran, 10, atrazine, 11, bensulfuron-methyl, 12, pyrazosulfuron-ethyl, 13, bitertanol, 14, diniconazole, 15, tetramethrin, 16, cyhalothrin.
Detailed Description
Preferred embodiments of the present invention will be described below with reference to the accompanying drawings. It should be understood that the description of the preferred embodiment is only for purposes of illustration and understanding, and is not intended to limit the invention.
Example 1 suspension polymerization preparation method of Mixed eight-template imprinted polymers
In this example, eight templates of imprinted polymer are mixed, and fig. 1 to 8 are chemical structural formulas of the template material, which are performed according to the following steps:
s1 preparation of polyvinyl alcohol dispersant
Firstly, a certain amount of polyvinyl alcohol is put into cold purified water to swell for 6 hours. Gradually raising the water temperature to 90 ℃, keeping for 60min until the water is completely dissolved, and continuously stirring in the dissolving process to fully disperse the polyvinyl alcohol in the water to obtain a product A.
S2, dissolving
Respectively dissolving 50ml of product A, 0.1mol of bitertanol, 0.1mmol of cyhalothrin, 0.1mmol of atrazine, 0.1mmol of carbofuran, 0.1mmol of buthiuron, 0.1mmol of thiabendazole, 0.1mmol of bensulfuron methyl and 0.1mmol of imidacloprid in a mixed eight-template substance in a dispersion medium, adding 3.2mmol of functional monomer, and carrying out the dissolving process under the stirring condition, wherein the stirring speed is 350r/min, thus obtaining solution B;
s3 prepolymerization
Placing the solution B in a refrigerator with the temperature of 4 ℃ for 12 hours under the frequency of 200Hz for ultrasonic treatment for 30min to obtain a product C;
s4 polymerization
Adding 8mmol of crosslinking agent ethylene glycol dimethacrylate and 0.25mmol of initiator azobisisobutyronitrile into the product C, ultrasonically degassing at the frequency of 200Hz for 15min to obtain a mixture, dropwise adding the mixture into the water phase, and mixing to obtain a product D;
placing the product D in a constant-temperature water bath oscillator at 65 ℃ for oscillation reaction for 24h to obtain a product E;
s5 elution of template molecules
Standing the product E to obtain a polymer product F, removing mixed octatemplate substances by using a methanol-acetic acid mixed solution with the volume ratio of 9:1, and then soaking by using methanol to remove excessive acetic acid to obtain a product G;
s6, drying
And drying the product G for 6H at the temperature of 45 ℃ and the vacuum degree of 0.04MPa, and then putting the product G into a dryer for later use to obtain a final product H, namely the mixed eight-template imprinted polymer.
In order to efficiently prepare an imprinted polymer having high stability and good dispersibility, before step S2, it is necessary to select the most suitable functional monomer and dispersion medium according to the specifically adopted template molecule.
In this embodiment, Hyperchem software simulation is used to theoretically analyze the mechanism of action of the template molecule and the functional monomer, and further to select the functional monomer, the specific steps are as follows:
a1, constructing a model by using Hyperchem software, and respectively optimizing the structures of the functional monomer, the template molecule and the functional monomer-template molecule compound by adopting an Amber force field to search the energy minimum conformation of the molecular model.
a2, after convergence (RMS is 0.01), further fitting by adopting a semi-empirical quantification method (PM3), wherein the convergence standard is also 0.01, and after the two steps are calculated, respectively obtaining the single-point energy of the functional monomer, the template molecule and the functional monomer-template molecule compound.
a3, calculating the binding energy (delta E) between the functional monomer and the template molecule, and the calculation result is shown in Table 1. The force field parameters are set as: the dielectric constant, van der Waals force, and electrostatic range were all 0.5. The specific formula is as follows:
ΔE＝Epolymer-Efunction-Etemplate(1)
wherein Δ E is binding energy, EpolymerIs a functional monomer-template molecule complex single-point energy, EfunctionAs a functional monomer with a single point of energy, EtemplateIs the template molecule single-point energy.
TABLE 1 binding energy (. DELTA.E, kcal/mol) of template molecules to functional monomers
Figure BDA0002446101160000091
Figure BDA0002446101160000101
Note that MAA is α -methacrylic acid, HEMA is hydroxyethyl methacrylate, AM is acrylamide, MAM is methacrylamide, 4-VP is 4-vinylpyridine, and 2-VP is 2-vinylpyridine.
a4, comparing and analyzing the binding energy between the above various functional monomers and the template molecule, and selecting the functional monomer.
As can be seen from the data in Table 1, 8 template molecules have strong binding capacity with MAM, AM and MAA, but the dispersing effect of the dispersing agent is greatly reduced due to the strong capacity of forming hydrogen bonds between polyvinyl alcohol (PVA) and water and amide bonds between MAM and AM, so that the oil-water separation phenomenon is caused, and a block polymer is formed during polymerization, so that the MAA is comprehensively considered and selected as a functional monomer.
In this embodiment, a Gaussian View software simulation mode is adopted, and a suitable dispersion medium is selected based on solvation energy. The method comprises the following specific steps:
b1, constructing a model by means of Gaussian View software, and performing structural optimization on template molecules by using a B3L YP density functional theory and taking 6-31G (d, p) as a base group.
b2, and calculating the solvation energy of the continuous medium by using an IEFPCM polarization continuous medium model, wherein the calculation result is shown in a table 2, and the calculation formula is as follows:
|ΔE*|＝ES-EV(2)
wherein E isSIs the interaction energy of the functional monomer and the template molecule in the solvent environment, EVIs the interaction energy of the functional monomer and the template molecule under the gas phase condition.
b3, selecting a dispersion medium using solvation energy as a criterion.
Usually with Δ E*To reflect the difference between the dispersion medium and the template molecule-functional monomer prepolymerThe action strength and the strong solvent action can weaken the interaction between the template molecules and the functional monomers, thereby reducing the molecular recognition capability of the molecularly imprinted polymer and being not beneficial to the preparation of the molecularly imprinted polymer.
From the data in table 2, the interaction strengths of the eight template molecules with the dispersion medium are: dimethyl sulfoxide > acetonitrile > methanol > acetone > tetrahydrofuran > chloroform > toluene, but since toluene is toxic and post-treatment is troublesome, chloroform was selected as the dispersion medium.
TABLE 2 solvation energy (kcal/mol) of template molecules in the dispersing medium
Figure BDA0002446101160000111
To be noted: the template molecules are selected from any one of eight pesticides including bitertanol, cyhalothrin, atrazine, carbofuran, thidiazuron, thiabendazole, bensulfuron methyl and imidacloprid.
Example 2-6 suspension polymerization preparation of Mixed eight template imprinted polymers
Examples 2-6 are suspension polymerization processes for preparing mixed eight-template imprinted polymers, respectively, and the processes are the same as in example 1, except that: the corresponding technical parameters are different, and the specific results are shown in Table 3.
TABLE 3
Figure BDA0002446101160000112
Figure BDA0002446101160000121
Example 7 template molecule to functional monomer ratio determination assay
This example explores the determination of the ratio of mixed octatemplate material to functional monomer during polymerization. In the embodiment, ultraviolet spectroscopy is adopted to respectively perform ultraviolet spectrum scanning on mixed eight-template material-MAA systems with different proportions.
Preparing MAA-acetonitrile solution and mixed octatemplate substance-acetonitrile solution with certain concentrations respectively, preparing mixed acetonitrile solution of functional monomer and template substance at the same time, making the molar ratio of them respectively be 1:0,1:2,1:4,1:6,1:8 and 1:10, and making UV spectrum scanning between wavelength 190 and 400 nm.
FIG. 9 is a graph a of UV scans of mixtures of F and T at different ratios; FIG. b is a plot of the maximum absorption wavelength and the corresponding absorbance for the mixture of FIG. a; wherein: in the diagram a, T is mixed eight-template substances, F is a functional monomer, and the upper right corner of the diagram a is marked with a molar ratio; in the figure b, 1-5 are respectively T and F molar ratio of 1: 2-1: 10.
As can be seen from graph a in FIG. 9, the maximum absorption wavelength of the mixture is red-shifted due to hydrogen bonding between the mixed octatemplate material and the functional monomer. When the change of the absorption value is nearly flat, the mixture corresponding to the system in the flat area tends to be stable in the range, and the mixture ratio corresponding to the turning point entering the flat area is the optimal ratio.
From the b-plot in FIG. 9, it can be seen that the absorbance and wavelength change are relatively flat after mixing the octatemplate material with MAA at a molar ratio of 1:4 (corresponding to point 2 in the plot). From this, it can be inferred that the mixing ratio of the octatemplate substance to MAA of 1:4 is the optimum concentration ratio in the polymerization.
Example 8 mixed eight template species testing at different ratios
When the proportion of the eight template substances is proper, a polymerization system with lower energy and more stability can be formed with the functional monomer, so that the polymer has more specific adsorption sites after eluting a target object. As can be seen from Table 4, the adsorption amount was large and the effect of adsorbing the target was good when the ratio of mixed octatemplate substances was 2:2:1.3:1.3:1.3: 1: 1.
TABLE 4 Effect of mixing eight templates in different proportions on Polymer adsorption Performance
Figure BDA0002446101160000131
Figure BDA0002446101160000141
Note: a is thiabendazole, B is atrazine, C is carbofuran, D is thifensulfuron, E is imidacloprid, F is bitertanol, G is bensulfuron-methyl, and H is cyhalothrin.
Example 9 optimization of the suspension polymerization method for preparing molecularly imprinted polymers
One, one factor optimization test
(1) Optimization of dispersant mass concentration
The mass concentration of the dispersing agent is large, the particle size of the polymer is small, the monodispersity is good, and the particle size distribution is narrow; the dispersant concentration is small, and not only does it fail to obtain an ideal particle diameter, but also the stability of the system is deteriorated.
Respectively taking 0.5% PVA, 1% PVA, 1.5% PVA, 2% PVA and 2.5% PVA as dispersing agents, MAA as a functional monomer, chloroform as a dispersing medium and ethylene glycol dimethacrylate (EDMA) as a cross-linking agent, synthesizing MIP by adopting a suspension polymerization thermal initiation mode at a certain stirring speed, and comparing the influence of dispersing agents with different mass fractions on the MIP specific surface area.
TABLE 5 Effect of dispersant Mass concentration versus surface area
Polymer and method of making same Amount of dispersant (%) Specific surface area (m2/kg)
MIP1 0.5 17.63
MIP2 1.0 20.54
MIP3 1.5 25.44
MIP4 2.0 23.96
MIP5 2.5 22.54
(2) Optimization of the amount of dispersion medium
The amount of the dispersion medium is increased, that is, the amount of the dispersion medium used is controlled within a certain range from the economical viewpoint, although the monomer droplets are less likely to aggregate and the average particle diameter is smaller than the monomer phase (the amount of the dispersion medium is larger than the monomer phase).
Respectively taking chloroform with the concentration of 3m L, 5m L, 7m L and 9m L as dispersion media, MAA as a functional monomer and EDMA as a cross-linking agent, synthesizing MIP by adopting a suspension polymerization thermal initiation mode at a certain stirring speed, and comparing the influence of different dosage of dispersion media on the specific surface area of the MIP.
TABLE 6 Effect of amount of dispersing Medium versus surface area
Polymer and method of making same Amount of dispersion medium (m L) Specific surface area (m2/kg)
MIP6 2 Irregular block shape
MIP7
5 28.32
MIP8 7 22.73
MIP9 9 20.56
(3) Optimization of the stirring speed
The size of the polymer particles can be controlled by varying the stirring speed. The stirring speed is increased, the polymer particle size is reduced, but when the stirring speed is too high, the probability of collision and coalescence of liquid drops is increased, so that the polymer particle size is increased, and therefore, the proper stirring speed is selected, the particle size is reduced, and the specific surface area is increased.
The stirring speeds are respectively set to be 100r/min, 200r/min, 300r/min and 400r/min, MAA is a functional monomer, chloroform is a dispersion medium, EDMA is a cross-linking agent, MI P is synthesized by adopting a suspension polymerization thermal initiation mode, and the influences of different stirring speeds on the MIP specific surface area are compared.
TABLE 7 Effect of speed of rotation on surface area
Polymer and method of making same Rotating speed (r/min) Specific surface area (m2/kg)
MIP10 100 Irregular block shape
MIP11
200 20.54
MIP12 300 25.44
MIP13 400 23.65
Secondly, optimizing MIP synthetic process conditions by using response surface method
Through single factor tests, the factors such as the mass concentration of the dispersing agent, the dosage of the dispersing medium, the stirring speed and the like have certain influence on the specific surface area of the polymer, and certain interaction influence may exist among the factors. The experiment adopts a Box-Behnken center Design method in Design-Expert 8.0.6 software to optimize the synthetic process of preparing MIP by suspension polymerization, and the Design of the experimental factor level is shown in Table 8. The test protocol was entered into the software and the test design and results are shown in table 9.
TABLE 8 level of test factors
Figure BDA0002446101160000161
Table 9 test design and results
Figure BDA0002446101160000162
Figure BDA0002446101160000171
TABLE 10 test ANOVA
Figure BDA0002446101160000172
Figure BDA0002446101160000181
The results show that the Y1 model P is less than 0.01, the response surface model achieves a significant level, the primary and secondary sequence of the factors influencing the surface area is C > A > B, wherein the influence of the factor A (dispersant content (%), the factor B (dispersion medium (m L)) and the factor C (stirring speed (r/min)) is very significant (P is less than 0.01), the P of all interaction items is more than 0.05, the interaction is not significant, and the mismatching item indicates that the predicted value and the actual value of the quadratic equation are high in goodness of match.
As can be seen from FIG. 10, the specific surface area increases with the increase of the rotating speed, and increases and then decreases with the increase of the mass concentration of the polyvinyl alcohol, the response curve surface changes faster along the X3 direction and slower along the X1 direction, which shows that the influence of the rotating speed on the specific surface area is more remarkable than that of the polyvinyl alcohol at the test level, the optimal process is obtained by comprehensively analyzing the specific surface area (Y1) of the influencing polymer by applying Design-Expert 8.0.6 software, wherein the polyvinyl alcohol is 1.51%, the chloroform is 5.23m L, the stirring speed is 350r/min, the specific surface area is 35.0014m 2/kg., the average value of the process parameter is 34.8800m2/kg, the deviation from the predicted value of the model is 1.44%, and the optimization result of the model is the credibly determined optimal process.
Example 10 competitive adsorption test
In this example, the specific adsorption capacity of the molecularly imprinted polymer was examined, and the prepared polymer was tested for the adsorption performance of eight types of pesticides and structural analogs thereof.
Putting 20mg MIP into a 25m L colorimetric cylinder, then adding 5m L of a certain concentration of 2-aminobenzimidazole, thiabendazole, methomyl, simazine, imidacloprid, acetamiprid, buthiuron, metoxuron, carbofuran, bensulfuron-methyl, pyrazosulfuron-ethyl, atrazine, diniconazole, bitertanol, tetramethrin and cyhalothrin acetonitrile solution, oscillating the mixture at a constant temperature of 25 ℃ for 24h, collecting supernatant, and passing the supernatant through a membrane for HP L C analysis.
As can be seen from FIG. 11, the polymer adsorbs 16 pesticides, but the adsorption sizes are different, and the adsorption effect of template molecules is better than that of structural analogues under common conditions; the small molecular pesticide has large adsorption capacity compared with the large molecular pesticide. The reason is the specific adsorption performance of the imprinted polymer, and the steric hindrance of the small molecular substance in the adsorption process is small.
Example 11 characterization of suspension polymerized microspheres-scanning Electron microscopy analysis
In this embodiment, a vacuum dried and stored sample is attached to a sample stage of a scanning electron microscope by using a conductive adhesive, then, ion sputtering is performed to spray gold with a thickness of 60nm, and then, electron microscope observation is performed, so that the sample presents a regular spherical shape in a micron-sized range, the particle size is about 85 μm, the shape is uniform and round, and the result is shown in fig. 12.
Example 12 application of Mixed eight-template molecularly imprinted polymer microspheres in corn sample detection
Firstly, sample treatment
(1) Pretreatment of samples
Weighing 3.000g of sample, grinding or cutting, placing in a 50m L centrifuge tube, adding excessive anhydrous sodium sulfate into fruit and vegetable samples to remove excessive water, adding no extract into grains, using 20m L acetonitrile as an extractant (extracting twice), stirring, performing ultrasonic treatment for 20min, then centrifuging (7000r/min, 5min), absorbing 1m L supernatant, extracting with imprinted polymer, rinsing with 10m L water, eluting with 5m L10% acetic acid-methanol solution, centrifuging, collecting eluate, filtering with 0.45 μm microporous membrane, and analyzing with HP L C.
(2) Measurement conditions of HP L C
The chromatographic column comprises Xbridge C18(250mm × 4.6.6 mm, 5 μm), acetonitrile-0.02% phosphoric acid water solution as mobile phase, solvent gradient and wavelength gradient, and is shown in tables 11 and 12, and has a column temperature of 30 deg.C and a sample introduction amount of 20 μ L.
TABLE 11 gradient elution procedure
Figure BDA0002446101160000191
Figure BDA0002446101160000201
TABLE 12 wavelength gradient parameter program
Components Retention time/min Program time/min Detection wavelength/nm Channel
2-aminobenzimidazole 5.81 0 210 A
Thiabendazole 7.00 6.25 300 A
Methomyl 7.83 7.20 235 A
Simazine 9.12 8.50 210 A
Imidacloprid 11.54 10.30 270 A
Acetamiprid 12.60 11.98 245 A
Thidiazuron 16.49 13.50 255 A
Mesonalong-leaf swertia herb 15.37 16.90 250 A
Carbofuran 16.36 15.90 210 A
Atrazine 16.84 16.66 225 A
Bensulfuron methyl 17.36 17.20 235 A
Pyrazosulfuron-ethyl 18.15 17.78 245 A
Biphenyltriazolyl alcohols 19.31 18.35 255 A
Diniconazole 19.97 19.70 250 A
Amethrin 24.65 21.00 225 A
Cyhalothrin 25.65 25.36 210 A
Wherein, the high performance liquid chromatogram of the corn sample extract is shown in fig. 14, the high performance liquid chromatogram of the eluate of the corn extract after MIP treatment is shown in fig. 15, and the high performance liquid chromatogram of the eluate of the corn labeled extract after MIP treatment is shown in fig. 16.
The molecularly imprinted extraction material utilizes non-covalent bonds to specifically adsorb a target object, removes impurity components in a sample by leaching, and then elutes the target object by using an eluant. From the comparison of fig. 14 and 15, it can be seen that the molecular imprinting extraction material has no adsorption capacity for impurities, and the sample purification effect is good. As can be seen from FIG. 16, the molecularly imprinted extraction material has adsorption capacity only for the template substance and its structural analogs, which indicates the superior performance of the polymer in specific separation and enrichment of the target substance from the sample with complex composition.
Second, linear relationship and detection limit
2-aminobenzimidazole, probenazole, methomyl, simazine, imidacloprid, acetamiprid, thifensulfuron-methyl, metocloprid, bensulfuron-methyl, pyrazosulfuron-ethyl, atrazine, diniconazole, bitertanol, tetramethrin and cyhalothrin are respectively prepared into a series of standard solutions with the mass concentration of 0.01-50 mg/L, and a standard curve is drawn, and the linear relation and the detection limit are shown in Table 13.
TABLE 1316 Linear relationships and detection limits for pesticides
Figure BDA0002446101160000211
Figure BDA0002446101160000221
As can be seen from table 13, 16 pesticides have good linear correlations, the linear range of 16 pesticides is between 0.03 and 50 mg/L, the detection limit (determined by S/N ═ 3) is between 0.01 and 0.06 mg/L, and the linear correlation coefficient of 16 pesticides is between 0.9967 and 1.0000.
Recovery rate and precision test of three-eight template molecularly imprinted polymer
The results of the standard recovery rate tests of 1 mg/L and 10 mg/L on samples of cucumber, corn, citrus, banana and peanut kernel are shown in Table 14, the average recovery rate (AR) of 16 pesticides is 82.3-98.7%, and the Relative Standard Deviation (RSD) is less than or equal to 5.35%.
TABLE 14 sample recovery and precision tests
Figure BDA0002446101160000222
Figure BDA0002446101160000231
Figure BDA0002446101160000241
Although the present invention has been described in detail with reference to the above embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A suspension polymerization preparation method of a mixed eight-template imprinted polymer is characterized by comprising the following steps: comprises the following steps which are carried out in sequence:
s1 selection of functional monomer and dispersion medium
Respectively selecting proper functional monomers and dispersion media aiming at the mixed eight-template substances by utilizing a mode of constructing a model by software; wherein the mixed octatemplate substance consists of triazole compounds, pyrethroid compounds, triazine compounds, carbamate compounds, phenylurea compounds, benzimidazole compounds, sulfonylurea compounds and neonicotinoid compounds;
s2, dissolving
Dissolving a polyvinyl alcohol dispersant and a mixed octatemplate substance into a dispersion medium, and then adding a functional monomer to obtain a solution B;
the molar ratio of the triazole compound, the pyrethroid compound, the triazine compound, the carbamate compound, the phenylurea compound, the benzimidazole compound, the sulfonylurea compound and the neonicotinoid compound in the mixed octatemplate substance is 1-1.3: 1-2: 1-1.3: 1-1.5;
the molar ratio of the mixed octatemplate substance to the functional monomer is 1: 0.5-10;
the molar volume ratio of the mixed octatemplate substance to the dispersion medium is 1mmol: 1-15 m L;
s3 prepolymerization
Performing ultrasonic treatment on the solution B at the frequency of 200Hz for 30-60 min, and then standing at the temperature of 4 ℃ for 8-16 h to obtain a product C;
s4 polymerization
Adding a crosslinking agent ethylene glycol dimethacrylate and an initiator azobisisobutyronitrile into the product C, performing ultrasonic treatment at the frequency of 200Hz for 10-30 min to obtain a mixture, dropwise adding the mixture into a water phase, and mixing to obtain a product D;
placing the product D in a constant-temperature water bath oscillator at 50-70 ℃, and carrying out oscillation reaction for 12-24 h to obtain a product E;
s5 elution of template molecules
Standing the product E to obtain a polymer product F, removing mixed octatemplate substances by using a methanol-acetic acid mixed solution, and then soaking by using methanol to remove excessive acetic acid to obtain a product G;
s6, drying
And drying the product G for 6H at the temperature of 45 ℃ and the vacuum degree of 0.04MPa to obtain a final product H, namely the mixed eight-template imprinted polymer.
2. The method for preparing mixed eight-template imprinted polymer according to claim 1, characterized in that: in step S1, a Hyperchem software simulation mode is used to select a functional monomer, which includes the following steps:
a1, constructing a model by using Hyperchem software, and respectively optimizing a functional monomer, a template molecule and a functional monomer-template molecule compound structure by using an Amber force field to search the energy minimum conformation of the molecular model;
a2, after convergence is finished, namely when RMS =0.01, further fitting by adopting a semi-empirical quantification method, wherein the convergence standard is RMS =0.01, and obtaining single-point energy of the template molecules and the functional monomers;
a3, calculating the binding energy between the functional monomer and the template molecule, and the formula is as follows:
ΔE=Epolymer-Efunction-Etemplate
wherein Δ E is binding energy, EpolymerIs a functional monomer-template molecule complex single-point energy, EfunctionAs a functional monomer with a single point of energy, EtemplateIs template molecule single point energy;
a4, comparing the binding energy between various functional monomers and template molecules, and selecting the functional monomers with the binding energy of the template molecules within the range of 1.9-12.0 kcal/mol.
3. The method for preparing a mixed eight-template imprinted polymer by suspension polymerization according to claim 1 or 2, characterized in that: in step S1, the dispersion medium is selected by using Gaussian View software simulation, and the steps are as follows:
b1, constructing a model by using Gaussian View software, and performing structural optimization on the template molecules;
b2, and then calculating the solvation energy of the template molecule by adopting an IEFPCM polarized continuous medium model, wherein the calculation formula is as follows: | Δ E*|=ES-EV；
Wherein, Delta E*Is the solvation energy of the template molecule in the dispersing medium, ESIs the interaction energy of the functional monomer and the template molecule in the solvent environment, EVIs the interaction energy of the functional monomer and the template molecule under the gas phase condition;
b3, selecting a dispersion medium having a small solvation energy as a criterion for the solvation energy.
4. The method for preparing mixed eight-template imprinted polymer according to claim 1, characterized in that: in step S2, polyvinyl alcohol dispersant accounts for 1.51% of the total mass of the solution B; adding 5.23ml of dispersion medium into every 1mmol of mixed eight-template substance; the dissolution process of the polyvinyl alcohol dispersant and the mixed octatemplate substance is carried out under the stirring condition, wherein the stirring speed is 350 r/min.
5. The method for preparing mixed eight-template imprinted polymer according to any one of claims 1 to 2 and 4, characterized in that: the triazole compound is bitertanol;
the pyrethroid compound is cyhalothrin;
the triazine compound is atrazine;
the carbamate compound is carbofuran;
the phenylurea compound is buthiuron;
the benzimidazole compound is probenazole;
the sulfonylurea compound is bensulfuron-methyl;
the neonicotinoid compound is imidacloprid;
the functional monomer is α -methacrylic acid;
the dispersion medium is chloroform.
6. The method for preparing mixed eight-template imprinted polymer according to claim 5, characterized in that: the molar ratio of the bitertanol, the cyhalothrin, the atrazine, the carbofuran, the tebuthiuron, the probenazole, the bensulfuron methyl and the imidacloprid is 1.3:1: 2:1.3:1.3: 2: 1: 1.3.
7. the method for preparing mixed eight-template imprinted polymer according to claim 1, characterized in that: the molar ratio of the molar weight of the cross-linking agent to the total amount of the mixed octatemplate substances is 15-40: 1;
the molar ratio of the molar amount of the initiator to the total amount of the mixed octatemplate substances is 0.4-1.2: 1.
8. The suspension polymerization preparation method of mixed eight-template imprinted polymer according to claim 7, characterized in that: in the methanol-acetic acid mixed solution, the volume ratio of methanol to acetic acid is 9: 1.
9. The application of the mixed eight-template imprinted polymer, wherein the mixed eight-template imprinted polymer is prepared by the suspension polymerization preparation method of the mixed eight-template imprinted polymer as claimed in claim 1, and is characterized in that: it is used for specifically adsorbing any one or more of triazole substances, pyrethroid substances, triazine substances, carbamate substances, phenylurea substances, benzimidazole substances, sulfonylurea substances and neonicotinoid substances.
10. Use of a mixed eight-template imprinted polymer according to claim 9, characterized in that: the method is used for purifying any one or more of triazole compounds, pyrethroid compounds, triazine compounds, carbamate compounds, phenylurea compounds, benzimidazole compounds, sulfonylurea compounds and neonicotinoid compounds in a sample; or used for enriching and extracting any one or more of triazole compounds, pyrethroid compounds, triazine compounds, carbamate compounds, phenylurea compounds, benzimidazole compounds, sulfonylurea compounds and neonicotinoid compounds which are residual in the sample.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113209948A (en) * 2021-05-19 2021-08-06 齐鲁工业大学 Preparation method and application of multi-template molecularly imprinted composite material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030134296A1 (en) * 2000-01-25 2003-07-17 Beining Chen Molecularly imprinted polymer
CN103396512A (en) * 2013-07-24 2013-11-20 河北科技大学 Hybrid template molecularly imprinted polymer as well as preparation method and application of hybrid template molecularly imprinted solid-phase extraction column
CN105330782A (en) * 2015-12-10 2016-02-17 新疆农垦科学院 Oleanic acid molecularly imprinted polymer based on computer simulation and preparation method thereof and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030134296A1 (en) * 2000-01-25 2003-07-17 Beining Chen Molecularly imprinted polymer
CN103396512A (en) * 2013-07-24 2013-11-20 河北科技大学 Hybrid template molecularly imprinted polymer as well as preparation method and application of hybrid template molecularly imprinted solid-phase extraction column
CN105330782A (en) * 2015-12-10 2016-02-17 新疆农垦科学院 Oleanic acid molecularly imprinted polymer based on computer simulation and preparation method thereof and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
刘英等: "分子模拟在分子印迹技术中的应用", 《化工学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113209948A (en) * 2021-05-19 2021-08-06 齐鲁工业大学 Preparation method and application of multi-template molecularly imprinted composite material

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