CN114653347A - Molecularly imprinted magnetic nanofiber membrane and preparation method and application thereof - Google Patents
Molecularly imprinted magnetic nanofiber membrane and preparation method and application thereof Download PDFInfo
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- CN114653347A CN114653347A CN202111561576.1A CN202111561576A CN114653347A CN 114653347 A CN114653347 A CN 114653347A CN 202111561576 A CN202111561576 A CN 202111561576A CN 114653347 A CN114653347 A CN 114653347A
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- 239000012528 membrane Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000002121 nanofiber Substances 0.000 title claims abstract description 33
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 20
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 108
- 239000000243 solution Substances 0.000 claims description 75
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 49
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 39
- BBFQZRXNYIEMAW-UHFFFAOYSA-N aristolochic acid I Chemical class C1=C([N+]([O-])=O)C2=C(C(O)=O)C=C3OCOC3=C2C2=C1C(OC)=CC=C2 BBFQZRXNYIEMAW-UHFFFAOYSA-N 0.000 claims description 38
- 238000009987 spinning Methods 0.000 claims description 37
- 229920000344 molecularly imprinted polymer Polymers 0.000 claims description 33
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 33
- 239000012498 ultrapure water Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 18
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 238000001291 vacuum drying Methods 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003431 cross linking reagent Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- ZCHPKWUIAASXPV-UHFFFAOYSA-N acetic acid;methanol Chemical compound OC.CC(O)=O ZCHPKWUIAASXPV-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- AUALQMFGWLZREY-UHFFFAOYSA-N acetonitrile;methanol Chemical group OC.CC#N AUALQMFGWLZREY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000006249 magnetic particle Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007872 degassing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical group C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 2
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005891 Cyromazine Substances 0.000 claims description 2
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical group CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229940076810 beta sitosterol Drugs 0.000 claims description 2
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 claims description 2
- NJKOMDUNNDKEAI-UHFFFAOYSA-N beta-sitosterol Natural products CCC(CCC(C)C1CCC2(C)C3CC=C4CC(O)CCC4C3CCC12C)C(C)C NJKOMDUNNDKEAI-UHFFFAOYSA-N 0.000 claims description 2
- LVQDKIWDGQRHTE-UHFFFAOYSA-N cyromazine Chemical compound NC1=NC(N)=NC(NC2CC2)=N1 LVQDKIWDGQRHTE-UHFFFAOYSA-N 0.000 claims description 2
- 229950000775 cyromazine Drugs 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- KZJWDPNRJALLNS-VJSFXXLFSA-N sitosterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CC[C@@H](CC)C(C)C)[C@@]1(C)CC2 KZJWDPNRJALLNS-VJSFXXLFSA-N 0.000 claims description 2
- 229950005143 sitosterol Drugs 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 description 30
- 239000000835 fiber Substances 0.000 description 13
- 238000005303 weighing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000007885 magnetic separation Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
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- 238000000622 liquid--liquid extraction Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- 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
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- 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
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- 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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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Abstract
The invention belongs to the technical field of molecular imprinting technology, and particularly relates to a molecular imprinting magnetic nanofiber membrane and a preparation method and application thereof. The invention combines three processes of magnetic nano particles, electrostatic spinning technology and molecular imprinting technology, successfully prepares the magnetic molecular imprinting electrostatic spinning nanofiber membrane, and has the advantages of large specific surface area, high porosity, good flexibility, mechanical strength, reusability and the like.
Description
Technical Field
The invention belongs to the technical field of molecular imprinting, and particularly relates to a molecular imprinting magnetic nanofiber membrane and a preparation method and application thereof.
Background
Conventional methods such as liquid-liquid extraction and solid-phase extraction are often used for enriching and separating toxic and harmful substances in traditional Chinese medicine samples, and because the traditional Chinese medicine samples have complex components and low content of substances to be detected, the existing solid-phase extractants such as C18, C8 and silica gel lack selectivity on specific molecules, and the enriching and separating effect is not obvious; the ion exchange type solid phase extractant can be used for purifying weakly acidic or weakly alkaline substances, but has wider selectivity range; the molecular imprinting technology can realize the specific recognition of target molecules, however, the molecular imprinting polymer used for solid phase extraction has the problem that residual template molecules are easy to leak, the preparation process is easy to be limited by physicochemical properties such as the solubility of the template molecules, and toxic substances such as aristolochic acid are used as the template molecules to cause human body and environmental pollution.
The molecular imprinting sol-gel technology is characterized in that imprinting molecules are introduced into inorganic and inorganic-organic network structures through a sol-gel process to obtain an imprinting polymer with high stability, and the polymer shows good affinity. The obtained polymer has the characteristics of small particle size, large specific surface area, specific selectivity and the like, and the three-dimensional network space structure of the polymer has good adsorption performance. The molecular imprinting sol-gel technology gives consideration to the advantages of both sol-gel and molecular imprinting, and the defects of poor mechanical stability and easy swelling of the organic high molecular polymer are well solved in the technology. Electrospinning techniques utilize electrostatic forces to produce fine fibers from a spinning solution, which produces fibers that are finer in diameter than conventional spinning processes, and have a larger surface area and higher porosity. The electrostatic spinning technology is combined with the molecular imprinting technology, so that the specific adsorption capacity of the electrostatic spinning membrane is endowed, the specific surface area of the molecular imprinting polymer is increased, and the adsorption capacity and the mass transfer rate are improved. The superparamagnetic nano particle has good dust compatibility and special magnetic effect, and is widely applied to the separation field. The electrostatic spinning superparamagnetic polymer nanofiber membrane integrates the characteristics of an electrospinning nanofiber membrane material and superparamagnetic nanoparticles, and provides a new idea for developing a magnetic separation and identification membrane material.
Disclosure of Invention
The invention aims to provide a magnetic molecularly imprinted nanofiber membrane which can be used for removing aristolochic acid.
The invention has the technical scheme that the preparation method of the molecularly imprinted magnetic nanofiber membrane comprises the following steps:
step A: preparing magnetic nano particles;
and B: dissolving template molecules in an organic solvent, adding a functional monomer for prepolymerization, and then adding 50-200 mg of magnetic nanoparticles, a cross-linking agent and an initiator; ultrasonic dissolution degassing, deoxidizing and reacting for 8-48 h at 30-80 ℃ under a shaking condition; separating the precipitate, eluting the template with acetic acid-methanol solution, and drying; obtaining a magnetic Molecularly Imprinted Polymer (MIP); the template molecule is a structural analogue of aristolochic acid, namely melamine or cyromazine; the cross-linking agent is trimethylolpropane Trimethacrylate (TRIM) or Ethylene Glycol Dimethacrylate (EGDMA); the functional monomer is 4-vinylpyridine or methacrylic acid (MAA); the initiator is Azobisisobutyronitrile (AIBN); the organic solvent is acetonitrile-methanol with volume ratio of 3: 1;
and C: adding MIP into PVA solution to obtain PVA spinning solution; carrying out electrostatic spinning for 0.5-10 h under the conditions of voltage of 8-23 kV, spinning distance of 8-20 cm, flow speed of 10-40 mu L/min and relative humidity of 40-50%, and obtaining molecularly imprinted nanofiber membranes (MINFMMs) after spinning is finished;
step D: soaking MINFMs in Glutaraldehyde (GA) water solution with the mass concentration of 1-6%, crosslinking for 10-60 min, drying the molecularly imprinted nanofiber membrane in vacuum for 8-24 h, and sealing to obtain a crosslinked molecularly imprinted nanofiber membrane; the mass concentration of sulfuric acid in the aqueous solution is 1-8%.
Specifically, the operation of step a is as follows: (1) mixing Fe3O4Dispersing the nano particles in an ethanol solution with the volume fraction of 70-80%, dropwise adding Tetraethoxysilane (TEOS) and ammonia water with the volume fraction of 25%, stirring and reacting for 10-48 h at room temperature, and separating precipitates after the reaction is finished; washing to be neutral; drying to obtain Fe3O4@SiO2；(2)Fe3O4@SiO2Dispersing in 10% acetic acid solution, adding 3- (methacryloyloxy) propyltrimethoxysilane (MPS), stirring at 40-60 deg.C for 10-24 hr, separating precipitateWashing to neutrality, drying to obtain magnetic nano particle Fe3O4@SiO2-NH2。
Specifically, in the step A, the drying is vacuum drying at 50 ℃.
Wherein, in the step A (1), methanol and ultrapure water are sequentially used for washing until the solution is neutral; in step A (2), the solution is washed to neutrality with ethanol.
Further, in the step A (1), a coprecipitation method is adopted to prepare Fe3O4Magnetic nanoparticles: 1-3 g FeCl3·6H2O and 0.1-1 g FeCl2·4H2Respectively ultrasonically dispersing O in an ultrapure water solution, mixing, adding ammonia water with the volume fraction of 25% at 70 ℃, adding 0.05-0.2 g of sodium citrate under the stirring condition at 50-80 ℃, cooling to room temperature after the reaction is finished, and collecting Fe3O4Magnetic particles and ethanol are repeatedly washed to precipitate to be neutral.
Further, in the step B, the molar ratio of the cross-linking agent to the template molecule is 5-20: 1; the molar ratio of the functional monomer to the template molecule is 2-10: 1.
Preferably, in step B, the mass ratio of the template molecule, the functional monomer and the cross-linking agent is 1: 4: 12, the mass ratio of the initiator to the polymerization system is 0.1%, and the mass ratio of the magnetic nanoparticles to the polymerization system is 0.5%.
In the step B, the prepolymerization time is 3-5 h; ultrasonic dissolving and degassing for 5-20 min; the deoxidization is performed by introducing nitrogen for 10-15 min; the oscillation speed is 150-200 rpm/min; the drying is vacuum drying at 55 ℃.
Further, in step C, a PVA spinning solution is prepared as follows: ultrasonically dispersing MIP solid powder in methanol uniformly; heating and stirring PVA and ultrapure water at the mass ratio of 1: 10-25 at 90 ℃ until the PVA and the ultrapure water are completely dissolved, and cooling to room temperature; and mixing the two solutions according to a volume ratio of 1: 2-4, and ultrasonically treating the mixture uniformly, wherein the mass fraction of MIP in PVA is 10-40%.
The invention also provides the molecularly imprinted nanofiber membrane prepared by the method.
The invention also provides application of the molecularly imprinted nanofiber membrane in adsorption of aristolochic acid or aristolochic acid analogues.
The invention has the beneficial effects that:
the invention combines three processes of magnetic nano particles, an electrostatic spinning technology and a molecular imprinting technology, successfully prepares the magnetic molecular imprinting electrostatic spinning nanofiber membrane, has the advantages of large specific surface area, high porosity, good flexibility, mechanical strength, good stability and the like, has easy separation with a sample to be detected, higher mass transfer rate and binding capacity compared with MIPs, improves the capability of the electrostatic spinning fiber membrane without specific adsorption, omits an aristolochic acid extraction and enrichment solid phase extraction device, simplifies the operation steps, and can be used for enriching and purifying aristolochic acid in an actual sample. The molecularly imprinted nanofiber membrane has good specific adsorption and reutilization property for aristolochic acid, can realize the application of specific identification, efficient separation and enrichment for aristolochic acid in agricultural products by a molecularly imprinted identification technology, has good adsorption and separation performance, and can realize the specific removal of aristolochic acid.
Drawings
FIG. 1 is a schematic scanning electron microscope of aristolochic acid magnetic molecularly imprinted polymer according to example 4 of the present invention;
fig. 2 is a scanning electron microscope schematic diagram of aristolochic acid molecularly imprinted magnetic nanofiber membrane in example 4 of the present invention.
Detailed Description
The invention will be further explained with reference to the drawings.
Example 1 preparation and application of molecularly imprinted nanofiber membranes
Fe3O4Preparing nano particles: preparation of Fe by coprecipitation3O4Magnetic nanoparticles. 2.35g FeCl was weighed out separately3·6H2O and 0.9g FeCl3·4H2O in 10mL centrifuge tubes, 5mL of ultrapure water was added, and the mixture was dissolved completely by sonication for 5 min. Pouring the two into a 250mL three-neck flask filled with 90mL of ultrapure water, adding 10mL of 25% ammonia water with volume fraction when the temperature is raised to 70 ℃, and stirring to fully and uniformly mixStirring at 80 deg.C for 30min, adding 0.1g sodium citrate, and stirring for 30 min. After the reaction, the reaction mixture was cooled to room temperature, and Fe was collected with a magnet3O4The precipitate was washed repeatedly with magnetic particles and ethanol until the pH paper showed neutrality.
Fe3O4@SiO2Preparation by hydrolysis of the silylating agent: the obtained Fe3O4The nanoparticles are put into a 250mL three-neck flask, 20mL of ultrapure water and 50mL of ethanol are added, and ultrasonic treatment is carried out for 30min to uniformly disperse the nanoparticles. 1mL of 25% ammonia water and 2mL of Tetraethoxysilane (TEOS) were added, and the reaction was stirred at room temperature for 48 hours. After the reaction is finished, magnetic separation is carried out, ultrapure water and methanol are repeatedly used for washing for a plurality of times until pH test paper shows neutrality, and drying is carried out at the temperature of 50 ℃ in vacuum for later use.
Fe3O4@SiO2-NH2The preparation of (1): fe to be prepared3O4@SiO2Dispersing magnetic nanoparticles in 10% acetic acid solution, adding 3- (methacryloyloxy) propyl trimethoxy silane (MPS), stirring at 40 deg.C for 24 hr, separating with magnet, washing with ethanol until eluate pH is neutral, and vacuum drying at 50 deg.C.
Preparation of Aristolochic Acid (AAI) magnetic molecularly imprinted polymer: weighing 0.028mmol of aristolochic acid structure analogue phenanthrenequinone, adding 30mL of acetonitrile-methanol (3: 1, v/v) solution into a 100mL round-bottom flask, dissolving template molecules, adding methacrylic acid (the molar ratio of the methacrylic acid to the template molecules is 2: 1), and performing prepolymerization for 4 h. Then 50mg of Fe3O4@SiO2-NH2Ethylene glycol dimethacrylate (at a molar ratio of 20: 1 to the template molecule) and 10mg of azobisisobutyronitrile were dispersed in the above solution. The mixed solution was degassed in an ultrasonic bath for 5min and then bubbled with nitrogen for 5min to remove oxygen. Shaking (200rpm/min) in a sealed water bath to react for 12h, wherein the reaction temperature is 50 ℃. Collecting the black product with magnet, sequentially washing the obtained polymer with methanol-acetic acid solution (methanol/acetic acid volume ratio of 7: 1) until AAI is not detected by HPLC, and vacuum drying at 55 deg.C.
Preparation of non-molecularly imprinted polymer (NIP) the same procedure as for Molecularly Imprinted Polymer (MIP) was followed except that no template was added, and it was used for comparative experiments.
Preparing a spinning solution: accurately weighing 0.5g of PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature, weighing 10mg of MIPs powder which is sieved, and selecting small-particle polymers to be evenly dispersed in methanol by ultrasonic wave (the mass of the MIPs accounts for 10% of the mass of the PVA). And finally, transferring the MIPs-containing methanol dispersion liquid into a PVA solution (the volume ratio of the MIPs-containing methanol dispersion liquid to the PVA solution is 1: 1), uniformly mixing, and preparing 4% of molecular imprinting nano-fiber membrane PVA spinning solution. 4% non-imprinted nanofiber membrane (NINFMs) PVA spinning solution was prepared according to the same method.
Preparing an electrostatic spinning fiber membrane: the prepared PVA spinning solution (with the concentration of 10%) is added into an injector and is carried out under the conditions that the spinning voltage is 23kv, the spinning distance is 20cm, the flow rate is 10 mu L/min and the relative humidity is 40%, and the obtained MINFMs have good fiber morphology.
Crosslinking of the electrospun fiber membrane: soaking the prepared MINFMs (or NINFMs) in 1% glutaraldehyde water solution (with sulfuric acid concentration of 8% and sodium sulfate saturated), crosslinking for 60min, vacuum drying the crosslinked film for 24h, and packaging into sealed bags.
Extraction and enrichment of aristolochic acid: weighing 1g of MINFMMs in 5mL of aristolochic acid solution, oscillating and adsorbing for 4h, simply washing the solution with methanol, eluting with an eluent methanol-acetic acid solution, and determining the free concentration of aristolochic acid in the eluent, wherein the recovery rate can reach 98%.
Example 2 preparation of molecularly imprinted cellulose film
Fe3O4Preparing nano particles: preparation of Fe by coprecipitation method3O4Magnetic nanoparticles. 2.12g FeCl was weighed out separately3·6H2O and 0.5g FeCl3·4H2O in 10mL centrifuge tubes, 5mL of ultrapure water was added, and the mixture was dissolved completely by sonication for 5 min. Pouring the two into a 250mL three-neck flask filled with 90mL of ultrapure water, adding 6mL of 25% ammonia water by volume when the temperature is raised to 70 ℃, stirring to fully mix the two, stirring for 10min at 50 ℃, adding 0.05g of sodium citrate, and continuing to stir for 10 min. After the reaction is finished, cooling to room temperature,collecting Fe with magnet3O4The precipitate was washed repeatedly with magnetic particles and ethanol until the pH paper showed neutrality.
Fe3O4@SiO2Preparation by hydrolysis of the silylating agent: the obtained Fe3O4The nanoparticles were put in a 250mL three-necked flask, 12mL of ultrapure water and 48mL of ethanol were added, and the mixture was subjected to ultrasonic treatment for 20min to be uniformly dispersed. Adding 2mL of ammonia water with volume fraction of 25% and 1mL of Tetraethoxysilane (TEOS), stirring and reacting at room temperature for 12h, carrying out magnetic separation after the reaction is finished, repeatedly washing with ultrapure water and methanol for several times until pH test paper shows neutrality, and drying at 50 ℃ in vacuum for later use.
Fe3O4@SiO2-NH2The preparation of (1): fe to be prepared3O4@SiO2Dissolving magnetic nanoparticles in 60mL of ultrapure water containing 10% acetic acid solution, adding 200uL of 3- (methacryloyloxy) propyl trimethoxy silane (MPS), stirring at 60 deg.C for 10h, washing with ultrapure water until the product is neutral, and vacuum drying at 50 deg.C for 24 h.
Preparation of Aristolochic Acid (AAI) magnetic molecularly imprinted polymer: weighing 0.140mmol of aristolochic acid structural analogue beta-sitosterol in a 100mL round-bottom flask, adding 40mL of acetonitrile-methanol (3: 1, v/v) solution, dissolving template molecules, adding methacrylic acid (the molar ratio of the methacrylic acid to the template molecules is 4: 1), and performing prepolymerization for 3 h. Then 100mg of Fe3O4@SiO2-NH2Ethylene glycol dimethacrylate (at a molar ratio of 20: 1 to the template molecule) and 20mg of azobisisobutyronitrile were dispersed in the above solution. The mixed solution was degassed in an ultrasonic bath for 10min and then bubbled with nitrogen for 10min to remove oxygen. Shaking (150-200rpm/min) in a sealed water bath for 24h, and the reaction temperature is 60 ℃. Collecting the obtained black product with magnet, sequentially washing the obtained polymer with methanol-acetic acid solution (7: 3, v/v), drying the filtrate at 55 deg.C under vacuum until AAI is not detected by HPLC.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
(2) Eluting the polymer solids: after washing the polymer solid 3 times with methanol, after drying and aging under vacuum at 40 ℃ for 6h, the dried polymer was placed in a 100mL round bottom flask, 20mL acetic acid: methanol (1: 5, v/v), magnetic stirring for 3h, washing with methanol several times, washing with methanol, vacuum drying at 40 deg.C for 6h, placing the polymer in a soxhlet, adding acetic acid: eluting the template with methanol (1: 8, v/v) solution until the template molecule is not detected by ultraviolet spectrophotometer.
(3) Preparing a spinning solution: accurately weighing 0.5g of PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature to prepare a PVA solution, weighing a certain mass of properly sieved MIPs powder (accounting for 30% of the mass of the PVA), and ultrasonically dispersing small-particle polymers in methanol uniformly. And finally, ultrasonically mixing the methanol dispersion liquid of the MIP and the PVA solution (the volume ratio of the methanol dispersion liquid to the PVA solution is 1:2) to obtain 5% PVA spinning solution, and preparing 5% PVA spinning solution of non-imprinted nanofiber membranes (NINFMs) according to the same method.
(4) Preparing an electrostatic spinning fiber membrane: adding the prepared PVA spinning solution into an injector, and performing under the conditions that the concentration of the spinning solution is 5%, the spinning voltage is 8kv, the spinning distance is 10cm, the flow rate is 20 mu L/min and the relative humidity is 50% to obtain the MINFMs. Non-imprinted nanofiber membranes (NINFMs) were prepared in the same manner.
(5) Crosslinking of the electrospun fiber membrane: soaking the prepared MINFMs (or NINFMs) in 2% GA water solution (sulfuric acid concentration is 2%, sodium sulfate is saturated), crosslinking for 10min, vacuum drying the crosslinked film for 10h, and packaging into sealed bags.
Example 3 preparation of molecularly imprinted cellulose film
(1) Preparing an aristolochic acid magnetic molecularly imprinted polymer:
Fe3O4preparing nanoparticles: preparation of Fe by coprecipitation3O4Magnetic nanoparticles. 2.31g FeCl was weighed out separately3·6H2O and 0.9g FeCl3·4H2O in 10mL centrifuge tubes, 5mL of ultrapure water was added, and the mixture was dissolved completely by sonication for 5 min. Both were poured into 250mL of three filled with 90mL of ultrapure waterAnd (3) adding 10mL of 25% ammonia water with volume fraction when the temperature rises to 70 ℃ into a neck flask, stirring to fully mix the mixture, timing and stirring for 40min at 70 ℃, adding 0.1g of sodium citrate, and continuing stirring for 20 min. After the reaction, the reaction mixture was cooled to room temperature, and Fe was collected with a magnet3O4The precipitate was washed repeatedly with magnetic particles and ethanol until the pH paper showed neutrality.
Fe3O4@SiO2Preparation by hydrolysis of the silylating agent: the prepared Fe3O4The nanoparticles are put into a 250mL three-neck flask, 20mL of ultrapure water and 80mL of ethanol are added, and ultrasonic treatment is carried out for 40min to uniformly disperse the nanoparticles. Adding 1mL of ammonia water with volume fraction of 25% and 2mL of Tetraethoxysilane (TEOS), stirring and reacting for 24h at room temperature, carrying out magnetic separation after the reaction is finished, repeatedly washing with ultrapure water and methanol for several times until pH test paper shows neutrality, and drying under vacuum at 50 ℃ for later use.
Fe3O4@SiO2-NH2The preparation of (1): fe to be prepared3O4@SiO2Dissolving magnetic nanoparticles in 100mL of ultrapure water containing 10% acetic acid solution, adding 400 μ L of 3- (methacryloyloxy) propyltrimethoxysilane (MPS), stirring at 50 deg.C for 16h, washing with ultrapure water until the product is neutral, and vacuum drying at 50 deg.C for 24 h.
Preparation of Aristolochic Acid (AAI) magnetic molecularly imprinted polymer: weighing 0.278mmol of aristolochic acid structural analogue (1-10 phenanthroline-4, 7 dicarboxylic acid) into a 100mL round-bottomed flask, adding 50mL of acetonitrile-methanol (3: 1, v/v) solution, adding methacrylic acid (molar ratio of methacrylic acid to template molecule is 4: 1) after template molecules are dissolved, and carrying out prepolymerization for 4 h. 200mg of Fe3O4@SiO2-NH2Ethylene glycol dimethacrylate (molar ratio 15: 1 to template molecule) and 15mg of azobisisobutyronitrile were dispersed in the above solution. The mixed solution was degassed in an ultrasonic bath for 15min and then bubbled with nitrogen for 15min to remove oxygen. Shaking (200rpm/min) in a sealed water bath to react for 48h, wherein the reaction temperature is 40 ℃. Collecting the black product with magnet, sequentially washing the obtained polymer with methanol-acetic acid solution (8: 2, v/v) until the filtrate is undetectable by HPLCDrying at 55 deg.C under vacuum in the presence of AAI.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
(2) Eluting the polymer solids: washing the polymer solid with methanol for 3 times, drying and aging at 40 ℃ in vacuum for 6h, placing the dried polymer into a 100mL round-bottomed flask, adding 20mL acetic acid: methanol (1: 5, v/v), magnetically stirring for 3h, washing with methanol for several times, washing with methanol, drying at 40 ℃ in vacuum for 6h, placing the polymer in a soxhlet, adding acetic acid: the template was eluted with methanol (1: 8, v/v) until no template molecules were detected by UV spectrophotometer.
(3) Preparing a spinning solution: accurately weighing 0.5g of PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature to prepare a PVA solution, weighing proper sieved MIPs powder (accounting for 30% of the mass of the PVA), and ultrasonically dispersing small-particle polymer in methanol uniformly. Finally, ultrasonically mixing the methanol dispersion liquid of the MIP and the PVA solution (the volume ratio of the methanol dispersion liquid to the PVA solution is 1:2) to obtain 10% PVA spinning solution, and preparing 5% PVA spinning solution of non-imprinted nanofiber membranes (NINFMs) according to the same method.
(4) Preparing an electrostatic spinning fiber membrane: adding the prepared PVA spinning solution into an injector, and performing under the conditions that the concentration of the spinning solution is 5%, the spinning voltage is 23kv, the spinning distance is 20cm, the flow rate is 20 mu L/min and the relative humidity is 50% to obtain the MINFMs. Non-imprinted nanofiber membranes (NINFMs) were prepared in the same manner.
(5) Crosslinking of the electrospun fiber membrane: soaking the prepared MINFMs (or NINFMs) in 2% GA water solution (sulfuric acid concentration is 2%, sodium sulfate is saturated), crosslinking for 10min, vacuum drying the crosslinked film for 10h, and packaging into sealed bags.
Example 4 preparation of molecularly imprinted cellulose film
(1) Preparing an aristolochic acid magnetic molecularly imprinted polymer:
Fe3O4preparing nano particles: preparation of Fe by coprecipitation3O4Magnetic nanoparticles. Respectively weighing2.78g FeCl3·6H2O and 1.0g FeCl3·4H2O is put into 10mL centrifuge tubes, 5mL of ultrapure water is added into each centrifuge tube, and the mixture is completely dissolved by ultrasonic treatment for 5 min. Pouring the two into a 250mL three-neck flask filled with 90mL of ultrapure water, adding 15mL of 25% ammonia water by volume when the temperature is raised to 70 ℃, stirring to fully mix the two, stirring for 40min at 60 ℃, adding 0.2g of sodium citrate, and continuing to stir for 30 min. After the reaction, the reaction mixture was cooled to room temperature, and Fe was collected with a magnet3O4The precipitate was washed repeatedly with magnetic particles and ethanol until the pH paper showed neutrality.
Fe3O4@SiO2Preparation by hydrolysis of the silylating agent: the obtained Fe3O4The nanoparticles are put into a 250mL three-neck flask, 20mL of ultrapure water and 70mL of ethanol are added, and ultrasonic treatment is carried out for 30min to uniformly disperse the nanoparticles. Adding 5mL of ammonia water with volume fraction of 25% and 3mL of Tetraethoxysilane (TEOS), stirring and reacting at room temperature for 36h, carrying out magnetic separation after the reaction is finished, repeatedly washing with ultrapure water and methanol for several times until pH test paper shows neutrality, and drying at 50 ℃ in vacuum for later use.
Fe3O4@SiO2-NH2The preparation of (1): fe to be prepared3O4@SiO2Dissolving magnetic nanoparticles in 120mL of ultrapure water containing 10% acetic acid solution, adding 600uL of 3- (methacryloyloxy) propyl trimethoxy silane (MPS), stirring and reacting at 60 ℃ for 24h, washing the obtained product with ultrapure water until the product is neutral after the reaction is finished, and drying the product under vacuum at 50 ℃ for 24h for later use.
Preparation of Aristolochic Acid (AAI) magnetic molecularly imprinted polymer: weighing 0.196mmol of aristolochic acid structural analogue (melamine) in a 100mL round-bottom flask, adding 60mL acetonitrile-methanol (3: 1, v/v) solution, adding methacrylic acid (the molar ratio of the methacrylic acid to the template molecule is 4: 1) after the template molecule is dissolved, and performing prepolymerization for 5 h. 200mg of Fe3O4@SiO2-NH2Ethylene glycol dimethacrylate (molar ratio to template molecule 25: 1) and 20mg of azobisisobutyronitrile were dispersed in the above solution. The mixed solution was degassed in an ultrasonic bath for 15min and then bubbled with nitrogen for 15min to remove oxygen. In a sealed water bathThe reaction was carried out for 48h with shaking (150-. Collecting the black product with magnet, sequentially washing the obtained polymer with methanol-acetic acid solution (8: 2, v/v) until AAI is not detected by HPLC, and vacuum drying at 55 deg.C.
Preparation of non-molecularly imprinted polymer (NIP) the procedure was the same as for Molecularly Imprinted Polymer (MIP) except that no template was added.
(2) Eluting the polymer solids: after washing the polymer solid 3 times with methanol, after drying and aging under vacuum at 70 ℃ for 6h, the dried polymer was placed in a 100mL round bottom flask, 40mL acetic acid: methanol (1: 5, v/v), magnetic stirring for 4h, washing several times with methanol, washing with methanol, vacuum drying at 60 ℃ for 8h, finally placing the polymer in a soxhlet, washing with acetic acid: the template was eluted with methanol (1: 8, v/v) until no template molecules were detected by UV spectrophotometer.
(3) Preparing a spinning solution: weighing PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature to prepare a PVA solution, weighing sieved MIPs powder (accounting for 30% of the mass of the PVA), and ultrasonically dispersing small-particle polymer in methanol uniformly. Finally, the methanol dispersion liquid of MIP and PVA solution are mixed ultrasonically (the volume ratio of the two is 1:4) to obtain 6% PVA spinning solution, and 5% PVA spinning solution of non-imprinted nanofiber membranes (NINFMs) is prepared according to the same method.
(4) Preparing an electrostatic spinning fiber membrane: adding the prepared PVA spinning solution into an injector, and performing under the conditions that the concentration of the spinning solution is 6%, the spinning voltage is 15kv, the spinning distance is 15cm, the flow rate is 40 mu L/min, and the relative humidity is 50% to obtain the MINFMs. Non-imprinted nanofiber membranes (NINFMs) were prepared in the same manner.
(5) Crosslinking of the electrospun fiber membrane: soaking the prepared MINFMs (or NINFMs) in 3% GA water solution (sulfuric acid concentration is 5%, sodium sulfate is saturated), crosslinking for 20min, vacuum drying the crosslinked film for 10h, and packaging into sealed bags.
FIG. 1 is a schematic scanning electron microscope of a molecularly imprinted polymer of aristolochic acid in example 4, wherein the polymer particles are uniform and have more wrinkles; FIG. 2 is a schematic scanning electron microscope of the molecularly imprinted nanofiber membrane of aristolochic acid in example 4, wherein the fibers are in good condition and have uniform diameter, and the polymer is uniformly dispersed in the nanofibers.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a molecularly imprinted magnetic nanofiber membrane is characterized by comprising the following steps:
step A: preparing magnetic nano particles;
and B: dissolving template molecules in an organic solvent, adding a functional monomer for prepolymerization, and then adding magnetic nanoparticles, a cross-linking agent and an initiator; ultrasonic dissolution degassing, deoxidizing and reacting for 8-48 h at 30-80 ℃ under a shaking condition; separating the precipitate, eluting the template with acetic acid-methanol solution, and drying; obtaining a magnetic Molecularly Imprinted Polymer (MIP); the template molecule is structural analogues of aristolochic acid, namely phenanthrenequinone, beta-sitosterol, 1-10 phenanthroline-4, 7 dicarboxylic acid, melamine or cyromazine; the cross-linking agent is trimethylolpropane Trimethacrylate (TRIM) or Ethylene Glycol Dimethacrylate (EGDMA); the functional monomer is 4-vinylpyridine or methacrylic acid (MAA); the initiator is Azobisisobutyronitrile (AIBN); the organic solvent is acetonitrile-methanol with volume ratio of 3: 1;
and C: adding MIP into PVA solution to obtain PVA spinning solution; carrying out electrostatic spinning for 0.5-10 h under the conditions of voltage of 8-23 kV, spinning distance of 8-20 cm, flow speed of 10-40 mu L/min and relative humidity of 40-50%, and obtaining molecularly imprinted nanofiber membranes (MINFMMs) after spinning is finished;
step D: soaking MINFMs in Glutaraldehyde (GA) water solution with the mass concentration of 1-6%, crosslinking for 10-60 min, drying the molecularly imprinted nanofiber membrane in vacuum for 8-24 h, and sealing to obtain a crosslinked molecularly imprinted nanofiber membrane; the concentration of sulfuric acid in the aqueous solution is 1-8% by mass.
2. The method of claim 1, wherein step a is performed by: (1) mixing Fe3O4Dispersing the nano particles in an ethanol solution with the volume fraction of 70-80%, dropwise adding Tetraethoxysilane (TEOS) and ammonia water with the volume fraction of 25%, stirring and reacting for 10-48 h at room temperature, and separating precipitates after the reaction is finished; washing to be neutral; drying to obtain Fe3O4@SiO2；(2)Fe3O4@SiO2Dispersing in 10% acetic acid solution, adding 3- (methacryloyloxy) propyl trimethoxy silane (MPS), stirring and reacting at 40-60 deg.C for 10-24 h, separating precipitate, washing to neutrality, and drying to obtain magnetic nanoparticles Fe3O4@SiO2-NH2(ii) a The drying is vacuum drying at 50 ℃.
3. The method according to claim 2, wherein in step A (1), methanol and ultrapure water are sequentially used for washing to neutrality; in step A (2), the solution is washed to neutrality with ethanol.
4. The production method according to claim 2 or 3, wherein Fe is produced by coprecipitation in step A (1)3O4Magnetic nanoparticles: 1-3 g FeCl3·6H2O and 0.1-1 g FeCl2·4H2Respectively ultrasonically dispersing O in an ultrapure water solution, mixing, adding ammonia water with the volume fraction of 25% at 70 ℃, adding 0.05-0.2 g of sodium citrate under the stirring condition at 50-80 ℃, cooling to room temperature after the reaction is finished, and collecting Fe3O4Magnetic particles and ethanol are repeatedly washed to precipitate to be neutral.
5. The preparation method of claim 1, wherein in step B, the molar ratio of the cross-linking agent to the template molecule is 5-20: 1; the molar ratio of the functional monomer to the template molecule is 2-10: 1.
6. The preparation method of claim 5, wherein in step B, the mass ratio of the template molecule, the functional monomer and the cross-linking agent is 1: 4: 12, the mass ratio of the initiator to the polymerization system is 0.1%, and the mass ratio of the magnetic nanoparticles to the polymerization system is 0.5%.
7. The preparation method according to claim 1, wherein in the step B, the prepolymerization time is 3-5 h; ultrasonic dissolving and degassing for 5-20 min; the deoxidization is performed by introducing nitrogen for 10-15 min; the oscillation speed is 150-200 rpm/min; the drying is vacuum drying at 55 ℃.
8. The method of claim 1, wherein in step C, the PVA spinning solution is prepared as follows: ultrasonically dispersing MIP solid powder in methanol uniformly; heating and stirring PVA and ultrapure water at the mass ratio of 1: 10-25 at 90 ℃ until the PVA and the ultrapure water are completely dissolved, and cooling to room temperature; and mixing the two solutions according to a volume ratio of 1: 2-4, and ultrasonically treating the mixture uniformly, wherein the mass fraction of MIP in PVA is 10-40%.
9. The molecularly imprinted nanofiber membrane prepared by the method of any one of claims 1 to 8.
10. Use of the molecularly imprinted nanofibrous membrane of claim 9 for adsorbing aristolochic acid or aristolochic acid analogues.
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