CN113248650B - Eutectic solvent type molecularly imprinted polymer with hydroxyapatite as carrier and preparation method and application thereof - Google Patents

Eutectic solvent type molecularly imprinted polymer with hydroxyapatite as carrier and preparation method and application thereof Download PDF

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CN113248650B
CN113248650B CN202110696128.6A CN202110696128A CN113248650B CN 113248650 B CN113248650 B CN 113248650B CN 202110696128 A CN202110696128 A CN 202110696128A CN 113248650 B CN113248650 B CN 113248650B
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eutectic solvent
hydroxyapatite
molecularly imprinted
imprinted polymer
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CN113248650A (en
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张艳鸽
孙燕华
姚川
朱兆梅
朱巧玲
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Xuchang University
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Abstract

The invention discloses a eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier and a preparation method and application thereof. Hydroxyapatite is used as a carrier, two different eutectic solvents are respectively used as a functional monomer and a cross-linking agent, template molecules are introduced, and the molecularly imprinted polymer is obtained by polymerization reaction and elution of the template molecules. The molecularly imprinted polymer takes hydroxyapatite as a carrier framework, and imprinting layers are uniformly distributed on the surface of the carrier, so that the problem that imprinting sites of the traditional molecularly imprinted polymer are easy to embed is solved, and simultaneously, target molecules can reach the imprinting sites more easily, so that the molecularly imprinted polymer is quicker in adsorption and larger in adsorption capacity, is easy to design according to the target molecules, can be widely applied to selective recognition and separation extraction of the target molecules in a complex system, and is low in raw material cost, simple to operate, environment-friendly and easy to produce in a large scale.

Description

Eutectic solvent type molecularly imprinted polymer with hydroxyapatite as carrier and preparation method and application thereof
Technical Field
The invention relates to a molecularly imprinted polymer, in particular to a eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier, a preparation method thereof, and application of the eutectic solvent type molecularly imprinted polymer taking the hydroxyapatite as the carrier in extraction of erucic acid in rapeseed cakes, belonging to the technical field of functional high molecular materials.
Background
Sinapic acid (4-hydroxy-3, 5-dimethoxycinnamic acid) is one of the aromatic phenolic compounds, widely occurring in the plant kingdom in the form of secondary metabolites. According to the reports of the literature, sinapic acid can scavenge free radicals, inhibit lipid peroxidation, protect liver (alcoholic liver disease), and has broad-spectrum biological activities of resisting inflammation, bacteria, anxiety, tumor, oxidation, diabetes, virus and the like. Because of these medicinal and nutritional values and health benefits, sinapic acid has been proposed for use in the pharmaceutical industry, food processing, cosmetics, and the like. Sinapic acid is widely present in the plant world and is contained in high content in spice crops, cereals, citrus fruits, vegetables and oil crops. The content of the rapeseed cake squeezed from agricultural byproducts is up to 12.81mg/g. These valuable compounds are left in the by-product rapeseed cake after oil extraction, which causes great resource waste. Therefore, the extraction of sinapic acid from rapeseed cakes pressed from agricultural by-products is necessary and significant. For the extraction of sinapic acid, the most classical method in the prior art is solvent extraction (Limwachiranon J, jiang L, huang H, sun J, luo z. Improvement of Phenolic compounds extraction from high-stage wells (New membrane nutrients g.) -used glycerol: new intermediates to amides/oligomers-Phenolic reactions food chem.2019, 174 933-41.) which has a large treatment amount and high extraction efficiency, but the process is complicated, requires the use of a large amount of organic solvent and has the problem that the organic solvent is easy to remain. In recent years, new methods, such as pressurized fluid extraction and supercritical fluid extraction, have been introduced, which have good effect on the extraction of phenolic acids (Setyaningsih W, sapurro IE, palma M, barroso CG. Compressed liquid extraction of phenolic compounds from room rice (Oryza sativa) grains. Food chem.2016, 192-452 9), ("research on subcritical fluid extraction technique for low-temperature pressing of rapeseed cake", xuhan, jiang, riverSu university, 2019). In addition, an emerging extraction method is to use adsorbents, and common adsorbents include granular activated carbon, hollow fiber membranes, and macroporous adsorbent resins [ Sepiolite, bentonite, and the like, such as (Gholladeh A, kermani M, gholami M, farzadkia M.Kinetic and isocompom students of adsorption and biological processes in the removal of phosphoric compounds from free sources solutions, comparative study. J environmental Sci Eng.2013, 11
Figure BDA0003120692030000021
M. Characterisation and determination of the thermal and kinetic properties of p-CP adsorption on to organic bed from solution. J Colloid Interface Sci.2004, 280-299-304). However, the common disadvantage of these methods is that only phenolic acids can be extracted simultaneously, and selective and specific recognition ability for sinapic acid is lacking.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier, the molecularly imprinted polymer has specific recognition capability on target molecules, so that selective recognition and separation extraction of the target molecules in a complex system can be realized, in addition, the molecularly imprinted polymer takes the hydroxyapatite as a carrier framework, and an imprinted layer is uniformly distributed on the surface of the carrier, so that imprinted sites are uniformly distributed on the surface of a polymer material, the problem that the imprinted sites of the traditional molecularly imprinted polymerization are easy to embed is solved, meanwhile, the target molecules can more easily reach the imprinted sites, the mass transfer efficiency is favorably improved, the adsorption is faster, and the adsorption capacity is larger.
The second purpose of the invention is to provide a method for synthesizing a eutectic solvent type molecularly imprinted polymer by taking hydroxyapatite as a carrier, the method has the advantages of high utilization rate of raw materials, simple preparation process, low cost and environmental friendliness, no additional organic solvent is required to be added in the polymerization reaction process, polymerization is completed after initiation by ammonium persulfate at room temperature, heating is not required, the reaction condition is mild, and the potential safety hazard is reduced.
The third purpose of the invention is to provide the application of the eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier, and the molecularly imprinted polymer is designed according to different target molecules, so that the molecularly imprinted polymer has specific recognition capability on the target molecules, selective recognition, separation and extraction and the like on the target molecules are realized, and the molecularly imprinted polymer can be widely applied in the fields of extraction of plant active ingredients, separation and purification of small molecules, pretreatment of analytical samples and the like, for example, the molecularly imprinted polymer synthesized by taking sinapic acid as a template molecule can be applied to extraction of sinapic acid in rapeseed cakes.
In order to realize the technical purpose, the invention provides a method for synthesizing a eutectic solvent type molecularly imprinted polymer by taking hydroxyapatite as a carrier, which comprises the steps of adding a eutectic solvent I, a eutectic solvent II and template molecules into a hydroxyapatite solution, firstly carrying out self-assembly reaction, then adding ammonium persulfate and tetramethylethylenediamine for polymerization reaction, and eluting the template molecules from the polymerization reaction product to obtain the product;
the eutectic solvent I (DES 1) is prepared by mixing 2-hydroxyethyl methacrylate and tetrabutyl ammonium chloride according to a molar ratio of (1-5) to 1, or mixing caffeic acid, choline chloride and formic acid according to a molar ratio of 1 (1-7) to (1-8), or mixing tetrabutyl ammonium chloride and ethylene glycol according to a molar ratio of 1: (1-4), or choline chloride, 3, 4-dihydroxybenzoic acid and ethylene glycol are reacted according to the molar ratio of 1 to (1-3), or choline chloride and acrylic acid are reacted according to the molar ratio of 1 to (1-3), or (3-acrylamidopropyl) trimethyl ammonium chloride and urea are reacted according to the molar ratio of 1 to (1-3), or alpha-methacrylic acid and benzyltriethyl ammonium chloride are reacted according to the molar ratio of (1-5) to (1);
the eutectic solvent II (DES 2) is obtained by reacting (3-acrylamido propyl) trimethyl ammonium chloride and acrylamide according to the molar ratio of 1 (1-6), or lauric acid and caprylic acid according to the molar ratio of 1 (1-2), or ibuprofen and citric acid according to the molar ratio of 1 (1-3).
According to the technical scheme, hydroxyapatite is selected as a carrier material, the surface of the hydroxyapatite is rich in active groups such as hydroxyl groups and the like, the specific surface area is large, an adsorption eutectic solvent is easy to adsorb on the surface of the hydroxyapatite to modify the surface of the hydroxyapatite, so that an imprinting film is coated on the surface of the hydroxyapatite, imprinting sites can be uniformly distributed on the surface of the hydroxyapatite, and more molecular imprinting sites are exposed.
The eutectic solvent is a eutectic mixture formed by two or more components of a hydrogen bond acceptor and a hydrogen bond donor in a certain proportion through hydrogen bond interaction, and the eutectic mixture has the property similar to that of an ionic liquid. According to the invention, the eutectic solvent is selected as a polymerization monomer and a cross-linking agent, and the formed molecularly imprinted polymer layer can be combined with a target analyte by utilizing the acting forces of hydrogen bond action, van der Waals force and the like of the eutectic solvent, so that the adsorption capacity of the molecularly imprinted polymer layer on the target analyte is improved, and more importantly, the selectivity of the molecularly imprinted polymer layer on the target analyte can be regulated and controlled by regulating the type and the proportion of a hydrogen bond acceptor and a hydrogen bond donor so as to achieve the optimal adsorption effect.
The most preferred eutectic solvent DES1 is obtained by reacting 2-hydroxyethyl methacrylate and tetrabutylammonium chloride according to a molar ratio of (1-3): 1. The most preferred eutectic solvent DES2 is obtained by reacting (3-acrylamidopropyl) trimethyl ammonium chloride and acrylamide according to a molar ratio of 1. The preferred eutectic solvent I and eutectic solvent II in combination show a particularly outstanding adsorption effect on sinapic acid.
As a preferable scheme, the usage ratio of the eutectic solvent I, the eutectic solvent II and the template molecule is: 200 μ L: 30-100 μ L: 0.10-0.30 mmol.
In a preferred embodiment, the template molecule is sinapic acid. The template molecule can be any small molecule organic matter, and the technical scheme of the invention is only explained by taking sinapic acid as an example.
As a preferred scheme, the eutectic solvent I, the hydroxyapatite solution, the ammonium persulfate solution and the tetramethylethylenediamine are used in the following ratio: 200 μ L: (30-80 mL): (100-300. Mu.L): (100-300. Mu.L); the hydroxyapatite solution is PBS buffer solution with the concentration ranging from 4 mg/mL to 8 mg/mL; the w/v concentration of the ammonium persulfate solution is 5-15%. Tetramethylethylenediamine is mainly used for catalyzing ammonium persulfate to generate free radicals and is used as an accelerator.
As a preferred scheme, the conditions of the self-assembly reaction are as follows: reacting for 1-3 hours at room temperature.
As a preferred embodiment, the polymerization conditions are: reacting at room temperature for 18-30 hours.
The invention also provides a eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier, which is obtained by the synthesis method.
The invention also provides application of the eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier, and the eutectic solvent type molecularly imprinted polymer is applied to adsorption and separation of target substances which are the same as template molecules. The molecular imprinting design in the eutectic solvent type molecularly imprinted polymer using hydroxyapatite as a carrier, provided by the technical scheme of the invention, endows the molecularly imprinted polymer with high selective recognition performance on different target molecules according to different selected template molecules, so that the corresponding molecularly imprinted polymer can be designed in a targeted manner according to the target molecules to be separated, and the molecularly imprinted polymer can be widely applied to enrichment and separation of different target molecules.
As a preferable scheme, the eutectic solvent type molecularly imprinted polymer which is prepared by taking sinapic acid as a template molecule and takes hydroxyapatite as a carrier is applied to extracting the sinapic acid in the rapeseed cakes.
The technical scheme of the invention is that the eutectic solvent type molecularly imprinted polymer which is prepared by taking the sinapic acid as a template molecule and takes the hydroxyapatite as a carrier has a high-selectivity recognition effect on the sinapic acid, the sinapic acid can be adsorbed and enriched in a rapeseed cake system with complex components at high selectivity, and the high-purity sinapic acid is recovered by elution, wherein an elution solvent can be a mixed solution (9.
In the invention, in the process of extracting the sinapic acid in the rapeseed cakes by utilizing the deep eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier, the rapeseed cakes are firstly subjected to alkaline hydrolysis pretreatment so that the sinapic acid is fully dissolved out, and a sinapic acid extracting solution is obtained. The dried rapeseed cake was pulverized and sieved, and then 200ml of an NaOH solution (12 wt%) was added to the rapeseed cake, and stirred at 75 ℃ for 5 hours, after which the solid-liquid separation was carried out by a centrifuge (5000 rpm, 10min) to obtain a sinapic acid extract.
The eutectic solvent I is mainly used as a functional monomer, and the synthesis method comprises the steps of mixing 2-hydroxyethyl methacrylate and tetrabutyl ammonium chloride according to the mol ratio of (1-5) to 1, and stirring at 70-90 ℃ for 0.5-1.5 hours to form clear, uniform and viscous liquid. And the other methods for synthesizing the eutectic solvent I are synthesized according to the method.
The eutectic solvent II is mainly used as a cross-linking agent, and the synthesis method comprises the steps of mixing (3-acrylamido propyl) trimethyl ammonium chloride and acrylamide according to the molar ratio of 1 (1-6), and stirring at 70-90 ℃ for 0.5-1.5 h to obtain a transparent and clear solution. Other methods of synthesis of the eutectic solvent II were synthesized according to this method.
The hydroxyapatite adopted by the invention is a conventional commercial product.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) The eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier provided by the technical scheme of the invention has the advantages of high utilization rate of raw materials, simple preparation process, lower cost, environmental friendliness, no need of additional organic solvent in the synthesis process, polymerization completion after initiation of ammonium persulfate at room temperature, no need of heating, mild reaction conditions and potential safety hazard reduction.
2) According to the eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as the carrier, provided by the technical scheme of the invention, the hydroxyapatite is taken as the carrier skeleton, so that an imprinting layer can be uniformly distributed on the surface of the carrier, imprinting sites can be almost distributed on the surface of a polymer material, the problem that the imprinting sites are easily embedded in the traditional imprinting method is solved, when the molecularly imprinted polymer is used for adsorption, target molecules in a mixed solution can more easily reach the imprinting sites, the mass transfer efficiency is improved, and the adsorption is faster and the adsorption capacity is larger.
3) The eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier provided by the technical scheme of the invention can be used for designing molecularly imprinted polymers according to different target molecules, and the prepared molecularly imprinted polymers have specific identification capability on the target molecules, so that selective identification, separation and extraction and the like of the target molecules are realized, and the molecularly imprinted polymers can be widely applied to the fields of plant active ingredient extraction, micromolecule separation and purification, analysis sample pretreatment and the like.
Drawings
Fig. 1 is a scanning electron microscope picture (a) and a partially enlarged picture (b) of the molecularly imprinted polymer MIPs prepared in example 1;
FIG. 2 is an infrared spectrum of DES1, DES2, MIPs and NIPs synthesized in example 1;
FIG. 3 is an isotherm plot (a) and kinetic plot (b) of the MIPs and NIPs prepared in example 1;
FIG. 4 is a graph showing the selective adsorption of MIPs and NIPs prepared in example 1 to different target molecules;
FIG. 5 is the cyclic regeneration capability of the MIPs prepared in example 1.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
Preparation of eutectic solvent DES1: 2-hydroxyethyl methacrylate and tetrabutylammonium chloride were mixed according to a 2:1 (molar ratio), and stirring at 80 ℃ for 1h to obtain a clear, uniform and viscous liquid serving as a functional monomer DES1 in the preparation of a molecularly imprinted polymer.
Preparation of eutectic solvent DES2: (3-acrylamidopropyl) trimethylammonium chloride and acrylamide were mixed in a ratio of 1 (molar ratio) and stirred at 80 ℃ for 1h to obtain a clear solution, which was used as a cross-linking agent DES2 in the preparation of molecularly imprinted polymers.
Preparation of molecularly imprinted polymers MIPs: hydroxyapatite is used as a carrier, and DES1 and DES2 are respectively used as a functional monomer and a cross-linking agent. First, DES1 (200. Mu.L), DES2 (50. Mu.L) and sinapic acid (33.6 mg, 0.15mmol) were sequentially added to a PBS buffer (45.0 mL) containing hydroxyapatite (250.0 mg), the mixture was stirred at room temperature for 2 hours to allow prepolymerization, and then the mixture was sealed and purged with nitrogen for 10min to remove oxygen. Ammonium persulfate solution (10%, w/v, 150. Mu.L) and tetramethylethylenediamine (150. Mu.L) were sequentially injected into the reaction solution, and stirred at room temperature for 1 day until complete polymerization. The product was isolated by centrifugation and washed twice with deionized water to remove the residue. The template molecule was washed again with a mixture of methanol and acetic acid (9, v). Washed with deionized water and dried in vacuum at 60 ℃ for 24h. The obtained product is named MIPs. As a control, non-imprinted polymer NIPs were prepared simultaneously, in the same manner as MIPs, except that no sinapic acid was added.
(1) Static adsorption experiment
Weighing 5.0mg of MIPs or NIPs into a plastic centrifuge tube, respectively adding 150mg/L sinapic acid solution, oscillating for 3h at room temperature, centrifuging, taking supernate, testing the absorbance of the supernate at 320nm by using an ultraviolet spectrophotometer, and calculating the adsorption capacity to obtain a static adsorption curve.
(2) Adsorption kinetics experiment
5.0mg of MIPs or NIPs are weighed into a plastic centrifuge tube, and sinapic acid solution with the concentration of 150mg/L is respectively added to the centrifuge tube to shake the centrifuge tube at room temperature. Oscillation times were set to 5, 10, 20, 30, 60, 90, 120, 180, 360, 720min, respectively. Centrifuging after the oscillation is finished, taking the supernatant to test the absorbance of the supernatant at 320nm, calculating the adsorption quantity, and drawing an adsorption kinetic curve.
(3) Selective adsorption experiment
Weighing 5.0mg of MIPs or NIPs, adding sinapic acid solution (or ferulic acid solution, cinnamic acid solution and vanillic acid solution) with concentration of 150mg/L into a plastic centrifuge tube, shaking for 3h at room temperature, centrifuging after shaking is finished, taking supernate, testing the absorbance of the supernate at 320nm, and calculating the corresponding adsorption capacity.
(4) Extraction experiment of sinapic acid from rapeseed cake
Pretreatment of rapeseed cakes: the dried rapeseed cake was first crushed and sieved, and then 200ml of a solution of LNaOH (12% by weight) was added to the rapeseed cake, and stirred for 5 hours while maintaining 75 ℃. After the alkaline lysis, the solid was separated by a centrifuge (5000rpm, 10min), and then the pH of the extract was adjusted to 10 with HCl or NaOH, and analyzed by High Performance Liquid Chromatography (HPLC).
Adsorption of the rapeseed cake crude extract: 5mL of the extract was added to a screw-top bottle containing MIPs or NIPs (50 mg), shaken in a shaker at room temperature for 12 hours, and then the solid was separated by a centrifuge (5000 rpm, 10min), and the components were analyzed at 320nm by HPLC.
Chromatographic column conditions: the chromatographic column has the following composition for Knauer 100-5C18 (250X 4.6 mm) mobile phase: solution A: 0.2% phosphoric acid solution; and B, liquid B: methanol; and C, liquid C: and (3) acetonitrile.
Figure BDA0003120692030000071
Figure BDA0003120692030000081
FIG. 1 shows the micro-morphology of the MIPs prepared in example 1, which are regular spheres, uniformly distributed, with an average particle size of about 40 μm, and whose surface is a rough structure as seen from a partial enlargement.
Figure 2 is an infrared spectrum of DES1, DES2 and MIPs prepared in example 1. DES1 in 3309cm -1 Has strong and wide absorption peak, which is caused by the expansion and contraction vibration of a large amount of O-H. DES2 at 3336cm -1 Has strong and wide absorptionPeak, which is due to the stretching vibration of N — H. Absorption peaks at the same positions appear in the polymers MIPs and NIPs, indicating that DES1 and DES2 have been successfully used in the preparation of imprinted polymers.
FIG. 3a is a graph of the isotherms of the MIPs and NIPs prepared in example 1, with the relationship between the amount adsorbed and the initial concentration of sinapic acid solution being primarily examined. The initial concentration of the sinapic acid solution prior to adsorption was 10, 20, 30, 50, 80, 100, 150, 200, 300mg L, respectively -1 . The experimental result shows that when the concentration of the sinapinic acid solution is 10-100 mg L -1 In between, the adsorption amounts of MIPs and NIPs rapidly increased with the initial concentration increase and at a concentration of 150mgL -1 The time reaches a maximum value. Maximum adsorption amounts of MIPs and NIPs were 121 and 23mg g, respectively -1 . It can be seen that the recognition and adsorption capacity of NIPs for sinapic acid is much lower than MIPs, and the significant difference in adsorption levels is mainly due to the presence or absence of the imprinted sites. Figure 3b is a graph of kinetic adsorption data for MIPs and NIPs. Both MIPs and NIPs grow rapidly within the first 120min until adsorption dynamic equilibrium is reached at 180 min.
FIG. 4 shows the selective adsorption of MIPs and NIPs prepared in example 1 to different target molecules (sinapinic acid, ferulic acid, cinnamic acid, vanillic acid). When adsorption equilibrium is reached, the adsorption amounts of the four target molecules by the MIPs are respectively: 121. 25, 19 and 22mg g -1 . The obvious difference of the adsorption amount is caused by the difference of the molecular structures of other molecules and sinapic acid, and the difference of the structures leads to the failure of effective recognition and matching with the imprinting sites, so the adsorption amount is small.
FIG. 5 is the cyclic regeneration capability of the MIPs prepared in example 1. As can be seen from the figure, after the MIPs are regenerated for 8 times, the adsorption quantity of the MIPs on sinapic acid is only reduced by 13%, and good regeneration performance is shown.
Example 2
Preparation of a eutectic solvent DES1: the preparation of DES1 adopts ternary composition, caffeic acid, choline chloride and formic acid are mixed according to the molar ratio of 1.
Preparation of eutectic solvent DES2: (3-acrylamidopropyl) trimethylammonium chloride and acrylamide were mixed in a ratio of 1:2 (molar ratio) and stirred at 80 ℃ for 1h to obtain a clear solution, which was used as a cross-linking agent DES2 in the preparation of molecularly imprinted polymers.
Preparation of molecularly imprinted polymers MIPs: hydroxyapatite is used as a carrier, and DES1 and DES2 are respectively used as a functional monomer and a cross-linking agent. First, DES1 (200. Mu.L), DES2 (30. Mu.L) and sinapic acid (22.4 mg,0.10 mmol) were sequentially added to a PBS buffer (40.0 mL) containing hydroxyapatite (220.0 mg), the mixture was stirred at room temperature for 2 hours to pre-polymerize, and then the mixture was sealed and purged with nitrogen for 10min to remove oxygen. Potassium persulfate solution (10 w/v%, 100. Mu.L) and tetramethylethylenediamine (100. Mu.L) were poured into the reaction solution in this order, and stirred at room temperature for 1 day until complete polymerization. The product was isolated by centrifugation and washed twice with deionized water to remove the residue. The template molecule was washed again with a mixture of methanol and acetic acid (9, v). Washed with deionized water and dried in vacuum at 60 ℃ for 24h. The obtained product is named as MIPs. As a control, non-imprinted polymer NIPs were prepared simultaneously, in the same manner as MIPs, except that no sinapic acid was added. The maximum adsorption capacities of MIPs and NIPs on sinapic acid prepared by the method are respectively 97mg g -1 And 25mg g -1 Wherein the adsorption of sinapic acid by MIPs can reach dynamic equilibrium in 210 min.
Example 3
Preparation of eutectic solvent DES1: mixing (3-acrylamide propyl) trimethyl ammonium chloride and urea according to a molar ratio of 1.
Preparation of a eutectic solvent DES2: (3-acrylamidopropyl) trimethylammonium chloride and acrylamide were mixed in a ratio of 1.
Preparation of molecularly imprinted polymers MIPs: hydroxyapatite is used as a carrier, and DES1 and DES2 are respectively used as a functional monomer and a cross-linking agent. Firstly, the methodDES1 (200. Mu.L), DES2 (100. Mu.L) and sinapic acid (44.8mg, 0.20mmol) were sequentially added to a PBS buffer (45.0 mL) containing hydroxyapatite (200.0 mg), the mixture was stirred at room temperature for 2 hours to effect prepolymerization, and then the mixture was sealed and purged with nitrogen for 10min to remove oxygen. Ammonium persulfate solution (10 w/v%, 200. Mu.L) and tetramethylethylenediamine (200. Mu.L) were sequentially poured into the reaction solution, and stirred at room temperature for 1 day until complete polymerization. The product was isolated by centrifugation and washed twice with deionized water to remove the residue. The template molecule was washed again with a mixture of methanol and acetic acid (8, v). Washed with deionized water and dried in vacuum at 60 ℃ for 24h. The obtained product is named as MIPs. As a control, non-imprinted polymer NIPs were prepared simultaneously, in the same manner as MIPs, except that no sinapic acid was added. The maximum adsorption capacities of MIPs and NIPs on sinapic acid prepared by the method are respectively 102mg g -1 And 27mg g -1 Wherein the adsorption of sinapic acid by MIPs can reach dynamic equilibrium at 180 min.
Example 4
Preparation of eutectic solvent DES1: alpha-methacrylic acid and benzyltriethylammonium chloride are mixed according to a molar ratio of 2.
Preparation of a eutectic solvent DES2: (3-acrylamidopropyl) trimethyl ammonium chloride and acrylamide were mixed in a ratio of 1.5 (molar ratio) and stirred at 75 ℃ for 1.5 hours to obtain a clear solution, which was used as a cross-linking agent DES2 in the preparation of a molecularly imprinted polymer.
Preparation of molecularly imprinted polymers MIPs: hydroxyapatite is used as a carrier, and DES1 and DES2 are respectively used as a functional monomer and a cross-linking agent. First, DES1 (200. Mu.L), DES2 (70. Mu.L) and sinapic acid (56.0 mg, 0.25mmol) were sequentially added to PBS buffer (50.0 mL) containing hydroxyapatite (290.0 mg), the mixture was stirred at room temperature for 2 hours to pre-polymerize, and then the mixture was liquid-sealed and purged with nitrogen for 10min to remove oxygen. Potassium persulfate (300. Mu.L) and tetramethylethylenediamine (300. Mu.L) were sequentially poured into the reaction solution, and the mixture was stirred at room temperature for 1 day until complete polymerization. The product is separated by centrifugation and is deionizedWater was washed twice to remove the residue. The template molecule was washed again with a mixture of methanol and acetic acid (8.5, v). Washed with deionized water and dried in vacuum at 60 ℃ for 24h. The obtained product is named MIPs. As a control, non-imprinted polymer NIPs were prepared simultaneously, in the same way as MIPs, except that no sinapinic acid was added. The maximum adsorption capacities of MIPs and NIPs on sinapic acid prepared by the method are respectively 85mg g -1 And 19mg g -1 Wherein the adsorption of the sinapic acid by the MIPs can reach dynamic balance when the MIPs adsorb the sinapic acid for 240 min.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and the technical solution and the inventive concept thereof according to the present invention should be equally exchanged or changed within the scope of the present invention.

Claims (6)

1. A synthetic method of eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier is characterized in that: adding the eutectic solvent I, the eutectic solvent II and template molecules into a hydroxyapatite solution, firstly carrying out self-assembly reaction, then adding an ammonium persulfate solution and tetramethylethylenediamine for polymerization reaction, and eluting the template molecules from the polymerization reaction product to obtain the product;
the eutectic solvent I is prepared from 2-hydroxyethyl methacrylate and tetrabutyl ammonium chloride according to a molar ratio of (1-5) to 1, or caffeic acid, choline chloride and formic acid according to a molar ratio of 1 (1-7) to (1-8), or tetrabutyl ammonium chloride and ethylene glycol according to a molar ratio of 1: (1-4), or choline chloride, 3, 4-dihydroxybenzoic acid and ethylene glycol are reacted according to the molar ratio of 1 to (1-3), or choline chloride and acrylic acid are reacted according to the molar ratio of 1 to (1-3), or (3-acrylamidopropyl) trimethyl ammonium chloride and urea are reacted according to the molar ratio of 1 to (1-3), or alpha-methacrylic acid and benzyltriethyl ammonium chloride are reacted according to the molar ratio of (1-5) to (1);
the eutectic solvent II is obtained by reacting (3-acrylamide propyl) trimethyl ammonium chloride and acrylamide according to the molar ratio of 1 (1-6);
the dosage proportion of the eutectic solvent I, the eutectic solvent II and the template molecule is as follows: 200 μ L: 30-100 μ L: 0.10-0.30 mmol;
the template molecule is sinapic acid.
2. The method for synthesizing the eutectic solvent type molecularly imprinted polymer with hydroxyapatite as the carrier according to claim 1, characterized in that: the usage ratio of the eutectic solvent I, the hydroxyapatite solution, the ammonium persulfate solution and the tetramethyl ethylene diamine is as follows: 200 μ L: (30-80 mL): (100-300. Mu.L): (100-300. Mu.L);
the hydroxyapatite solution is PBS buffer solution with the concentration ranging from 4 mg/mL to 8 mg/mL;
the w/v concentration of the ammonium persulfate solution is 5-15%.
3. The method for synthesizing the eutectic solvent type molecularly imprinted polymer with hydroxyapatite as the carrier according to claim 1, characterized in that: the conditions of the self-assembly reaction are as follows: reacting for 1-3 hours at room temperature.
4. The method for synthesizing the eutectic solvent type molecularly imprinted polymer with hydroxyapatite as the carrier according to claim 1, characterized in that: the conditions of the polymerization reaction are as follows: reacting at room temperature for 18-30 hours.
5. A eutectic solvent type molecularly imprinted polymer taking hydroxyapatite as a carrier is characterized in that: obtained by the synthesis method according to any one of claims 1 to 4.
6. The use of the eutectic solvent type molecularly imprinted polymer with hydroxyapatite as a carrier according to claim 5, wherein: the method is applied to the adsorption and separation of target substances identical to the template molecules.
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