CN110684163A - Preparation method of dendrimer-modified magnetic chitosan surface imprinted polymer - Google Patents
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Abstract
The invention relates to the technical field of molecular imprinting, and discloses a preparation method of a dendrimer-modified magnetic chitosan surface imprinted polymer. The method comprises the following steps: 1) alkylating the ferroferric oxide particles to obtain alkylated ferroferric oxide particles; 2) polymerizing chitosan and itaconic acid on the surface of alkylated ferroferric oxide particles to obtain polymer composite magnetic particles; 3) adding the polymer composite magnetic particles into a dendrimer polyamidoamine solution for reaction at room temperature to obtain dendrimer composite magnetic particles; 4) mixing template molecules, dendrimer composite magnetic particles and acetonitrile, standing, separating solid particles, adding the solid particles, functional monomers, a cross-linking agent and an initiator into the acetonitrile, carrying out magnetic stirring reaction, and cleaning the template molecules through Soxhlet extraction. The imprinted polymer has good adsorption effect and large adsorption capacity, and is not easy to desorb template substances.
Description
Technical Field
The invention relates to the technical field of molecular imprinting, in particular to a preparation method of a dendrimer-modified magnetic chitosan surface imprinted polymer.
Background
The molecular imprinting technology is a technology for preparing a high molecular polymer with specific recognition performance on target molecules, and surface molecular imprinting is one of the key research points in the technical field of molecular imprinting at present. The molecular imprinting technology is a new technology for preparing polymers with molecular recognition capability, but has some serious defects, such as incomplete template molecule removal, low utilization rate of active sites, poor adsorption-desorption performance, poor mechanical performance and the like. The surface molecular imprinting technology can better solve the limitation of the traditional molecular imprinting technology by establishing the molecular recognition sites on the surface of the matrix material. Chinese patent publication No. CN108059700 discloses a modified imprinted polymer with improved adsorption capacity and a preparation method thereof, wherein the preparation method of the modified imprinted polymer with improved adsorption capacity comprises the following steps: (1) preparing modified silicon dioxide; (2) preparing a metal complex; (3) preparing functional microcapsule monomers; (4) preparing imprinted macromolecules; (5) and removing the template agent. According to the technical scheme, the molecular imprinting is prepared on the surface of the modified silicon dioxide, the microcapsule structure is adopted to enable metal ions to be uniformly dispersed in the polymer, agglomeration is avoided, the uniformity of imprinting sites is improved, however, the desorption phenomenon is easy to occur after adsorption on a template type substance, the adsorption capacity is small, and the adsorption saturation state is easy to achieve.
Disclosure of Invention
The invention aims to overcome the problems that the imprinted polymer in the prior art is easy to desorb adsorbed template substances and has small adsorption capacity and is easy to reach adsorption saturation, and provides a preparation method of a dendrimer-modified magnetic chitosan surface imprinted polymer.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of a dendrimer modified magnetic chitosan surface imprinted polymer comprises the following steps:
1) adding 3- (methacryloyloxy) propyl trimethoxy silane into deionized water, stirring for dissolving, heating to 30-40 ℃, adding ferroferric oxide particles, reacting at constant temperature under stirring, performing magnetic separation, and drying to obtain alkylated ferroferric oxide particles;
2) adding chitosan and itaconic acid into an aqueous solution of acetic acid, and stirring and dissolving to obtain a mixed solution; adding alkylated ferroferric oxide particles into the mixed solution, heating to 45-50 ℃, adding an initiator potassium persulfate, carrying out heat preservation reaction, carrying out magnetic separation, and drying to obtain polymer composite magnetic particles;
3) adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding polymer composite magnetic particles into the dendrimer polyamidoamine solution, adding a condensing agent EDCI, reacting at room temperature, performing magnetic separation, and drying to obtain dendrimer composite magnetic particles;
4) mixing template molecules, dendrimer composite magnetic particles and acetonitrile, magnetically stirring, standing, separating solid particles, adding the solid particles, functional monomers, a cross-linking agent and an initiator into the acetonitrile, uniformly mixing, magnetically stirring for reaction at 50-60 ℃, magnetically separating, drying, cleaning the template molecules through Soxhlet extraction, separating and drying to obtain the nano-composite magnetic material.
The method comprises the steps of firstly, carrying out alkylation treatment modification on ferroferric oxide particles by using a silane coupling agent to organize the surfaces of the ferroferric oxide particles, carrying out polymerization reaction on chitosan and itaconic acid on the surfaces of the alkylated ferroferric oxide particles to generate a three-dimensional reticular high polymer with an adsorption effect, and then grafting dendritic high polymer polyamidoamine on the surfaces of the three-dimensional reticular polymer, wherein the dendritic high polymer polyamidoamine has a regular macromolecular structure, a large number of cavities exist in the dendritic high polymer polyamidoamine, and the cavities can adsorb and contain template high polymer substances, so that a double-layer three-dimensional adsorption structure is formed; the surface of the compound has a large amount of amino groups, so that abundant imprinting sites are improved, and the imprinting efficiency is improved. The invention uses a double-layer three-dimensional adsorption structure, has larger adsorption space, better adsorption capacity to template macromolecules, large adsorption capacity and difficult desorption to template substances. In addition, the three-dimensional adsorption structure can effectively overcome the defects of irregular polymer shape, few effective binding sites, low mass transfer speed and the like in the traditional imprinting. Chitosan is a commonly used and easily available cationic polysaccharide, and can be used as a carrier for surface molecular imprinting due to its high specific surface area, chemical stability and biocompatibility. The modified magnetic ferroferric oxide nano-particles have better biocompatibility, magnetic property and dispersibility, narrow particle size distribution and can be quickly and effectively bonded with biomolecules; the surface functional group of the dendrimer can form a composite material through stable metal ions such as chain ion interaction, acid-base interaction and the like, and can also realize multifunctional modification through covalent bond grafting, and an internal cavity can be loaded with target molecules in a wrapping mode and used as host molecules to be selectively combined with guest molecules.
Preferably, the mass ratio of the chitosan to the itaconic acid in the step 2) is 1: 2-3.
Preferably, the heat preservation reaction time in the step 2) is 30-50 min.
Preferably, the mass ratio of the polymer composite magnetic particles to the dendrimer polyamidoamine in the step 3) is 1: 3-6.
Preferably, the functional monomer in the step 4) is methacrylic acid.
Preferably, the template molecule in step 4) is a phenolic substance.
Preferably, the mass ratio of the template molecules to the functional monomers in the step 4) is 1: 4-6.
Preferably, the initiator in the step 4) is at least one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
Preferably, the crosslinking agent in the step 4) is ethylene glycol dimethacrylate.
Therefore, the invention has the following beneficial effects: (1) the double-layer three-dimensional adsorption structure is used, so that the adsorption structure has a larger adsorption space, has better adsorption capacity on template macromolecules, has large adsorption capacity and is not easy to desorb template substances; and (2) the three-dimensional adsorption structure can effectively overcome the defects of irregular polymer shape, few effective binding sites, low mass transfer speed and the like in the traditional imprinting. Chitosan is a commonly used and easily available cationic polysaccharide, and can be used as a carrier for surface molecular imprinting due to its high specific surface area, chemical stability and biocompatibility. The modified magnetic ferroferric oxide nano-particles have better biocompatibility, magnetic property and dispersibility, narrow particle size distribution and can be quickly and effectively bonded with biomolecules.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
Example 1
The preparation method of the dendrimer modified magnetic chitosan surface imprinted polymer comprises the following steps:
1) adding 0.5g of 3- (methacryloyloxy) propyl trimethoxy silane into 50mL of deionized water, stirring for dissolving, heating to 35 ℃, adding 1.5g of ferroferric oxide particles, reacting for 2 hours at constant temperature under the condition of stirring, performing magnetic separation, and drying to obtain alkylated ferroferric oxide particles;
2) adding 3g of chitosan and 7g of itaconic acid into 250mL of an aqueous solution of 10 wt% acetic acid, and stirring and dissolving to obtain a mixed solution; adding 2g of alkylated ferroferric oxide particles into the mixed solution, heating to 50 ℃, adding 0.05g of initiator potassium persulfate, carrying out heat preservation reaction for 40min, carrying out magnetic separation, and drying to obtain polymer composite magnetic particles;
3) adding 8g of dendrimer polyamidoamine into 300mL of deionized water to prepare a dendrimer polyamidoamine solution, adding 2g of polymer composite magnetic particles into the dendrimer polyamidoamine solution, adding 0.1g of condensing agent EDCI, reacting at room temperature for 1.5h, performing magnetic separation, and drying to obtain dendrimer composite magnetic particles;
4) mixing 2g of template molecule 4-chlorophenol, 5g of dendrimer composite magnetic particles and 300mL of acetonitrile, magnetically stirring, standing for 15h, separating solid particles, adding the solid particles, 10g of functional monomer methacrylic acid, 0.5g of cross-linking agent ethylene glycol dimethacrylate and 0.05g of initiator azobisisobutyronitrile into 350mL of acetonitrile, uniformly mixing, magnetically stirring and reacting for 2h at 55 ℃, magnetically separating, drying, washing the template molecule through Soxhlet extraction, separating and drying to obtain the compound magnetic material.
Example 2
The preparation method of the dendrimer modified magnetic chitosan surface imprinted polymer comprises the following steps:
1) adding 0.5g of 3- (methacryloyloxy) propyl trimethoxy silane into 50mL of deionized water, stirring for dissolving, heating to 40 ℃, adding 1.5g of ferroferric oxide particles, reacting for 2 hours at constant temperature under the condition of stirring, performing magnetic separation, and drying to obtain alkylated ferroferric oxide particles;
2) adding 3g of chitosan and 8g of itaconic acid into 250mL of an aqueous solution of 10 wt% acetic acid, and stirring and dissolving to obtain a mixed solution; adding 2g of alkylated ferroferric oxide particles into the mixed solution, heating to 50 ℃, adding 0.05g of initiator potassium persulfate, carrying out heat preservation reaction for 45min, carrying out magnetic separation, and drying to obtain polymer composite magnetic particles;
3) adding 10g of dendrimer polyamidoamine into 300mL of deionized water to prepare a dendrimer polyamidoamine solution, adding 2g of polymer composite magnetic particles into the dendrimer polyamidoamine solution, adding 0.1g of condensing agent EDCI, reacting for 2h at room temperature, performing magnetic separation, and drying to obtain dendrimer composite magnetic particles;
4) mixing 2g of template molecule 4-chlorophenol, 5g of dendrimer composite magnetic particles and 300mL of acetonitrile, magnetically stirring, standing for 16h, separating solid particles, adding the solid particles, 10g of functional monomer methacrylic acid, 0.5g of cross-linking agent ethylene glycol dimethacrylate and 0.05g of initiator azobisisoheptonitrile into 350mL of acetonitrile, uniformly mixing, magnetically stirring and reacting for 2h at 55 ℃, magnetically separating, drying, washing the template molecule through Soxhlet extraction, separating and drying to obtain the compound magnetic nanoparticle.
Example 3
The preparation method of the dendrimer modified magnetic chitosan surface imprinted polymer comprises the following steps:
1) adding 0.5g of 3- (methacryloyloxy) propyl trimethoxy silane into 50mL of deionized water, stirring for dissolving, heating to 30 ℃, adding 1g of ferroferric oxide particles, reacting for 1 hour at constant temperature under the condition of stirring, performing magnetic separation, and drying to obtain alkylated ferroferric oxide particles;
2) adding 3g of chitosan and 7g of itaconic acid into 250mL of an aqueous solution of 10 wt% acetic acid, and stirring and dissolving to obtain a mixed solution; adding 2g of alkylated ferroferric oxide particles into the mixed solution, heating to 45 ℃, adding 0.05g of initiator potassium persulfate, carrying out heat preservation reaction for 40min, carrying out magnetic separation, and drying to obtain polymer composite magnetic particles;
3) adding 7g of dendrimer polyamidoamine into 300mL of deionized water to prepare a dendrimer polyamidoamine solution, adding 2g of polymer composite magnetic particles into the dendrimer polyamidoamine solution, adding 0.1g of condensing agent EDCI, reacting for 1h at room temperature, performing magnetic separation, and drying to obtain dendrimer composite magnetic particles;
4) mixing 2g of template molecule 4-chlorophenol, 5g of dendrimer composite magnetic particles and 300mL of acetonitrile, magnetically stirring, standing for 12h, separating solid particles, adding the solid particles, 9g of functional monomer methacrylic acid, 0.5g of cross-linking agent ethylene glycol dimethacrylate and 0.05g of initiator dimethyl azodiisobutyrate into 350mL of acetonitrile, uniformly mixing, magnetically stirring at 50 ℃ for reaction for 2h, magnetically separating, drying, washing the template molecule through Soxhlet extraction, separating and drying to obtain the compound magnetic material.
Example 4
The preparation method of the dendrimer modified magnetic chitosan surface imprinted polymer comprises the following steps:
1) adding 0.5g of 3- (methacryloyloxy) propyl trimethoxy silane into 50mL of deionized water, stirring for dissolving, heating to 40 ℃, adding 2g of ferroferric oxide particles, reacting for 3 hours at constant temperature under the condition of stirring, performing magnetic separation, and drying to obtain alkylated ferroferric oxide particles;
2) adding 3g of chitosan and 9g of itaconic acid into 250mL of an aqueous solution of 10 wt% acetic acid, and stirring and dissolving to obtain a mixed solution; adding 2g of alkylated ferroferric oxide particles into the mixed solution, heating to 50 ℃, adding 0.05g of initiator potassium persulfate, carrying out heat preservation reaction for 50min, carrying out magnetic separation, and drying to obtain polymer composite magnetic particles;
3) adding 12g of dendrimer polyamidoamine into 300mL of deionized water to prepare a dendrimer polyamidoamine solution, adding 2g of polymer composite magnetic particles into the dendrimer polyamidoamine solution, adding 0.1g of condensing agent EDCI, reacting for 2h at room temperature, performing magnetic separation, and drying to obtain dendrimer composite magnetic particles;
4) mixing 2g of template molecule 4-chlorophenol, 5g of dendrimer composite magnetic particles and 300mL of acetonitrile, magnetically stirring, standing for 10-20h, separating solid particles, adding the solid particles, 12g of functional monomer methacrylic acid, 0.5g of cross-linking agent ethylene glycol dimethacrylate and 0.05g of initiator azobisisobutyronitrile into 350mL of acetonitrile, uniformly mixing, magnetically stirring and reacting for 2h at 60 ℃, magnetically separating, drying, washing the template molecule through Soxhlet extraction, separating and drying to obtain the compound magnetic material.
Example 5
The preparation method of the dendrimer modified magnetic chitosan surface imprinted polymer comprises the following steps:
1) adding 0.5g of 3- (methacryloyloxy) propyl trimethoxy silane into 50mL of deionized water, stirring for dissolving, heating to 30 ℃, adding 1g of ferroferric oxide particles, reacting for 1 hour at constant temperature under the condition of stirring, performing magnetic separation, and drying to obtain alkylated ferroferric oxide particles;
2) adding 3g of chitosan and 6g of itaconic acid into 250mL of an aqueous solution of 10 wt% acetic acid, and stirring and dissolving to obtain a mixed solution; adding 2g of alkylated ferroferric oxide particles into the mixed solution, heating to 45 ℃, adding 0.05g of initiator potassium persulfate, carrying out heat preservation reaction for 30min, carrying out magnetic separation, and drying to obtain polymer composite magnetic particles;
3) adding 6g of dendrimer polyamidoamine into 300mL of deionized water to prepare a dendrimer polyamidoamine solution, adding 2g of polymer composite magnetic particles into the dendrimer polyamidoamine solution, adding 0.1g of condensing agent EDCI, reacting for 1h at room temperature, performing magnetic separation, and drying to obtain dendrimer composite magnetic particles;
4) mixing 2g of template molecule 4-chlorophenol, 5g of dendrimer composite magnetic particles and 300mL of acetonitrile, magnetically stirring, standing for 10h, separating solid particles, adding the solid particles, 8g of functional monomer methacrylic acid, 0.5g of cross-linking agent ethylene glycol dimethacrylate and 0.05g of initiator azobisisoheptonitrile into 350mL of acetonitrile, uniformly mixing, magnetically stirring at 50 ℃ for 2h, magnetically separating, drying, washing the template molecule through Soxhlet extraction, separating and drying to obtain the compound magnetic material.
And (3) sample detection:
experimental tests show that the imprinted polymer prepared by the method has large specific surface area and pore volume, strong adsorption capacity and capacity, and is not easy to reach a saturated state when adsorbed on a template substance.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A preparation method of a dendrimer modified magnetic chitosan surface imprinted polymer is characterized by comprising the following steps:
1) adding 3- (methacryloyloxy) propyl trimethoxy silane into deionized water, stirring for dissolving, heating to 30-40 ℃, adding ferroferric oxide particles, reacting at constant temperature under stirring, performing magnetic separation, and drying to obtain alkylated ferroferric oxide particles;
2) adding chitosan and itaconic acid into an aqueous solution of acetic acid, and stirring and dissolving to obtain a mixed solution; adding alkylated ferroferric oxide particles into the mixed solution, heating to 45-50 ℃, adding an initiator potassium persulfate, carrying out heat preservation reaction, carrying out magnetic separation, and drying to obtain polymer composite magnetic particles;
3) adding dendrimer polyamidoamine into deionized water to prepare dendrimer polyamidoamine solution, adding polymer composite magnetic particles into the dendrimer polyamidoamine solution, adding a condensing agent EDCI, reacting at room temperature, performing magnetic separation, and drying to obtain dendrimer composite magnetic particles;
4) mixing template molecules, dendrimer composite magnetic particles and acetonitrile, magnetically stirring, standing, separating solid particles, adding the solid particles, functional monomers, a cross-linking agent and an initiator into the acetonitrile, uniformly mixing, magnetically stirring for reaction at 50-60 ℃, magnetically separating, drying, cleaning the template molecules through Soxhlet extraction, separating and drying to obtain the nano-composite magnetic material.
2. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the mass ratio of chitosan to itaconic acid in the step 2) is 1: 2-3.
3. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the temperature preservation reaction time in the step 2) is 30-50 min.
4. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the mass ratio of the polymer composite magnetic particles to the dendrimer polyamidoamine in the step 3) is 1: 3-6.
5. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the functional monomer in the step 4) is methacrylic acid.
6. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the template molecules in the step 4) are phenols.
7. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the mass ratio of the template molecules to the functional monomers in the step 4) is 1: 4-6.
8. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the initiator in the step 4) is at least one of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.
9. The method for preparing the dendrimer-modified magnetic chitosan surface imprinted polymer according to claim 1, wherein the cross-linking agent in the step 4) is ethylene glycol dimethacrylate.
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| CN110684163B (en) | 2021-12-17 |
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