CN111363185B - Preparation method and application of molecularly imprinted composite membrane initiated by surface functional monomer prepolymerization system - Google Patents
Preparation method and application of molecularly imprinted composite membrane initiated by surface functional monomer prepolymerization system Download PDFInfo
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Abstract
The invention belongs to the technical field of material preparation, and relates to a preparation method and application of a molecularly imprinted composite membrane initiated by a surface functional monomer prepolymerization system; the method comprises the following steps: firstly, preparing 2-methacrylamide glutamic acid and poly (HEMA-MAGA); then preparing poly (HEMA-MAGA) particles doped with PVDF nano composite membrane by using a latex blending method to prepare PPMs, and then modifying the modified PPMs by using gamma-methacryloxypropyltrimethoxysilane (KH-570) on the surface; finally, preparing the TC-molecularly imprinted composite membrane by using an ATRP method; according to the invention, imprinting polymerization is carried out on the surface of the multi-layer nano composite membrane material modified by the functional monomer, so that the problem that a part of template molecules cannot be eluted due to too deep embedding is avoided, the obtained imprinting membrane is high temperature resistant, the recognition points are not easy to damage, the nonspecific adsorption is reduced by 70%, and the imprinting membrane has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of material preparation, and relates to a preparation method and application of a molecularly imprinted composite membrane initiated by a surface functional monomer prepolymerization system.
Background
With the continuous development of separation and purification technology, membrane technology has become the subject of research of many workers as a simple, low-cost and efficient method. However, the conventional separation membrane has difficulty in solving many technical problems such as selective separation, specific recognition and separation ability. In recent years, the application of membrane-specific recognition and separation techniques has greatly helped not only the development of bioscience but also the development of bioscience. Therefore, it is very necessary to develop a membrane having specific recognition ability and specific selectivity. Molecular imprinting has received much attention as a simple and mature technique.
It is well known that Molecular Imprinting (MIT) is considered as an attractive technical means to create recognition cavities to complement the size, shape and function of template molecules. Molecularly Imprinted Polymers (MIPs) are synthetic polymers with a predetermined selectivity for a given analyte or a group of structurally related species. Among various film surface modification methods, surface initiator Atom Transfer Radical Polymerization (ATRP) is a relatively new method. In recent years, due to the advantages of simple preparation, low cost, good chemical stability and the like, the method has been rapidly developed in many fields such as separation, sensors, catalysis, water treatment, drug design and the like. Thus, a Molecularly Imprinted Membrane (MIM) consists of or contains a molecularly imprinted polymer. The addition of the molecular imprinting polymer can improve the specific recognition capability of the membrane, and the molecular imprinting on the surface of the porous membrane can realize the separation and purification of template molecules. It has good binding capacity and fast separation performance. In recent years, porous molecularly imprinted membranes have different pore sizes and layered structures, and the unique separation performance thereof has attracted much attention. Currently, the common method of synthesizing MIMs is to cast or graft an imprinting layer on the surface. Although a large number of reports indicate that the problems of high diffusion barrier, low regeneration, low selectivity and structural resistance still exist in the molecularly imprinted membrane, the problem of how to widely apply the molecularly imprinted membrane becomes one of the core problems of research. Molecular imprinting membranes have been studied to find an effective way to uniformly disperse inorganic particles into membrane materials, thereby improving the recognition and selectivity of specific compounds.
Polyvinylidene fluoride (PVDF) is an ideal membrane material, and due to its high hydrophobicity and low surface energy, selective separation performance of PVDF membrane is poor, which becomes a significant challenge in practical application. The inorganic nanoparticle mixed membrane can combine the high selectivity of stable and processable high molecular materials and inorganic materials. Nanoparticles have many special properties due to their ultra-thin size. Cryogel (Cryogel) is a loose, macroporous gel prepared by polymerization or crosslinking reaction, which attracts more and more attention with a specific macroporous structure, good mechanical properties and stability, and has wide applications in adsorption, immobilization, catalytic carriers and the like. Recently, the structure of polymeric surface polydopamine (pDA) is a very versatile nanoparticle integration platform. Nanoparticles (TiO)2/SiO2Ag/Au, etc.) is attached to the surface of the membrane, and since it has a synergistic effect with the chemical stability and mechanical strength of the uniformly dispersed porous membrane, the durability, mechanical strength and anti-pollution performance of the membrane are all significantly improved and the modified nanoparticles are tightly bonded on the surface of the membrane.
Under the environment of urbanization and population aging, target pollutants such as domestic medical products, endocrine disruptors and the like are continuously discharged to pollute the environment. Tetracycline is again the second largest broad spectrum antibiotic in humans for widespread use in humans and animals. Because the traditional wastewater treatment process cannot remove tetracycline in water, such pollutants are currently present in wastewater discharge from sewage treatment, and surface water, groundwater, deposit on sediments, even in drinking water. In addition, ecotoxicity studies have shown that PPS can affect the growth, reproduction, and behavior of birds, fish, invertebrates, plants, and bacteria. Therefore, the low concentration of the antibiotics in the wastewater can cause the bacteria to generate resistance to the antibiotics, and the existence of TC can cause adverse effects on the environment, thereby becoming an important source of future public health problems. Therefore, the preparation of the synthesized molecular imprinting membrane by combining MST, FPT and MIT has the advantages of low energy consumption, convenient separation, easy operation, easy realization of continuous operation and the likeHas the advantages of simple process and low cost. However, generally conventional polymer particles such as SiO2The most significant problem with blended separation membranes is the large flow resistance. Cryogels have found widespread use in separation processes in recent years due to the interconnection of large pores within cryogels, which have relatively low back pressures. Cryogels are gel matrices formed by the polymerization of frozen solutions of polymer precursors or monomers, and therefore also have high mechanical and chemical resistance, and are attractive materials for adsorptive separation processes.
Disclosure of Invention
The invention aims to overcome the defects, and the molecular imprinting composite membrane with specific recognition and separation capacity on tetracycline is prepared by taking a non-covalent imprinting system as a basis and combining a latex blending technology, a surface molecular imprinting technology and a membrane separation technology.
In order to achieve the above purpose, the specific steps are as follows:
(1) 2-methacrylamide glutamic acid (MAGA) synthesis;
firstly, adding glutamic acid and hydroquinone into dichloromethane, mixing and storing at low temperature; then introducing nitrogen to exhaust oxygen in water, adding triethylamine and methacryloyl chloride, and magnetically stirring at room temperature; after the reaction is finished, adding NaOH, evaporating the water phase in the solution through a rotary evaporator, and putting the residue into a vacuum drying oven to obtain a dried substance, namely MAGA;
(2) preparing poly (HEMA-MAGA) particles;
mixing benzoyl peroxide, polypropylene alcohol, hydroxyethyl methacrylate (HEMA) and the MAGA prepared in the step (1) for copolymerization reaction; after the reaction is finished, filtering, washing, drying in a vacuum oven, and grinding to obtain poly (HEMA-MAGA) particles;
(3) preparing poly (HEMA-MAGA) particle doped PVDF nano composite membranes (PPMs) by using a latex blending method;
mixing poly (HEMA-MAGA) particles prepared in the step (2), polyvinylidene fluoride (PVDF), polyethylene glycol (PEG4000, Mr 4000) and N-methylpyrrolidone (NMP), mechanically stirring at a constant temperature, standing for a period of time, pouring the mixed solution on a glass plate, scraping a membrane by using a glass rod, obliquely inserting the glass plate into water, and obtaining poly (HEMA-MAGA) particle doped PVDF nano composite membranes by a phase transfer method, wherein the poly (HEMA-MAGA) particles are recorded as PPMs;
(4) surface modification of modified PPMs using gamma-methacryloxypropyltrimethoxysilane (KH-570);
cutting the PPMs substrate membrane prepared in the step (3), immersing the cut PPMs substrate membrane in a mixed solution consisting of ethanol and water, adding KH-570 into the mixed solution, adding magnetons into the mixed solution, introducing nitrogen into the mixed solution to discharge oxygen in a reaction vessel, and then sealing the reaction vessel; placing the mixture in a constant-temperature water bath for reaction, soaking and cleaning the mixture by using ethanol and water respectively after the reaction, and drying the mixture to obtain the KH-570 surface modification modified PPMs;
(5) preparing a TC-molecularly imprinted composite membrane by using an ATRP method;
in order to realize the immobilization of the ATRP initiator, the segments of the KH-570 surface modification modified PPMs obtained in the step (4) are soaked in ethanol, and Acrylamide (AM), Tetracycline (TC) and Ethylene Glycol Dimethacrylate (EGDMA) are sequentially added; carrying out ultrasonic treatment to obtain a homogeneous solution; adding Azodiisobutyronitrile (AIBN) as an initiator, introducing nitrogen for a period of time, and sealing; and (2) carrying out immobilization after sealing, wherein the immobilization process is carried out under the protection of nitrogen, and the product obtained after immobilization is cleaned by methanol and acetic acid solution and then dried in a vacuum drying oven to obtain the molecularly imprinted composite membrane initiated by a surface functional monomer prepolymerization system, which is marked as Tc-KH570@ PPMs.
Preferably, the dosage ratio of the dichloromethane, the glutamic acid and the hydroquinone in the step (1) is 100 mL: 5.0 g: 0.2 g; the temperature for the low-temperature preservation is 0 ℃.
Preferably, the amount ratio of the dichloromethane, the triethylamine, the methacryloyl chloride and the NaOH in the step (1) is 100 mL: 13.0 g: 4.0 mL: 1.3 g.
Preferably, the room-temperature magnetic stirring time in the step (1) is 2 hours; the temperature of the vacuum drying is 60 ℃, and the time is 24-48 h.
Preferably, the ratio of the hydroxyethyl methacrylate, the MAGA, the benzoyl oxide and the polyallyl alcohol in the step (2) is 10 mL: 0.5 g: 0.5 g: 0.5 g.
Preferably, the temperature of the copolymerization reaction in the step (2) is 40 ℃, and the reaction time is 24 h.
Preferably, the dosage ratio of the PVDF, the PEG4000, the poly (HEMA-MAGA) and the NMP in the step (3) is 2.4-3.6 g: 0.6 g: 0.5 g; 26.8 g.
Preferably, the temperature of the constant temperature condition in the step (3) is 50 ℃; the mechanical stirring time is 6 hours; the standing time is 12-24 h.
Preferably, the dimensions of the PPMs substrate film cut in step (4) are 7.5mm by 15mm by 10 mm.
Preferably, the ratio of the number of pieces of the base film of the PPMs, ethanol, water and KH-570 in the step (4) is 6: 80mL of: 20mL of: 3 mL.
Preferably, the sealing in the step (4) is performed by using a vacuum plug, a degreasing adhesive tape and a preservative film; the temperature of the constant-temperature water bath is 80 ℃, and the reaction time in the constant-temperature water bath is 16-24 hours.
Preferably, the ratio of the ethanol, the acrylamide, the tetracycline, the ethylene glycol dimethacrylate and the AIBN used in the step (5) is 60 mL: 1.0 mmol: 0.25-0.5 mmol: 4.0 mmol: 30 mg.
Preferably, the nitrogen is introduced in the step (5) for a period of time of 15-20 min.
Preferably, the immobilization process in step (5) is: firstly, reacting for 6 hours at 50 ℃; and then reacting for 18-24 h at 60 ℃.
Preferably, the temperature of the vacuum drying in the step (5) is 35 ℃ and the time is 24 h.
Preparation of non-imprinted nanocomposite membranes (KH570@ PPMs): the preparation method is the same as the steps (1) to (4), the difference is that the non-imprinted nano composite membrane without adding the template molecule TC is prepared for comparison, and the subsequent non-imprinted membranes are marked as KH570@ PPMs for convenience.
The tetracycline in the technical scheme is used 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 described in the above technical scheme is used as an initiator for ATRP reaction.
The Poly (HEMA-MAGA)/PVDF nano blended membrane in the technical scheme has the function of a membrane material.
The method for analyzing and testing the adsorption performance in the technical scheme comprises the following steps:
(i) static adsorption test
Adding certain mass of blotting membrane into corresponding test solution, oscillating in constant temperature water bath, examining influence of initial concentration of different adsorption solutions on the composite membrane, measuring unadsorbed tetracycline molecular concentration with ultraviolet-visible spectrophotometer after adsorption is completed, and calculating adsorption capacity (Q) according to the resulte，mg/g)：
Wherein C is0(mg/L) and Ce(mg/L) is the concentration of tetracycline before and after adsorption, W (g) is the amount of adsorbent, and V (mL) is the volume of test solution.
In the same way, the influence of the adsorption time of different adsorption solutions on the composite membrane is examined, after adsorption is finished, the concentration of unadsorbed tetracycline molecules is measured by an ultraviolet-visible spectrophotometer, and the adsorption capacity (Q) is calculated according to the resultt，mg/g)：
Wherein C is0(mg/L) and Ct(mg/L) is the concentration of tetracycline before and after adsorption, W (g) is the amount of adsorbent, and V (mL) is the volume of test solution.
(iii) Permselectivity test
Two identical glass tanks with ground branch pipes are manufactured, a blotting membrane or a blank membrane is fixed between the two glass tanks by a clamp to form an H-shaped permeability device, the two tanks are ensured not to leak, substrates, namely tetracycline, cephalexin and sulfadiazine aqueous solution, are added into one tank, ethanol solvent is added into the other tank, sampling is carried out at certain intervals, the concentration of the substrate penetrating through the polymer membrane is measured, and the permeability is calculated according to the concentration.
The invention has the beneficial effects that:
(1) the invention successfully constructs a TC-imprinted nano composite membrane (Tc-KH570@ PPMs) by using poly (HEMA-MAGA) ice glue particles doped with PVDF as a substrate, using a silane coupling agent to establish a secondary reaction platform, using TC as a template and based on a molecular imprinting technology.
(2) The tetracycline molecular imprinting film obtained by the invention has good thermal stability, fast adsorption kinetics property and obvious tetracycline molecular recognition performance; the results of the selective adsorption and permeation experiments show that the prepared Tc-KH570@ PPMs are at a lower working concentration (100mg L)-1) I.e., exhibit high adsorption selectivity (and permselectivity) to TC.
(4) According to the invention, imprinting polymerization is carried out on the surface of the multi-layer nano composite membrane material modified by the functional monomer, so that the problem that a part of template molecules cannot be eluted due to too deep embedding is avoided, the obtained imprinting membrane is high temperature resistant, the recognition points are not easy to damage, and the nonspecific adsorption is reduced by 70%.
(5) The invention adopts a non-covalent imprinting principle and a membrane separation principle combined with a modified membrane prepolymerization system to synthesize the tetracycline molecular imprinting composite membrane on the surface of the multilayer nano composite membrane.
Drawings
FIG. 1 (a) shows the synthesis of Poly (HEMA-MAGA) prepared in example 1; (b) a schematic diagram of the TC synthesis for selective recognition of the Tc-KH570@ PPMs prepared in example 1 was isolated.
FIG. 2 is a scanning electron micrograph of PVDF membrane starting materials (a-b), PPMs (c-d), KH570@ PPMs (e-f) and Tc-KH570@ PPMs (g-h), respectively.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples.
Example 1:
(1) 2-methacrylamide glutamic acid (MAGA) synthesis;
firstly, adding 5.0g of glutamic acid and 0.2g of hydroquinone into 100mL of dichloromethane, and storing at 0 ℃; then adding nitrogen, adding 13.0g of triethylamine and 4.0mL of methacryloyl chloride, and magnetically stirring for 2 hours at room temperature; after the reaction, 1.3g of NaOH was added, and the aqueous phase in the solution was evaporated by a rotary evaporator; putting the residue into a vacuum drying oven at 60 ℃ for 24 hours; obtaining a dried substance, namely MAGA; 10g of MAGA can be dissolved in 40mL of ethanol and stored for later use;
(2) preparing poly (HEMA-MAGA) particles;
0.5g of benzoyl peroxide, 0.5g of polypropylene glycol, 10mL of hydroxyethyl methacrylate (HEMA) and 0.5g of MAGA are mixed for copolymerization reaction, the temperature of the copolymerization reaction is 40 ℃, and the reaction time is 24 hours; after the reaction is finished, filtering, washing, drying in a vacuum oven, and grinding to obtain poly (HEMA-MAGA) particles;
(3) preparation of poly (HEMA-MAGA) particle doped PVDF nano composite membrane by latex blending method
3.6g PVDF, 0.6g PEG4000, 26.8g NMP, 0.5g poly (HEMA-MAGA) were put in a 100mL round-bottomed flask, mechanically stirred at 50 ℃ for 6 hours and allowed to stand at room temperature for 12 hours to remove air bubbles. Then, the resulting solution was poured onto a glass plate, and the film was scraped with a glass rod. Then the glass plate is rapidly inserted into water in an inclined way, and the PPMs are finally obtained by a phase transfer method;
(4) preparation of poly (HEMA-MAGA)/PVDF nano composite membrane modified by KH-570 surface modification
Cutting the prepared PPMs substrate film into long strips (7.5mm multiplied by 15mm multiplied by 10mm), immersing 6 cut PPMs substrate films into a mixed solution consisting of 80mL of ethanol and 20mL of water, adding 3mL of KH570, adding magnetons, introducing nitrogen, discharging oxygen in a reaction container, and then sealing by using a vacuum plug, a degreasing adhesive tape and a preservative film; reacting in 80 ℃ constant temperature water bath for 16h, soaking and cleaning the mixture with ethanol and water respectively, and drying to obtain KH570@ PPMs;
(5) preparation of TC-molecularly imprinted composite membrane by ATRP (atom transfer radical polymerization) method
To achieve immobilization of the ATRP initiator, fragments of KH570@ PPMs were soaked in 60mL of ethanol, 1.0mmol of AM, 0.1mmol of TC, and 4.0mmol of EGDMA were added. Sonication results in a homogeneous solution. 30mg of AIBN were added as initiator. And continuously introducing nitrogen for 15min, and sealing with a vacuum glass plug, a degreasing adhesive tape and a preservative film. The immobilization process comprises the steps of reacting for 6 hours at 50 ℃, then reacting for 18 hours at 60 ℃, performing the whole experiment process under the protection of nitrogen, thoroughly cleaning the obtained product with methanol and acetic acid solution, and then performing vacuum drying for 24 hours at 35 ℃ to obtain the molecular imprinting composite membrane initiated by the surface functional monomer prepolymerization system, wherein the molecular imprinting composite membrane is marked as Tc-KH570@ PPMs.
(6) Preparation of non-imprinted nanocomposite membranes (KH570@ PPMs): the preparation method is the same as the steps (1) to (4), the difference is that the non-imprinted nano composite membrane without adding the template molecule TC is prepared for comparison, and the subsequent non-imprinted membranes are all KH570@ PPMs for convenience.
Static adsorption test:
weighing 9 parts of blotting membrane and 9 parts of non-blotting membrane respectively, placing the blotting membrane and the non-blotting membrane into 18 test tubes respectively, adding 10mL of tetracycline aqueous solution with the concentration of 5,10,15,20,25,30,60,90 and 125mg/L respectively, oscillating the tetracycline aqueous solution in thermostatic waterbath for 3 hours at the temperature of 25 ℃, measuring the concentration of non-adsorbed tetracycline molecules by using UV-vis after adsorption is finished, and calculating the adsorption capacity according to the result.
The result shows that the highest saturated adsorption capacity of the tetracycline molecular imprinted membrane is 37.5mg/g, which is obviously higher than that of a non-imprinted membrane by 11.32 mg/g.
Similarly, adsorption tests were performed in 100mg/L tetracycline aqueous solution for various periods of time (5, 15, 30, 45, 60,90, 120, 180, 240 min). The concentration of non-adsorbed tetracycline molecules was determined by UV-vis and the adsorption capacity was calculated from the results.
The result shows that the highest saturated adsorption capacity of the tetracycline molecular imprinted membrane is 38.23mg/g, which is obviously higher than that of the non-imprinted membrane by 11.42 mg/g.
Selective permeability test:
two identical glass tanks with ground branch pipes are manufactured, the blotting membrane is fixed between the two glass tanks by a clamp to form an H-shaped permeability device, the two tanks are ensured not to leak, aqueous solution of tetracycline, cefalexin and sulfamethazine with the substrate concentration of 100mg/L is respectively added into one tank, aqueous solvent is added into the other tank, the sampling time is respectively 5, 15, 30, 45, 60,90, 120, 180 and 240min, the concentration of the substrate penetrating through the polymer membrane is measured, and the permeability is calculated according to the concentration.
The results show that at an initial concentration of 100mg/L of tetracycline, cephalexin and sulfamethazine in water, the sampling time is 5, 15, 30, 45, 60,90, 120, 180 and 240min, the concentration of tetracycline in the blank sample pool is 4.32, 5.22, 5.65, 6.52, 6.95, 7.22, 7.90, 8.32 and 8.85mg/L, the concentration of cephalexin is 7.75, 15.62, 24.53, 29.42, 30.43, 31.24, 31.58, 32.45 and 33.54mg/L, and the concentration of sulfamethazine is 7.52, 14.56, 25.43, 28.64, 30.54, 31.33, 31.85, 32.34 and 32.52 mg/L.
The experimental result shows that the tetracycline molecular imprinting film has specific recognition on tetracycline and the performance of promoting the permeation of non-tetracycline molecules (cefalexin and sulfamethazine).
Example 2:
(1) 2-methacrylamide glutamic acid (MAGA) synthesis;
first, 5.0g of glutamic acid and 0.2g of hydroquinone were added to 100mL of methylene chloride, and the mixture was stored at 0 ℃. Nitrogen was then added, 13.0g triethylamine and 4.0mL methacryloyl chloride were added, and the mixture was magnetically stirred at room temperature for 2 h. After the reaction was completed, 1.3g of NaOH was added, and the aqueous phase in the solution was evaporated by a rotary evaporator. The residue was placed in a vacuum oven at 60 ℃ for 36 hours. 10g of MAGA was then dissolved in 40mL of ethanol and stored for later use;
(2) preparing poly (HEMA-MAGA) particles;
0.5g of benzoyl peroxide, 0.5g of polypropylene glycol, 10mL of hydroxyethyl methacrylate (HEMA) and 0.5g of MAGA are mixed for copolymerization reaction, the temperature of the copolymerization reaction is 40 ℃, and the reaction time is 24 hours; after the reaction is finished, filtering, washing, drying in a vacuum oven, and grinding to obtain poly (HEMA-MAGA) particles;
(3) preparation of poly (HEMA-MAGA) particle doped PVDF nano composite membrane by latex blending method
2.4g PVDF, 0.6g PEG4000, 26.8g NMP, 0.5g poly (HEMA-MAGA) were added to a 100mL round bottom flask, mechanically stirred at 50 ℃ for 6h, and allowed to stand at room temperature for 24h to remove air bubbles; then, the resulting solution was poured onto a glass plate, and the film was scraped with a glass rod. Then the glass plate is rapidly inserted into water in an inclined way, and the PPMs are finally obtained by a phase transfer method;
(4) preparation of poly (HEMA-MAGA)/PVDF nano composite membrane modified by KH-570 surface modification
Cutting the prepared PPMs substrate film into long strips (7.5mm multiplied by 15mm multiplied by 10mm), immersing 6 cut PPMs substrate films into a mixed solution consisting of 80mL of ethanol and 20mL of water, adding 3mL of KH570, adding magnetons, introducing nitrogen, discharging oxygen in a reaction container, and then sealing by using a vacuum plug, a degreasing adhesive tape and a preservative film; reacting in 80 ℃ constant temperature water bath for 16h, soaking and cleaning the mixture with ethanol and water respectively, and drying to obtain KH570@ PPMs;
(5) preparing a TC-molecularly imprinted composite membrane by using an ATRP method;
to achieve immobilization of the ATRP initiator, fragments of KH570@ PPMs were soaked in 60mL of ethanol, and 1.0mmol of Acrylamide (AM), 0.5mmol of Tetracycline (TC), and 4.0mmol of EGDMA were added. Sonication results in a homogeneous solution. 30mg of AIBN were added as initiator. And continuously introducing nitrogen for 15min, and sealing with a vacuum glass plug, a degreasing adhesive tape and a preservative film. The immobilization process comprises the steps of reacting for 6 hours at 50 ℃, then reacting for 24 hours at 60 ℃, performing the whole experiment process under the protection of nitrogen, thoroughly cleaning the obtained product with methanol and acetic acid solution, and then performing vacuum drying for 24 hours at 35 ℃ to obtain the molecular imprinting composite membrane initiated by the surface functional monomer prepolymerization system, wherein the molecular imprinting composite membrane is marked as Tc-KH570@ PPMs.
(6) Preparation of non-imprinted nanocomposite membranes (KH570@ PPMs)
The preparation method is the same as the steps (1) to (4), the difference is that the non-imprinted nano composite membrane without adding the template molecule TC is prepared for comparison, and the subsequent non-imprinted membranes are all KH570@ PPMs for convenience.
Static adsorption test;
weighing 9 parts of blotting membrane and 9 parts of non-blotting membrane respectively, placing the blotting membrane and the non-blotting membrane into 18 test tubes respectively, adding 10mL of tetracycline aqueous solution with the concentration of 5,10,15,20,25,30,60,90 and 125mg/L respectively, oscillating the tetracycline aqueous solution in thermostatic waterbath for 3 hours at the temperature of 25 ℃, measuring the concentration of non-adsorbed tetracycline molecules by using UV-vis after adsorption is finished, and calculating the adsorption capacity according to the result.
The result shows that the highest saturated adsorption capacity of the tetracycline molecular imprinted membrane is 35.2mg/g, which is obviously higher than that of a non-imprinted membrane by 9.32 mg/g.
Similarly, adsorption tests were performed in 100mg/L tetracycline aqueous solution for various periods of time (5, 15, 30, 45, 60,90, 120, 180, 240 min). The concentration of non-adsorbed tetracycline molecules was determined by UV-vis and the adsorption capacity was calculated from the results.
The result shows that the highest saturated adsorption capacity of the tetracycline molecular imprinted membrane is 37.23mg/g, which is obviously higher than that of a non-imprinted membrane, namely 9.92 mg/g.
A selective permeability test;
two identical glass tanks with ground branch pipes are manufactured, the blotting membrane is fixed between the two glass tanks by a clamp to form an H-shaped permeability device, the two tanks are ensured not to leak, aqueous solution of tetracycline, cefalexin and sulfamethazine with the substrate concentration of 100mg/L is respectively added into one tank, aqueous solvent is added into the other tank, the sampling time is respectively 5, 15, 30, 45, 60,90, 120, 180 and 240min, the concentration of the substrate penetrating through the polymer membrane is measured, and the permeability is calculated according to the concentration.
The results show that at an initial concentration of 100mg/L of tetracycline, cephalexin and sulfamethazine in water, the sampling time is 5, 15, 30, 45, 60,90, 120, 180 and 240min, the concentration of tetracycline in the blank sample pool is 5.32, 6.23, 6.65, 7.55, 7.85, 8.12, 9.90, 10.42 and 10.55mg/L, the concentration of cephalexin is 7.85, 14.62, 23.53, 26.45, 29.55, 30.25, 30.48, 30.69 and 30.88mg/L, and the concentration of sulfamethazine is 7.42, 14.46, 23.33, 25.65, 28.64, 29.36, 29.88, 30.33 and 30.56 mg/L.
The experimental result shows that the tetracycline molecular imprinting film has specific recognition on tetracycline and the performance of promoting the permeation of non-tetracycline molecules (cefalexin and sulfamethazine).
FIG. 2 is a scanning electron micrograph of PVDF membrane starting materials (a-b), PPMs (c-d), KH570@ PPMs (e-f) and Tc-KH570@ PPMs (g-h), respectively; as can be seen from FIG. 2, compared with other membranes, after the imprinted membrane is synthesized, the surface of the base membrane of the PPMs is rough and irregular, and has a thin coral-shaped imprinted layer, and the surface imprinting is successful by combining the excellent selectivity.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (10)
1. A preparation method of a molecularly imprinted composite membrane initiated by a surface functional monomer prepolymerization system is characterized by comprising the following specific steps:
(1) firstly, adding glutamic acid and hydroquinone into dichloromethane, mixing and storing at low temperature; then introducing nitrogen to exhaust oxygen in water, adding triethylamine and methacryloyl chloride, and magnetically stirring at room temperature; after the reaction is finished, adding NaOH, evaporating the water phase in the solution through a rotary evaporator, and putting the residue into a vacuum drying oven to obtain 2-methacrylamide glutamic acid, namely MAGA;
(2) mixing benzoyl peroxide, polyacrylic alcohol and hydroxyethyl methacrylate with the MAGA prepared in the step (1) for copolymerization reaction; after the reaction is finished, filtering, washing, drying in a vacuum oven, and grinding to obtain poly (HEMA-MAGA) particles;
(3) mixing the poly (HEMA-MAGA) particles prepared in the step (2), polyvinylidene fluoride, polyethylene glycol and N-methyl pyrrolidone, mechanically stirring under a constant temperature condition, standing for a period of time, pouring the mixed solution on a glass plate, scraping a film by using a glass rod, obliquely inserting the glass plate into water, and obtaining poly (HEMA-MAGA) particle doped PVDF nano composite films by a phase transfer method, wherein the poly (HEMA-MAGA) particles are marked as PPMs;
(4) cutting the PPMs substrate membrane prepared in the step (3), immersing the cut PPMs substrate membrane in a mixed solution consisting of ethanol and water, adding KH-570 into the mixed solution, adding magnetons into the mixed solution, introducing nitrogen into the mixed solution to discharge oxygen in a reaction vessel, and then sealing the reaction vessel; placing the mixture in a constant-temperature water bath for reaction, soaking and cleaning the mixture by using ethanol and water respectively after the reaction, and drying the mixture to obtain the KH-570 surface modification modified PPMs;
(5) soaking the segments of the KH-570 surface-modified PPMs obtained in the step (4) in ethanol, and sequentially adding acrylamide, tetracycline and ethylene glycol dimethacrylate; carrying out ultrasonic treatment to obtain a homogeneous solution; adding Azodiisobutyronitrile (AIBN) as an initiator, introducing nitrogen for a period of time, and sealing; and (2) carrying out immobilization after sealing, wherein the immobilization process is carried out under the protection of nitrogen, and the product obtained after immobilization is cleaned by methanol and acetic acid solution and then dried in a vacuum drying oven to obtain the molecularly imprinted composite membrane initiated by a surface functional monomer prepolymerization system, which is marked as Tc-KH570@ PPMs.
2. The method for preparing the molecularly imprinted composite membrane initiated by the surface functional monomer prepolymerization system according to claim 1, wherein the dosage ratio of the dichloromethane, the glutamic acid and the hydroquinone in step (1) is 100 mL: 5.0 g: 0.2 g; the temperature for the low-temperature preservation is 0 ℃.
3. The method for preparing the molecularly imprinted composite membrane initiated by the surface functional monomer prepolymerization system according to claim 1, wherein the amount ratio of the dichloromethane, the triethylamine, the methacryloyl chloride and the NaOH in step (1) is 100 mL: 13.0 g: 4.0 mL: 1.3 g; the room-temperature magnetic stirring time is 2 hours; the temperature of the vacuum drying is 60 ℃, and the time is 24-48 h.
4. The method for preparing the molecularly imprinted composite membrane initiated by the surface functional monomer prepolymerization system according to claim 1, wherein the amount ratio of the hydroxyethyl methacrylate, the MAGA, the benzoyl oxide and the polypropylene glycol in the step (2) is 10 mL: 0.5 g: 0.5 g: 0.5 g; the temperature of the copolymerization reaction is 40 ℃, and the reaction time is 24 h.
5. The preparation method of the surface functional monomer prepolymerization system-initiated molecularly imprinted composite membrane according to claim 1, wherein the dosage ratio of the PVDF, the PEG4000, the poly (HEMA-MAGA) and the NMP in the step (3) is 2.4-3.6 g: 0.6 g: 0.5 g; 26.8 g; the temperature of the constant temperature condition is 50 ℃; the mechanical stirring time is 6 hours; the standing time is 12-24 h.
6. The method for preparing the surface functional monomer prepolymerization system initiated molecularly imprinted composite membrane according to claim 1, wherein the cutting size of the base membrane of the PPMs in step (4) is 7.5mm x 15mm x 10 mm.
7. The method for preparing the surface functional monomer prepolymerization system initiated molecularly imprinted composite membrane according to claim 1, wherein the amount ratio of the number of the PPMs substrate membrane, ethanol, water and KH-570 in step (4) is 6: 80mL of: 20mL of: 3 mL; the sealing is performed by using a vacuum plug, a degreasing adhesive tape and a preservative film; the temperature of the constant-temperature water bath is 80 ℃, and the reaction time in the constant-temperature water bath is 16-24 hours.
8. The method for preparing the molecularly imprinted composite membrane initiated by the surface functional monomer prepolymerization system according to claim 1, wherein the dosage ratio of ethanol, acrylamide, tetracycline, ethylene glycol dimethacrylate and AIBN in step (5) is 60 mL: 1.0 mmol: 0.25-0.5 mmol: 4.0 mmol: 30 mg.
9. The preparation method of the molecularly imprinted composite membrane initiated by the surface functional monomer prepolymerization system according to claim 1, wherein in the step (5), nitrogen is introduced for a period of 15-20 min; the immobilization process comprises the following steps: firstly, reacting for 6 hours at 50 ℃; then reacting for 18-24 h at 60 ℃; the temperature of the vacuum drying is 35 ℃, and the time is 24 h.
10. The molecularly imprinted composite membrane prepared by the method according to any one of claims 1 to 9 is applied to selective adsorption of tetracycline.
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