CN103833942A - Preparation method and use of diethylstibestrol molecularly-imprinted magnetic microspheres - Google Patents
Preparation method and use of diethylstibestrol molecularly-imprinted magnetic microspheres Download PDFInfo
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- CN103833942A CN103833942A CN201310633342.2A CN201310633342A CN103833942A CN 103833942 A CN103833942 A CN 103833942A CN 201310633342 A CN201310633342 A CN 201310633342A CN 103833942 A CN103833942 A CN 103833942A
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- stilboestrol
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- molecular blotting
- magnetic microsphere
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Abstract
The invention discloses a preparation method and a use of diethylstibestrol molecularly-imprinted magnetic microspheres. The preparation method comprises the following steps of preparing Fe3O4 magnetic nanometer particles by a wet chemical coprecipitation polymerization method, modifying surfaces of the Fe3O4 magnetic nanometer particles by oleic acid, and coating the Fe3O4 magnetic nanometer particles based on diethylstibestrol as a template molecule by a surface molecular imprinting deposition polymerization method to obtain the diethylstibestrol molecularly-imprinted magnetic microspheres. The diethylstibestrol molecularly-imprinted magnetic microspheres can separate and analyze diethylstibestrol in a complex sample. The diethylstibestrol molecularly-imprinted magnetic microspheres have good chemical and mechanical stability, magnetization intensity and recycle performances, have a biomimetic recognition capacity and realize separation in an applied magnetic field. Compared with the traditional molecularly-imprinted material, the diethylstibestrol molecularly-imprinted magnetic microspheres can be separated simply and conveniently and has a wide application prospect in the field of separation analysis and detection.
Description
Technical field
The present invention relates to magnetic molecularly imprinted technology and field of new, particularly relate to a kind of preparation method and application thereof of stilboestrol molecular blotting magnetic microsphere.
Background technology
In environment phenolic estrogen, stilboestrol is the stronger synthetic oestrogenic hormon of a kind of effect.Because this type of material has hormesis to the normal anabolism of animal, can impel nitrogen in animal body to stop increase, cause the speed of amino acid synthetic protein accelerate and increase weight, once in fodder industry, be used widely.But take in for a long time this type of material, the hormonal equilibrium that can disturb human normal, causes organism metabolic disorder, occurs heteroplasia tumour, the problem that women with breast cancer and endometriosis and fetal anomaly etc. are serious, all forbids using this material in animal cultivation process in China and American-European many countries.But, still there are at present some illegal retailers to be added in feed, stilboestrol inevitably residues in the Organ and tissue of food animal or by movement entered environment with the form of its original shape or meta-bolites.In soil, city domestic sewage and breeding wastewater etc., all detect this material at present.
Molecularly imprinted polymer (Molecularly Imprinted polymers, MIPs) be a kind of new separation material that development in recent years is got up, it is first to form Host-guest Complexes by template molecule (molecule to be separated) and polymerisable function monomer by supramolecule effects such as ionization, hydrogen bond and hydrophobic interactions, and then makes by a large amount of linking agent polymerizations.When removing after template molecule, in molecularly imprinted polymer, stay and the hole of template molecule space structure exact matching, and on hole with functional group template molecule is had to specific binding capacity.Due to the special molecular recognition capability of the precordainment of molecularly imprinted polymer and stable chemical physical property, molecular imprinting has now been widely used in the aspects such as chiral separation and enrichment, enzyme acceptor simulation and biosensor.As the composition analysis of the complex samples such as medicine, environment and biology, need to carry out multi-section processing, when process complexity, consumption energy consumption, separation efficiency is low, using the molecular engram material with specific recognition performance as parting material, the similar component of enrichment class formation, remove the impurity that other character are close, there is the step of simplification, efficient advantage.
The advantages such as it is high that molecular engram microsphere (molecularly imprinted microspheres, MIMs) has molecular recognition efficiency, and preparation and application are convenient, the preparation of imprinted polymer microballoon at present and application have become the focus of research.Simultaneously along with people's improving constantly magnetic Nano material performance understanding and application requiring, prepare single magnetic Nano material and be more and more difficult to meet application requiring, in order to improve the performance of material, the surperficial coating material that preparation has nanostructure becomes a kind of effectively means.
Magnetic nanoparticle can promptly locate, separate under externally-applied magnetic field, is subject to extensive concern at numerous areas such as biomedicine, magnetic separation.Magnetic molecularly imprinted technology, compared with molecular imprinting, separates simple and conveniently, can under externally-applied magnetic field, complete magnetic sepn process; Compared with independent magneticsubstance, there is specific recognition and detect performance, high sensitivity, high stability and separate the advantages such as simple and convenient.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of preparation method and application thereof of stilboestrol molecular blotting magnetic microsphere.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: a kind of preparation method of stilboestrol molecular blotting magnetic microsphere is provided, comprises the following steps:
(1) prepare magnetic Fe
3o
4nano microsphere carrier:
Preparation FeSO
47H
2o and FeCl
36H
2the mixing solutions of O then at the uniform velocity splashes into ammoniacal liquor under agitation condition in above-mentioned mixing solutions, to the pH=9.0 of mixing solutions, reaction finish after by gained Fe
3o
4nanoparticle is water and absolute ethanol washing respectively, and vacuum-drying is spent the night;
(2) magnetic Fe
3o
4the finishing of Nano microsphere carrier:
By the Fe of preparation in step (1)
3o
4nanoparticle is scattered in water, passes into nitrogen, then prepared suspension is heated to 80 ℃, dropwise adds oleic acid and ammoniacal liquor under stirring, is then incubated, then by the Fe of the surface modification of gained
3o
4nanoparticle cleans with water and ethanol respectively, and vacuum-drying is spent the night;
(3) prepare stilboestrol molecular blotting magnetic microsphere:
By the Fe of oleic acid modified in step (2)
3o
4microballoon is prepared into the Fe of pre-determined volume mass ratio
3o
4/ acetonitrile suspension, add stilboestrol and function monomer fully to dissolve, add again linking agent and initiator, ultrasonic dispersion, after passing into nitrogen, seal, carry out after isothermal reaction, utilize magnetic to isolate stilboestrol molecular blotting magnetic microsphere, collecting precipitation polymkeric substance, vacuum-drying, is placed in apparatus,Soxhlet's by resulting polymers, with methyl alcohol-acetic acid mixed solution wash-out 24～48h removal stilboestrol template molecule, finally wash away residual acetic acid with methyl alcohol, vacuum-drying, to constant weight, obtains molecular blotting magnetic microsphere.
In a preferred embodiment of the present invention, in described step (3), described Fe
3o
4the volume mass of/acetonitrile suspension is than being 1g/200mL.
In a preferred embodiment of the present invention, in described step (3), the temperature of described isothermal reaction is 60 ℃, and the time is 24h.
In a preferred embodiment of the present invention, the function monomer in described step (3) is at least one in vinylformic acid, methacrylic acid, trifluoromethyl acrylate, vinyl benzoic acid, methylene-succinic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 2-vinyl pyridine, 4-vinylpridine, vinyl imidazole, methyl methacrylate, hydroxyethyl methylacrylate, acrylamide and Methacrylamide.
In a preferred embodiment of the present invention, linking agent in described step (3) is Ethylene glycol dimethacrylate, Vinylstyrene, trimethoxy propane trimethyl acrylic ester, pentaerythritol triacrylate and N, at least one in N '-methylene-bisacrylamide.
In a preferred embodiment of the present invention, in described step (3), the molar ratio of described stilboestrol template molecule, function monomer and linking agent is 1:2～12:2～40.
In a preferred embodiment of the present invention, in described step (3), the volume ratio of methyl alcohol and acetic acid is 4～9:1.
For solving the problems of the technologies described above, another technical solution used in the present invention is: the application method that a kind of stilboestrol molecular blotting magnetic microsphere is provided, the molecular blotting magnetic microsphere of preparation in claim 1 is put into the solution that contains stilboestrol, realize the compartment analysis to stilboestrol by adsorption and desorption.
The invention has the beneficial effects as follows: stilboestrol molecular blotting magnetic microsphere prepared by the present invention has good chemistry and mechanical stability, the specific magnetising moment and recycling performance, its bionical recognition capability having can under externally-applied magnetic field, separate and Analysis of Complex sample in stilboestrol, separate simple and conveniently, there is more wide application prospect at compartment analysis and detection field.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of a kind of stilboestrol molecular blotting magnetic microsphere of the present invention;
Fig. 2 is magnetic Fe
3o
4the magnetic hysteresis tropic with molecular blotting magnetic microsphere.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in detail, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that, protection scope of the present invention is made to more explicit defining.
Refer to Fig. 1 and Fig. 2, the embodiment of the present invention comprises:
The present invention is combined molecular engram microsphere with magneticsubstance, prepared Fe by wet-chemical co-precipitation polymerization
3o
4magnetic nanoparticle, then its surface is modified with oleic acid, finally take stilboestrol as template molecule, the method by surface molecule print precipitation polymerization is by magnetic Fe
3o
4particle parcel becomes magnetic molecularly imprinted complex microsphere matrix material, and specific embodiment is as follows:
Embodiment 1
By 5.41g FeCl
36H
2o and 3.34g FeSO
47H
2o is dissolved in 200mL distilled water and forms mixing solutions, and 2.5% ammonia soln is at the uniform velocity splashed into above-mentioned mixing solutions to pH=9.0, continue stir 40min, reaction finish after by products therefrom (Fe
3o
4nanoparticle) water and absolute ethanol washing 5 times, 40 ℃ of vacuum-dryings are spent the night.
Get 2.0g gained Fe
3o
4nanoparticle is ultrasonic to be scattered in 200mL distilled water, and passes into wherein nitrogen 30min, then prepared suspension is heated to 80 ℃, drips respectively 3mL oleic acid and 1mL ammoniacal liquor under stirring, insulation 30min.Products therefrom (the Fe of oleic acid modified
3o
4nanoparticle) respectively water and ethanol clean 5 times, vacuum-drying is spent the night.
To the Fe of the above-mentioned oleic acid modified of 1.0g
3o
4in nanoparticle, add a small amount of cetyl trimethylammonium bromide and be dispersed in 200 mL acetonitriles, forming the acetonitrile solution of Z 250/oleic acid.0.13 g stilboestrol and 0.14g function monomer acrylamide are fully dissolved in the acetonitrile solution of Z 250/oleic acid of above-mentioned 200mL, ultrasonic 5min, add again 1.90 mL linking agent Ethylene glycol dimethacrylate and 0.019g initiator A IBN(Diisopropyl azodicarboxylate), ultrasonic 5min, logical N
2after 10min, seal 60 ℃ of reaction 24h.Utilize magnetic to isolate stilboestrol molecular blotting magnetic microsphere, 15min can reach complete separate stage, collecting precipitation polymkeric substance, vacuum-drying.Resulting polymers is placed in to apparatus,Soxhlet's, with methyl alcohol-acetic acid (volume ratio is 4～9:1) wash-out 24～48 h, until can't detect template molecule in elutriant, finally wash away residual acetic acid with methyl alcohol, vacuum-drying, to constant weight, obtains molecular blotting magnetic microsphere.
The molecular blotting magnetic microsphere that aforesaid method is obtained is observed under scanning electron microscope, see Fig. 1, the molecular blotting magnetic microsphere that discovery obtains has good sphericity, dispersed relatively good, without adhesion phenomenon, size distribution is even, and recording its median size is 1.05 μ m, and saturated extent of adsorption is 19.12mg/g.
By 5.41g FeCl
36H
2o and 3.34g FeSO
47H
2o is dissolved in 200mL distilled water and forms mixing solutions, and 2.5% ammonia soln is at the uniform velocity splashed into above-mentioned mixing solutions to pH=9.0, continue stir 40min, reaction finish after by products therefrom (Fe
3o
4nanoparticle) water and absolute ethanol washing 5 times, 40 ℃ of vacuum-dryings are spent the night.
Get 2.0g gained Fe
3o
4nanoparticle is ultrasonic to be scattered in 200mL distilled water, and passes into wherein nitrogen 30min, then prepared suspension is heated to 80 ℃, drips respectively 3mL oleic acid and 1mL ammoniacal liquor under stirring, insulation 30min.Products therefrom (the Fe of oleic acid modified
3o
4nanoparticle) respectively water and ethanol clean 5 times, vacuum-drying is spent the night.
To the Fe of the above-mentioned oleic acid modified of 1.0g
3o
4in nanoparticle, add a small amount of cetyl trimethylammonium bromide and be dispersed in 200 mL acetonitriles, forming the acetonitrile solution of Z 250/oleic acid.0.13 g stilboestrol and 1.54 mL function monomer methacrylic acids are fully dissolved in the acetonitrile solution of Z 250/oleic acid of above-mentioned 200mL, ultrasonic 5min, add again 0.50mL linking agent pentaerythritol triacrylate and 0.019g initiator A IBN, ultrasonic 5min, logical N
2after 10min, seal 60 ℃ of reaction 24h.Utilize magnetic to isolate stilboestrol molecular blotting magnetic microsphere, 15min can reach complete separate stage, collecting precipitation polymkeric substance, vacuum-drying.Resulting polymers is placed in to apparatus,Soxhlet's, with methyl alcohol-acetic acid (volume ratio is 4～9:1) wash-out 24～48 h, until can't detect template molecule in elutriant, finally wash away residual acetic acid with methyl alcohol, vacuum-drying, to constant weight, obtains molecular blotting magnetic microsphere.
The molecular blotting magnetic microsphere that aforesaid method is obtained is observed under scanning electron microscope, finds that the molecular blotting magnetic microsphere obtaining has good sphericity, dispersed relatively good, without adhesion phenomenon, size distribution is even, and recording its median size is 1.12 μ m, and saturated extent of adsorption is 17.65mg/g.
Embodiment 3
By 5.41g FeCl
36H
2o and 3.34g FeSO
47H
2o is dissolved in 200mL distilled water and forms mixing solutions, and 2.5% ammonia soln is at the uniform velocity splashed into above-mentioned mixing solutions to pH=9.0, continue stir 40min, reaction finish after by products therefrom (Fe
3o
4nanoparticle) water and absolute ethanol washing 5 times, 40 ℃ of vacuum-dryings are spent the night.
Get 2.0g gained Fe
3o
4nanoparticle is ultrasonic to be scattered in 200mL distilled water, and passes into wherein nitrogen 30min, then prepared suspension is heated to 80 ℃, drips respectively 3mL oleic acid and 1mL ammoniacal liquor under stirring, insulation 30min.Products therefrom (the Fe of oleic acid modified
3o
4nanoparticle) respectively water and ethanol clean 5 times, vacuum-drying is spent the night.
To the Fe of the above-mentioned oleic acid modified of 1.0g
3o
4in nanoparticle, add a small amount of cetyl trimethylammonium bromide and be dispersed in 200 mL acetonitriles, forming the acetonitrile solution of Z 250/oleic acid.0.13 g stilboestrol and 0.07g function monomer acrylamide and 0.11mL function monomer 4-vinylpyridine are fully dissolved in the acetonitrile solution of Z 250/oleic acid of above-mentioned 200mL, ultrasonic 5min, add again 0.65mL linking agent trimethylolpropane trimethacrylate and 0.019g(0.12mmol) initiator A IBN, ultrasonic 5min, logical N
2after 10min, seal 60 ℃ of reaction 24h.Utilize magnetic to isolate stilboestrol molecular blotting magnetic microsphere, 15min can reach complete separate stage, collecting precipitation polymkeric substance, vacuum-drying.Resulting polymers is placed in to apparatus,Soxhlet's, with methyl alcohol-acetic acid (volume ratio is 4～9:1) wash-out 24～48 h, until can't detect template molecule in elutriant, finally wash away residual acetic acid with methyl alcohol, vacuum-drying, to constant weight, obtains molecular blotting magnetic microsphere.
The molecular blotting magnetic microsphere that aforesaid method is obtained is observed under scanning electron microscope, finds that the molecular blotting magnetic microsphere obtaining has good sphericity, dispersed relatively good, without adhesion phenomenon, size distribution is even, and recording its median size is 1.01 μ m, and saturated extent of adsorption is 20.93mg/g.
Embodiment 4
The performance test of stilboestrol molecular blotting magnetic microsphere
In order to investigate the recycling performance of molecular blotting magnetic microsphere, adopt with the molecular blotting magnetic microsphere of a 25mg respectively the stilboestrol milk soln of the stilboestrol acetonitrile solution to 6 parts of same concentrations and 6 parts of same concentrations carried out successively adsorption-desorption experiment.
Test result analysis is as follows:
After tested, the stilboestrol molecular engram microsphere particle obtaining has good chemistry and mechanical stability, and extraction test is repeatedly rear without cracked and surface peeling phenomenon.Microballoon has the good specific magnetising moment, and the magnetic hysteresis tropic is longer and narrower, and coercive force and remanent magnetism are less, is respectively 3.376A/m and 1.952emu/g, has soft magnetism, (as shown in Figure 2).
Utilize molecular blotting magnetic microsphere prepared by the method for the invention to there is good recycling performance, stilboestrol in acetonitrile solution is carried out to enrichment, average recovery rate is 84.97%, relative standard deviation is 3.23%, stilboestrol in milk soln is carried out to enrichment, average recovery rate is 80.08%, and relative standard deviation is 3.97%.
The foregoing is only embodiments of the invention; not thereby limit the scope of the claims of the present invention; every equivalent structure or conversion of equivalent flow process that utilizes specification sheets of the present invention and accompanying drawing content to do; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (8)
1. a preparation method for stilboestrol molecular blotting magnetic microsphere, is characterized in that, comprises the following steps:
(1) prepare magnetic Fe
3o
4nano microsphere carrier:
Preparation FeSO
47H
2o and FeCl
36H
2the mixing solutions of O then at the uniform velocity splashes into ammoniacal liquor under agitation condition in above-mentioned mixing solutions, to the pH=9.0 of mixing solutions, reaction finish after by gained Fe
3o
4nanoparticle is water and absolute ethanol washing respectively, and vacuum-drying is spent the night;
(2) magnetic Fe
3o
4the finishing of Nano microsphere carrier:
By the Fe of preparation in step (1)
3o
4nanoparticle is scattered in water, passes into nitrogen, then prepared suspension is heated to 80 ℃, dropwise adds oleic acid and ammoniacal liquor under stirring, is then incubated, then by the Fe of the surface modification of gained
3o
4nanoparticle cleans with water and ethanol respectively, and vacuum-drying is spent the night;
(3) prepare stilboestrol molecular blotting magnetic microsphere:
By the Fe of oleic acid modified in step (2)
3o
4microballoon is prepared into the Fe of pre-determined volume mass ratio
3o
4/ acetonitrile suspension, add stilboestrol and function monomer fully to dissolve, add again linking agent and initiator, ultrasonic dispersion, after passing into nitrogen, seal, carry out after isothermal reaction, utilize magnetic to isolate stilboestrol molecular blotting magnetic microsphere, collecting precipitation polymkeric substance, vacuum-drying, is placed in apparatus,Soxhlet's by resulting polymers, with methyl alcohol-acetic acid mixed solution wash-out 24～48h removal stilboestrol template molecule, finally wash away residual acetic acid with methyl alcohol, vacuum-drying, to constant weight, obtains molecular blotting magnetic microsphere.
2. the preparation method of stilboestrol molecular blotting magnetic microsphere according to claim 1, is characterized in that, in described step (3), and described Fe
3o
4the volume mass of/acetonitrile suspension is than being 1g/200mL.
3. the preparation method of stilboestrol molecular blotting magnetic microsphere according to claim 1, is characterized in that, in described step (3), the temperature of described isothermal reaction is 60 ℃, and the time is 24h.
4. the preparation method of stilboestrol molecular blotting magnetic microsphere according to claim 1, it is characterized in that, the function monomer in described step (3) is at least one in vinylformic acid, methacrylic acid, trifluoromethyl acrylate, vinyl benzoic acid, methylene-succinic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 2-vinyl pyridine, 4-vinylpridine, vinyl imidazole, methyl methacrylate, hydroxyethyl methylacrylate, acrylamide and Methacrylamide.
5. the preparation method of stilboestrol molecular blotting magnetic microsphere according to claim 1, it is characterized in that, linking agent in described step (3) is Ethylene glycol dimethacrylate, Vinylstyrene, trimethoxy propane trimethyl acrylic ester, pentaerythritol triacrylate and N, at least one in N '-methylene-bisacrylamide.
6. the preparation method of stilboestrol molecular blotting magnetic microsphere according to claim 1, is characterized in that, in described step (3), the molar ratio of described stilboestrol template molecule, function monomer and linking agent is 1:2～12:2～40.
7. the preparation method of stilboestrol molecular blotting magnetic microsphere according to claim 1, is characterized in that, in described step (3), the volume ratio of methyl alcohol and acetic acid is 4～9:1.
8. the application method of a stilboestrol molecular blotting magnetic microsphere as claimed in claim 1, it is characterized in that, the molecular blotting magnetic microsphere of preparation in claim 1 is put into the solution that contains stilboestrol, realize the compartment analysis to stilboestrol by adsorption and desorption.
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| CN104193875A (en) * | 2014-06-25 | 2014-12-10 | 齐鲁工业大学 | Preparation method and application of magnetic diethylstilbestrol molecularly-imprinted polymer |
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| CN102585119A (en) * | 2012-02-23 | 2012-07-18 | 宁波市疾病预防控制中心 | Preparation method of magnetic nanometer molecular imprinting composite material related to estrogen |
| CN103100377A (en) * | 2013-02-27 | 2013-05-15 | 江苏大学 | Green preparation method of magnetic molecular imprinting sorbent |
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| CN102585119A (en) * | 2012-02-23 | 2012-07-18 | 宁波市疾病预防控制中心 | Preparation method of magnetic nanometer molecular imprinting composite material related to estrogen |
| CN103100377A (en) * | 2013-02-27 | 2013-05-15 | 江苏大学 | Green preparation method of magnetic molecular imprinting sorbent |
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| CN104193875A (en) * | 2014-06-25 | 2014-12-10 | 齐鲁工业大学 | Preparation method and application of magnetic diethylstilbestrol molecularly-imprinted polymer |
| CN104193875B (en) * | 2014-06-25 | 2016-03-23 | 齐鲁工业大学 | The preparation method of stilboestrol magnetic molecularly imprinted polymer and application thereof |
| CN104140487A (en) * | 2014-07-22 | 2014-11-12 | 中国科学院烟台海岸带研究所 | Method for preparing estradiol molecularly imprinted magnetic microsphere |
| CN104140487B (en) * | 2014-07-22 | 2017-02-22 | 中国科学院烟台海岸带研究所 | Method for preparing estradiol molecularly imprinted magnetic microsphere |
| CN104483295A (en) * | 2014-11-27 | 2015-04-01 | 陕西师范大学 | Method for detecting glycoprotein by molecularly imprinted microspheres based on boric acid fluorescence probe |
| CN105688444A (en) * | 2014-11-27 | 2016-06-22 | 宁波市疾病预防控制中心 | Chlorophenol graphene-based molecularly imprinted solid-phase extraction column and preparation method and application thereof |
| CN106749903A (en) * | 2016-12-12 | 2017-05-31 | 山东省分析测试中心 | A kind of amphiphilic Acetochlor magnetic molecularly imprinted polymer and its preparation method and application |
| CN109293855A (en) * | 2018-09-05 | 2019-02-01 | 江西中医药大学 | A kind of preparation method and applications of surface-functionalized magnetic nanomolecules imprinted polymer |
| CN109293855B (en) * | 2018-09-05 | 2020-12-01 | 江西中医药大学 | Preparation method and application of surface functionalized magnetic nano molecularly imprinted polymer |
| CN110327899A (en) * | 2019-07-08 | 2019-10-15 | 苏州大学 | Magnetic Prussian blue analogue material and its preparation and the application for adsorbing cesium ion |
| CN110327899B (en) * | 2019-07-08 | 2021-12-28 | 苏州大学 | Magnetic Prussian-like blue material, preparation thereof and application thereof in adsorption of cesium ions |
| CN112321776A (en) * | 2020-11-17 | 2021-02-05 | 吉林化工学院 | Preparation method, application and use method of capsaicin molecularly imprinted magnetic beads |
| CN114733496A (en) * | 2022-04-13 | 2022-07-12 | 安徽大学 | Preparation of diflubenzuron molecularly imprinted magnetic microspheres and application thereof in solid phase extraction |
| CN114950394A (en) * | 2022-06-01 | 2022-08-30 | 江苏大学 | Preparation method of magnetic surface molecularly imprinted nano material for selective adsorption separation of diethylstilbestrol |
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