CN114733496A - Preparation of diflubenzuron molecularly imprinted magnetic microspheres and application thereof in solid phase extraction - Google Patents
Preparation of diflubenzuron molecularly imprinted magnetic microspheres and application thereof in solid phase extraction Download PDFInfo
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- 239000005893 Diflubenzuron Substances 0.000 title claims abstract description 69
- QQQYTWIFVNKMRW-UHFFFAOYSA-N diflubenzuron Chemical compound FC1=CC=CC(F)=C1C(=O)NC(=O)NC1=CC=C(Cl)C=C1 QQQYTWIFVNKMRW-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229940019503 diflubenzuron Drugs 0.000 title claims abstract description 69
- 239000004005 microsphere Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000002414 normal-phase solid-phase extraction Methods 0.000 title claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 14
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 238000007885 magnetic separation Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- BTXFTCVNWMNXKH-UHFFFAOYSA-N NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC Chemical compound NC1=CC=CC=C1.CCO[Si](C)(OCC)OCC BTXFTCVNWMNXKH-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000002917 insecticide Substances 0.000 abstract description 7
- 230000005415 magnetization Effects 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- HRYILSDLIGTCOP-UHFFFAOYSA-N N-benzoylurea Chemical compound NC(=O)NC(=O)C1=CC=CC=C1 HRYILSDLIGTCOP-UHFFFAOYSA-N 0.000 description 6
- 235000015205 orange juice Nutrition 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 2
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 description 1
- XUYAAIUFZVWSSJ-UHFFFAOYSA-N 1-chloro-1-phenylurea Chemical compound NC(=O)N(Cl)C1=CC=CC=C1 XUYAAIUFZVWSSJ-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000005942 Triflumuron Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229960003760 florfenicol Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- XAIPTRIXGHTTNT-UHFFFAOYSA-N triflumuron Chemical compound C1=CC(OC(F)(F)F)=CC=C1NC(=O)NC(=O)C1=CC=CC=C1Cl XAIPTRIXGHTTNT-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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Abstract
The invention discloses a preparation method of diflubenzuron molecularly imprinted magnetic microspheres and application thereof in solid phase extraction. The diflubenzuron magnetic imprinted polymer has good magnetism, the saturation magnetization of the diflubenzuron magnetic imprinted polymer can reach 41.7emu/g, and diflubenzuron in a complex sample can be separated and analyzed under an external magnetic field. The diflubenzuron magnetic imprinted polymer prepared by the method is used for analyzing mixed solution containing insecticides with similar structures, has the characteristics of high selectivity and simple and convenient operation, and the recovery rate can reach 87-98%.
Description
Technical Field
The invention relates to a preparation method of diflubenzuron molecularly imprinted magnetic microspheres and application thereof in solid phase extraction.
Background
As a benzoylurea insecticide with low toxicity, diflubenzuron is widely applied to the insecticidal treatment of fruit trees, cotton and vegetables. But the long-term overuse can cause pollution to the environment and food, thereby causing potential harm to human beings. And the products obtained by photodegradation of diflubenzuron, such as p-chlorobenzene and chlorophenylurea, may have carcinogenicity. Most of the traditional solid phase extraction methods use porous materials as adsorbents, and loss or coprecipitation can be caused in the separation treatment process, so that the application of the traditional solid phase extraction methods is limited. Therefore, it is important to establish a new and efficient method for enriching and separating diflubenzuron.
The molecularly imprinted polymer has specific recognition capability, can selectively adsorb template molecules from a complex environmental matrix, and can be used as an adsorbent of a solid phase extraction column to achieve good adsorption capacity and extract a target substance.
Most of the molecularly imprinted polymers prepared by the traditional method have some disadvantages, such as uneven distribution of binding sites and complete embedding of template molecules and functional monomers into the polymer matrix, resulting in that target molecules are not easily combined with recognition sites, and the like. To overcome these drawbacks, surface imprinting techniques have been developed. Surface imprinting is a technique in which a polymerization reaction is performed on the surface of a solid phase carrier, and imprinting sites of the polymer are exposed on the surface. The magnetic imprinted polymer prepared by taking ferroferric oxide as a carrier has high selectivity and superparamagnetism, does not need to fill an adsorbent into a solid phase extraction column, can be directly added into a sample solution for adsorption, is simple and convenient to operate, and has wider application prospects in the fields of separation analysis and detection.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of diflubenzuron molecularly imprinted magnetic microspheres and application thereof in solid phase extraction.
The preparation method of the diflubenzuron molecularly imprinted magnetic microsphere comprises the following steps:
step 1: magnetic Fe3O4Surface modification of nano-microspheres
1.0g of Fe3O4Dispersing the nanoparticles in ethanol/water mixed system, adding silane into the above dispersion, mixing with ultrasonic wave, and charging nitrogenSealing, stirring at constant temperature of 40-80 ℃ for reaction for 4-8 h, washing the obtained reaction product with ethanol, carrying out magnetic separation, and carrying out vacuum drying;
the volume ratio of ethanol to water in the ethanol/water mixed system in the step 1 is 1: (1-8). The water is deionized water, distilled water or ultrapure water.
The silane in the step 1 is at least one of tetraethoxysilane, 3- (methacryloyl chloride) propyl trimethoxy silane and aniline methyl triethoxy silane, and the dosage is 0.1-2 mL.
Step 2: synthesis of prepolymerized product
Adding 0.31g of diflubenzuron and a functional monomer into 50mL of a solvent for full dissolution, and reacting at room temperature for 1-5 h to obtain a mixed solution a;
the functional monomer in the step 2 is at least one of itaconic acid, hydroxyethyl methacrylate, vinyl benzoic acid, acrylamide, methacrylic acid, 4-vinylpyridine and 2-vinylpyridine. The molar ratio of the diflubenzuron to the functional monomer is 1: 1 to 12.
The solvent in the step 2 is at least one of chloroform, ethanol and acetonitrile.
And step 3: preparation of molecularly imprinted magnetic microspheres
0.1g to 2.0g of Fe obtained in step 13O4Adding the nano-microspheres into the mixed solution a, adding a cross-linking agent and an initiator, performing ultrasonic dispersion, introducing nitrogen, and performing heating reaction at 40-80 ℃; and (3) carrying out magnetic separation to obtain a product, washing the product by using an acetic acid/methanol mixed solution to remove the template molecules until the template molecules cannot be detected in the eluent, and drying the product in vacuum until the weight is constant to obtain the diflubenzuron molecularly imprinted magnetic microspheres.
The cross-linking agent in the step 3 is at least one of ethylene glycol methacrylate, trimethylolpropane trimethacrylate, N-methylene bisacrylamide and divinylbenzene. The molar ratio of diflubenzuron to cross-linking agent is 1: (12-24).
The initiator in the step 3 is at least one of azobisisobutyronitrile and azobisdimethylisovaleronitrile. The mass ratio of the initiator to the mixed solution a is 1 g: (0.4-2L).
The volume ratio of acetic acid to methanol in the acetic acid/methanol mixed solution in the step 3 is 1: 5 to 15.
The application of the diflubenzuron molecularly imprinted magnetic microsphere prepared by the invention is to use the diflubenzuron molecularly imprinted magnetic microsphere in solid phase extraction to realize effective separation of diflubenzuron.
The invention has the beneficial effects that:
(1) the invention takes diflubenzuron as a template molecule, prepares the magnetic imprinted polymer by utilizing the surface imprinting technology, and improves the adsorption efficiency of the polymer because the imprinted sites are formed on the surface.
(2) The diflubenzuron magnetic imprinted polymer has good magnetism, the saturation magnetization of the diflubenzuron magnetic imprinted polymer can reach 41.7emu/g, and diflubenzuron in a complex sample can be separated and analyzed under an external magnetic field.
(3) When the diflubenzuron magnetic imprinted polymer prepared by the method is used for analyzing mixed solution containing insecticides with similar structures, the diflubenzuron magnetic imprinted polymer has the characteristics of high selectivity and simple and convenient operation, and the recovery rate can reach 87-98%.
Drawings
FIG. 1 is a scanning electron microscope image of a diflubenzuron molecularly imprinted magnetic microsphere prepared in example 1 of the invention;
FIG. 2 is a scanning electron microscope image of a diflubenzuron molecularly imprinted magnetic microsphere prepared in example 2 of the invention;
FIG. 3 is a scanning electron microscope image of a diflubenzuron molecularly imprinted magnetic microsphere prepared in example 3 of the invention;
FIG. 4 is a hysteresis regression line of the diflubenzuron molecularly imprinted magnetic microspheres prepared in example 4 of the invention;
FIG. 5 shows the adsorption results of the mixed solution of benzoyl urea insecticides by the molecularly imprinted magnetic microspheres and the non-imprinted magnetic microspheres;
FIG. 6a is the high performance liquid chromatogram of the direct sample injection of the standard orange juice sample, and FIG. 6b is the high performance liquid chromatogram of the standard orange juice sample after the enrichment and separation of the molecular engram magnetic material.
Detailed Description
The present invention will be described in detail below by way of examples.
Example 1:
the preparation method of the diflubenzuron molecularly imprinted magnetic microsphere in the embodiment is as follows:
step 1: magnetic Fe3O4Surface modification of nano-microspheres
1.0g of Fe3O4The nano particles are dispersed in 25mL of mixed solution of ethanol and 25mL of deionized water by ultrasonic dispersion, 1mL of 3- (methacryloyl chloride) propyl trimethoxy silane is added, and the mixture is uniformly mixed by ultrasonic. Introducing nitrogen gas into the suspension liquid for sealing, heating the prepared suspension liquid to 50 ℃, stirring the suspension liquid for reaction for 6 hours, and naturally cooling the suspension liquid to room temperature. Collecting the obtained product by magnetic separation, washing with ethanol for several times, and placing in a vacuum drying oven overnight to obtain silane-modified Fe3O4Nanoparticles.
Step 2: synthesis of prepolymerized product
Dissolving 0.31g of diflubenzuron and 0.34g of methacrylic acid in 50mL of chloroform solution sufficiently, and reacting for 1h at room temperature to obtain a mixed solution a;
and step 3: preparation of molecularly imprinted magnetic microspheres
0.5g of Fe obtained in step 13O4Adding the nano-microspheres into the mixed solution a, adding 3.96g of ethylene glycol methacrylate and 0.05g of azobisisobutyronitrile, performing ultrasonic treatment for 10min, and introducing N2Sealing after 10min, and reacting for 24h at 60 ℃; separating the diflubenzuron molecularly imprinted magnetic microspheres by magnetic separation, finally washing with acetic acid-methanol solution (1: 5-15, v: v) to remove template molecules until the template molecules cannot be detected in eluent, and drying in vacuum to constant weight to obtain the diflubenzuron molecularly imprinted magnetic microspheres.
The diflubenzuron molecularly imprinted microspheres obtained by the method are observed under a scanning electron microscope, and the result is shown in figure 1, and the obtained molecularly imprinted magnetic microspheres are similar to the irregular structure of sponges.
Example 2:
the preparation method of the diflubenzuron molecularly imprinted magnetic microsphere in the embodiment is as follows:
step 1: magnetic Fe3O4Surface modification of nano-microspheres
1.0g of Fe was taken3O4The nano particles are dispersed in 25mL of mixed solution of ethanol and 25mL of deionized water by ultrasonic dispersion, 1mL of 3- (methacryloyl chloride) propyl trimethoxy silane is added, and the mixture is uniformly mixed by ultrasonic. Introducing nitrogen gas into the suspension liquid for sealing, heating the prepared suspension liquid to 50 ℃, stirring and reacting for 6 hours, and naturally cooling to room temperature. Collecting the obtained product by magnetic separation, washing with ethanol for several times, and placing in a vacuum drying oven overnight to obtain silane-modified Fe3O4Nanoparticles.
Step 2: synthesis of prepolymerized product
Fully dissolving 0.31g of diflubenzuron and 0.34g of methacrylic acid in 50mL of ethanol solution, and reacting for 1h at room temperature to obtain a mixed solution a;
and 3, step 3: preparation of molecularly imprinted magnetic microspheres
0.5g of Fe obtained in step 13O4Adding the nano-microspheres into the mixed solution a, adding 3.96g of ethylene glycol methacrylate and 0.05g of azobisisobutyronitrile, performing ultrasonic treatment for 10min, and introducing N2Sealing after 10min, and reacting for 24h at 60 ℃; separating the diflubenzuron molecularly imprinted magnetic microspheres by magnetic separation, finally washing with acetic acid-methanol solution (1: 5-15, v: v) to remove template molecules until the template molecules cannot be detected in eluent, and drying in vacuum to constant weight to obtain the diflubenzuron molecularly imprinted magnetic microspheres.
When the diflubenzuron molecularly imprinted microspheres obtained by the method are observed under a scanning electron microscope, the result is shown in figure 2, and the obtained molecularly imprinted magnetic microspheres are uneven spheres and have different sizes.
Example 3:
the preparation method of the diflubenzuron molecularly imprinted magnetic microsphere in the embodiment is as follows:
step 1: magnetic Fe3O4Surface modification of nano-microspheres
1.0g of Fe3O4The nano particles are dispersed in 25mL of mixed solution of ethanol and 25mL of deionized water by ultrasonic dispersion, 1mL of 3- (methacryloyl chloride) propyl trimethoxy silane is added, and the mixture is uniformly mixed by ultrasonic. Introducing nitrogen gas into the mixture for sealing, and then preparingThe suspension is heated to 50 ℃, stirred and reacted for 6 hours, and naturally cooled to room temperature. Collecting the obtained product by magnetic separation, washing with ethanol for several times, and placing in a vacuum drying oven overnight to obtain silane-modified Fe3O4Nanoparticles.
Step 2: synthesis of prepolymerized product
Fully dissolving 0.31g of diflubenzuron and 0.34g of methacrylic acid in 50mL of acetonitrile solution, and reacting for 1h at room temperature to obtain a mixed solution a;
and step 3: preparation of molecularly imprinted magnetic microspheres
0.5g of Fe obtained in step 13O4Adding the nano-microspheres into the mixed solution a, adding 3.96g of ethylene glycol methacrylate and 0.05g of azobisisobutyronitrile, performing ultrasonic treatment for 10min, and introducing N2Sealing after 10min, and reacting for 24h at 60 ℃; separating the diflubenzuron molecularly imprinted magnetic microspheres by magnetic separation, finally washing with acetic acid-methanol solution (1: 5-15, v: v) to remove template molecules until the template molecules cannot be detected in eluent, and drying in vacuum to constant weight to obtain the diflubenzuron molecularly imprinted magnetic microspheres.
The results of observing the diflubenzuron molecularly imprinted microspheres obtained by the method under a scanning electron microscope are shown in fig. 3, and the obtained molecularly imprinted magnetic microspheres are regular spheres, uniform in size and good in dispersibility.
Example 4: determination of magnetic property of diflubenzuron molecularly imprinted magnetic microspheres
The preparation method of the diflubenzuron molecularly imprinted magnetic microsphere in the embodiment is the same as that of the embodiment 3.
The specific evaluation method of the magnetic properties in this example is as follows: the result of analysis of 30mg of the molecularly imprinted magnetic microsphere, which was packed in a plastic vial having a length of about 1cm and detected by a vibrating sample magnetometer, is shown in fig. 4, and it is known that the diflubenzuron molecularly imprinted magnetic microsphere prepared in example 4 has superparamagnetism and a saturation magnetization of 41.7 emu/g.
Example 5: selective adsorption experiment of diflubenzuron molecularly imprinted magnetic microspheres
The preparation method of the diflubenzuron molecularly imprinted magnetic microspheres in the embodiment is the same as that in the embodiment 3.
The preparation method of the non-imprinted magnetic microspheres was the same as that of example 3 except that diflubenzuron was not added in step 2, and the other steps were the same as those for the preparation of diflubenzuron molecularly imprinted magnetic microspheres.
The specific method for evaluating the selective adsorption property in this example is as follows: two benzoylurea insecticides (i.e., triflumuron HFM, florfenicol TBZ) were selected as competitors with diflubenzuron DBZ. Weighing 20mg of molecularly imprinted magnetic microspheres (or non-imprinted magnetic microspheres) in 5mL of a mixed solution of three benzoylurea insecticides, oscillating for 3h at room temperature, performing magnetic separation, filtering supernatant, and determining the concentrations of the three benzoylurea insecticides in the mixed solution by using a high performance liquid chromatograph.
The adsorption result is shown in fig. 5, the synthesized diflubenzuron molecularly imprinted magnetic microsphere has the best adsorption effect on diflubenzuron in a complex benzoyl urea pesticide mixed solution.
Example 6: application of diflubenzuron molecularly imprinted magnetic microspheres in magnetic solid phase extraction
The preparation method of the diflubenzuron molecularly imprinted magnetic microsphere in the embodiment is the same as that of the embodiment 3.
The diflubenzuron molecularly imprinted magnetic microsphere prepared in the embodiment is applied to magnetic solid phase extraction, and the specific method is as follows: 20mg of diflubenzuron molecularly imprinted magnetic microspheres are weighed into a conical flask, and 5mL of orange juice (10mg/L) containing diflubenzuron is added to be tested. Oscillating for 20min at room temperature, performing magnetic separation, adding acetonitrile, performing ultrasonic leaching, and adding an eluent into the leached polymer for ultrasonic elution. The eluted solution is used for high performance liquid chromatography detection and analysis after being filtered.
FIG. 6a is a high performance liquid chromatogram of a directly injected standard sample, and FIG. 6b is a high performance liquid chromatogram of a standard orange juice sample after enrichment and separation of a molecularly imprinted magnetic material. The detection result shows that the molecularly imprinted magnetic microspheres enrich the diflubenzuron in the standard orange juice sample, the recovery rate is 97.2%, and the relative standard deviation RSD is 1.63%.
Claims (9)
1. A preparation method of diflubenzuron molecularly imprinted magnetic microspheres is characterized by comprising the following steps:
step 1: magnetic Fe3O4Surface modification of nano-microspheres
1.0g of Fe3O4Dispersing nano particles in an ethanol/water mixed system, adding silane into the dispersion liquid, ultrasonically mixing uniformly, filling nitrogen for sealing, stirring at the constant temperature of 40-80 ℃ for reacting for 4-8 hours, washing the obtained reaction product with ethanol, carrying out magnetic separation, and carrying out vacuum drying;
step 2: synthesis of prepolymerized product
Adding 0.31g of diflubenzuron and a functional monomer into 50mL of a solvent for full dissolution, and reacting at room temperature for 1-5 h to obtain a mixed solution a;
and step 3: preparation of molecularly imprinted magnetic microspheres
0.1g to 2.0g of Fe obtained in step 13O4Adding the nano-microspheres into the mixed solution a, adding a cross-linking agent and an initiator, performing ultrasonic dispersion, introducing nitrogen, and performing heating reaction at 40-80 ℃; and (3) performing magnetic separation to obtain a product, washing the product by using an acetic acid/methanol mixed solution to remove the template molecules until the template molecules cannot be detected in the eluent, and performing vacuum drying until the weight is constant to obtain the diflubenzuron molecularly imprinted magnetic microspheres.
2. The production method according to claim 1, characterized in that:
in step 1, the volume ratio of ethanol to water in the ethanol/water mixed system is 1: (1-8).
3. The method of claim 1, wherein:
in the step 1, the silane is at least one of tetraethoxysilane, 3- (methacryloyl chloride) propyl trimethoxy silane and aniline methyl triethoxy silane, and the dosage is 0.1-2 mL.
4. The method of claim 1, wherein:
in the step 2, the functional monomer is at least one of itaconic acid, hydroxyethyl methacrylate, vinyl benzoic acid, acrylamide, methacrylic acid, 4-vinylpyridine and 2-vinylpyridine; the molar ratio of the diflubenzuron to the functional monomer is 1: 1 to 12.
5. The method of claim 1, wherein:
in the step 2, the solvent is at least one of chloroform, ethanol and acetonitrile.
6. The method of claim 1, wherein:
in the step 3, the cross-linking agent is at least one of ethylene glycol methacrylate, trimethylolpropane trimethacrylate, N-methylene bisacrylamide and divinylbenzene; the molar ratio of diflubenzuron to cross-linking agent is 1: (12-24).
7. The method of claim 1, wherein:
in the step 3, the initiator is at least one of azobisisobutyronitrile and azobisdimethylisovaleronitrile; the mass ratio of the initiator to the mixed solution a is 1 g: (0.4-2L).
8. The method of claim 1, wherein:
in step 3, the volume ratio of acetic acid to methanol in the acetic acid/methanol mixed solution is 1: 5 to 15.
9. The use of diflubenzuron molecularly imprinted magnetic microspheres obtained by the preparation method according to any one of claims 1 to 8, characterized in that: the diflubenzuron molecularly imprinted magnetic microsphere is used for solid phase extraction to realize effective separation of diflubenzuron.
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