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CN110193290B - Preparation method and application of click chemistry imprinting-based lincomycin molecular composite membrane - Google Patents

Preparation method and application of click chemistry imprinting-based lincomycin molecular composite membrane Download PDF

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CN110193290B
CN110193290B CN201910463268.1A CN201910463268A CN110193290B CN 110193290 B CN110193290 B CN 110193290B CN 201910463268 A CN201910463268 A CN 201910463268A CN 110193290 B CN110193290 B CN 110193290B
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lincomycin
composite membrane
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membrane
mixed solution
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CN110193290A (en
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董泽清
卢健
秦莹莹
于超
吴易霖
孟敏佳
李春香
闫永胜
笪祖林
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Jiangsu University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method and application of a lincomycin molecular composite membrane based on click chemical imprinting; the preparation steps are as follows: the preparation method comprises the following steps of preparing a lincomycin molecularly imprinted composite membrane based on a click chemistry polymerization method by using dopamine and polyethyleneimine as hydrophilic modification materials, lincomycin as a template molecule, 4-vinylpyridine as a functional monomer, pentaerythritol tetrakis (3-mercaptopropionate) as a cross-linking agent and dipentaerythritol penta/hexa-acrylic acid as an auxiliary cross-linking agent; the lincomycin molecularly imprinted composite membrane prepared by the invention effectively solves the defects of difficult recovery, easy generation of secondary pollution and the like of the existing lincomycin molecularly imprinted polymer; in addition, the lincomycin has good specific recognition capability and adsorption separation capability.

Description

Preparation method and application of click chemistry imprinting-based lincomycin molecular composite membrane
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a preparation method of a lincomycin molecular composite membrane based on click chemistry imprinting and an application background technology
Background
Lincomycin is a lincomamine alkaline antibiotic produced by streptomyces, and has strong antibacterial activity on gram-positive bacteria, anaerobic bacteria and certain actinomycetes. The composition can be used as veterinary drug for preventing and treating pig diarrhea, pig mycoplasma pneumonia, and chronic respiratory disease of chicken, and promoting chicken growth. But has large toxic and side effects and strong side effects on sensitive people, and can cause digestive tract reactions such as abdominal or gastric colic, vomiting, diarrhea, pseudomembranous enteritis and the like. According to the regulation of the highest residual quantity of veterinary drugs in animal-derived foods established in China, the highest residual quantity of lincomycin in cow and sheep milk is 150 mug/kg, and the highest residual quantity of lincomycin in animal muscles is 100 mug/kg. Therefore, the development of a method capable of efficiently and selectively separating lincomycin from the solution has important social and economic values.
In the currently reported research on the imprinting material of lincomycin, the traditional free radical polymerization mode is mainly used for realizing the combination of lincomycin and functional monomers, and although effective molecular imprinting recognition sites can be constructed, the imprinting material has the defects of complicated experimental steps and unobvious imprinting effect due to the defects of high requirements on carriers, long polymerization reaction time, difficult control of the polymerization process and the like; and the blotting material using the membrane as a carrier has low requirements on antifouling performance, so that the service life and the regeneration performance of the membrane are weakened.
The molecularly imprinted membrane is a novel separation material developed based on a membrane separation technology and a molecular imprinting technology, and under the condition that template molecules (target molecules) exist, a molecular recognition site with the size and acting force matched with the target molecules is constructed in a membrane surface polymer by utilizing the process of polymerizing a functional monomer on the surface of the membrane. The mixed solution containing a plurality of molecules permeates through the molecularly imprinted membrane under the action of external driving force (pressure, concentration difference and the like), target molecules can be selectively identified and adsorbed due to the existence of molecularly imprinted identification sites, and non-target molecules can smoothly diffuse to the other side through the molecularly imprinted membrane, so that the molecules with similar sizes and properties can be selectively separated.
At present, the molecular imprinting technology mainly utilizes polymerization modes such as traditional free radical polymerization, atom transfer free radical polymerization, reversible addition-fragmentation chain transfer polymerization and the like to realize the construction of molecular imprinting recognition sites, but the method has the characteristics of high energy consumption, long reaction time, difficult control of the polymerization process and the like, so that the combination of the membrane separation technology and the molecular imprinting technology is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to overcome the technical defects in the prior art and solve the problems of long preparation time, high temperature, low selectivity and the like of the traditional molecularly imprinted membrane, so that the requirement on the thermal stability of the basement membrane is greatly reduced, the preparation time is greatly shortened, and the selective separation efficiency of target molecules (lincomycin) is greatly improved.
The present invention achieves the above-described object by the following technical means.
A preparation method of a lincomycin molecularly imprinted composite membrane based on a click chemistry technology comprises the following steps:
s1, preparing a PVDF blank film: dissolving PVDF powder in an organic solvent N-methyl pyrrolidone, stirring and mixing to obtain a membrane casting solution, standing for a period of time, obtaining a PVDF membrane through phase inversion, and drying to obtain a base membrane;
s2, preparing a PVDF hydrophilic modified membrane: dissolving tris (hydroxymethyl) aminomethane hydrochloride, polyethyleneimine and dopamine hydrochloride in water to obtain a mixed solution, adjusting the pH value of the solution, immersing a base membrane in the mixed solution, oscillating for a period of time at room temperature, washing with water, and drying to obtain a PVDF hydrophilic modified membrane;
s3, preparing a KH570 modified PVDF hydrophilic membrane: firstly, preparing a mixed solution of ethanol and water, then adding the PVDF hydrophilic modified membrane prepared in S2, adding a certain amount of 3- (methacryloyloxy) propyl trimethoxy silane, heating and refluxing, and then washing with alcohol and drying to obtain the KH570 modified PVDF hydrophilic membrane;
s4, preparing a lincomycin molecular imprinting composite membrane: dissolving lincomycin in a methanol solution, uniformly mixing, adding 4-vinylpyridine, dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution, finally soaking the KH570 modified PVDF hydrophilic membrane prepared in S3 into the mixed solution, purifying by using nitrogen, sealing, carrying out imprinting polymerization reaction under ultraviolet irradiation, carrying out alcohol washing and drying to obtain an imprinting polymerization membrane, eluting template molecules by using an eluent, and carrying out alcohol washing, water washing and drying to obtain the lincomycin molecular imprinting composite membrane.
Preferably, the dosage ratio of the PVDF powder to the N-methylpyrrolidone in step S1 is 3 to 5 g: 25 ml.
Preferably, the stirring condition in the step S1 is 50 ℃ and the time is 12-36 h.
Preferably, the standing time in step S1 is 24 h.
Preferably, the amount ratio of the tris (hydroxymethyl) aminomethane hydrochloride, the polyethyleneimine, the dopamine hydrochloride and the water in step S2 is 0.1211 g: 0.4-0.6 g: 0.2 g: 100 mL; the pH of the conditioning solution was 8.5.
Preferably, the oscillating time in step S2 is 6-24 h.
Preferably, the volume ratio of ethanol to water in the mixed solution described in step S3 is 4: 1; the volume ratio of the 3- (methacryloyloxy) propyl trimethoxy silane to the mixed solution is (1-5): 100.
preferably, the heating reflux temperature in the step S3 is 60-100 ℃; the heating reflux time is 12-24 h.
Preferably, the dosage ratio of the lincomycin to the methanol in the step S4 is 0.5-4 mmol: 75 mL.
Preferably, the dosage ratio of the lincomycin, the 4-vinylpyridine, the dipentaerythritol penta-/hexa-acrylic acid, the pentaerythritol tetrakis (3-mercaptopropionate) and the 2, 2-dimethoxy-2-phenylacetophenone in the step S4 is 0.5-4 mmol: 4 mmol: 1 mmol: 2 mmol: 10-30 mg.
Preferably, in step S4, the wavelength of the ultraviolet light is 365 nm; the time of the imprinting polymerization reaction is 1-7 h.
Preferably, in step S4, 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 N-methyl pyrrolidone in the technical scheme has the function of serving as an organic solvent.
The tris (hydroxymethyl) aminomethane hydrochloride described in the above technical scheme functions as a buffer.
The polyethyleneimine in the technical scheme is used as a membrane hydrophilicity modification reagent.
The dopamine hydrochloride in the technical scheme has the function of a basement membrane bionic modification reagent.
The 3- (methacryloyloxy) propyl trimethoxysilane in the technical scheme is used as a membrane activation modification reagent.
The lincomycin in the technical scheme is used as a template molecule.
The methanol in the technical scheme is used as a solvent.
The 4-vinylpyridine described in the above technical scheme functions as a functional monomer.
The dipentaerythritol penta-/hexa-acrylic acid in the technical scheme is used as an auxiliary crosslinking agent.
The pentaerythritol tetrakis (3-mercaptopropionate) described in the above technical scheme acts as a cross-linking agent.
The 2, 2-dimethoxy-2-phenylacetophenone in the technical scheme has the function of a photoinitiator.
The invention also comprises the application of the lincomycin molecular imprinting composite membrane in selective adsorption and separation of lincomycin in the lincomycin-containing mixed solution, in particular to the selective adsorption and separation of lincomycin in the lincomycin and clindamycin-containing mixed solution.
And (3) testing the material performance:
(1) isothermal adsorption experiment
Weighing 8 parts of lincomycin molecular imprinting composite membrane, respectively putting the composite membrane into test tubes, respectively adding 10mL of 5, 10, 25, 50, 75, 100, 150 and 200mg/L lincomycin and clindamycin mixed solution, standing and adsorbing for 180min at room temperature, measuring the concentration of the non-adsorbed lincomycin and clindamycin in the solution by an ultraviolet-visible spectrophotometer after adsorption is finished, and calculating the adsorption capacity (Q) according to the resulte，mg/g)：
Q＝(C0-Ce)×V/m (1)
Wherein C is0(mg/L) and Ce(mg/L) is the concentration of the same molecule in the solution before and after adsorption, V (mL) is the volume of the adsorption solution, and m (g) is the mass of the added lincomycin molecularly imprinted composite membrane.
(2) Dynamic adsorption experiment
Respectively weighing 10 parts of lincomycin molecular imprinting composite membrane, putting the composite membrane into a test tube, respectively adding 10mL of mixed solution of lincomycin and clindamycin with the concentration of 50mg/L, standing and adsorbing for 0, 5, 10, 15, 30, 60, 90, 120, 150 and 180min at room temperature, measuring the concentration of the non-adsorbed lincomycin and clindamycin in the solution by an ultraviolet-visible spectrophotometer after adsorption is finished, and calculating the adsorption quantity (Q) according to the resultt，mg/g)：
Qt＝(C0-Ct)×V/m (2)
Wherein C is0(mg/L) and Ct(mg/L) is the concentration of the same molecule in the solution before and after adsorption, V (mL) is the volume of the adsorption solution, and m (g) is the mass of the added lincomycin molecularly imprinted composite membrane.
The invention has the advantages and technical effects that:
(1) the invention takes the membrane as a carrier, greatly improves the toughness and the anti-pollution performance of the membrane by hydrophilic modification of the membrane, and combines a target molecule (lincomycin) with a polymerization method of 'click chemistry' for the first time, takes pentaerythritol tetra (3-mercaptopropionate) as a cross-linking agent and dipentaerythritol penta-/hexa-acrylic acid as an auxiliary cross-linking agent, and leads the surface of the membrane to form an effective imprinting point under the initiation condition of ultraviolet light, and has short polymerization reaction time and obvious imprinting effect. From the adsorption result, the specific porous structure of the membrane provides enough imprinting holes, so that the good adsorption effect on lincomycin is reflected.
(2) Compared with the existing lincomycin molecularly imprinted polymer, the lincomycin molecularly imprinted composite membrane prepared by the invention has the advantages of easy recovery, convenient subsequent separation, no secondary pollution to separated substances, applicability to continuous process and the like, and effectively solves the defects of difficult recovery, easy generation of secondary pollution and the like of the existing lincomycin molecularly imprinted polymer; in addition, the lincomycin molecular imprinting composite membrane prepared by the invention has higher selectivity on lincomycin, and can effectively separate lincomycin molecules from a mixed solution of lincomycin and clindamycin.
(3) Compared with the existing molecularly imprinted membrane, the preparation method disclosed by the invention is based on the click chemical imprinting polymerization technology to prepare and synthesize the high-efficiency and stable lincomycin molecularly imprinted composite membrane; the prepared lincomycin molecular imprinting composite membrane has the advantages of high selectivity, strong stability and stable regeneration performance, so that the selective separation efficiency of the lincomycin molecular imprinting composite membrane on lincomycin in a complex mixed system is greatly improved; in addition, due to hydrophilic modification of the PVDF membrane, the prepared lincomycin molecular imprinting composite membrane has great improvement on the aspects of hydrophilicity, mechanical strength, chemical stability, material toughness and the like.
Drawings
In fig. 1, a and b are respectively an isothermal adsorption curve and a kinetic adsorption curve of the lincomycin molecularly imprinted composite membrane in example 1.
In fig. 2, a and b are respectively an isothermal adsorption curve and a kinetic adsorption curve of the lincomycin molecularly imprinted composite membrane in example 2.
In fig. 3, a and b are respectively an isothermal adsorption curve and a kinetic adsorption curve of the lincomycin molecularly imprinted composite membrane in example 3.
Detailed Description
The invention is further described with reference to the drawings and the detailed description.
Example 1:
s1, preparation of a PVDF blank film:
dissolving 3g of PVDF powder in 25ml of an organic solvent N-methyl pyrrolidone, stirring and mixing at 50 ℃ for 12h to obtain a membrane casting solution, standing for 24h, obtaining a PVDF membrane through phase conversion, and airing;
s2, preparation of a PVDF hydrophilic modified membrane:
0.1211g of tris (hydroxymethyl) aminomethane hydrochloride, 0.4g of polyethyleneimine and 0.2g of dopamine hydrochloride are dissolved in 100ml of water to obtain a mixed solution, the pH value of the solution is adjusted to 8.5 by using hydrochloric acid and sodium hydroxide, a basement membrane is immersed in the mixed solution, the mixed solution is oscillated for 6 hours at room temperature, and the PVDF hydrophilic modified membrane is obtained after washing and drying;
preparation of S3 and KH570 modified PVDF hydrophilic membrane:
dispersing the PVDF hydrophilic modified membrane prepared by S2 in a mixed solution containing 80mL of ethanol and 20mL of water, adding 1mL of 3- (methacryloyloxy) propyl trimethoxy silane, refluxing at 60 ℃ for 12h, washing with alcohol, and drying to obtain the KH570 modified PVDF hydrophilic membrane;
s4, preparation of the lincomycin molecular imprinting composite membrane:
dissolving 0.5mmol of lincomycin in 75mL of methanol, respectively adding 4mmol of 4-vinylpyridine, 1mmol of dipentaerythritol penta-/hexan-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 10mg of 2, 2-dimethoxy-2-phenylacetophenone after uniformly mixing, adding the KH570 modified PVDF hydrophilic modified membrane prepared by S3, purifying by using nitrogen, sealing, reacting for 1h under 365nm ultraviolet light, washing with alcohol, drying to obtain an imprinted polymeric membrane, eluting a template molecule by using a mixed solution of methanol and acetic acid (v/v ═ 95:5), washing with alcohol, washing with water, and drying to obtain the lincomycin molecularly imprinted composite membrane.
Fig. 1(a) is an isothermal adsorption curve of the prepared lincomycin molecularly imprinted composite membrane, and the adsorption amounts of the prepared lincomycin molecularly imprinted composite membrane to lincomycin and clindamycin for 180min in the mixed solution with the concentrations of 5, 10, 25, 50, 75, 100, 150 and 200mg/L are shown in table 1 (a). The experiment result shows that the prepared lincomycin molecular imprinting composite membrane has higher lincomycin adsorption amount than clindamycin in a mixed solution with the concentration of 5-200 mg/L, namely, the prepared lincomycin molecular imprinting composite membrane has a selective adsorption and separation effect on lincomycin.
TABLE 1(a) isothermal adsorption data for lincomycin molecularly imprinted composite membranes
Figure BDA0002078683290000061
FIG. 1(b) is a kinetic adsorption curve of the prepared lincomycin molecularly imprinted composite membrane, wherein the adsorption amounts of the prepared lincomycin molecularly imprinted composite membrane to lincomycin and clindamycin for 0, 5, 10, 15, 30, 60, 90, 120, 150 and 180min in a mixed solution with a concentration of 50mg/L are shown in Table 1 (b). The experimental result shows that the prepared lincomycin molecular imprinting composite membrane has higher adsorption capacity to lincomycin than clindamycin before reaching the equilibrium adsorption capacity, namely has the effect of selective adsorption and separation on lincomycin.
TABLE 1(b) kinetic adsorption data of lincomycin molecular imprinting composite membranes
Figure BDA0002078683290000071
Example 2:
s1, preparation of a PVDF blank film:
dissolving 4g of PVDF powder in 25ml of organic solvent N-methyl pyrrolidone, stirring and mixing for 24h at 50 ℃ to obtain a membrane casting solution, standing for 24h, obtaining a PVDF membrane through phase conversion, and airing;
s2, preparation of a PVDF hydrophilic modified membrane:
0.1211g of tris (hydroxymethyl) aminomethane hydrochloride, 0.5g of polyethyleneimine and 0.2g of dopamine hydrochloride are dissolved in 100ml of water to obtain a mixed solution, the pH value of the solution is adjusted to 8.5 by using hydrochloric acid and sodium hydroxide, a basement membrane is immersed in the mixed solution, oscillation is carried out for 12 hours at room temperature, and the PVDF hydrophilic modified membrane is obtained after water washing and drying;
preparation of S3 and KH570 modified PVDF hydrophilic membrane:
dispersing the PVDF hydrophilic modified membrane prepared by S2 in a mixed solution containing 80mL of ethanol and 20mL of water, adding 3mL of 3- (methacryloyloxy) propyl trimethoxy silane, refluxing for 16h at 80 ℃, washing with alcohol, and drying to obtain the KH570 modified PVDF hydrophilic membrane;
s4, preparation of the lincomycin molecular imprinting composite membrane:
dissolving 1mmol of lincomycin in 75mL of methanol, respectively adding 4mmol of 4-vinylpyridine, 1mmol of dipentaerythritol penta-/hexan-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 20mg of 2, 2-dimethoxy-2-phenylacetophenone after uniformly mixing, adding the KH570 modified PVDF hydrophilic modified membrane prepared by S3, purifying by using nitrogen, sealing, reacting for 4 hours under 365nm ultraviolet light, washing by using alcohol, drying to obtain an imprinted polymeric membrane, eluting a template molecule by using a mixed solution of methanol and acetic acid (v/v ═ 95:5), washing by using alcohol, washing by using water, and drying to obtain the lincomycin molecularly imprinted composite membrane.
Fig. 2(a) is an isothermal adsorption curve of the prepared lincomycin molecularly imprinted composite membrane, and the adsorption amounts of the prepared lincomycin molecularly imprinted composite membrane to lincomycin and clindamycin for 180min in the mixed solution with the concentrations of 5, 10, 25, 50, 75, 100, 150 and 200mg/L are shown in table 2 (a). The experiment result shows that the prepared lincomycin molecular imprinting composite membrane has higher lincomycin adsorption amount than clindamycin in a mixed solution with the concentration of 5-200 mg/L, namely, the prepared lincomycin molecular imprinting composite membrane has a selective adsorption and separation effect on lincomycin.
TABLE 2(a) isothermal adsorption data for lincomycin molecularly imprinted composite membranes
Figure BDA0002078683290000081
FIG. 2(b) is a kinetic adsorption curve of the prepared lincomycin molecularly imprinted composite membrane, wherein the adsorption amounts of the prepared pyrimethamine molecularly imprinted composite membrane to lincomycin and clindamycin for 0, 5, 10, 15, 30, 60, 90, 120, 150 and 180min in a mixed solution with a concentration of 50mg/L are shown in Table 2 (b). The experimental result shows that the prepared lincomycin molecular imprinting composite membrane has higher adsorption capacity to lincomycin than clindamycin before reaching the equilibrium adsorption capacity, namely has the effect of selective adsorption and separation on lincomycin.
TABLE 2(b) kinetic adsorption data of lincomycin molecular imprinting composite membranes
Figure BDA0002078683290000082
Figure BDA0002078683290000091
Example 3:
s1, preparation of a PVDF blank film:
dissolving 5g of PVDF powder in 25ml of organic solvent N-methyl pyrrolidone, stirring and mixing at 50 ℃ for 36h to obtain a membrane casting solution, standing for 24h, obtaining a PVDF membrane through phase conversion, and airing;
s2, preparation of a PVDF hydrophilic modified membrane:
0.1211g of tris (hydroxymethyl) aminomethane hydrochloride, 0.6g of polyethyleneimine and 0.2g of dopamine hydrochloride are dissolved in 100ml of water to obtain a mixed solution, the pH value of the solution is adjusted to 8.5 by using hydrochloric acid and sodium hydroxide, a basement membrane is immersed in the mixed solution, the mixed solution is oscillated for 24 hours at room temperature, and the PVDF hydrophilic modified membrane is obtained after washing and drying;
preparation of S3 and KH570 modified PVDF hydrophilic membrane:
dispersing the PVDF hydrophilic modified membrane prepared by S2 in a mixed solution containing 80mL of ethanol and 20mL of water, adding 5mL of 3- (methacryloyloxy) propyl trimethoxy silane, refluxing at 100 ℃ for 24h, washing with alcohol, and drying to obtain the KH570 modified PVDF hydrophilic membrane;
s4, preparation of the lincomycin molecular imprinting composite membrane:
dissolving 4mmol of lincomycin in 75mL of methanol, respectively adding 4mmol of 4-vinylpyridine, 1mmol of dipentaerythritol penta-/hexan-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 30mg of 2, 2-dimethoxy-2-phenylacetophenone after uniformly mixing, adding the KH570 modified PVDF hydrophilic modified membrane prepared by S3, purifying by using nitrogen, sealing, reacting for 7 hours under 365nm ultraviolet light, washing by using alcohol, drying to obtain an imprinted polymeric membrane, eluting a template molecule by using a mixed solution of methanol and acetic acid (v/v ═ 95:5), washing by using alcohol, washing by using water, and drying to obtain the lincomycin molecularly imprinted composite membrane.
Fig. 3(a) is an isothermal adsorption curve of the prepared lincomycin molecularly imprinted composite membrane, and the adsorption amounts of the prepared lincomycin molecularly imprinted composite membrane to lincomycin and clindamycin for 180min in the mixed solution with the concentrations of 5, 10, 25, 50, 75, 100, 150 and 200mg/L are shown in table 3 (a). The experiment result shows that the prepared lincomycin molecular imprinting composite membrane has higher lincomycin adsorption amount than clindamycin in a mixed solution with the concentration of 5-200 mg/L, namely, the prepared lincomycin molecular imprinting composite membrane has a selective adsorption and separation effect on lincomycin.
TABLE 3(a) isothermal adsorption data for lincomycin molecularly imprinted composite membranes
Figure BDA0002078683290000101
FIG. 3(b) is a kinetic adsorption curve of the prepared lincomycin molecularly imprinted composite membrane, wherein the adsorption amounts of the prepared lincomycin molecularly imprinted composite membrane to lincomycin and clindamycin for 0, 5, 10, 15, 30, 60, 90, 120, 150 and 180min in a mixed solution with a concentration of 50mg/L are shown in Table 3 (b). The experimental result shows that the prepared lincomycin molecular imprinting composite membrane has higher adsorption capacity to lincomycin than clindamycin before reaching the equilibrium adsorption capacity, namely has the effect of selective adsorption and separation on lincomycin.
TABLE 3(b) kinetic adsorption data of lincomycin molecular imprinting composite membranes
Figure BDA0002078683290000102
Figure BDA0002078683290000111
As can be seen from the isothermal adsorption curve and the kinetic adsorption curve of the lincomycin molecularly imprinted composite membrane on lincomycin in figures 1 to 3, the lincomycin molecularly imprinted composite membrane prepared by the invention has higher adsorption selectivity on lincomycin in a mixed solution of lincomycin and structural analogues thereof.
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 (7)

1.一种基于点击化学印迹林可霉素分子复合膜的制备方法，其特征在于，步骤如下：1. a preparation method based on click chemistry imprinting lincomycin molecular composite membrane, is characterized in that, step is as follows: S1.制备PVDF空白膜；S1. Prepare PVDF blank film; S2.制备PVDF亲水改性膜；将三(羟甲基)氨基甲烷盐酸盐、聚乙烯亚胺和盐酸多巴胺溶解在水中得到混合溶液，调节溶液pH值，将基底膜浸入混合溶液中，在室温条件下振荡一段时间，水洗、干燥后得PVDF亲水改性膜；所述三(羟甲基)氨基甲烷盐酸盐、聚乙烯亚胺、盐酸多巴胺和水的用量比为0.1211g：0.4～0.6g：0.2g：100mL；所述调节溶液的pH值为8.5；所述的振荡一段时间为6～24h；S2. Preparation of PVDF hydrophilic modified membrane; dissolving tris(hydroxymethyl)aminomethane hydrochloride, polyethyleneimine and dopamine hydrochloride in water to obtain a mixed solution, adjusting the pH value of the solution, and immersing the basement membrane in the mixed solution, Vibrate for a period of time at room temperature, wash with water and dry to obtain a PVDF hydrophilic modified membrane; the dosage ratio of the tris(hydroxymethyl)aminomethane hydrochloride, polyethyleneimine, dopamine hydrochloride and water is 0.1211g: 0.4～0.6g: 0.2g: 100mL; the pH value of the adjustment solution is 8.5; the oscillation period of time is 6～24h; S3.制备KH570改性PVDF亲水膜；S3. Preparation of KH570 modified PVDF hydrophilic membrane; S4.先将林可霉素溶解在甲醇溶液中，林可霉素、甲醇的用量比为0.5～4mmol：75mL，混合均匀后再加入4-乙烯基吡啶、二季戊四醇戊-/己-丙烯酸、四(3-巯基丙酸)季戊四醇酯和2,2-二甲氧基-2-苯基苯乙酮，得到混合溶液，最后将S3制备的KH570改性PVDF亲水膜浸入混合溶液中，利用氮气纯化后密封，在紫外光照射下进行印迹聚合反应，反应后取出产物经醇洗、干燥得到印迹聚合膜，利用洗脱液对模板分子进行洗脱，然后再经醇洗、水洗、干燥，得到林可霉素分子印迹复合膜。S4. First dissolve lincomycin in methanol solution, the dosage ratio of lincomycin and methanol is 0.5～4mmol: 75mL, and then add 4-vinylpyridine, dipentaerythritol pentane-/hexyl-acrylic acid, Tetrakis(3-mercaptopropionate) pentaerythritol ester and 2,2-dimethoxy-2-phenylacetophenone were obtained to obtain a mixed solution. Finally, the KH570 modified PVDF hydrophilic membrane prepared by S3 was immersed in the mixed solution, using After nitrogen purification, it was sealed, and the imprinted polymerization reaction was carried out under ultraviolet light irradiation. After the reaction, the product was taken out, washed with alcohol, and dried to obtain an imprinted polymer film. The template molecules were eluted with the eluent, and then washed with alcohol, washed with water, and dried. The lincomycin molecularly imprinted composite membrane was obtained. 2.根据权利要求1所述的一种基于点击化学印迹林可霉素分子复合膜的制备方法，其特征在于，步骤S4中，所述的林可霉素、4-乙烯基吡啶、二季戊四醇戊-/己-丙烯酸、四(3-巯基丙酸)季戊四醇酯和2,2-二甲氧基-2-苯基苯乙酮的用量比为0.5～4mmol：4mmol：1mmol：2mmol：10～30mg。2. a kind of preparation method based on click chemistry imprinting lincomycin molecular composite membrane according to claim 1, is characterized in that, in step S4, described lincomycin, 4-vinylpyridine, dipentaerythritol The dosage ratio of pentane-/hexyl-acrylic acid, tetrakis(3-mercaptopropionic acid) pentaerythritol ester and 2,2-dimethoxy-2-phenylacetophenone is 0.5～4mmol: 4mmol: 1mmol: 2mmol: 10～ 30mg. 3.根据权利要求1所述的一种基于点击化学印迹林可霉素分子复合膜的制备方法，其特征在于，步骤S4中，所述的紫外光的波长为365nm；所述的印迹聚合反应的时间为1-7h。3. a kind of preparation method based on click chemistry imprinting lincomycin molecular composite membrane according to claim 1, is characterized in that, in step S4, the wavelength of described ultraviolet light is 365nm; Described imprinting polymerization reaction The time is 1-7h. 4.根据权利要求1所述的一种基于点击化学印迹林可霉素分子复合膜的制备方法，其特征在于，步骤S4中，所述的密封方式为，用真空塞、脱脂胶带或保鲜膜进行密封。4. a kind of preparation method based on click chemistry imprinting lincomycin molecular composite membrane according to claim 1, is characterized in that, in step S4, described sealing method is, with vacuum plug, degreased tape or fresh-keeping film Seal. 5.根据权利要求1所述的一种基于点击化学印迹林可霉素分子复合膜的制备方法，其特征在于，步骤S4中，所述的洗脱液为甲醇和乙酸的混合溶液，其中甲醇和乙酸的体积比为95:5；所述的洗脱方式为，在室温下振荡，每3小时换一次洗脱液，洗脱过程持续3天。5. a kind of preparation method based on click chemistry imprinting lincomycin molecular composite membrane according to claim 1, is characterized in that, in step S4, described eluent is the mixed solution of methyl alcohol and acetic acid, wherein methyl alcohol The volume ratio of acetic acid and acetic acid is 95:5; the elution mode is, shaking at room temperature, changing the eluent every 3 hours, and the elution process lasts for 3 days. 6.根据权利要求1～5任一项所述的一种基于点击化学印迹林可霉素分子复合膜的制备方法制备的复合膜应用于含有林可霉素混合溶液中林可霉素的选择性吸附和分离。6. The composite membrane prepared based on the preparation method of a click chemistry imprinted lincomycin molecular composite membrane according to any one of claims 1 to 5 is applied to the selection of lincomycin in a mixed solution containing lincomycin adsorption and separation. 7.根据权利要求6所述的应用，其特征在于，所述复合膜应用于林可霉素和克林霉素的混合溶液中林可霉素的选择性吸附和分离。7. The application according to claim 6, wherein the composite membrane is applied to the selective adsorption and separation of lincomycin in the mixed solution of lincomycin and clindamycin.
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