CN113603843B - Limited medium-molecularly imprinted polymer and preparation method and application thereof - Google Patents
Limited medium-molecularly imprinted polymer and preparation method and application thereof Download PDFInfo
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- 229920000344 molecularly imprinted polymer Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000002070 nanowire Substances 0.000 claims abstract description 53
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims abstract description 33
- 229960005309 estradiol Drugs 0.000 claims abstract description 33
- 229930182833 estradiol Natural products 0.000 claims abstract description 33
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 32
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 21
- 238000012546 transfer Methods 0.000 claims abstract description 20
- 239000008267 milk Substances 0.000 claims abstract description 17
- 210000004080 milk Anatomy 0.000 claims abstract description 17
- 235000013336 milk Nutrition 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000005574 benzylation reaction Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 96
- 238000003756 stirring Methods 0.000 claims description 65
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 54
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 238000005406 washing Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 22
- 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 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- YBYBQFPZMKPGPJ-UHFFFAOYSA-N trichloro-[4-(chloromethyl)phenyl]silane Chemical compound ClCC1=CC=C([Si](Cl)(Cl)Cl)C=C1 YBYBQFPZMKPGPJ-UHFFFAOYSA-N 0.000 claims description 16
- 230000035484 reaction time Effects 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 13
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000000944 Soxhlet extraction Methods 0.000 claims description 11
- -1 acrylic ester Chemical class 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 21
- 238000001179 sorption measurement Methods 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 229920002521 macromolecule Polymers 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 108010031480 Artificial Receptors Proteins 0.000 description 2
- MSPCIZMDDUQPGJ-UHFFFAOYSA-N N-methyl-N-(trimethylsilyl)trifluoroacetamide Chemical compound C[Si](C)(C)N(C)C(=O)C(F)(F)F MSPCIZMDDUQPGJ-UHFFFAOYSA-N 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 108020003175 receptors Proteins 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- VHJLVAABSRFDPM-ZXZARUISSA-N dithioerythritol Chemical compound SC[C@H](O)[C@H](O)CS VHJLVAABSRFDPM-ZXZARUISSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 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
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- IDIOJRGTRFRIJL-UHFFFAOYSA-N iodosilane Chemical compound I[SiH3] IDIOJRGTRFRIJL-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
- B01J20/22—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- G—PHYSICS
- 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
-
- G—PHYSICS
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- 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
- G01N30/50—Conditioning of the sorbent material or stationary liquid
- G01N30/52—Physical parameters
- G01N30/54—Temperature
-
- G—PHYSICS
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/72—Mass spectrometers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/042—Elimination of an organic solid phase
- C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/10—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to inorganic materials
Abstract
The application relates to the technical field of biochemical materials, in particular to a limited-access medium-molecularly imprinted polymer and a preparation method and application thereof. The application firstly uses TiO 2 Surface benzylation of nanowires, and surface benzylated TiO 2 And synthesizing a RAFT chain transfer reagent by the nanowire, and finally limiting the RAFT chain transfer reagent into the medium-molecularly imprinted polymer. The polymer with narrow molecular weight distribution and uniform structure of the limited medium-molecularly imprinted polymer prepared by the preparation method has better adsorption performance, and can effectively remove milk powder when being applied to estradiol test in milk powderThe interference of macromolecular impurities can be used for specifically adsorbing the estradiol, and can be applied to detecting the residual quantity of the estradiol in the milk powder.
Description
Technical Field
The application relates to the technical field of biochemical materials, in particular to a limited-access medium-molecularly imprinted polymer and a preparation method and application thereof.
Background
The molecular imprinting technique is a process of preparing imprinted polymers (Molecular Imprinting Polymer, MIP) having specific recognition for a certain target molecule by studying weak interactions between supermolecules and combining with polymer chemistry. Molecularly imprinted polymers, also known as "artificial receptors", have the greatest advantage of being highly selective and adsorptive for target molecules. The artificial receptor has better stability to temperature and pressure changes than the traditional biological macromolecule receptor, and can be used in the environments of acid, alkali, metal ions, organic solvents and the like. Meanwhile, the molecularly imprinted polymer has the advantages of low preparation cost, long service life and the like. The molecular imprinting technology has wide application range, and can be used for identifying biological macromolecules such as amino acid, protein, nucleotide 5 and the like, and also can be used for identifying chemical micromolecules in food, medicines and environmental samples. Has good application prospect in the fields of chromatographic separation, purification, chemical sensors, catalysis, drug delivery, biological antibodies, receptor systems and the like.
The limited material is a mixed extractant with proper aperture, can adsorb target and discharge macromolecules simultaneously, and prevents the macromolecules from being denatured and adsorbed on the outer surface of the material due to hydrophilic modification on the outer surface. While the inner surface is still hydrophobic or ion-exchangeable, which ensures that the target can be extracted in the presence of macromolecules.
The limited medium-molecular imprinting material combines the advantages of the limited medium material and the molecular imprinting material, has the functions of volume exclusion of biological macromolecules and specific recognition performance of target micromolecules, and is focused on as a novel material, and a free radical polymerization mode is generally adopted in the traditional preparation method. However, the polymer chain length, the molecular weight and the molecular structure of the polymerization product in the traditional free radical polymerization reaction are difficult to control, so that the morphology of the functional polymer layer is uneven.
Therefore, how to provide a limited medium-molecularly imprinted polymer with narrower molecular weight distribution and uniform structure, so as to improve the adsorption performance of the limited medium-molecularly imprinted material is a technical problem to be solved by the technicians in the field.
Disclosure of Invention
The application aims to provide a limited medium-molecular imprinting polymer with narrow molecular weight distribution and uniform structure, so as to improve the adsorption performance of the limited medium-molecular imprinting material.
In order to achieve the above object, the present application provides the following technical solutions:
the application provides a preparation method of a limited medium-molecularly imprinted polymer, which comprises the following preparation steps:
(1)TiO 2 surface benzylation of nanowires
TiO is mixed with 2 Dispersing the nanowires in toluene, stirring, adding 4- (chloromethyl) phenyl trichlorosilane after stirring, continuously stirring, adding triethylamine after stirring, stirring for reaction under nitrogen protection, and carrying out suction filtration after the reaction is finished to obtain the surface benzylated TiO 2 A nanowire;
(2)TiO 2 RAFT chain transfer reagent for nanowire synthesis
Adding phenylmagnesium bromide into tetrahydrofuran, stirring uniformly, heating, and adding carbon disulfide for reaction after heating is finished; after the reaction is finished, adding surface benzylated TiO 2 Stirring the nanowires for reaction, and washing and drying the reacted product to obtain a RAFT chain transfer reagent;
(3) Preparation of limited in Medium-molecularly imprinted Polymer
Dissolving estradiol and methacrylic acid in acetonitrile/toluene, standing, adding trimethylol acrylic ester, azodiisobutyronitrile, glycidyl methacrylate and the RAFT chain transfer reagent prepared in the step (2) after standing, reacting under the protection of nitrogen, filtering after the reaction, washing and drying to obtain a polymerization product, performing Soxhlet extraction on the polymerization product, washing and drying, and grinding to obtain a molecularly imprinted polymer; and adding perchloric acid/water solution into the molecularly imprinted polymer, sealing and stirring, and washing and drying after stirring is finished to obtain the restricted medium-molecularly imprinted polymer prepared based on the RAFT method.
Preferably, in step (1) TiO 2 Weight of nanowire, toluene, 4- (chloromethyl) phenyl trichlorosilane, triethylamineThe volume ratio is 1 (g), 15-20 (ml), 0.8-1.2 (ml) and 0.4-0.6 (ml).
Preferably, step (1) TiO 2 The nanowire is dispersed in toluene and stirred for 25-35 min; the stirring time after adding 4- (chloromethyl) phenyl trichlorosilane is 28-32 min; after triethylamine is added, stirring reaction time under the protection of nitrogen is 18-30 h.
Preferably, tetrahydrofuran, phenylmagnesium bromide, carbon disulphide, surface benzylated TiO in step (2) 2 The volume weight ratio of the nano wire is 6-10 (ml), 2-4 (ml), 4-6 (ml) and 1 (g).
Preferably, the heating temperature in the step (2) is 45-55 ℃, the reaction time after adding carbon disulfide is 0.5-1.5 h, and the surface benzylated TiO is added 2 The stirring reaction time after the nanowire is 5-7 h.
Preferably, the washing in the step (2) is sequentially carried out by using tetrahydrofuran for 2 to 3 times and then ethanol for 5 to 7 times; the drying temperature is 60-80 ℃.
Preferably, in the step (3), the volume weight ratio of the estradiol, the methacrylic acid, the acetonitrile/toluene, the trimethylol acrylic ester, the azobisisobutyronitrile, the glycidyl methacrylate and the RAFT chain transfer agent is 0.25 to 0.3 (g): 0.4 to 0.6 (g): 140 to 160 (ml): 6 to 7.5 (g): 0.1 to 0.2 (g): 0.1 to 0.3 (ml): 1.0 to 2.0 (g).
Preferably, the standing temperature in the step (3) is 3-5 ℃ and the time is 30-42 h; the reaction temperature is 65-75 ℃ under the protection of nitrogen, and the reaction time is 12-36 h; the Soxhlet extraction time is 36 to 60 hours.
Preferably, the volume ratio of acetonitrile to toluene in the acetonitrile/toluene solution in step (3) is 3:1.
Preferably, the first wash in step (3) is: sequentially washing with methanol/acetic acid, water and methanol for 2-4 times, and drying at 65-75deg.C; wherein the volume ratio of methanol to acetic acid in the methanol/acetic acid solution is 9:1.
Preferably, after the Soxhlet extraction in the step (3) is finished, washing with deionized water to be neutral, and then washing with methanol for 2-4 times; and then drying at 65-75 ℃.
Preferably, in step (3), the weight to volume ratio of molecularly imprinted polymer to perchloric acid/water solution is 5 (g): 90-110 (ml), stirring for 12-36 h, washing with water, methanol and n-hexane for 2-3 times, and drying at 65-75 deg.C.
The application also provides the limited medium-molecularly imprinted polymer prepared by the preparation method.
The application also provides application of the limited medium-molecularly imprinted polymer in detecting the residual amount of estradiol in milk powder.
Compared with the prior art, the application has the following beneficial effects:
the limited medium-molecularly imprinted polymer prepared by the preparation method disclosed by the application has the advantages that the molecular weight distribution is narrower, the structure is uniform, the main pore diameter of the material is about 40nm, the material has better adsorption performance, and when the material is applied to the test of the estradiol in milk powder, the material can effectively remove the interference of macromolecular impurities in the milk powder, has specific adsorption on the estradiol, and can be applied to the detection of the residual quantity of the estradiol in the milk powder.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present application, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of the preparation of RAFT chain transfer agent according to example 2 of the present application;
FIG. 2 is a schematic diagram of the process of synthesizing a limited medium-molecularly imprinted polymer according to example 2 of the present application;
FIG. 3 is an infrared spectrum of a limited access medium-molecularly imprinted polymer prepared in example 2 of the present application;
FIG. 4 is a pore size distribution diagram of a limiting medium-molecularly imprinted polymer prepared in example 2 of the present application;
FIG. 5 is a selective ion flow diagram of a sample prepared in example 2 of the present application.
Detailed Description
The application provides a preparation method of a limited medium-molecularly imprinted polymer, which comprises the following preparation steps:
(1)TiO 2 surface benzylation of nanowires
TiO is mixed with 2 Dispersing the nanowires in toluene, stirring, adding 4- (chloromethyl) phenyl trichlorosilane after stirring, continuously stirring, adding triethylamine after stirring, stirring for reaction under nitrogen protection, and carrying out suction filtration after the reaction is finished to obtain the surface benzylated TiO 2 A nanowire;
(2)TiO 2 RAFT chain transfer reagent for nanowire synthesis
Adding phenylmagnesium bromide into tetrahydrofuran, stirring uniformly, heating, and adding carbon disulfide for reaction after heating is finished; after the reaction is finished, adding surface benzylated TiO 2 Stirring the nanowires for reaction, and washing and drying the reacted product to obtain a RAFT chain transfer reagent;
(3) Preparation of limited in Medium-molecularly imprinted Polymer
Dissolving estradiol and methacrylic acid in acetonitrile/toluene, standing, adding trimethylol acrylic ester, azodiisobutyronitrile, glycidyl methacrylate and the RAFT chain transfer reagent prepared in the step (2) after standing, reacting under the protection of nitrogen, filtering after the reaction, washing and drying to obtain a polymerization product, performing Soxhlet extraction on the polymerization product, washing and drying, and grinding to obtain a molecularly imprinted polymer; and adding perchloric acid/water solution into the molecularly imprinted polymer, sealing and stirring, and washing and drying after stirring is finished to obtain the restricted medium-molecularly imprinted polymer prepared based on the RAFT method.
Preferably, in step (1) TiO 2 The weight volume ratio of the nanowire, toluene, 4- (chloromethyl) phenyl trichlorosilane and triethylamine is 1 (g), 15-20 (ml), 0.8-1.2 (ml), 0.4-0.6 (ml), more preferably TiO 2 The weight volume ratio of the nanowire to toluene to 4- (chloromethyl) phenyl trichlorosilane to triethylamine is 1 (g) 17-18 (ml) 0.9-to1.1(ml):0.45～0.55(ml)。
Preferably, step (1) TiO 2 The nanowire is dispersed in toluene and stirred for 25-35 min; the stirring time after adding 4- (chloromethyl) phenyl trichlorosilane is 28-32 min; after triethylamine is added, stirring reaction time under the protection of nitrogen is 18-30 h.
Preferably, tetrahydrofuran, phenylmagnesium bromide, carbon disulphide, surface benzylated TiO in step (2) 2 The volume weight ratio of the nano wire is 6-10 (ml): 2-4 (ml): 4-6 (ml): 1 (g), more preferably tetrahydrofuran, phenylmagnesium bromide, carbon disulfide, surface benzylated TiO 2 The volume weight ratio of the nano wire is 7-9 (ml), 2.5-3 (ml), 5-5.5 (ml) and 1 (g).
Preferably, the heating temperature in the step (2) is 45-55 ℃, and more preferably, the heating temperature is 47-52 ℃; the reaction time after adding carbon disulfide is 0.5-1.5 h, and more preferably, the reaction time after adding carbon disulfide is 0.8-1.2 h; adding surface benzylated TiO 2 The stirring reaction time after the nanowire is 5 to 7 hours, and further preferably, the surface-benzylated TiO is added 2 The stirring reaction time after the nanowire is 5.5-6.5 h.
Preferably, the washing in the step (2) is sequentially carried out by using tetrahydrofuran for 2 to 3 times and then ethanol for 5 to 7 times; the drying temperature is 60-80 ℃.
Preferably, in the step (3), the volume weight ratio of the estradiol, the methacrylic acid, the acetonitrile/toluene, the trimethylol acrylic ester, the azobisisobutyronitrile, the glycidyl methacrylate and the RAFT chain transfer agent is 0.25 to 0.3 (g): 0.4 to 0.6 (g): 140 to 160 (ml): 6 to 7.5 (g): 0.1 to 0.2 (g): 0.1 to 0.3 (ml): 1.0 to 2.0 (g), more preferably, the volume weight ratio of the estradiol, the methacrylic acid, the acetonitrile/toluene, the trimethacrylate, the azobisisobutyronitrile, the glycidyl methacrylate and the RAFT chain transfer agent is 0.26 to 0.28 (g): 0.4.5 to 0.55 (g): 144 to 151 (ml): 6.5 to 7.1 (g): 0.1.2 to 0.17 (g): 0.15 to 0.23 (ml): 1.3 to 1.7 (g).
Preferably, the standing temperature in the step (3) is 3-5 ℃ and the time is 30-42 h; the reaction temperature is 65-75 ℃ under the protection of nitrogen, and the reaction time is 12-36 h; the Soxhlet extraction time is 36 to 60 hours.
Preferably, the volume ratio of acetonitrile to toluene in the acetonitrile/toluene solution in step (3) is 3:1.
Preferably, the first wash in step (3) is: sequentially washing with methanol/acetic acid, water and methanol for 2-4 times, and drying at 65-75deg.C; wherein the volume ratio of methanol to acetic acid in the methanol/acetic acid solution is 9:1.
Preferably, after the Soxhlet extraction in the step (3) is finished, washing with deionized water to be neutral, and then washing with methanol for 2-4 times; and then drying at 65-75 ℃.
Preferably, in step (3), the weight to volume ratio of molecularly imprinted polymer to perchloric acid/water solution is 5 (g): 90-110 (ml), stirring for 12-36 h, washing with water, methanol and n-hexane for 2-3 times, and drying at 65-75 deg.C.
The application also provides the limited medium-molecularly imprinted polymer prepared by the preparation method.
The application also provides application of the limited medium-molecularly imprinted polymer in detecting the residual amount of estradiol in milk powder.
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Example 1
A preparation method of a limited medium-molecularly imprinted polymer, which comprises the following preparation steps:
(1)TiO 2 surface benzylation of nanowires
TiO is mixed with 2 Dispersing nanowire in toluene, stirring for 25min, adding 4- (chloromethyl) phenyl trichlorosilane after stirring is finished, continuously stirring for 28min, adding triethylamine after stirring is finished, and stirring to obtain the final productStirring and reacting for 18h under the protection of nitrogen, and filtering after the reaction is finished to obtain the surface benzylated TiO 2 A nanowire;
(2)TiO 2 RAFT chain transfer reagent for nanowire synthesis
Adding phenylmagnesium bromide into tetrahydrofuran, uniformly stirring, heating to 45 ℃, and adding carbon disulfide to react for 0.5h after heating is finished; after the reaction is finished, adding surface benzylated TiO 2 Stirring the nanowires for reaction for 5 hours, washing the reacted product with tetrahydrofuran for 2 times, washing the product with ethanol for 7 times, and drying the product at 60 ℃ to obtain a RAFT chain transfer reagent;
(3) Preparation of limited in Medium-molecularly imprinted Polymer
Dissolving estradiol and methacrylic acid in acetonitrile/toluene, standing for 30 hours at the temperature of 3 ℃, adding trimethylol acrylic ester, azodiisobutyronitrile, glycidyl methacrylate and the RAFT chain transfer reagent prepared in the step (2) after standing, carrying out nitrogen protection reaction for 36 hours at 65 ℃, carrying out suction filtration after the reaction is finished, washing 2 times by methanol/acetic acid, water and methanol respectively, drying at 65 ℃ to obtain a polymerization product, carrying out Soxhlet extraction on the polymerization product for 36 hours, washing to neutrality by deionized water, and washing by methanol for 2 times; drying at 65 ℃ and grinding to obtain a molecularly imprinted polymer;
the weight volume ratio of the molecularly imprinted polymer to the perchloric acid/water solution in the molecularly imprinted polymer is 5 (g): 90 Adding perchloric acid/water solution into the ratio of (ml), sealing and stirring for 12h, after stirring, washing with water, methanol and n-hexane for 2 times in turn, and drying at 65 ℃ to obtain the limited medium-molecularly imprinted polymer prepared based on the RAFT method.
In step (1) of this embodiment, tiO 2 The weight-volume ratio of the nanowire, toluene, 4- (chloromethyl) phenyl trichlorosilane and triethylamine is 1 (g): 15 (ml): 0.8 (ml): 0.4 (ml).
Tetrahydrofuran, phenylmagnesium bromide, carbon disulfide, surface-benzylated TiO in step (2) of this example 2 The volume weight ratio of the nanowire is 6 (ml): 2 (ml): 4 (ml): 1 (g).
In step (3) of this example, the volume weight ratio of estradiol, methacrylic acid, acetonitrile/toluene, trimethacrylate, azobisisobutyronitrile, glycidyl methacrylate, RAFT chain transfer agent was 0.25 (g): 0.4 (g): 140 (ml): 6 (g): 0.1 (g): 0.1 (ml): 1 (g).
Example 2
A preparation method of a limited medium-molecularly imprinted polymer, which comprises the following preparation steps:
(1)TiO 2 surface benzylation of nanowires
TiO is mixed with 2 Dispersing the nanowires in toluene, stirring for 30min, adding 4- (chloromethyl) phenyl trichlorosilane after stirring is finished, continuously stirring for 30min, adding triethylamine after stirring is finished, stirring under nitrogen protection for reaction for 24h, and carrying out suction filtration after the reaction is finished to obtain the TiO with the surface benzylated 2 A nanowire;
(2)TiO 2 RAFT chain transfer reagent for nanowire synthesis
Adding phenylmagnesium bromide into tetrahydrofuran, uniformly stirring, heating to 50 ℃, and adding carbon disulfide to react for 1h after heating is finished; after the reaction is finished, adding surface benzylated TiO 2 Stirring the nanowires for reaction for 6 hours, washing the reacted product with tetrahydrofuran for 2 times, washing with ethanol for 6 times, and drying at 70 ℃ to obtain a RAFT chain transfer reagent;
(3) Preparation of limited in Medium-molecularly imprinted Polymer
Dissolving estradiol and methacrylic acid in acetonitrile/toluene, standing for 36h at the temperature of 4 ℃, adding trimethylol acrylic ester, azodiisobutyronitrile, glycidyl methacrylate and the RAFT chain transfer reagent prepared in the step (2) after standing, carrying out nitrogen protection reaction for 24h at 70 ℃, carrying out suction filtration after the reaction is finished, washing 3 times by methanol/acetic acid, water and methanol respectively, drying at 70 ℃ to obtain a polymerization product, carrying out Soxhlet extraction on the polymerization product for 48h, washing to neutrality by deionized water, and washing 3 times by methanol; drying at 70 ℃ and grinding to obtain a molecularly imprinted polymer;
the weight volume ratio of the molecularly imprinted polymer to the perchloric acid/water solution in the molecularly imprinted polymer is 5 (g): 100 Adding perchloric acid/water solution in the ratio of (ml), sealing and stirring for 24 hours, after stirring, washing with water, methanol and n-hexane for 2 times in sequence, and drying at 70 ℃ to obtain the limited medium-molecularly imprinted polymer prepared based on the RAFT method.
In step (1) of this embodiment, tiO 2 The weight-volume ratio of the nanowire, toluene, 4- (chloromethyl) phenyl trichlorosilane and triethylamine is 1 (g): 17 (ml): 1 (ml): 0.5 (ml).
Tetrahydrofuran, phenylmagnesium bromide, carbon disulfide, surface-benzylated TiO in step (2) of this example 2 The volume weight ratio of the nanowire is 8 (ml): 3 (ml): 5 (ml): 1 (g).
In step (3) of this example, the volume weight ratio of estradiol, methacrylic acid, acetonitrile/toluene, trimethylol acrylate, azobisisobutyronitrile, glycidyl methacrylate, RAFT chain transfer agent was 0.27 (g): 0.5 (g): 150 (ml): 6.76 (g): 0.15 (g): 0.2 (ml): 1.5 (g).
Example 3
A preparation method of a limited medium-molecularly imprinted polymer, which comprises the following preparation steps:
(1)TiO 2 surface benzylation of nanowires
TiO is mixed with 2 Dispersing the nanowires in toluene, stirring for 35min, adding 4- (chloromethyl) phenyl trichlorosilane after stirring, continuously stirring for 32min, adding triethylamine after stirring, stirring under nitrogen protection for reaction for 30h, and suction filtering after the reaction is finished to obtain the TiO with the surface benzylated 2 A nanowire;
(2)TiO 2 RAFT chain transfer reagent for nanowire synthesis
Adding phenylmagnesium bromide into tetrahydrofuran, uniformly stirring, heating to 55 ℃, and adding carbon disulfide to react for 1.5h after heating is finished; after the reaction is finished, adding surface benzylated TiO 2 Stirring the nanowires for reaction for 7 hours, washing the reacted product with tetrahydrofuran for 3 times, washing the product with ethanol for 7 times, and drying the product at 80 ℃ to obtain a RAFT chain transfer reagent;
(3) Preparation of limited in Medium-molecularly imprinted Polymer
Dissolving estradiol and methacrylic acid in acetonitrile/toluene, standing for 42 hours at the temperature of 5 ℃, adding trimethylol acrylic ester, azodiisobutyronitrile, glycidyl methacrylate and the RAFT chain transfer reagent prepared in the step (2) after standing, carrying out nitrogen protection reaction at 75 ℃ for 36 hours, carrying out suction filtration after the reaction is finished, washing with methanol/acetic acid, water and methanol for 4 times in sequence, drying at 75 ℃ to obtain a polymerization product, carrying out Soxhlet extraction on the polymerization product for 60 hours, washing with deionized water to neutrality, and washing with methanol for 4 times; drying at 75 ℃ and grinding to obtain a molecularly imprinted polymer;
the weight volume ratio of the molecularly imprinted polymer to the perchloric acid/water solution in the molecularly imprinted polymer is 5 (g): 110 Adding perchloric acid/water solution in the ratio of (ml), sealing and stirring for 36h, after stirring, washing with water, methanol and n-hexane for 3 times in sequence, and drying at 75 ℃ to obtain the limited medium-molecularly imprinted polymer prepared based on the RAFT method.
In step (1) of this embodiment, tiO 2 The weight-volume ratio of the nanowire, toluene, 4- (chloromethyl) phenyl trichlorosilane and triethylamine is 1 (g): 20 (ml): 1.2 (ml): 0.6 (ml).
Tetrahydrofuran, phenylmagnesium bromide, carbon disulfide, surface-benzylated TiO in step (2) of this example 2 The volume weight ratio of the nanowire is 10 (ml): 4 (ml): 6 (ml): 1 (g).
In step (3) of this example, the volume weight ratio of estradiol, methacrylic acid, acetonitrile/toluene, trimethylol acrylate, azobisisobutyronitrile, glycidyl methacrylate, RAFT chain transfer agent was 0.3 (g): 0.6 (g): 160 (ml): 7.5 (g): 0.2 (g): 0.3 (ml): 2 (g).
The limiting medium-molecularly imprinted polymers prepared in examples 1-3 of the application all have narrower molecular weight distribution and uniform structure through detection, and the limiting medium-molecularly imprinted polymer prepared in example 2 is now characterized in detail:
FIG. 3 is an infrared spectrum of a limited access medium-molecularly imprinted polymer prepared in example 2 of the application, and as can be seen from FIG. 3, 3478cm -1 Extension of-OHStrong absorption peak of shrinkage vibration, 2963cm -1 Characteristic peak is-CH 3 Is 1733cm -1 Is characteristic absorption peak of Ti-O, 1149cm -1 The C-O telescopic vibration absorption peak is in accordance with the infrared spectrum of the characteristics of the limited medium molecular imprinting material based on nano titanium dioxide.
Fig. 4 is a pore size distribution diagram of a limited medium-molecularly imprinted polymer prepared in example 2 of the present application, and as can be seen from fig. 4, the main pore size of the material is about 40nm, and the limited medium molecularly imprinted material belongs to mesoporous materials.
Application example
According to the method for adding and recycling, the method is used for evaluating the method, the standard solution of the estradiol with different concentration levels is respectively added into the milk powder in the sample without the analyte background, the estradiol with different concentration levels (1, 5 and 10 mug/kg) is respectively added according to the limit requirement of the estradiol residue, and 4 parallel experiments are carried out on each adding level.
Taking 1g of MIP in a test tube, adding methanol to remove tiny particles, and filling the mixture into a solid phase extraction empty column to prepare the molecular imprinting solid phase extraction column. 0.5g of milk powder is weighed into a test tube, added with 10ml of water for vortex dissolution, transferred onto a molecular imprinting solid phase extraction column (activated by 5 ml), eluted by 10ml of water, added with 20ml of acetonitrile for elution, collected and concentrated to dryness, and after derivatization by a derivatization reagent N-methyl-N-trimethylsilyl trifluoroacetamide (MSTFA) -trimethoxy iodosilane (TMIS) -Dithioerythritol (DTE), the total eluent is determined by a gas chromatograph mass spectrometer. According to the above-described test methods, the test results of estradiol in milk powder were shown in Table 1 using MIPs prepared in examples 1 to 3 at concentration levels corresponding to (1, 5, 10. Mu.g/kg), respectively.
Wherein, the instrument measures the condition:
1) Chromatographic conditions:
a) Chromatographic column: 30m×0.25mm (inner diameter), a quartz capillary column with a film thickness of 0.25 μm, rxi-5ms, or the equivalent;
b) Carrier gas: helium with purity more than or equal to 99.999 percent and flow rate of 1.5ml/min;
c) Chromatographic column temperature: the temperature was maintained at 100deg.C for 1min, then at 20deg.C/min programmed to 280℃for 5min.
d) Sample inlet temperature: 240 ℃;
e) Sample injection mode: no split sample injection, and opening a valve after 0.75 min;
f) Sample injection amount: 1 μl;
2) Mass spectrometry conditions:
a) Ionization mode: EI;
b) Chromatographic-mass spectrometry interface temperature: 260 ℃;
c) Ion source temperature: 230 ℃;
d) Solvent delay: 5min;
e) Ion detection mode: ion reaction monitoring (SIM) was selected to monitor the ions and their abundance ratios 416, 285, 232.
TABLE 1 measurement results of MIP prepared in examples 1 to 3 on estradiol in milk powder
| Estradiol content (μg/kg) | Recovery (%) | Relative standard deviation (%) | |
| Example 1 | 1.0 | 87.0 | 5.4 |
| Example 2 | 5.0 | 92.6 | 5.8 |
| Example 3 | 10.0 | 104.9 | 2.9 |
The result shows that the recovery rate range is 87-104.9% and the relative standard deviation is 2.9-5.8% when the estradiol is added into the milk powder sample by 1-10 mug/kg.
Fig. 5 is a sample-selective ion flow diagram obtained in example 2, with retention time on the abscissa and response value on the ordinate. Wherein m/z416 is a quantitative ion, m/z285, 232 is a qualitative ion, the retention time of the target is 11.72min, and the peaks at other times are impurity peaks. From fig. 5, it can be derived that: no matter the quantitative ion peak and the qualitative ion peak are not interfered by impurity peaks, the quantitative determination of the estradiol is not affected, and the purification has better effect.
According to the embodiment and the application example, the limited medium-molecularly imprinted polymer provided by the application has the advantages that the molecular weight distribution is narrower, the structure is uniform, the main pore diameter of the material is about 40nm, the material has good adsorption performance, and when the material is applied to the test of the estradiol in the milk powder, the material can effectively remove the interference of macromolecular impurities in the milk powder, has specific adsorption on the estradiol, and can accurately detect the residual quantity of the estradiol in the milk powder.
The foregoing is merely a preferred embodiment of the present application and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present application, which are intended to be comprehended within the scope of the present application.
Claims (7)
1. The preparation method of the limited medium-molecularly imprinted polymer is characterized by comprising the following preparation steps:
(1)TiO 2 surface benzylation of nanowires
TiO is mixed with 2 The nanowires are dispersed in tolueneStirring, adding 4- (chloromethyl) phenyl trichlorosilane after stirring, continuously stirring, adding triethylamine after stirring, stirring under nitrogen protection for reaction, and carrying out suction filtration after the reaction is finished to obtain the surface benzylated TiO 2 A nanowire;
(2)TiO 2 RAFT chain transfer reagent for nanowire synthesis
Adding phenylmagnesium bromide into tetrahydrofuran, stirring uniformly, heating, and adding carbon disulfide for reaction after heating is finished; after the reaction is finished, adding surface benzylated TiO 2 Stirring the nanowires for reaction, and washing and drying the reacted product to obtain a RAFT chain transfer reagent;
(3) Preparation of limited in Medium-molecularly imprinted Polymer
Dissolving estradiol and methacrylic acid in acetonitrile/toluene, standing, adding trimethylol acrylic ester, azodiisobutyronitrile, glycidyl methacrylate and the RAFT chain transfer reagent prepared in the step (2) after standing, reacting under the protection of nitrogen, filtering after the reaction, washing and drying to obtain a polymerization product, performing Soxhlet extraction on the polymerization product, washing and drying, and grinding to obtain a molecularly imprinted polymer; adding perchloric acid/water solution into the molecularly imprinted polymer, stirring, washing and drying after stirring is finished to obtain a limited-access medium molecularly imprinted polymer prepared based on a RAFT method;
TiO in the step (1) 2 The weight-volume ratio of the nanowire to toluene to 4- (chloromethyl) phenyl trichlorosilane to triethylamine is 1 (g): 15-20 (ml): 0.8 to 1.2 (ml): 0.4 to 0.6 (ml);
tetrahydrofuran, phenylmagnesium bromide, carbon disulfide and surface benzylated TiO in the step (2) 2 The volume weight ratio of the nanowire is 6-10 (ml): 2 to 4 (ml): 4 to 6 (ml): 1 (g);
in the step (3), the volume weight ratio of the estradiol, the methacrylic acid, the acetonitrile/toluene, the trimethylol acrylic ester, the azodiisobutyronitrile, the glycidyl methacrylate and the RAFT chain transfer agent is 0.25-0.3 (g): 0.4 to 0.6 (g): 140-160 (ml): 6 to 7.5 (g): 0.1 to 0.2 (g): 0.1 to 0.3 (ml): 1.0 to 2.0 (g).
2. The method for preparing a limited access medium-molecularly imprinted polymer according to claim 1, wherein the step (1) is TiO 2 The nanowire is dispersed in toluene and stirred for 25-35 min; the stirring time after adding 4- (chloromethyl) phenyl trichlorosilane is 28-32 min; after triethylamine is added, stirring reaction time under the protection of nitrogen is 18-30 h.
3. The method for preparing a limited medium-molecularly imprinted polymer according to claim 1, wherein the heating temperature of the step (2) is 45-55 ℃, the reaction time after adding carbon disulfide is 0.5-1.5 h, and the surface-benzylated TiO is added 2 The stirring reaction time after the nanowire is 5-7 h.
4. The method for preparing a limited medium-molecularly imprinted polymer according to claim 3, wherein the washing in the step (2) is sequentially performed 2 to 3 times by using tetrahydrofuran and 5 to 7 times by using ethanol; the drying temperature is 60-80 ℃.
5. The method for preparing a limited medium-molecularly imprinted polymer according to claim 1, wherein the standing temperature of the step (3) is 3-5 ℃ for 30-42 h; the reaction temperature is 65-75 ℃ under the protection of nitrogen, and the reaction time is 12-36 h; the Soxhlet extraction time is 36 to 60 hours.
6. The limited mediator-molecularly imprinted polymer prepared by the preparation method of any one of claims 1 to 5.
7. Use of the limited access medium-molecularly imprinted polymer according to claim 6 for detecting the residual amount of estradiol in milk powder.
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