CN114950394A - Preparation method of magnetic surface molecularly imprinted nano material for selective adsorption separation of diethylstilbestrol - Google Patents
Preparation method of magnetic surface molecularly imprinted nano material for selective adsorption separation of diethylstilbestrol Download PDFInfo
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Abstract
The invention belongs to the technical fields of surface molecular imprinting, magnetic separation, selective adsorption and the like, and discloses a preparation method of a magnetic surface molecular imprinting nano material for selectively adsorbing and separating diethylstilbestrol. Firstly, the methodPreparing ferroferric oxide nano particles by adopting a solvothermal method, then coating a layer of silicon dioxide on the surface of the ferroferric oxide, and then using a surface modifier to react SiO 2 ‑Fe 3 O 4 And (2) carrying out surface modification to obtain a magnetic molecularly imprinted carrier, finally putting the magnetic carrier, template molecules, a monomer, a cross-linking agent and an initiator into a solvent to carry out polymerization reaction on the surface of the carrier, washing the prepared product by a methanol-acetic acid solution to remove the template molecules, and obtaining the magnetic surface molecularly imprinted material (MMIP). MMIP shows superparamagnetism, can be quickly separated under the action of a magnet, has strong selective recognition and adsorption capacity on template molecules, can be used for pretreatment of diethylstilbestrol content detection in food, is convenient and quick in material recovery, and can be repeatedly used for multiple times.
Description
Technical Field
The invention belongs to the technical fields of surface molecular imprinting, material engineering, magnetic separation, selective adsorption and the like, and particularly relates to a preparation method of a magnetic surface molecular imprinting nano material for selectively adsorbing and separating diethylstilbestrol.
Background
The Diethylstilbestrol (DES) is an artificially synthesized estrogen substance, and the estrogen refers to a steroid hormone which can affect the life systems of animals and plants, has similar structure, can act on an endocrine system, a visual system, a metabolic system, a reproductive system and the like after entering a human body, can interfere the synthesis and metabolism of the endocrine hormone, influence the body function, destroy the coordination and the stability of the internal environment of the human body, and has wide and lasting physiological action. DES is mainly used in animal husbandry and the treatment of some diseases, in animal husbandry, after the animal uses, can make the protein in the animal assimilate, promote the animal to grow, abused in the breeding by some producers, through research verification, DES has teratogenicity and carcinogenicity. On day 27, 12 months 2019, DES is listed as a prohibited drug and other compounds for food animals. When a sample is directly detected, an interferent can influence the reliability of a detection result, pretreatment is required before detection, and a method for accurately and efficiently enriching trace DES (DES) by using a material capable of specifically adsorbing a detected substance is necessary to be researched and significant.
The molecular imprinting technology simulates specific interaction between an antibody and an antigen or between an enzyme and a substrate, and specifically recognizes an imprinted molecule, also called a template molecule, as the relationship between a key and a lock, which correspond to each other. The surface molecular imprinting technology is a new molecular imprinting technology developed for increasing the recognition sites of template molecules and improving the mass transfer rate, and is a technology for polymerizing on the surface of a solid material serving as a carrier. Most of the recognition sites obtained by polymerization are located on the surface of the polymer, so that the adsorption and desorption are easier, and the accessibility of the molecularly imprinted polymer to target molecules is improved. The prior surface molecular imprinting polymer methods comprise a chemical grafting method, a sacrificial silica gel method and the like, and common carriers comprise ferroferric oxide, silicon dioxide, carbon nano tubes and the like. The chemical grafting method is a surface imprinting technique which is widely applied at present, namely, a surface molecularly imprinted material can be obtained by carrying out polymerization reaction on the surface of a modified solid material.
At present, the molecular imprinting technology has made good progress in the research of harmful substance adsorption, but there are few reports on the research of artificially synthesized estrogen DES. Magnetic material (Fe) 3 O 4 ) The magnetic surface molecular imprinting material is prepared by combining with a surface molecular imprinting technology, can selectively adsorb target substances, has superparamagnetism, can realize rapid separation under the action of an external magnetic field, improves the recovery rate and the reuse rate of the material, greatly reduces the traditional adsorption separation operation steps, and is convenient and rapid to use.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic surface molecularly imprinted nano material for selectively adsorbing and separating diethylstilbestrol, which is used for enriching and separating DES and is convenient for more quickly and accurately measuring the content of DES.
In order to achieve the purpose, the preparation technical scheme adopted by the invention is as follows:
a preparation method of a magnetic surface molecularly imprinted nano material for selectively adsorbing and separating diethylstilbestrol comprises the following steps;
1) preparing ferroferric oxide nano particles:
adding ferric trichloride hexahydrate, anhydrous sodium acetate and polyethylene glycol 2000 into ethylene glycol, dissolving and mixing uniformly, pouring the solution into a polytetrafluoroethylene reaction kettle for high-temperature reaction, washing a product with ethanol, and drying in a vacuum box to obtain ferroferric oxide nanoparticles;
2) preparing silicon dioxide coated ferroferric oxide:
dispersing ferroferric oxide nano particles in a solution of ethanol and water, performing ultrasonic dispersion, adding ammonia water, uniformly stirring, dropwise adding ethyl orthosilicate under the stirring condition, continuously stirring for reaction, washing with ethanol after the reaction, separating with a magnet, and drying to obtain SiO 2 -Fe 3 O 4 Nanoparticles;
3)SiO 2 -Fe 3 O 4 surface modification of nanoparticles:
mixing SiO 2 -Fe 3 O 4 Dispersing the nano particles in a toluene solvent, dropwise adding a silane coupling agent while stirring, continuously stirring for reacting for a period of time, collecting a product by using a magnet, washing the product by using ethanol, and drying the product in a drying box to obtain SiO with the surface grafted with a functional group 2 -Fe 3 O 4 A nanoparticle;
4) preparation of diethylstilbestrol magnetic surface molecularly imprinted material (MMIP):
firstly, diethylstilbestrol and methacrylic acid are added into acetonitrile solvent for preassembling, ethylene glycol dimethacrylate and azobisisobutyronitrile are added, and the surface modified nano SiO obtained in the step 3) is added 2 -Fe 3 O 4 And (3) carrying out ultrasonic dispersion on the carrier uniformly, carrying out mechanical stirring reaction at a certain temperature, eluting diethylstilbestrol by using a methanol-acetic acid solution, washing acetic acid by using ethanol and water, and carrying out magnet separation and drying to obtain the magnetic surface molecularly imprinted nanomaterial MMIP.
In the step 1), the use amount ratio of ferric trichloride hexahydrate, anhydrous sodium acetate, polyethylene glycol 2000 and glycol is (8-9) g: (18-20) g: (5-6) g: (170-180) mL; the reaction temperature is 190-200 ℃, the reaction time is 8-9 hours, the drying temperature is 40-60 ℃, and the drying time is 8-12 hours.
In step 2), the Fe 3 O 4 The dosage proportion of the nano particles, the ammonia water and the ethyl orthosilicate solution is 150-300 mg: 2-4 mL: 2.5-5 mL; wherein the mass fraction of the ammonia water is 25-28%, the ultrasonic dispersion time is 30-60 min, the stirring reaction time is 6-8 hours, and the drying condition is drying in an oven at 40-60 ℃ for 8-12 hours.
In the solution of ethanol and water, the volume ratio of ethanol to water is 4: 1.
In step 3), the SiO 2 -Fe 3 O 4 The using amount ratio of the nano particles to the silane coupling agent to the toluene is (0.1-0.3) g: (3-9) mL: (60-120) mL, and the silane coupling agent is KH-570 or KH-550.
In the step 3), the reaction time is 20-30 hours, the reaction temperature is 60-70 ℃, the drying temperature is 40-60 ℃, and the drying time is 8-12 hours.
In the step 4), the dosage ratio of diethylstilbestrol, methacrylic acid, ethylene glycol dimethacrylate, azobisisobutyronitrile and acetonitrile is (0.1-0.2) g: (0.1-0.3) mL: (1.5-3) mL: (60-110) mg: (60-120) mL, diethylstilbestrol and surface modified nano SiO 2 -Fe 3 O 4 The dosage ratio of the carrier is 0.1-0.2 g: 0.2-0.3 g; the ultrasonic dispersion time is 30-60 minutes, the temperature of the mechanical stirring reaction is 64-66 ℃, and the reaction time is 22-26 hours. In the step 4), when the diethylstilbestrol and the methacrylic acid are added into the acetonitrile solvent for preassembly, the diethylstilbestrol and the methacrylic acid are preferably preassembled for 6-12 hours in a dark environment at room temperature.
In the step 4), the volume ratio of methanol to acetic acid is 4: (1-1.5), the elution time is 30-60 min, the elution mode is shaking, the elution times are 5-10, the drying temperature is 50-60 ℃, and the drying time is 12-24 hours.
The magnetic surface molecularly imprinted nanomaterial MMIP prepared by the invention is used for enriching and separating diethylstilbestrol.
By adopting the technical scheme, the invention has the advantages that:
magnetic material (Fe) 3 O 4 ) The magnetic surface molecular imprinting material is prepared by combining with a surface molecular imprinting technology, the saturation magnetic strength of MMIP is 67.6emu/g, no hysteresis phenomenon exists, the coercive force is zero, and superparamagnetism is shown. When DES is selectively adsorbed, the super-paramagnetism of DES can realize rapid separation under the action of an additional magnet.
Solid materials are used as carriers, polymerization is carried out on the surfaces of the solid materials, most of recognition sites obtained by polymerization are located on the surfaces of polymers, adsorption and desorption are easy, the accessibility of the molecularly imprinted polymer to target molecules is improved, and the thickness of a prepared MMIP surface molecularly imprinted polymer layer is about 30 nm; the nano MMIP has larger specific surface area.
The imprinting factors of the MMIP to the DES are respectively 3.7, and the DES has larger identification capability; MMIP can be reused for more than six times, and has good renewable performance; in the separation and elution processes, the solution can be separated from the solution in 17 seconds under the action of a magnet, the centrifugal operation is not needed, and the method is simple and rapid.
Drawings
FIG. 1 is a schematic diagram of a preparation scheme of a magnetic surface molecularly imprinted nanomaterial of example 1 of the present invention;
FIG. 2 is a transmission electron microscope photograph of an MMIP of example 1 of the present invention;
FIG. 3 is an infrared spectrum of a preparation material of example 1 of the present invention;
FIG. 4 is an MMIP hysteresis loop of embodiment 1 of the present invention;
FIG. 5 is a comparison of the magnet of example 2 of the present invention before and after separation;
FIG. 6 is a MMIP adsorption equilibrium curve of example 2 of the present invention;
FIG. 7 shows the selective recognition adsorption effect of MMIP in example 3 of the present invention;
FIG. 8 is the reproducibility of the MMIP of example 4 of the present invention.
Detailed Description
In order to make the reader better understand the scheme of the present invention, the specific embodiments and effects of the present invention will be illustrated by the following examples, but the scope of the present invention is not limited thereto.
Example 1
The preparation of the magnetic surface molecularly imprinted nano material for selectively adsorbing and separating diethylstilbestrol comprises the following steps;
(a) preparation of Fe by solvothermal method 3 O 4 Nanoparticle:
8.7g of ferric chloride hexahydrate is added into 175mL of ethylene glycol solution and dissolved completely by ultrasonic wave, 5.1g of polyethylene glycol 2000 and 19.1g of anhydrous sodium acetate are added, and the mixture is stirred by magnetic force at 50 ℃ to be dissolved completely and mixed uniformly. Pouring the solution into a polytetrafluoroethylene reaction kettle, putting the reaction kettle into a stainless steel shell, putting the stainless steel shell into an oven after the reaction kettle is installed, and heating to 200 ℃ to react for 8 hours. Washing the product with ethanol, separating with magnet, washing, drying in 50 deg.C oven for 12 hr to obtain Fe 3 O 4 And (3) nanoparticles.
(b) Silicon dioxide coated nano ferroferric oxide:
200mL of ethanol and 50mL of water were measured, and the mixture was put into a three-necked flask, and 300mg of Fe was added 3 O 4 Adding the nanoparticles into the solution, ultrasonically dispersing for 30min by using an ultrasonic instrument, fixing the three-neck flask on a mechanical stirrer, and mechanically stirring at 400 r/min. Pouring 4mL of 28 mass percent ammonia water into a three-neck flask, stirring for 5 minutes to uniformly mix, slowly dripping 5mL of ethyl orthosilicate solution into the flask under the condition of stirring, not dripping the solution onto the wall of the flask, and after the dripping is finished, continuing to mechanically stir at room temperature for 6 hours. Collecting a product magnet, and washing the product magnet by using ethanol and ultrapure water to obtain SiO 2 -Fe 3 O 4 Nanoparticles were dried in an oven for 10 hours.
(c)SiO 2 -Fe 3 O 4 Surface modification of nanoparticles:
120mL of toluene was measured and charged into a three-necked flask, and 0.3g of SiO was added 2 -Fe 3 O 4 Adding the nano particles into the solution, and fixing the flask on a mechanical stirrer for stirring after the ultrasonic dispersion is uniform. Slowly dripping 9mL of silane coupling agent KH-570 under stirring, placing the flask in a 65 ℃ water bath after the reaction is finished, mechanically stirring for 24 hours, collecting the product by using a magnet, washing the product with ethanol and water, and drying the product in a vacuum drying oven for 12 hours to obtain SiO with the surface grafted with functional groups 2 -Fe 3 O 4 And (3) nanoparticles.
(d) Preparation of diethylstilbestrol magnetic surface molecularly imprinted nanomaterial (MMIP):
a100 mL three-neck flask is filled with 65mL of acetonitrile, then 100mg of diethylstilbestrol and 128 mu L of methacrylic acid are added, the solution is sealed and placed in a dark environment at room temperature for preassembly for 12h, and after the assembly is finished, 60mg of azobisisobutyronitrile, 1.5mL of ethylene glycol dimethacrylate and 200mg of the surface modified SiO obtained in the step 3) are added 2 -Fe 3 O 4 And (3) after the nano particle carrier is uniformly dispersed by ultrasonic, fixing the flask on a mechanical stirring device, and inserting a stirring rod for mechanical stirring. Adding while stirring, placing the flask in a water bath, and heating toThe reaction was carried out at 65 ℃ for 24h with mechanical stirring. The product was collected with a magnet, dispersed in 50mL of methanol-acetic acid eluent, and the eluent was changed every half hour until diethylstilbestrol was eluted well, followed by washing with ethanol and water to obtain MMIP, which was then dried in an oven at 50 ℃ for 12 hours. The whole preparation process is schematically shown in figure 1.
The diethylstilbestrol magnetic surface non-molecular engram Material (MNIP) was prepared in the same way as MMIP, but without addition of the imprinted molecule diethylstilbestrol.
The transmission electron microscope analysis of the nano MMIP prepared in the example 1 is carried out, and the transmission electron microscope picture is shown in figure 2, so that the nano MMIP prepared is spherical particles with uniform particle size and regular appearance, the diameter is 350nm, and a layer of molecularly imprinted polymer is arranged on the surface of the carrier.
The infrared spectrum of the nano material prepared in example 1 is shown in figure 3, wherein a, b, c, d and e are Fe respectively 3 O 4 、SiO 2 -Fe 3 O 4 、KH570-SiO 2 -Fe 3 O 4 MMIP, MNIP. 583cm in graph a -1 The vibration absorption peaks of Fe-O bonds of ferroferric oxide exist in the graphs (b, c, d and e); 1095cm in graph b -1 Absorption peak at 796cm -1 The absorption peak is generated by stretching vibration of Si-O bonds, which indicates that the silicon dioxide is successfully coated; 2918cm in graph c -1 And 2852cm -1 Is located at 1632cm of vibration peak of C-H -1 The absorption peak is generated by the stretching vibration of C ═ C double bonds in KH-570, which indicates that KH570 is successfully grafted on the hydroxyl groups on the surface of the silica; 1350cm in graph d -1 The peak is vibration absorption peak of C-O bond and is at 1632cm -1 The characteristic absorption peak area and peak intensity of C ═ O are large, and the same change appears in graph e, indicating that methacrylic acid has polymerized and crosslinked on the surface of the carrier, and the molecularly imprinted layer has covered the surface of the magnetic carrier. Line e and line d are substantially identical, indicating that diethylstilbestrol elutes cleanly.
Example 2
Preparing 25mg/L, 50mg/L, 100mg/L, 150mg/L, 200mg/L and 300mg/L diethylstilbestrol ethanol solution, respectively filling 10mL into a centrifuge tube, and respectively dispersing 20mg MMIP and MNIP into the centrifuge tube. Placing the centrifuge tube in a constant temperature oscillation box, oscillating for 12 hours at 25 ℃, after adsorption equilibrium, using a magnet to rapidly separate MMIP from the solution, wherein the MMIP has superparamagnetism and high saturation magnetic strength, the experimental magnet can be rapidly separated, the hysteresis curve of the material is shown in figure 4, and the saturation magnetic strength is 67.6 emu/g; the magnet separation effect is shown in fig. 5. Measuring the concentration of the supernatant fluid, and obtaining the equilibrium adsorption capacity of the MMIP from the concentration change before and after adsorption, wherein the adsorption result is shown in figure 6, and the graph shows that the MMIP reaches the maximum equilibrium adsorption capacity when the MMIP is about 200mg/L, and the MNIP basically reaches the maximum adsorption capacity when the MNIP is 150mg/L, because the molecular imprinting material has the adsorption of a specific imprinting cavity, and the MNIP only has surface adsorption, and the adsorption saturation is faster; under the same concentration, the adsorption capacity of the MMIP to the DES is always larger than that of the MNIP to the DES, because the template molecules are added, specific cavities of diethylstilbestrol exist on the surface and inside of the molecularly imprinted material, specific selection can be carried out on the DES during adsorption, the DES is not added in MNIP preparation, and the adsorption of the DES is mainly physical adsorption without specific binding sites; the maximum adsorption capacity of MMIP to DES is 7.1mg/g and the maximum adsorption capacity of MNIP to DES is 2.8mg/g at 25 ℃.
Example 3
In order to verify the recognition capability of the magnetic molecular imprinting material, selective adsorption of MMIP and MNIP is carried out in a mixed solution of diethylstilbestrol and a structural analog thereof, namely bisphenol A (BPA) and estradiol (E2). 20mg of MMIP and MNIP are respectively added into 10mL of the mixed solution with the initial concentration of 200mg/L of diethylstilbestrol, estradiol and bisphenol A, and the mixed solution is shaken for 12h in a shaking box at the temperature of 25 ℃. After the oscillation is finished, the adsorbing material and the solution are separated by an additional magnet, the residual concentrations of the three substances in the supernatant after the adsorption are measured, the adsorption recognition capacity is calculated through the concentration change, and the adsorption effects of MMIP and MNIP are shown in figure 7. As can be seen from FIG. 7, the adsorption amount of the imprinted molecule DES by MMIP is the highest and is 4.89mg/g, and the adsorption amount is reduced compared with that of a DES solution, which is the result of interference of BPA and E2 and is the least as to estradiol; MNIP has basically the same adsorption amount of the three substances, has no special selectivity, and the adsorption amount of the three substances is always smaller than that of MMIP. It can be seen that MMIP has a large selective recognition capability for DES, because MMIP has the best adsorption effect for DES because the specific action site and the cavity matched with the template molecule are left on the surface after the template molecule is removed, and the adsorption effect for DES can be carried out by the MMIP through specific recognition adsorption on the template molecule.
Example 4
The reusability is an important factor for the practical application of the adsorbent material. Respectively adding MMIP and MNIP into 10mL diethylstilbestrol solution with initial concentration of 200mg/L for adsorption balance, measuring the equilibrium adsorption quantity after the adsorption balance is achieved, then eluting the template molecule, adding a magnet separation material, and performing re-adsorption under the same condition. The adsorption-desorption process is repeated for six times, the reusability is examined, the implementation result is shown in fig. 8, and the adsorption quantity of the MMIP to the DES is gradually reduced along with the increase of the use times of the material, the adsorption quantity of the MNIP is basically not changed greatly, and the adsorption quantity MMIP is always larger than the MNIP; after repeating the adsorption-desorption process six times, the adsorption amount of MMIP was 90.2% of the maximum adsorption amount, and the reason for the reduction of the adsorption amount may be that the imprinted cavity was occupied or destroyed after multiple uses, resulting in the reduction of binding sites. In general, it can be seen that the regeneration performance is better, and the regeneration can be repeatedly used.
Claims (10)
1. A preparation method of a magnetic surface molecularly imprinted nano material for selectively adsorbing and separating diethylstilbestrol is characterized by comprising the following steps;
1) preparing ferroferric oxide nano particles:
2) silica-coated ferroferric oxide SiO 2 -Fe 3 O 4 Preparing nano particles:
3)SiO 2 -Fe 3 O 4 surface modification of nanoparticles:
mixing SiO 2 -Fe 3 O 4 Dispersing the nano particles in toluene solvent, dripping silane coupling agent while stirring, and thenStirring and reacting for a period of time, collecting the product by using a magnet, washing the product by using ethanol, and drying the product in a drying box to obtain SiO with the surface grafted with the functional group 2 -Fe 3 O 4 A nanoparticle;
4) preparation of diethylstilbestrol magnetic surface molecularly imprinted material (MMIP):
firstly, diethylstilbestrol and methacrylic acid are added into acetonitrile solvent for preassembling, ethylene glycol dimethacrylate and azobisisobutyronitrile are added, and the surface modified nano SiO obtained in the step 3) is added 2 -Fe 3 O 4 And (3) carrying out ultrasonic dispersion on the carrier uniformly, carrying out mechanical stirring reaction at a certain temperature, eluting diethylstilbestrol by using a methanol-acetic acid solution, washing acetic acid by using ethanol and water, and carrying out magnet separation and drying to obtain the magnetic surface molecularly imprinted nanomaterial MMIP.
2. The preparation method according to claim 1, wherein in the step 1), the preparation of the ferroferric oxide nanoparticles comprises the following steps: adding ferric trichloride hexahydrate, anhydrous sodium acetate and polyethylene glycol 2000 into ethylene glycol, dissolving and mixing uniformly, pouring the solution into a polytetrafluoroethylene reaction kettle for high-temperature reaction, washing a product with ethanol, and drying in a vacuum box to obtain ferroferric oxide nanoparticles;
wherein the dosage ratio of ferric chloride hexahydrate, anhydrous sodium acetate, polyethylene glycol 2000 and glycol is (8-9) g: (18-20) g: (5-6) g: (170-180) mL; the reaction temperature is 190-200 ℃, the reaction time is 8-9 hours, the drying temperature is 40-60 ℃, and the drying time is 8-12 hours.
3. The preparation method according to claim 1, wherein in the step 2), the silicon dioxide is coated with ferroferric oxide SiO 2 -Fe 3 O 4 The preparation steps of the nano particles are as follows: mixing Fe 3 O 4 Dispersing nano particles in a solution of ethanol and water, performing ultrasonic dispersion, adding ammonia water, stirring uniformly, dropwise adding tetraethoxysilane under the condition of stirring, continuously stirring for reaction, washing with ethanol, separating with a magnet, and drying to obtain SiO 2 -Fe 3 O 4 Nanoparticles.
4. The method of claim 3, wherein Fe 3 O 4 The dosage proportion of the nano particles, the ammonia water and the ethyl orthosilicate solution is 150-300 mg: 2-4 mL: 2.5-5 mL; wherein the mass fraction of the ammonia water is 25-28%, the ultrasonic dispersion time is 30-60 min, the stirring reaction time is 6-8 hours, and the drying condition is drying in an oven at 40-60 ℃ for 8-12 hours; in the solution of ethanol and water, the volume ratio of ethanol to water is 4: 1.
5. The method of claim 1, wherein in step 3), SiO is 2 -Fe 3 O 4 The using amount ratio of the nano particles to the silane coupling agent to the toluene is (0.1-0.3) g: (3-9) mL: (60-120) mL, and the silane coupling agent is KH-570 or KH-550.
6. The preparation method according to claim 1, wherein in the step 3), the reaction time is 20 to 30 hours, and the reaction temperature is 60 to 70 ℃; the drying temperature is 40-60 ℃, and the drying time is 8-12 hours.
7. The method according to claim 1, wherein in the step 4), the ratio of the amount of diethylstilbestrol, methacrylic acid, ethylene glycol dimethacrylate, azobisisobutyronitrile and acetonitrile is (0.1 to 0.2) g: (0.1-0.3) mL: (1.5-3) mL: (60-110) mg: (60-120) mL, diethylstilbestrol and surface modified nano SiO 2 -Fe 3 O 4 The dosage ratio of the carrier is 0.1-0.2 g: 0.2-0.3 g; the ultrasonic dispersion time is 30-60 minutes, the temperature of the mechanical stirring reaction is 64-66 ℃, and the reaction time is 22-26 hours.
8. The preparation method of claim 1, wherein in the step 4), when the diethylstilbestrol and the methacrylic acid are added into the acetonitrile solvent for preassembly, the mixture is placed in a dark environment at room temperature for preassembly for 6 to 12 hours.
9. The method according to claim 1, wherein in the step 4), the volume ratio of methanol to acetic acid is 4: (1-1.5), the elution time is 30-60 min, the elution mode is shaking, the elution times are 5-10, the drying temperature is 50-60 ℃, and the drying time is 12-24 hours.
10. The magnetic surface molecularly imprinted nanomaterial MMIP prepared by the preparation method of any one of claims 1-9 is used for enriching and separating diethylstilbestrol.
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