CN111171233B - Preparation method and application of novel magnetic thin-layer imprinted membrane - Google Patents
Preparation method and application of novel magnetic thin-layer imprinted membrane Download PDFInfo
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Abstract
The invention provides a preparation method and application of a novel magnetic-induced artemisinin molecularly imprinted composite membrane, wherein the preparation method comprises the following steps: step 1, preparation of Fe 3 O 4 (ii) a Step 2, fe 3 O 4 Preparing a thin-layer magnetic artemisinin molecularly imprinted polymer by a surface one-step method; and 3, preparing the magnetic field induced artemisinin molecularly imprinted composite membrane. The molecularly imprinted membrane prepared by the magnetic field induction method can effectively overcome the defects of long time consumption and easy embedding of the identification sites in the traditional preparation of the blend imprinted membrane, and improves the molecularly imprinted efficiency by preparing the imprinted polymer by a one-step method, changing the elution mode and increasing the number of the effective identification sites by virtue of magnetic field force, thereby having the advantages of simple and efficient synthesis, high selectivity and efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of material preparation and separation, and particularly relates to a preparation method and application of a novel magnetic thin-layer imprinted membrane.
Background
Artemisinin (Artemisinin) is a sesquiterpene lactone drug with a peroxy group extracted from stems and leaves of plant artemisia annua by Chinese scientists, is an internationally recognized specific antimalarial drug with independent intellectual property rights, and is widely used in the world. Therefore, the artemisinin has wide development prospect and great development value. The extraction and separation of artemisinin mainly adopts methods of Soxhlet extraction, organic solvent extraction, water vapor extraction and the like, and the method of separation and extraction by adopting a molecular imprinting composite membrane is rarely reported.
The development and application of a Molecular Imprinted Membrane (MIM) combining a molecular imprinting technique with a Membrane separation technique is one of the most attractive studies. On one hand, the molecular imprinting technology generates a polymer through copolymerization of a functional monomer and a target molecule, then elutes the target molecule through a solvent, and finally a 'memory' cavity which can be completely matched with the original target molecule on a space shape and a determined functional group can be left in the polymer, and the cavity can be specifically combined with the target molecule in a mixture, so that the separation and analysis effects of a target object are achieved. On the other hand, the technology overcomes the defect that the current commercial membrane materials such as ultrafiltration, microfiltration and reverse osmosis membrane can not realize the selective separation of single substances, and provides a feasible and effective solution for separating specific molecules from the mixture with similar structure. However, the conventional molecularly imprinted membrane has many defects, such as that in the process of preparing a membrane by blending, the molecularly imprinted polymer is easily embedded in the membrane matrix, so that the recognition site cannot be in full contact with the target molecule, the mass transfer resistance is increased, the adsorption-desorption kinetic performance of the target molecule is poor, and the imprinting effect is limited.
Disclosure of Invention
The invention aims to provide a preparation method and application of a novel magnetic thin-layer imprinted membrane. The composite material imprinted membrane capable of greatly improving effective recognition sites is prepared. The method provides a new idea for improving the imprinting effect of the traditional blend imprinting membrane from a novel angle, solves the problems of embedding of recognition sites and small water flux in the blend membrane to a certain extent, and further improves the selective recognition and separation efficiency by increasing the number of effective recognition sites.
Technical scheme of the invention
A preparation method and application of a novel magnetic thin-layer imprinted membrane are carried out according to the following steps:
step 1, preparation of Fe 3 O 4 ：
Respectively weighing a certain amount of ferric chloride hexahydrate, sodium acetate and polyethylene glycol in a beaker, then adding ethylene glycol, uniformly stirring by magnetic force, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, transferring to an oven, calcining at a certain temperature for a certain time, taking out after natural cooling, grinding into powder by using a mortar to obtain Fe 3 O 4 For standby;
step 2, fe 3 O 4 Preparing a thin-layer magnetic artemisinin molecularly imprinted polymer by a surface one-step method:
measuring a certain amount of acetonitrile into a flask, and adding artemisinin, acrylamide, ethylene glycol dimethacrylate, azobisisobutyronitrile and Fe prepared in the first step 3 O 4 Placing in a hot water bath, mechanically stirring for a period of time at a certain temperature, heating to a test temperature for continuous reaction, magnetically separating the product after the reaction is finished, eluting the artemisinin by using a methanol/acetic acid mixed solution until the artemisinin cannot be detected by ultraviolet, and then washing the product for multiple times by using ethanol to finally obtain the artemisinin magnetic imprinted polymer.
Step 3, preparing a magnetic field induced artemisinin molecularly imprinted composite membrane:
adding the artemisinin magnetic imprinted polymer obtained in the step (2) into dimethyl sulfoxide, adding polyvinylidene fluoride, and mechanically stirring uniformly at 50 ℃ to obtain a membrane casting solution; standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution on a culture dish, standing for a period of time to make the thickness of the membrane casting solution uniform, introducing a magnetic field, after magnetic attraction for a period of time, freezing by using an ice bag, and finally slowly immersing the membrane casting solution in deionized water to complete phase conversion to obtain the blending magnetic force induced artemisinin molecularly imprinted composite membrane.
In the step 1, the molar weight ratio of ferric chloride hexahydrate, sodium acetate, polyethylene glycol and ethylene glycol used is 20; the stirring time is 4-5 h; the calcination temperature is 160 ℃; the calcination time is 6-9 h.
In the step 2, acetonitrile is weighed, the volume is 60mL, template molecules artemisinin, functional monomer acrylamide, cross-linking agent EGDMA, initiators AIBN and Fe 3 O 4 1: 9:2. The test temperature of the reaction is 50-60 ℃, the reaction time is 10h, the eluent is aqueous alkali with the mass fraction of 0.2%, and the elution time is more than 30min.
In the step 3, when the magnetic field induced artemisinin molecularly imprinted composite membrane is prepared, the mass of MMIPs, DMSO and PVDF powder respectively accounts for 0.5%, 89.5% and 10% of the mass of the membrane casting solution. The mechanical stirring time is 4-5 h; the magnetic attraction time is 3 min-8 min, and the soaking time in the deionized water is at least 30min.
The prepared magnetic thin-layer imprinted membrane can be effectively used for selectively identifying and separating artemisinin molecules in a mixture.
The invention has the advantages of
1. Magnetic Fe in the invention 3 O 4 The method has the advantages of being used as a carrier for synthesizing the imprinted polymer, and simultaneously being used as a key medium for improving the embedding defects of the traditional phase inversion imprinted membrane, and effectively organically combining the molecular imprinting technology with the membrane material. Therefore, the recognition site can be contacted with a target more effectively and can be firmly fixed on the membrane, thereby achieving the effect of improving the molecular imprinting.
2. The thickness of the imprinting polymerization layer can be regulated and controlled on the ferroferric oxide surface by a one-step method so as to construct a thin-layer imprinting.
3. And (3) freezing to prepare a membrane after magnetic induction, fixing the membrane casting solution by using a freezing method, firmly fixing the imprinted polymer on the surface of the membrane, forming an ordered crystal lattice macroporous structure in the membrane, and improving the membrane flux.
4. The artemisinin molecular imprinting film obtained by the method has the characteristics of good thermal stability, rapid adsorption kinetics and obvious artemisinin molecular recognition performance.
Drawings
FIG. 1 shows magnetic Fe 3 O 4 A transmission diagram of (a);
FIG. 2 is Fe 3 O 4 Transmission map of surface imprinted polymers;
FIG. 3 is a scanning electron micrograph of a thin magnetic imprinting film;
detailed description of the preferred embodiments
The invention is further illustrated by the following examples.
Example one
(1) Preparation of Fe 3 O 4
1.35g of ferric chloride hexahydrate, 3.6g of sodium acetate (sodium acetate) and 1.0g of polyethylene glycol were weighed into a beaker, respectively. Then adding 50mL of ethylene glycol, magnetically stirring for 4.5h, transferring the mixed solution to a polytetrafluoroethylene reaction kettle after uniform stirring, then transferring to an oven, calcining for 6h at 160 ℃, taking out after natural cooling, and grinding into powder by using a mortar to obtain 500nmFe 3 O 4 And (5) standby.
(2)Fe 3 O 4 Surface one-step method for preparing thin-layer magnetic artemisinin molecularly imprinted polymer
60mL of acetonitrile was measured in a flask, and 7.0mg of artemisinin, 7.1mg of acrylamide (MAA), 78mg of Ethylene Glycol Dimethacrylate (EGDMA), 3.8mg of Azobisisobutyronitrile (AIBN), and 25mg of Fe prepared in step one were added 3 O 4 Placing in a hot water bath, mechanically stirring at 50 ℃ for a period of time, heating to 60 ℃ and continuing to react for 10 hours. After the reaction is finished, the product is separated by magnetism, then the artemisinin is eluted by methanol/acetic acid mixed solution 9:1 (V: V) until the artemisinin can not be detected by ultraviolet, and then the product is washed by ethanol for a plurality of times, and finally the artemisinin magnetic imprinted polymers (MMIPs) are obtained.
(3) Preparation of magnetic field induced artemisinin molecular imprinting composite membrane
Adding 0.1g of MMIPsPs0.1 g obtained in the step (2) into 17.9g of dimethyl sulfoxide (DMSO), adding 2.0g of polyvinylidene fluoride (PVDF), and mechanically stirring at 50 ℃ for 4 hours until the mixture is uniform to obtain a casting solution; standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution on a culture dish, standing for a period of time to make the thickness of the membrane casting solution uniform, introducing a magnetic field, performing magnetic induction for 5min, freezing by using an ice bag, and finally slowly soaking the membrane casting solution in deionized water for 30min to complete phase conversion to obtain the blend magnetic induction artemisinin molecularly imprinted composite membrane. For comparison, the preparation method of the non-imprinted composite membrane is the same as the above method except that the template molecule artemisinin is not added.
Example two
(1) Preparation of Fe 3 O 4
1.35g of ferric chloride hexahydrate, 3.6g of sodium acetate (sodium acetate) and 1.0g of polyethylene glycol were weighed into a beaker, respectively. Then adding 50mL of ethylene glycol, magnetically stirring for 4.5h, transferring the mixed solution to a polytetrafluoroethylene reaction kettle after uniform stirring, then transferring to an oven, calcining for 9h at 160 ℃, taking out after natural cooling, and grinding into powder by using a mortar to obtain 500nmFe 3 O 4 And (5) standby.
(2)Fe 3 O 4 Surface one-step method for preparing thin-layer magnetic artemisinin molecularly imprinted polymer
60mL of acetonitrile was measured in a flask, and 14.0mg of artemisinin, 14.2mg of acrylamide (MAA), 158mg of Ethylene Glycol Dimethacrylate (EGDMA), 7.5mg of Azobisisobutyronitrile (AIBN), and 50mg of Fe prepared in step one were added 3 O 4 Placing in a hot water bath, mechanically stirring at 50 ℃ for a period of time, heating to 60 ℃ and continuing to react for 10 hours. After the reaction is finished, the product is separated by magnetism, then the artemisinin is eluted by methanol/acetic acid mixed solution 9:1 (V: V) until the artemisinin can not be detected by ultraviolet, and then the product is washed by ethanol for a plurality of times, and finally the artemisinin magnetic imprinted polymers (MMIPs) are obtained.
(3) Preparing magnetic field induced artemisinin molecular imprinting composite membrane
Adding 0.1g of MMIPsobtained in the step (2) into 17.9g of dimethyl sulfoxide (DMSO), adding 2.0g of polyvinylidene fluoride (PVDF), and mechanically stirring for 5 hours at 50 ℃ until the mixture is uniform to obtain a membrane casting solution; standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution on a culture dish, standing for a period of time to enable the thickness of the membrane casting solution to be uniform, introducing a magnetic field, freezing by means of an ice bag after magnetic induction for 8min, and finally slowly immersing the membrane casting solution in deionized water for 30min to complete phase transformation to obtain the blend magnetic induction artemisinin molecularly imprinted composite membrane. For comparison, the preparation method of the non-imprinted composite membrane is the same as the above except that the template molecule artemisinin is not added.
For comparison, the preparation of magnetic non-imprinted polymer was the same as above except that the template molecule artemisinin was not added.
The artemisinin described in the above technical scheme acts as a template molecule.
The acrylamide in the technical scheme is used as a functional monomer.
The ethylene glycol dimethacrylate in the technical scheme is used as a cross-linking agent.
The azobisisobutyronitrile in the technical scheme has the function of an initiator.
The dimethyl sulfoxide in the technical scheme is used as a solvent to dissolve PVDF so as to prepare a membrane casting solution.
The PVDF described in the above technical scheme acts as a matrix.
The deionized water in the technical scheme is used as a non-solvent.
(1) Static adsorption experiment
Adding certain mass of blotting membrane into corresponding test solution, oscillating in constant temperature water bath, examining influence of initial concentrations of different adsorption solutions on the composite membrane, measuring unadsorbed artemisinin molecule concentration by HPLC after adsorption is completed, and calculating adsorption capacity (Q) according to the result e ，mg/g)：
Wherein C is 0 (mg/L) and C e (mg/L) is the initial concentration of artemisinin and the equilibrium adsorption concentration, respectively. V (mL) and W (mg) are the volume of the solution and the mass of the different membranes, respectively.
(2) Selectivity test
Fixing the blotting membrane on a constant-pressure flat membrane machine, adding ethanol solution of artemisinin, artesunate and dihydroartemisinin as substrates into a storage tank of the machine, starting the machine, sampling at certain intervals, measuring the substrate concentration of the penetrating fluid, and calculating the adsorption amount according to the substrate concentration.
The imprinted polymer prepared in this application is in Fe 3 O 4 The surface of the imprinted polymer is prepared by a one-step method, in addition, the imprinted polymer is prepared by an elution mode of alkali liquor in an ultra-fast way, and the imprinted polymer membrane is prepared by magnetic field traction for the first time.
Claims (5)
1. A preparation method of a novel magnetic thin-layer imprinted membrane is characterized by comprising the following steps:
step 1, preparation of Fe 3 O 4 ：
Respectively weighing a certain amount of ferric chloride hexahydrate, sodium acetate and polyethylene glycol in a beaker, then adding ethylene glycol, uniformly stirring by magnetic force, transferring the mixed solution to a polytetrafluoroethylene reaction kettle, transferring to an oven, calcining at a certain temperature for a certain time, taking out after natural cooling, grinding into powder by using a mortar to obtain 500nmFe 3 O 4 For standby;
step 2, fe 3 O 4 Preparing a thin-layer magnetic artemisinin molecularly imprinted polymer by a surface one-step method:
weighing a certain amount of acetonitrile in a flask, and adding artemisinin, acrylamide, ethylene glycol dimethacrylate, azobisisobutyronitrile and pre-synthesized Fe 3 O 4 Placing in a hot water bath at a certain temperature, mechanically stirring for a period of time, heating to a test temperature, continuing to react, magnetically separating the product after the reaction is finished, eluting artemisinin molecules by using an alkali solution with a certain concentration until artemisinin is not detected, immediately washing the product for multiple times by using ethanol, and finally obtaining the artemisinin magnetic imprinted polymer;
in the step 2, acetonitrile with the volume of 60mL is measured, and template molecules of artemisinin, functional monomers of acrylamide, ethylene glycol dimethacrylate, azobisisobutyronitrile and Fe 3 O 4 In a molar weight ratio of 1:4:20:9:2, test temperature of reaction 50 o C ~ 60 o C, time 10 h;
step 3, preparing a magnetic field induced artemisinin molecularly imprinted composite membrane:
adding the artemisinin magnetic imprinted polymer obtained in the step 2 into dimethyl sulfoxide, adding polyvinylidene fluoride, and adding 50 parts of the artemisinin magnetic imprinted polymer o C, mechanically stirring uniformly to obtain a membrane casting solution; standing to remove air bubbles in the membrane casting solution, pouring the membrane casting solution on a culture dish, standing for a period of time to make the thickness of the membrane casting solution uniform, introducing a magnetic field, after magnetic attraction for a period of time, freezing by using an ice bag, and finally slowly immersing the membrane casting solution in deionized water to complete phase conversion to obtain the blending magnetic force induced artemisinin molecularly imprinted composite membrane.
2. The method for preparing the novel magnetic thin-layer imprinted membrane according to claim 1, wherein in the step 1, the molar weight ratio of ferric chloride hexahydrate, sodium acetate, polyethylene glycol and ethylene glycol is 20; the stirring time is 4 h-5 h; the calcination temperature is 160 DEG o C; the calcination time is 6 h-9 h.
3. The method for preparing a novel magnetic thin-layer imprinted membrane according to claim 1, wherein in the step 2, the eluent is an alkali solution with a mass fraction of 0.2%, and the elution time is more than 30min.
4. The preparation method of the novel magnetic thin-layer imprinted membrane according to claim 1, wherein in the step 3, when the magnetic attraction artemisinin molecular imprinted composite membrane is prepared, the mass of the magnetic imprinted polymer, the mass of dimethyl sulfoxide and the mass of polyvinylidene fluoride powder respectively account for 0.5%, 89.5% and 10% of the casting solution, and the mechanical stirring time is 4 h-5 h; the magnetic attraction time is 3 min-8 min, and the soaking time in deionized water is at least 30min.
5. The method for preparing a novel magnetic thin-layer imprinted membrane according to claim 1, wherein the prepared magnetic thin-layer imprinted membrane can be effectively used for selectively recognizing and separating artemisinin molecules in a mixture.
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| CN102600813A (en) * | 2012-04-06 | 2012-07-25 | 济南大学 | Preparation method and application of surface artemisinin molecule imprinting adsorbing material of vegetable sponge |
| CN105854844A (en) * | 2016-06-07 | 2016-08-17 | 吉首大学 | Artemisinic acid magnetic imprinting microspheres and preparation method and application thereof |
| WO2017031323A1 (en) * | 2015-08-18 | 2017-02-23 | Karyopharm Therapeutics Inc. | (s,e)-3-(6-aminopyridin-3-yl)-n-((5-(4-(3-fluoro-3-methylpyrrolidine-1-carbonyl)phenyl)-7-(4-fluorophenyl)benzofuran-2-yl)methyl)acrylamide for the treatment of cancer |
| CN108187715A (en) * | 2017-12-21 | 2018-06-22 | 江苏大学 | A kind of novel magnetic induces C3N4/Fe3O4The preparation method and its usage of composite membrane |
| CN110075923A (en) * | 2019-04-30 | 2019-08-02 | 江苏大学 | A kind of g-C3N4The bionical construction method and application thereof of/BiOI-pDA@PVDF photocatalysis membrana |
-
2020
- 2020-01-17 CN CN202010056878.2A patent/CN111171233B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600813A (en) * | 2012-04-06 | 2012-07-25 | 济南大学 | Preparation method and application of surface artemisinin molecule imprinting adsorbing material of vegetable sponge |
| WO2017031323A1 (en) * | 2015-08-18 | 2017-02-23 | Karyopharm Therapeutics Inc. | (s,e)-3-(6-aminopyridin-3-yl)-n-((5-(4-(3-fluoro-3-methylpyrrolidine-1-carbonyl)phenyl)-7-(4-fluorophenyl)benzofuran-2-yl)methyl)acrylamide for the treatment of cancer |
| CN105854844A (en) * | 2016-06-07 | 2016-08-17 | 吉首大学 | Artemisinic acid magnetic imprinting microspheres and preparation method and application thereof |
| CN108187715A (en) * | 2017-12-21 | 2018-06-22 | 江苏大学 | A kind of novel magnetic induces C3N4/Fe3O4The preparation method and its usage of composite membrane |
| CN110075923A (en) * | 2019-04-30 | 2019-08-02 | 江苏大学 | A kind of g-C3N4The bionical construction method and application thereof of/BiOI-pDA@PVDF photocatalysis membrana |
Non-Patent Citations (2)
| Title |
|---|
| Novel molecularly imprinted magnetic nanoparticles for the selective extraction of protoberberine alkaloids in herbs and rat plasma;Jiawei Meng et al;《JOURNAL OF SEPARATION SCIENCE》;20150630;第38卷(第12期);第2117-2125页 * |
| 青蒿素分子印迹聚合物分子识别性研究;李小燕 等;《中草药》;20120430;第43卷(第4期);第795-798页 * |
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