CN113817217B - Porous polymer microsphere for high selective adsorption of enrofloxacin and preparation method thereof - Google Patents

Porous polymer microsphere for high selective adsorption of enrofloxacin and preparation method thereof Download PDF

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CN113817217B
CN113817217B CN202111213536.8A CN202111213536A CN113817217B CN 113817217 B CN113817217 B CN 113817217B CN 202111213536 A CN202111213536 A CN 202111213536A CN 113817217 B CN113817217 B CN 113817217B
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enrofloxacin
porous polymer
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CN113817217A (en
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韦寿莲
谢春生
黄象金
陈美琳
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Zhaoqing University
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Abstract

The invention discloses a preparation method of porous polymer microspheres for high selective adsorption of enrofloxacin, which belongs to the technical field of porous adsorption material preparation, and is prepared by taking ternary mixed liquid consisting of hydrophobic ionic liquid, paraffin oil and surfactant as emulsion, beta-cyclodextrin as a template pore-forming agent and methacrylic acid as a functional monomer and adopting an emulsion polymerization method. The porous polymer microsphere has the characteristics of porosity, large adsorption capacity to enrofloxacin, high selectivity, fast mass transfer, good stability, simple preparation process and the like, and has wide application prospects in the fields of rapid separation, enrichment and analysis of enrofloxacin in aquatic products, livestock meat, milk and egg foods, environmental samples and biological samples, adsorption removal of environmental enrofloxacin pollutants and the like.

Description

Porous polymer microsphere for high selective adsorption of enrofloxacin and preparation method thereof
Technical Field
The invention relates to the technical field of porous adsorption material preparation, in particular to a porous polymer microsphere for highly selective adsorption of enrofloxacin and a preparation method thereof.
Background
Enrofloxacin (Enrofloxacin) has the functions of inhibiting and killing gram-positive bacteria, gram-negative bacteria, mycoplasmal bacteria and the like, has the characteristics of strong bactericidal activity, wide in-vivo distribution and the like, and is widely used for preventing and treating bacterial epidemic diseases and mycoplasma infections of aquatic products and livestock and poultry animals, such as various bacterial infections of gill rot and tail rot of fishes, chronic respiratory diseases of chickens, swine enzootic pneumonia, swine white dysentery, yellow scour of piglets, swine edema disease and the like; it can also be illegally used as a growth promoter. Because the enrofloxacin is widely used in aquatic and livestock breeding, the enrofloxacin lacks of medication guidance and supervision, and is abused in a large amount, and pollutes the environment, the aquatic products, the livestock meat, milk and eggs. Long-term eating of the food with residual enrofloxacin can lead to enhanced drug resistance of microbial strains, allergy, gastrointestinal disorder and damage of liver and kidney, and endanger human health. How to remove enrofloxacin pollutants in the environment and rapidly and sensitively detect enrofloxacin residues in foods is a problem to be solved in the high-speed development of the current green and environment-friendly breeding industry.
At present, methods such as solvent extraction, ion exchange extraction, active carbon adsorption, membrane separation and the like are generally adopted for separating and enriching enrofloxacin, and the methods have the defects of poor selectivity, low efficiency, environment friendliness, high cost and the like. The enrofloxacin imprinted polymer prepared by the molecular imprinting technology has good selective adsorption capacity on enrofloxacin, and has the advantages of high temperature resistance, acid and alkali resistance, organic solvent resistance, good mechanical strength, regeneration and reuse, low cost and the like, so that the enrofloxacin imprinted polymer is widely applied to the fields of separation, enrichment and analysis. For example, caro et al (Ester Caro, rosa M.Marce', peter A.G.Cormack, et al, analytical Chimica Acta,2006, 562:145-151) use methylene chloride as the porogen and enrofloxacin as the template molecule, and use a precipitation polymerization method to prepare enrofloxacin imprinted polymers for two-step solid phase extraction of enrofloxacin and ciprofloxacin in human urine and pork liver; wang et al (Wang J, pan M, fang G, et al, microchip Acta,2009, 166:295-302) used a sol-gel method, N dimethylformamide as a pore-forming agent, enrofloxacin as a template molecule, 3-aminopropyl triethoxysilane as a functional monomer, tetraethoxysilica gel as a cross-linking agent, and the preparation of enrofloxacin imprinted polymer was applied to on-line adsorption monitoring of enrofloxacin residue in fish and chicken; rodrguez et al (Rodri guez E, navarro-Villoslada F,
Figure BDA0003309732250000011
E, et al, analytical Chemistry,2011, 83:2046-2055) uses acetonitrile as a pore-forming agent, enrofloxacin as a template molecule, methacrylic acid and divinylbenzene as functional monomers, 2-hydroxyethyl methacrylate and ethylene glycol dimethacrylate as cross-linking agents, adopts a precipitation polymerization method to synthesize monodisperse enrofloxacin imprinted polymer microspheres, and is applied to automatic online molecularly imprinted solid phase extraction-high performance liquid chromatography-fluorescence detection of 6 quinolone drug residues in aquaculture water and drinking water; li et al (Xiao-Xia Li, li-Hong Bai, huan Wang, et al journal of Chromatography A,2012, 1251:141-147) prepared an enrofloxacin imprinting monolithic column by an in situ polymerization method using a mixture of tetrahydrofuran, toluene, and acetonitrile as a porogen, enrofloxacin as a template molecule, and polystyrene as a molecular crowding agent; he et al (Hai-Bo He, chen Dong, bin Li, et al journal of Chromatography A,2014, 1361:23-33) use chloroform as the porogen and enrofloxacin as the template molecule in magnetic polyhedral oligomeric silsesquioxane Fe 3 O 4 Copolymerization of the surface of a POSS matrix to prepare a magnetic imprinted polymer hybridization material, which is applied to separation and detection of ofloxacin, enrofloxacin and danofloxacin in milk; wang et al (WANG X X, ZHOU Y Q, NIU Y L, et al International Journal of Analytical Chemistry,2019,5970754.DOI: org/10.1155/2019/5970754.) to crosslink polymeric glycidyl methacrylate-ethylene glycol dimethacrylate microspheres (P) GMA-EDMA ) As a substrate, 3-methacryloyl propyl trimethoxysilane (MPS) was surface-bonded, followed by grafting methacrylic acid to obtain P GMA-EDMA The @ MPS @ MAA microsphere is used as a functional monomer, enrofloxacin is used as a template molecule, and a surface imprinting method is adopted to prepare an enrofloxacin imprinted polymer which is applied to solid phase extraction of enrofloxacin residues in milk; yan et al (Hongyuan Yan, fengxia Qiao, kyung Ho Row. Chromatographia,2009,70 (7-8): 1087-1093) synthesized an imprinted monolith for the on-line solid phase extraction of enrofloxacin and its active metabolite ciprofloxacin in urine in an aqueous system using in situ polymerization using norfloxacin as a template molecule and methanol-water (5:1, v/v) as a porogenic solventA star; the preparation method comprises the steps of taking dimethyl sulfoxide as a pore-forming agent, ofloxacin as a template molecule and a magnetic carbon nano tube as a matrix, and applying a surface imprinting method to extract and detect the ofloxacin, gatifloxacin, ciprofloxacin and norfloxacin in eggs by using a magnetic imprinting polymer.
However, the imprinting polymers reported in the literature mostly use organic small molecules such as methylene dichloride, acetonitrile, chloroform and the like as pore-forming agents, the obtained polymers are small in gap and slow in mass transfer, and the problems of low adsorption capacity, template leakage and the like of the polymers caused by the fact that recognition sites only exist on the surface of materials or are embedded too deeply and template molecules are not eluted sufficiently often, so that the application of the polymers in environmental pollution control and trace analysis is limited.
Disclosure of Invention
Aiming at the problems, the invention provides a porous polymer microsphere for highly selectively adsorbing enrofloxacin, and a preparation method and application thereof.
The aim of the invention is realized by adopting the following technical scheme:
the preparation method of the porous polymer microsphere for highly selectively adsorbing enrofloxacin comprises the following steps:
(1) Mixing and emulsifying a surfactant, a hydrophobic ionic liquid and paraffin oil to obtain emulsion; weighing beta-cyclodextrin and dissolving the beta-cyclodextrin in hot water to obtain beta-cyclodextrin solution, cooling, adding methacrylic acid, and uniformly mixing to obtain continuous phase solution;
(2) Mixing and emulsifying the continuous phase solution and the emulsion, adding a cross-linking agent and an initiator, introducing nitrogen to remove oxygen, sealing a reaction system, stirring at a constant temperature for reaction, and separating out white precipitate after the reaction is completed;
(3) Washing the white precipitate with water and ethanol in turn, leaching with acetic acid ethanol solution, and drying after leaching to obtain the porous polymer microsphere.
Preferably, the surfactant is one or more of Span80, tween80, cetyltrimethylammonium bromide and sodium dodecyl benzene sulfonate.
Preferably, the hydrophobic ionic liquid is one or more of 1-hexyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 2-chloro-1, 3-dimethylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazoline hexafluorophosphate, 1-butyl-4-methylpyridine hexafluorophosphate and N-octylpyridine hexafluorophosphate.
Preferably, the mixing mass ratio of the surfactant, the hydrophobic ionic liquid and the paraffin oil is (1-5): (10-25): (100-200).
Preferably, the concentration of the beta-cyclodextrin solution is 12-48g/L; the molar ratio of beta-cyclodextrin to methacrylic acid in the continuous phase solution is 1: (8-10).
Preferably, the mixing volume ratio of the continuous phase solution to the emulsion is 1: (2-7).
Preferably, the cross-linking agent is one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, trimethylol propane trimethacrylate, N '-methylene bisacrylamide, N' -1, 4-phenyl bisacrylamide, pentaerythritol triacrylate and pentaerythritol tetraacrylate; the initiator is one or more of potassium persulfate, ammonium persulfate, persulfate-tetramethyl ethylenediamine and azodiisobutyronitrile.
Preferably, the reaction conditions of the constant temperature stirring reaction are as follows: the reaction temperature is 70-75 ℃, and the magnetic stirring is carried out for 1h at 1000 r/min.
Another object of the present invention is to provide a porous polymeric microsphere of highly selective adsorption of enrofloxacin prepared by the aforementioned preparation method.
It is a further object of the present invention to provide the use of the porous polymeric microspheres, particularly for the detection, enrichment and/or separation of enrofloxacin in aquatic products, livestock, poultry, milk, egg products, environmental samples, biological samples waiting to be tested.
The beneficial effects of the invention are as follows:
aiming at least one of the defects of poor selectivity, low efficiency, slow mass transfer, low adsorption capacity and the like of a separation and enrichment method of enrofloxacin in the prior art, the invention provides a preparation method of porous polymer microspheres with high selective adsorption of enrofloxacin, and the preparation method is characterized in that ternary mixed liquid consisting of hydrophobic ionic liquid, paraffin oil and surfactant is used as emulsion, beta-cyclodextrin is used as a template pore-forming agent, methacrylic acid is used as a functional monomer, and the porous polymer microspheres are prepared by adopting an emulsion polymerization method. The porous polymer microsphere has the characteristics of porosity, large adsorption capacity to enrofloxacin, high selectivity, fast mass transfer, good stability, simple preparation process and the like, and has wide application prospects in the fields of rapid separation, enrichment and analysis of enrofloxacin in aquatic products, livestock meat, milk and egg foods, environmental samples and biological samples, adsorption removal of environmental enrofloxacin pollutants and the like.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a scanning electron microscope image of porous polymer microspheres according to example 1 of the present invention;
FIG. 2 is a graph showing the static adsorption curve of porous polymer microspheres according to example 1 of the present invention;
FIG. 3 is a graph showing the static adsorption curve of porous polymer microspheres according to example 3 of the present invention;
FIG. 4 is a dynamic adsorption curve of porous polymer microspheres according to example 1 of the present invention;
FIG. 5 is a thermogravimetric analysis of porous polymer microspheres according to example 2 and example 3 of the present invention.
Detailed Description
The invention will be further described with reference to the following examples.
Example 1
The preparation method of the porous polymer microsphere for highly selectively adsorbing enrofloxacin comprises the following steps:
(1) 1.0g of span80 and 10g of 1-hexyl-3-methylimidazole hexafluorophosphate ionic liquid are added into 100g of paraffin oil, and ultrasonic emulsification is carried out for 20min to obtain emulsion;
(2) Weighing 0.6g of beta-cyclodextrin, dissolving in 25mL of 80 ℃ hot water, cooling to room temperature, adding 0.4mL of methacrylic acid into the solution, and uniformly stirring to obtain a continuous phase solution;
(3) Slowly adding the continuous phase solution into the emulsion, stirring and emulsifying for 1h in a constant-temperature water bath at 40 ℃, and keeping the stirring speed at 1000r/min; then adding 4.0mL of ethylene glycol dimethacrylate and 0.12g of potassium persulfate into the emulsifying system, carrying out ultrasonic treatment for 20min, introducing nitrogen for 20min, and sealing; stirring in a constant-temperature water bath at 70 ℃ for 24 hours, wherein the stirring speed is kept at 1000r/min; filtering after the reaction is finished to obtain white precipitate;
(4) And (3) carrying out ultrasonic treatment on the white precipitate for 10min by using purified water at the temperature of 85 ℃, then carrying out ultrasonic treatment on the white precipitate for 10min by using ethanol, repeating the process for 4 times, carrying out Soxhlet extraction on the white precipitate by using 20% acetic acid ethanol solution (glacial acetic acid and ethanol are in a volume ratio of 2:8), and finally drying the white precipitate in a vacuum drying oven at the temperature of 70 ℃ for 12h to obtain the porous polymer microsphere.
Example 2
The preparation method of the porous polymer microsphere for highly selectively adsorbing enrofloxacin comprises the following steps:
(1) Adding 0.5g of cetyl trimethyl ammonium bromide and 10g of 2-fluoro-1, 3-dimethyl imidazoline hexafluorophosphate ionic liquid into 100g of paraffin oil, and performing ultrasonic emulsification for 20min to obtain emulsion;
(2) 1.2g of beta-cyclodextrin is weighed and dissolved in 25mL of hot water at 70 ℃, after cooling to room temperature, 0.85mL of methacrylic acid is added into the solution, and the solution is stirred uniformly to obtain a continuous phase solution;
(3) Slowly adding the continuous phase solution into the emulsion, stirring and emulsifying for 1h in a constant-temperature water bath at 40 ℃, and keeping the stirring speed at 1000r/min; then adding 4.0mL of polyethylene glycol diacrylate and 0.12g of azodiisobutyronitrile into the emulsifying system, carrying out ultrasonic treatment for 20min, introducing nitrogen for 20min, and sealing; stirring in a constant-temperature water bath at 75 ℃ for 24 hours, wherein the stirring speed is kept at 1000r/min; filtering after the reaction is finished to obtain white precipitate;
(4) And (3) carrying out ultrasonic treatment on the white precipitate for 10min by using purified water at the temperature of 85 ℃, then carrying out ultrasonic treatment on the white precipitate for 10min by using ethanol, repeating the process for 4 times, carrying out Soxhlet extraction on the white precipitate by using 20% acetic acid ethanol solution (glacial acetic acid and ethanol are in a volume ratio of 2:8), and finally drying the white precipitate in a vacuum drying oven at the temperature of 70 ℃ for 12h to obtain the porous polymer microsphere.
Example 3
The preparation method of the porous polymer microsphere for highly selectively adsorbing enrofloxacin comprises the following steps:
(1) Adding 0.5g of span80 and 10g of 1-hexyl-3-methylimidazole hexafluorophosphate ionic liquid into 100g of paraffin oil, and performing ultrasonic emulsification for 20min to obtain emulsion;
(2) Adding 0.4mL of methacrylic acid into 25mL of purified water, and uniformly stirring to obtain a continuous phase solution;
(3) Slowly adding the continuous phase solution into the emulsion, stirring and emulsifying for 1h in a constant-temperature water bath at 40 ℃, and keeping the stirring speed at 1000r/min; then adding 4.0mL of ethylene glycol dimethacrylate and 0.12g of potassium persulfate into the emulsifying system, carrying out ultrasonic treatment for 20min, introducing nitrogen for 20min, and sealing; stirring in a constant-temperature water bath at 70 ℃ for 24 hours, wherein the stirring speed is kept at 1000r/min; filtering after the reaction is finished to obtain white precipitate;
(4) The white precipitate is subjected to ultrasonic treatment with purified water at 85 ℃ for 10min, then ultrasonic treatment with ethanol for 10min, the process is repeated for 4 times, soxhlet extraction is performed with 20% acetic acid ethanol solution (glacial acetic acid and ethanol are in a volume ratio of 2:8) for 48h, and finally the blank porous polymer microsphere is obtained after drying in a vacuum drying oven at 70 ℃.
Experimental example
1. Characterization of topography
The porous polymer microsphere prepared in example 1 was observed by a scanning electron microscope, and the scanning electron microscope image is shown in fig. 1, and it can be seen that the polymer was clustered together by a plurality of spherical clusters having a non-uniform particle size distribution, and had a diameter of about 500 to 600nm, a rough surface, and a porosity.
2. Static adsorption experiments
30mg of each of the porous polymers prepared in example 1 and example 3 was accurately weighed, 10mL of a concentration of 10.0, 100.0, 200.0, 300.0, 400.0, 500.0, 600.0, 800.0, 1000.0. Mu.g/mL of a difloxacin acetonitrile solution, an enrofloxacin acetonitrile solution, a sarafloxacin acetonitrile solution and a ciprofloxacin acetonitrile solution were respectively added, the mixture was put into a constant temperature shaker and shaken at 25℃for 1 hour at 150rpm, the mixture was left to stand and separate, the supernatant was taken, the absorbance of Difloxacin (DIF), enrofloxacin (ENF), sarafloxacin (SAR) and Ciprofloxacin (CIP) in the solution was measured by an ultraviolet spectrophotometer, and the adsorption amounts Q (mg/g) of the polymer to difloxacin, enrofloxacin, sarafloxacin and ciprofloxacin were calculated from the concentration changes in the solution before and after adsorption, respectively. The calculation results are shown in fig. 2 and 3.
The experimental results show that: the porous polymer microsphere prepared in the embodiment 1 has high adsorption selectivity to enrofloxacin, and the adsorption capacity is up to 138.8mg/g; the blank porous polymer microspheres prepared in example 3 have no significant difference in adsorption capacity to difloxacin, enrofloxacin, salad sand and ciprofloxacin, and have low adsorption capacities of 20.2, 21.5, 18.3 and 18.6mg/g respectively.
3. Dynamic adsorption experiments
Respectively taking 10.0mL of bifloxacin acetonitrile solution, enrofloxacin acetonitrile solution, sarafloxacin acetonitrile solution and ciprofloxacin acetonitrile solution with the concentration of 500.0 mug/mL, adding 30.0mg of the porous polymer prepared in the example 1, oscillating and adsorbing for different time (2-30 mm) at 150rpm in a constant temperature oscillator at 25 ℃, standing for separation, taking supernatant, measuring absorbance of bifloxacin, enrofloxacin, sarafloxacin and ciprofloxacin in the solution by using an ultraviolet spectrophotometer, and calculating adsorption capacity of the polymer. The results are shown in FIG. 4.
Experimental results show that the porous polymer microsphere disclosed by the invention can achieve equilibrium in 5min for adsorption of the sarafloxacin and the difloxacin and 10min for adsorption of the enrofloxacin and the ciprofloxacin, so that the polymer is rapid in adsorption mass transfer.
4. Thermogravimetric experiments
The thermogravimetric analysis curves of the porous polymer microspheres described in example 2 and example 3 are shown in fig. 5, and the polymer starts to decompose at 250 ℃ and is completely decomposed at about 450 ℃, which indicates that the polymer has good stability.
5. Repeated use experiments
0.1g of the porous polymer prepared in example 1 was weighed and subjected to 10 static adsorption and elution cycle experiments in 10.0mL of enrofloxacin acetonitrile solution at a concentration of 500.0. Mu.g/mL. After each static adsorption experiment, the polymer is washed by 0.5mol/L hydrochloric acid and purified water in sequence, and is dried in vacuum at 70 ℃ for regeneration. The regenerated polymer adsorbs enrofloxacin again, the adsorption recovery (%) of the polymer to enrofloxacin is calculated, and the test result is shown in table 1. The stability is good and the service life is long.
TABLE 1 influence of the number of repeated uses on the adsorption performance
Number of repeated use 1 2 3 4 5 6 7 8 9 10
Recovery (%) 99.5 98.7 96.4 94.2 91.6 88.8 85.4 82.2 79.6 76.4
6. Application in aquatic product detection
The porous polymer microspheres prepared in example 1 were used to examine the content of 4 kinds FQs in different batches of tilapia sold in farmer's market in the east post community of the state region of culprit city.
Sample solution preparation: homogenizing a proper amount of fish flesh, accurately weighing 5.000g of homogenized fish flesh, placing the fish flesh into a 50mL polypropylene centrifuge tube, adding 10mL of 1% acetonitrile formate solution, carrying out vortex oscillation for 2min, carrying out ultrasonic extraction for 10min, centrifuging for 5min under the condition of 10000r/min, transferring the supernatant into another polypropylene centrifuge tube, repeatedly extracting fish residues for 2 times, combining the extracting solutions, carrying out rotary evaporation, and then carrying out constant volume treatment with 1% acetonitrile formate solution to 5.00mL to obtain a sample solution.
Filling a solid phase extraction column: 50.0mg of the porous polymer powder prepared in example 1 was weighed, put into a solid phase extraction column, and compressed with absorbent cotton over the packing to prepare a porous polymer solid phase extraction column.
The solid phase extraction method comprises the following steps: activated with 3.0mL of methanol at a flow rate controlled at 0.5mL/min, then added with 5.00mL of sample solution, rinsed with 2.0mL of 5% methanol water, and finally eluted with 10.0mL of 5% methanol-ammonia (V: V=95:5), the eluate was collected, and purified with N 2 Blow-dried, and the residue was dissolved in 1.00mL of mobile phase, and then filtered through 0.45 μm organic film for UPLC-MS/MS analysis.
UPLC-MS/MS analysis conditions: ACQUITY UPLCBEHC 18 Columns (50 mm. Times.2.1 mm,1.7 μm, waters, USA); mobile phase: methanol-0.1% formic acid water (gradient elution see table 2); the flow rate is 0.25mL/min; the sample injection amount is 10 mu L.
TABLE 2 Mobile phase ratios for different times of ultra high performance liquid chromatography
Time (min) Methanol (%) 0.1% formic acid aqueous solution (%)
0 30 70
1 50 50
3 95 5
8 30 70
TABLE 3 retention time, qualitative ion pair, quantitative ion pair, collision gas energy and declustering Voltage of quinolone drugs
Figure BDA0003309732250000071
The measurement results are shown in Table 4. None of the 10 batches of tilapia samples examined in the spot were examined for 4 FQs. In the tilapia sample labeling experiment, three quinolones with different concentration levels of 0.20, 2.0 and 10.0 mug/kg are added, each concentration is parallel to 5 parts, extraction is carried out under the optimized solid phase extraction condition, the UPLC-MS/MS measurement is combined, the continuous measurement is carried out for 3 days, and the labeling recovery rate and the relative standard deviation result are shown in Table 4. The standard recovery rate of the 4 FQs is 77.0-101%, and the RSD is 4.0-8.7%. The method has the advantages of good precision and high accuracy, and can be applied to actual sample detection.
Table 4 results of detection of residual amounts of 4 FQs species (n=5) in tilapia samples
Figure BDA0003309732250000081
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.

Claims (7)

1. The preparation method of the porous polymer microsphere for highly selectively adsorbing enrofloxacin is characterized by comprising the following steps of:
(1) Mixing and emulsifying a surfactant, a hydrophobic ionic liquid and paraffin oil to obtain emulsion; weighing beta-cyclodextrin and dissolving the beta-cyclodextrin in hot water to obtain beta-cyclodextrin solution, cooling, adding methacrylic acid, and uniformly mixing to obtain continuous phase solution;
the mixing mass ratio of the surfactant to the hydrophobic ionic liquid to the paraffin oil is (1-5): (10-25): (100-200); the concentration of the beta-cyclodextrin solution is 12-48g/L; the molar ratio of beta-cyclodextrin to methacrylic acid in the continuous phase solution is 1: (8-10);
(2) Mixing and emulsifying the continuous phase solution and the emulsion, adding a cross-linking agent and an initiator, introducing nitrogen to remove oxygen, sealing a reaction system, stirring at a constant temperature for reaction, and separating out white precipitate after the reaction is completed;
the mixing volume ratio of the continuous phase solution to the emulsion is 1: (2-7);
(3) Washing the white precipitate with water and ethanol in turn, leaching with acetic acid ethanol solution, and drying after leaching to obtain the porous polymer microsphere.
2. The method for preparing the porous polymer microsphere with high selective adsorption of enrofloxacin according to claim 1, wherein the surfactant is one or more of Span80, tween80, cetyltrimethylammonium bromide and sodium dodecyl benzene sulfonate.
3. The method for preparing the porous polymer microsphere for highly selectively adsorbing enrofloxacin according to claim 1, wherein the hydrophobic ionic liquid is one or more of 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 2-chloro-1, 3-dimethylimidazolium hexafluorophosphate, 2-fluoro-1, 3-dimethylimidazolinium hexafluorophosphate, 1-butyl-4-methylpyridine hexafluorophosphate and N-octylpyridine hexafluorophosphate.
4. The method for preparing the porous polymer microsphere with high selective adsorption of enrofloxacin according to claim 1, wherein the cross-linking agent is one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, trimethylol propane trimethacrylate, N '-methylenebisacrylamide, N' -1, 4-phenyl bisacrylamide, pentaerythritol triacrylate and pentaerythritol tetraacrylate; the initiator is one or more of potassium persulfate, ammonium persulfate, persulfate-tetramethyl ethylenediamine and azodiisobutyronitrile.
5. The method for preparing the porous polymer microsphere with high selective adsorption of enrofloxacin according to claim 1, wherein the reaction conditions of the stirring reaction at constant temperature are as follows: the reaction temperature is 70-75 ℃, and the magnetic stirring is carried out for 1h at 1000 r/min.
6. A highly selective adsorption enrofloxacin porous polymeric microsphere prepared by the method of any one of claims 1-5.
7. Use of the porous polymeric microspheres of claim 6 for the detection, enrichment and/or separation of enrofloxacin in a sample to be tested.
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