CN111849015B - Preparation method and application of beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane - Google Patents
Preparation method and application of beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane Download PDFInfo
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Abstract
The invention belongs to the technical field of functional material preparation, and discloses a preparation method and application of a beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane; the preparation steps are as follows: preparing a beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane by using polyvinylidene fluoride as a membrane preparation material, beta-cyclodextrin and polydopamine as a synergistic anti-fouling modification material, ciprofloxacin as a template molecule, trifluoromethyl acrylic acid as a functional monomer, pentaerythritol tetrakis (3-mercaptopropionate) as a cross-linking agent and dipentaerythritol penta-/hexan-acrylic acid as an auxiliary cross-linking agent in combination with a photoinitiated mercapto-alkene click chemical polymerization method; the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane prepared by the invention effectively solves the problem that the traditional beta-cyclodextrin-based molecularly imprinted membrane can improve the anti-fouling performance and limit the selectivity; in addition, the ciprofloxacin has good specific recognition and separation capacity.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method and application of a beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane.
Background
The molecularly imprinted membrane is a material with high-efficiency molecular selectivity developed by combining a membrane separation technology and a molecularly imprinted technology in recent years. The method takes a porous filter membrane as a carrier, combines a molecular selective recognition site constructed on the surface and in a pore passage by a molecular imprinting technology, and utilizes the characteristic that the molecular selective recognition site allows one part of substances to pass and prevents the other part of substances from passing to realize the efficient separation, enrichment or purification of target molecules in a solution by selective recognition and adsorption of specific molecules. Therefore, the method has huge application prospects in the fields of water treatment, resource extraction, biochemical separation, efficient selective detection and the like.
Most of the existing molecularly imprinted membranes are mainly organic polymer membranes, and although the existing molecularly imprinted membranes have good flexibility and plasticity, the existing molecularly imprinted membranes inevitably have good affinity with proteins. For practical application scenarios (such as natural water), the complex components are very likely to cause the contamination of the molecularly imprinted membrane. In the membrane fouling, almost all inorganic and organic pollutants can be removed by pretreatment, and only for microorganisms, even if the removal rate reaches 99.99%, a large amount of microbial metabolites (i.e., proteins) remain. Therefore, the improvement of the protein resistance of the molecularly imprinted membrane is an important means for improving the anti-fouling performance of the membrane and prolonging the service life of the membrane.
The beta-cyclodextrin is a cyclic molecule containing a large number of hydroxyl groups, and can be complexed with partial polymer chain molecules to form a supermolecule enveloping system, so that hydrophilic groups are exposed at the periphery, the overall hydrophilicity of the membrane is improved, and the overall stain resistance of the membrane material is further improved. In addition, hydroxyl in the beta-cyclodextrin can easily form intermolecular forces such as hydrogen bonds and the like with polymer membrane components, so that polymer chains can form a macromolecular network more easily. Therefore, for the organic polymer molecularly imprinted membrane, the beta-cyclodextrin is an ideal anti-fouling modification material. However, from the work reported in the prior art, the traditional modification strategy for improving the stain resistance of the molecularly imprinted membrane based on beta-cyclodextrin has a poor effect, and due to the defects of step design, the selectivity of the obtained molecularly imprinted membrane is often limited to a certain extent, which is not favorable for the deep development and application of materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to overcome the technical defects in the prior art, solve the problem that the traditional molecular imprinting membrane pollution resistance is improved and the selectivity is limited based on beta-cyclodextrin, and avoid the influence of pollution resistance modification on the selectivity of the traditional molecular imprinting membrane while the pollution resistance of the traditional molecular imprinting membrane is improved.
The present invention achieves the above-described object by the following technical means.
A preparation method of a beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane comprises the following steps:
s1, preparing a beta-cyclodextrin/polydopamine modified basement membrane: uniformly mixing polyvinylidene fluoride powder and beta-cyclodextrin powder, adding the mixture into dimethylacetamide, heating and stirring the mixture for a period of time to obtain a casting solution, cooling the casting solution, defoaming the casting solution under a vacuum condition, leveling the defoamed casting solution on a flat plate to form a liquid film with a certain thickness, immediately placing the flat plate in a dopamine aqueous solution for phase conversion for a period of time, transferring the cured film into a tris (hydroxymethyl) aminomethane solution, soaking for a period of time, washing with water, and drying to obtain a beta-cyclodextrin/polydopamine modified basement membrane;
s2, preparing a vinyl modified film: preparing a mixed solution of ethanol and water, adding the beta-cyclodextrin/polydopamine modified basement membrane prepared by S1, adding a certain amount of 3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture, cleaning with ethanol, and drying to obtain a vinyl modified membrane;
s3, preparing the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane: dissolving ciprofloxacin and trifluoromethyl acrylic acid in acetonitrile, stirring for a period of time to obtain a prepolymerization system, adding dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally immersing the vinyl modified membrane prepared by S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, carrying out imprinting polymerization reaction under ultraviolet irradiation, washing with alcohol, washing with water, eluting template molecules by using an eluent, and drying to obtain the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane.
Preferably, in step S1, the usage ratio of the polyvinylidene fluoride powder, the beta-cyclodextrin powder and the dimethylacetamide is 19 g: 0.2-2 g: 100 mL.
Preferably, in step S1, the heating time is 24h, and the heating temperature is 80 ℃.
Preferably, in step S1, the defoaming treatment time is 30 min.
Preferably, in step S1, the liquid film has a thickness of 50 to 400 μm.
Preferably, in step S1, the phase inversion time is 1 to 36 hours.
Preferably, in step S1, the tris (hydroxymethyl) aminomethane solution has a pH of 8.5, and the soaking time is 1 to 12 hours.
Preferably, in step S2, the volume ratio of ethanol, water and 3- (methacryloyloxy) propyltrimethoxysilane in the mixed solution is 80: 20: 3.
preferably, in step S2, the heating reflux temperature is 80 ℃; the heating reflux time is 16 h.
Preferably, in step S3, the ratio of the ciprofloxacin, the trifluoromethyl acrylic acid and the acetonitrile is 0.1 mmol: 0.2-0.8 mmol: 60 mL.
Preferably, in step S3, the prepolymerization time is 1-6 h.
Preferably, in step S3, the ratio of the amounts of the trifluoromethyl acrylic acid, the dipentaerythritol penta-/hexa-acrylic acid, the tetra (3-mercaptopropionic acid) pentaerythritol ester and the 2, 2-dimethoxy-2-phenylacetophenone is 0.6 mmol: 0.3-1.2 mL: 0.1-0.4 mL: 20 mg.
Preferably, in step S3, the wavelength of the ultraviolet light is 365 nm; the time of the imprinting polymerization reaction is 1-8 h.
Preferably, in step S3, the sealing method is to seal with a vacuum plug, a degreasing tape and a preservative film; the eluent is a mixed solution of methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is 95: 5; the elution mode is that the shaking is carried out at room temperature, the eluent is changed every 3 hours, and the elution process lasts for 3 days.
The polyvinylidene fluoride powder in the technical scheme is used as a film making material.
The beta-cyclodextrin powder in the technical scheme has the function of an anti-fouling modification material.
The dimethylacetamide in the technical scheme is used as a casting solution solvent.
The dopamine in the technical scheme has the function of being a synergistic anti-fouling modified material.
The tris (hydroxymethyl) aminomethane in the technical scheme is used as a dopamine polymerization buffer solution.
The 3- (methacryloyloxy) propyl trimethoxysilane in the technical scheme is used as a film surface vinyl modification reagent.
The ethanol in the technical scheme is used as a solvent.
The ciprofloxacin in the technical scheme is used as a template molecule.
The trifluoromethyl acrylic acid in the technical scheme is used as a functional monomer.
The acetonitrile in the technical scheme is used as a solvent.
The pentaerythritol tetrakis (3-mercaptopropionate) described in the above technical scheme acts as a cross-linking agent.
The dipentaerythritol penta-/hexa-acrylic acid in the technical scheme is used as an auxiliary crosslinking agent.
The 2, 2-dimethoxy-2-phenylacetophenone in the technical scheme has the function of an initiator.
The invention also comprises the application of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane in selective adsorption and separation of ciprofloxacin in the ciprofloxacin-containing mixed solution, and particularly in selective adsorption and separation of ciprofloxacin in the mixed solution of ciprofloxacin, enrofloxacin, norfloxacin and ofloxacin.
And (3) testing the material performance:
(1) anti-fouling experiment
The anti-fouling performance of different prepared membrane materials is evaluated by taking bovine serum albumin as a representative protein pollution source, and the smaller the adsorption quantity of the membrane materials to the bovine serum albumin is, the stronger the anti-fouling performance of the membrane materials is. Weighing 4 parts of beta-cyclodextrin/polydopamine synergistic anti-fouling molecular imprinting organic composite membrane, respectively placing the membrane into test tubes, respectively adding 10mL of bovine serum albumin solutions with the concentrations of 5, 10, 15 and 20mg/L, standing and adsorbing the membrane for 24 hours at room temperature, measuring the concentration of the bovine serum albumin which is not adsorbed in the solution at 280nm by using an ultraviolet-visible spectrophotometer after adsorption is finished, and calculating the adsorption capacity (Q) according to the resultBSA,mg/g):
QBSA=(CB0-CBe)×VB/m (1)
Wherein C isB0(mg/L) and CBe(mg/L) is the concentration of bovine serum albumin in the solution before and after adsorption, VB(mL) is the volume of bovine serum albumin solution, and m (g) is the mass of the added beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane.
(2) Permselectivity experiments
The prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane is arranged in the center of an H-shaped permeation device, so that an H-shaped glass tube is divided into two identical cavities by the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane, 100mL of a mixed solution of ciprofloxacin, enrofloxacin, norfloxacin and ofloxacin with the concentration of 100mg/L is added into one cavity, and 100mL of a pure solvent is added into the other cavity, at 5, 10, 15, 30, 60, 90, 120, 180 and 360min, 2mL of the solution (permeate) was taken from the pure solvent chamber and immediately backfilled with 2mL of pure solvent to ensure that there was no height difference between the two chambers, the concentrations of ciprofloxacin, enrofloxacin, norfloxacin and ofloxacin in the sampled penetrating fluid are measured by a high performance liquid chromatograph.
The invention has the advantages and technical effects that:
(1) compared with the existing ciprofloxacin selective separation material, the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane prepared by the method has the advantages that the material is easy to recover, the phase change is not needed in the separation process, no additional reagent is needed, no secondary pollution is caused to the separated substances, the composite membrane can be applied to the continuous separation process, and the like, and the defects that the existing ciprofloxacin selective separation material is difficult to recover, easy to generate secondary pollution, high in energy consumption and the like are effectively overcome; in addition, the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane prepared by the method has high selectivity on ciprofloxacin, and ciprofloxacin molecules can be effectively separated from ciprofloxacin structural analogues such as enrofloxacin, norfloxacin, ofloxacin and the like.
(2) According to the invention, polydopamine is introduced on the basis of a traditional beta-cyclodextrin anti-fouling modification strategy, the aim of synergistically improving the anti-fouling performance of the molecularly imprinted membrane is realized, the secondary reaction platform effect of the polydopamine is utilized to stably load the molecularly imprinted polymer on the surface of the membrane, and the anti-fouling performance is improved while the selectivity of the obtained molecularly imprinted membrane is maximally ensured. In addition, the polydopamine is introduced in a mode of 'phase conversion in a dopamine solution and in-situ self-polymerization in a buffer solution', so that the distribution of the polydopamine has a certain depth and is limited on the surface of the membrane, the structure effectively improves the overall anti-pollution performance of the obtained membrane material on one hand, and simultaneously effectively avoids the phenomenon of uneven dispersion of the molecularly imprinted polymer caused by the agglomeration of the polydopamine on the surface of the membrane.
Drawings
In fig. 1, a and b are respectively a bovine serum albumin adsorption curve and a permeate concentration curve of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane in example 1.
In fig. 2, a and b are a bovine serum albumin adsorption curve and a permeate concentration curve of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane in example 2, respectively.
In fig. 3, a and b are a bovine serum albumin adsorption curve and a permeate concentration curve of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane in example 3, respectively.
Detailed Description
The invention is further described with reference to the drawings and the detailed description.
Example 1:
s1, preparing a beta-cyclodextrin/polydopamine modified basement membrane: uniformly mixing 19g of polyvinylidene fluoride powder and 0.2g of beta-cyclodextrin powder, adding the mixture into 100mL of dimethylacetamide, heating and stirring the mixture at 80 ℃ for 24h to form a casting solution, cooling, defoaming the casting solution under a vacuum condition for 30min, leveling the defoamed casting solution on a flat plate to form a liquid film with the thickness of 50 microns, immediately placing the flat plate in a dopamine aqueous solution for phase conversion for 1h, transferring the cured film into a tris (hydroxymethyl) aminomethane solution for soaking for 1h, and washing and drying by water to obtain a beta-cyclodextrin/polydopamine modified basement membrane;
s2, preparing a vinyl modified film: preparing a mixed solution of 80mL of ethanol and 20mL of water, then adding the beta-cyclodextrin/polydopamine modified basement membrane prepared by S1, then adding 3mL of 3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture for 16h, and then washing and drying the mixture by ethanol to obtain a vinyl modified membrane;
s3, preparing the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane: dissolving 0.1mmol of ciprofloxacin and 0.2mmol of trifluoromethyl acrylic acid in 60mL of acetonitrile, stirring for 1h to obtain a prepolymerization system, adding 0.3mL of dipentaerythritol penta-/hexa-acrylic acid, 0.1mL of tetra (3-mercaptopropionic acid) pentaerythritol ester and 20mg of 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally immersing the vinyl modified membrane prepared by S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, carrying out imprinting polymerization reaction for 1h under 365nm ultraviolet light irradiation, washing with alcohol and water, eluting a template molecule by using an eluent, and drying to obtain the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane.
In fig. 1, (a) is a graph showing the adsorption capacity of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on bovine serum albumin with different concentrations. The results show that the adsorption capacity of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on bovine serum albumin in bovine serum albumin solutions with the concentrations of 5, 10, 15 and 20mg/L is lower than that of a molecularly imprinted membrane without polydopamine. The experimental result shows that the anti-fouling performance of the obtained molecularly imprinted membrane is effectively improved by the beta-cyclodextrin/polydopamine synergistic anti-fouling strategy.
In fig. 1, (b) is a concentration curve of a permeate obtained by the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane in a selective permeation experiment, a mixed solution with a concentration of 100mg/L is used as a stock solution, the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane is used as a permeation medium, and the concentrations of ciprofloxacin, enrofloxacin, norfloxacin and ofloxacin in the permeate at 5, 10, 15, 30, 60, 90, 120, 180 and 360min are shown in table 1. The experimental results show that the permeation amount of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on ciprofloxacin is lower than that of enrofloxacin, norfloxacin and ofloxacin, namely the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane has selective permeation and separation effects on ciprofloxacin.
TABLE 1 Selective permeation data of beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane
Example 2:
s1, preparing a beta-cyclodextrin/polydopamine modified basement membrane: uniformly mixing 19g of polyvinylidene fluoride powder and 1g of beta-cyclodextrin powder, adding the mixture into 100mL of dimethylacetamide, heating and stirring the mixture at 80 ℃ for 24h to form a casting solution, cooling, defoaming the casting solution for 30min under a vacuum condition, leveling the defoamed casting solution on a flat plate to form a liquid film with the thickness of 100 microns, immediately placing the flat plate in a dopamine aqueous solution for phase conversion for 24h, transferring the cured film into a tris (hydroxymethyl) aminomethane solution for soaking for 6h, and washing and drying by water to obtain a beta-cyclodextrin/polydopamine modified basement membrane;
s2, preparing a vinyl modified film: preparing a mixed solution of 80mL of ethanol and 20mL of water, then adding the beta-cyclodextrin/polydopamine modified basement membrane prepared by S1, then adding 3mL of 3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture for 16h, and then washing and drying the mixture by ethanol to obtain a vinyl modified membrane;
s3, preparing the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane: dissolving 0.1mmol of ciprofloxacin and 0.6mmol of trifluoromethyl acrylic acid in 60mL of acetonitrile, stirring for 2 hours to obtain a prepolymerization system, adding 0.6mL of dipentaerythritol penta-/hexa-acrylic acid, 0.2mL of tetra (3-mercaptopropionic acid) pentaerythritol ester and 20mg of 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally immersing the vinyl modified membrane prepared by S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, carrying out imprinting polymerization reaction for 2 hours under 365nm ultraviolet light irradiation, washing with alcohol and water, eluting a template molecule by using an eluent, and drying to obtain the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane.
Fig. 2(a) shows the adsorption capacity of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on bovine serum albumin with different concentrations. The results show that the adsorption capacity of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on bovine serum albumin in bovine serum albumin solutions with the concentrations of 5, 10, 15 and 20mg/L is lower than that of a molecularly imprinted membrane without polydopamine. The experimental result shows that the anti-fouling performance of the obtained molecularly imprinted membrane is effectively improved by the beta-cyclodextrin/polydopamine synergistic anti-fouling strategy.
Fig. 2(b) is a concentration curve of a permeate obtained by the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane in a selective permeation experiment, a mixed solution with a concentration of 100mg/L is used as a stock solution, the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane is used as a permeation medium, and the concentrations of ciprofloxacin, enrofloxacin, norfloxacin and ofloxacin in the permeate at 5, 10, 15, 30, 60, 90, 120, 180 and 360min are shown in table 2. The experimental results show that the permeation amount of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on ciprofloxacin is lower than that of enrofloxacin, norfloxacin and ofloxacin, namely the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane has selective permeation and separation effects on ciprofloxacin.
TABLE 2 Selective permeation data of beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane
Example 3:
s1, preparing a beta-cyclodextrin/polydopamine modified basement membrane: uniformly mixing 19g of polyvinylidene fluoride powder and 2g of beta-cyclodextrin powder, adding the mixture into 100mL of dimethylacetamide, heating and stirring the mixture at 80 ℃ for 24h to form a casting solution, cooling, defoaming the casting solution for 30min under a vacuum condition, leveling the defoamed casting solution on a flat plate to form a liquid film with the thickness of 400 mu m, immediately placing the flat plate in a dopamine aqueous solution for phase conversion for 36h, transferring the cured film into a tris (hydroxymethyl) aminomethane solution for soaking for 12h, and washing and drying by water to obtain a beta-cyclodextrin/polydopamine modified basement membrane;
s2, preparing a vinyl modified film: preparing a mixed solution of 80mL of ethanol and 20mL of water, then adding the beta-cyclodextrin/polydopamine modified basement membrane prepared by S1, then adding 3mL of 3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing the mixture for 16h, and then washing and drying the mixture by ethanol to obtain a vinyl modified membrane;
s3, preparing the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane: dissolving 0.1mmol of ciprofloxacin and 0.8mmol of trifluoromethyl acrylic acid in 60mL of acetonitrile, stirring for 6 hours to obtain a prepolymerization system, adding 1.2mL of dipentaerythritol penta-/hexa-acrylic acid, 0.4mL of tetra (3-mercaptopropionic acid) pentaerythritol ester and 20mg of 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally immersing the vinyl modified membrane prepared by S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, carrying out imprinting polymerization reaction for 8 hours under 365nm ultraviolet light irradiation, washing with alcohol and water, eluting a template molecule by using an eluent, and drying to obtain the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane.
Fig. 3(a) shows the adsorption capacity of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on bovine serum albumin with different concentrations. The results show that the adsorption capacity of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on bovine serum albumin in bovine serum albumin solutions with the concentrations of 5, 10, 15 and 20mg/L is lower than that of a molecularly imprinted membrane without polydopamine. The experimental result shows that the anti-fouling performance of the obtained molecularly imprinted membrane is effectively improved by the beta-cyclodextrin/polydopamine synergistic anti-fouling strategy.
Fig. 3(b) is a concentration curve of a permeate obtained by the prepared β -cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane in a selective permeation experiment, a mixed solution with a concentration of 100mg/L is used as a stock solution, the prepared β -cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane is used as a permeation medium, and the concentrations of ciprofloxacin, enrofloxacin, norfloxacin and ofloxacin in the permeate at 5, 10, 15, 30, 60, 90, 120, 180 and 360min are shown in table 3. The experimental results show that the permeation amount of the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane on ciprofloxacin is lower than that of enrofloxacin, norfloxacin and ofloxacin, namely the prepared beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane has selective permeation and separation effects on ciprofloxacin.
TABLE 3 Selective permeation data of beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane
As can be seen from the adsorption amounts of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane to bovine serum albumin with different concentrations in fig. 1 to 3, the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane prepared by the invention has good anti-fouling property, and compared with a molecularly imprinted membrane without polydopamine, the lower bovine serum albumin adsorption amount confirms the effectiveness of the beta-cyclodextrin/polydopamine synergistic anti-fouling strategy; in addition, the lower permeation amount of the ciprofloxacin in the mixed solution of the ciprofloxacin and the structural analogue thereof shows that the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane can effectively separate the ciprofloxacin from the analogue in the permeation process.
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 beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane is characterized by comprising the following steps:
s1, preparing a beta-cyclodextrin/polydopamine modified basement membrane: uniformly mixing polyvinylidene fluoride powder and beta-cyclodextrin powder, adding the mixture into dimethylacetamide, heating and stirring the mixture for a period of time to obtain a casting solution, cooling the casting solution, defoaming the casting solution under a vacuum condition, leveling the defoamed casting solution on a flat plate to form a liquid film with a certain thickness, immediately placing the flat plate in a dopamine aqueous solution for phase conversion for a period of time, transferring the cured film into a tris (hydroxymethyl) aminomethane solution, soaking for a period of time, washing with water, and drying to obtain a beta-cyclodextrin/polydopamine modified basement membrane;
s2, preparing a vinyl modified film: preparing a mixed solution of ethanol and water, then immersing the mixed solution into a beta-cyclodextrin/polydopamine modified basement membrane prepared by S1, adding a certain amount of 3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing, cleaning with ethanol, and drying to obtain a vinyl modified membrane;
s3, preparing the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane: dissolving ciprofloxacin and trifluoromethyl acrylic acid in acetonitrile, stirring for a period of time to obtain a prepolymerization system, adding dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally immersing the vinyl modified membrane prepared by S2 in the mixed solution, discharging oxygen by using nitrogen, sealing, carrying out imprinting polymerization reaction under ultraviolet irradiation, washing with alcohol, washing with water, eluting template molecules by using an eluent, and drying to obtain the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane.
2. The preparation method of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein the dosage ratio of the polyvinylidene fluoride powder, the beta-cyclodextrin powder and the dimethylacetamide in the step S1 is 19 g: 0.2-2 g: 100 mL.
3. The preparation method of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein the heating time in the step S1 is 24 hours, and the heating temperature is 80 ℃; the defoaming treatment time is 30 min; the thickness of the liquid film is 50-400 mu m.
4. The preparation method of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein the phase inversion time in the step S1 is 1-36 h.
5. The method for preparing a beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein the pH value of the tris (hydroxymethyl) aminomethane solution in the step S1 is 8.5; the soaking time is 1-12 h.
6. The method for preparing a beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein in step S2, the volume ratio of ethanol to water to 3- (methacryloyloxy) propyltrimethoxysilane in the mixed solution is 80: 20: 3; the heating reflux temperature is 80 ℃, and the time is 16 h.
7. The preparation method of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein the dosage ratio of ciprofloxacin, trifluoromethyl acrylic acid and acetonitrile in the step S3 is 0.1 mmol: 0.2-0.8 mmol: 60 mL.
8. The method for preparing a beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein the dosage ratio of the trifluoromethyl acrylic acid, the dipentaerythritol penta-/hexa-acrylic acid, the tetra (3-mercaptopropionic acid) pentaerythritol ester and the 2, 2-dimethoxy-2-phenylacetophenone in the step S3 is 0.6 mmol: 0.3-1.2 mL: 0.1-0.4 mL: 20 mg.
9. The preparation method of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to claim 1, wherein the prepolymerization time in the step S3 is 1-6 h; the time of the imprinting polymerization reaction is 1-8 h.
10. The membrane material prepared by the preparation method of the beta-cyclodextrin/polydopamine synergistic anti-fouling molecularly imprinted organic composite membrane according to any one of claims 1 to 9 is applied to selective recognition and separation of ciprofloxacin in a mixed solution of ciprofloxacin, enrofloxacin, norfloxacin and ofloxacin.
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