CN109772178B - Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading - Google Patents
Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading Download PDFInfo
- Publication number
- CN109772178B CN109772178B CN201811542607.7A CN201811542607A CN109772178B CN 109772178 B CN109772178 B CN 109772178B CN 201811542607 A CN201811542607 A CN 201811542607A CN 109772178 B CN109772178 B CN 109772178B
- Authority
- CN
- China
- Prior art keywords
- pyrimethamine
- molecularly imprinted
- composite membrane
- double
- sided
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of functional material preparation, and discloses a preparation method and application of a pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading; the preparation steps are as follows: preparing a double-sided loaded pyrimethamine molecularly imprinted composite membrane by using dopamine as a bionic modification material, using carbon nano tubes as a membrane loading material, using pyrimethamine as a template molecule, using methacrylic acid as a functional monomer, using pentaerythritol tetrakis (3-mercaptopropionate) as a cross-linking agent and using dipentaerythritol penta-/hexa-acrylic acid as an auxiliary cross-linking agent, and combining a double-sided suction filtration loading means based on a click chemistry polymerization method; the double-sided loaded pyrimethamine 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 pyrimethamine molecularly imprinted polymer; in addition, the compound has good specific recognition capability and adsorption separation capability on pyrimethamine.
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 pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading.
Background
Pyrimethamine is a broad-spectrum antibacterial veterinary drug, and is mainly used for preventing and treating chicken coccidiosis, fowl cholera, white scour of piglets, etc. In addition, pyrimethamine also has wide application in aquaculture industry, and can enhance the disease resistance of aquatic animals when being used in a proper amount. The pyrimethamine has high accumulation in aquatic products, exceeds a certain range, destroys the hematopoietic system of a human after being eaten by the human, causes hemolytic anemia, even has the possibility of causing potential carcinogenicity, and has direct toxic effect on the central nervous system. In 2017, the precancerogen list published by the international cancer research institution of the world health organization is preliminarily collated for reference, and pyrimethamine is in the three types of carcinogen list. Therefore, the development of a method capable of efficiently and selectively separating pyrimethamine in the solution has very important social and economic values.
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. The 'click chemistry' appearing in recent years is a novel polymerization method, has the advantages of rapid reaction, high yield, high selectivity, insensitivity of products to oxygen and water and the like, and is particularly suitable for the membrane surface molecular imprinting process with harsh condition requirements.
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 (pyrimethamine) is greatly improved.
The present invention achieves the above-described object by the following technical means.
A preparation method of a pyrimethamine molecularly imprinted composite membrane based on a double-sided loading technology comprises the following steps:
s1, preparing a dopamine modified base film: dissolving tris (hydroxymethyl) aminomethane hydrochloride and dopamine hydrochloride in water to obtain a mixed solution, adjusting the pH value of the solution, immersing a basement membrane in the mixed solution, oscillating for a period of time at room temperature, washing with water, and drying to obtain a dopamine modified basement membrane;
s2, preparing a double-sided carbon nanotube load film: mixing carbon nano tubes, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt and glycerol, grinding for the first time, adding a kappa-carrageenan aqueous solution, and grinding for the second time; centrifuging to obtain supernatant, and diluting the supernatant with water to obtain diluent; vacuum-filtering a certain volume of diluent on the upper surface of the dopamine modified basement membrane prepared in S1, drying, vacuum-filtering the diluent on the lower surface of the dopamine modified basement membrane again, and drying again to obtain the double-sided carbon nanotube supported membrane;
s3, preparing a KH570 modified double-sided carbon nanotube load film: firstly, preparing a mixed solution of ethanol and water, then adding the double-sided carbon nanotube load 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 double-sided carbon nanotube load membrane;
s4, preparing a pyrimethamine molecularly imprinted composite membrane: firstly, mixing ethanol and dimethyl sulfoxide, adding pyrimethamine to dissolve, adding methacrylic acid, dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone to obtain a mixed solution after mixing uniformly, finally immersing the KH570 modified double-sided carbon nanotube load membrane prepared in S3 into the mixed solution, purifying and sealing the membrane by using nitrogen, carrying out imprinting polymerization reaction under ultraviolet irradiation, washing with alcohol, drying to obtain an imprinting polymerization membrane, eluting a template molecule by using an eluent, and then washing with alcohol, water and drying to obtain the pyrimethamine molecularly imprinted composite membrane.
Preferably, the dosage ratio of the tris (hydroxymethyl) aminomethane hydrochloride, the dopamine hydrochloride and the water in step S1 is 0.1211 g: 0.2 g: 100 mL; the pH of the conditioning solution was 8.5.
Preferably, in step S1, the oscillating is performed for 3 to 24 hours.
Preferably, in step S2, the ratio of the carbon nanotube, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt, glycerol and kappa-carrageenan is 0.01 to 0.50 g: 0.42 g: 4mL of: 0.01 g.
Preferably, in step S2, the first grinding time is 0-30 min; the second grinding time is 0-60 min; the rotation speed of the centrifugation is 4250rpm, and the time is 15 min; and the dilution multiple of the supernatant diluted by water is 1-40 times.
Preferably, in step S2, the ratio of the diameter of the upper surface and the lower surface of the dopamine modified basement membrane to the volume of the suction filtration diluent is 25 mm: (0.1-5.0) mL.
Preferably, in step S3, the volume ratio of ethanol to water in the mixed solution is 4: 1; the volume ratio of the 3- (methacryloyloxy) propyl trimethoxy silane to the mixed solution is (1-5): 100.
preferably, in the step S3, the heating reflux temperature is 60-120 ℃; the heating reflux time is 12-24 h.
Preferably, in step S4, the dosage ratio of pyrimethamine, ethanol and dimethyl sulfoxide is 0.5 to 4 mmol: 75mL of: 5-30 mL.
Preferably, in step S4, the dosage ratio of pyrimethamine, methacrylic acid, dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone is 0.5 to 4 mmol: 4 mmol: 1 mmol: 2 mmol: 10-80 mg.
Preferably, in step S4, the wavelength of the ultraviolet light is 365 nm; the time of the imprinting polymerization reaction is 1-12 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 tris (hydroxymethyl) aminomethane hydrochloride described in the above technical scheme functions as a buffer.
The dopamine hydrochloride in the technical scheme has the function of a basement membrane bionic modification reagent.
The carbon nanotube in the above technical scheme is used as a base film loading material.
The N, N-dimethyl-N- (3-sulfopropyl) -1-octadecanaminium inner salt in the technical scheme is used as a carbon nano tube cross-linking agent.
The glycerol in the technical scheme is used as a carbon nano tube cross-linking agent.
The kappa-carrageenan in the technical scheme has the function of a carbon nano tube cross-linking agent.
The 3- (methacryloyloxy) propyl trimethoxysilane in the technical scheme is used as a membrane activation modification reagent.
The pyrimethamine in the above technical scheme functions as a template molecule.
The ethanol in the technical scheme is used as a solvent.
The dimethyl sulfoxide in the technical scheme is used as a solvent.
The methacrylic acid in the technical scheme is used 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 pyrimethamine molecularly imprinted composite membrane in selective adsorption and separation of pyrimethamine in the pyrimethamine-containing mixed solution, and particularly in selective adsorption and separation of pyrimethamine in the mixed solution of pyrimethamine, dimethachlon, bisphenol A and sulfadiazine.
And (3) testing the material performance:
(1) isothermal adsorption experiment
Weighing 8 parts of pyrimethamine molecularly imprinted composite membrane, respectively putting the membrane into test tubes, respectively adding 10mL of 5, 10, 25, 50, 75, 100, 150 and 200mg/L mixed solution of pyrimethamine, dimethachlon, bisphenol A and sulfadiazine, standing and adsorbing for 180min at room temperature, measuring the concentration of the unadsorbed pyrimethamine, dimethachlon, bisphenol A and sulfadiazine 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 pyrimethamine molecularly imprinted composite membrane.
(2) Dynamic adsorption experiment
Respectively weighing 9 parts of pyrimethamine molecularly imprinted composite membrane, putting the membrane into a test tube, respectively adding 10mL of mixed solution of pyrimethamine, dimethachlon, bisphenol A and sulfadiazine with the concentration of 50mg/L, standing and adsorbing for 0, 5, 10, 15, 30, 60, 90, 120 and 180min at room temperature, measuring the concentration of the unadsorbed pyrimethamine, dimethachlon, bisphenol A and sulfadiazine in the solution by an ultraviolet-visible spectrophotometer after adsorption is finished, and calculating the adsorption concentration according to the resultQuantity (Q)t，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 pyrimethamine molecularly imprinted composite membrane.
(3) Permselectivity experiments
The prepared pyrimethamine molecularly imprinted composite membrane is placed in the middle of an H-shaped glass tube, the H-shaped glass tube is divided into two cavities which are completely identical by the prepared pyrimethamine molecularly imprinted composite membrane, 100mL of mixed solution of pyrimethamine, diquinane, bisphenol A and sulfadiazine with the concentration of 50mg/L is added into one cavity, 100mL of pure solvent is added into the other cavity, 5mL of solution (penetrating fluid) is taken from the pure solvent cavity respectively when 0, 5, 10, 15, 30, 60, 90, 120, 180, 360 and 720min is carried out, 5mL of pure solvent is backfilled immediately to ensure that the two cavities have no pressure difference, and the concentrations of pyrimethamine, diquinane, bisphenol A and sulfadiazine in a sample are measured by an ultraviolet-visible penetrating fluid spectrophotometer.
The invention has the advantages and technical effects that:
(1) compared with the existing pyrimethamine molecularly imprinted polymer, the prepared pyrimethamine molecularly imprinted composite membrane has the advantages of easy recovery, convenient subsequent separation, no secondary pollution to separated substances, applicability to a continuous process and the like, and effectively solves the defects of difficult recovery, easy generation of secondary pollution and the like of the existing pyrimethamine molecularly imprinted polymer; in addition, the prepared pyrimethamine molecularly imprinted composite membrane has higher selectivity on pyrimethamine, and pyrimethamine molecules can be effectively separated from a mixed solution of pyrimethamine, fenaminoxidil, bisphenol A and sulfadiazine.
(2) Compared with the existing molecularly imprinted membrane, the method is based on the double-sided loading process of the carbon nano tube and combined with the imprinted polymerization technology to prepare and synthesize the efficient and stable pyrimethamine molecularly imprinted composite membrane; the prepared pyrimethamine molecularly imprinted composite membrane has the advantages of high selectivity, strong stability and stable regeneration performance, so that the selective separation efficiency of pyrimethamine in a complex mixed system is greatly improved; in addition, due to the unique design of the double-sided cross-linked loaded carbon nano tube, the prepared pyrimethamine molecularly imprinted composite membrane has great improvement on the aspects of mechanical strength, chemical stability, material toughness and the like.
Drawings
In fig. 1, a, b and c are respectively an isothermal adsorption curve, a kinetic adsorption curve and a permeate concentration curve of the pyrimethamine molecularly imprinted composite membrane in example 1.
In fig. 2, a, b and c are respectively an isothermal adsorption curve, a kinetic adsorption curve and a permeate concentration curve of the pyrimethamine molecularly imprinted composite membrane in example 2.
In fig. 3, a, b and c are respectively an isothermal adsorption curve, a kinetic adsorption curve and a permeate concentration curve of the pyrimethamine molecularly imprinted composite membrane in example 3.
Detailed Description
The invention is further described with reference to the drawings and the specific embodiments in the following description.
Example 1:
s1, preparation of dopamine modified basement membrane:
0.1211g of tris (hydroxymethyl) aminomethane hydrochloride 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 a dilute solution of hydrochloric acid and sodium hydroxide, a basement membrane (with the diameter of 25mm) is immersed in the mixed solution, the mixed solution is shaken for 3 hours at room temperature, and the basement membrane is washed and dried to obtain the dopamine modified basement membrane.
S2, preparing a double-sided carbon nanotube loaded film:
mixing 0.01g of carbon nano tube, 0.42g of N, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt and 4mL of glycerol, adding 4mL of aqueous solution containing 0.01g of kappa-carrageenan, centrifuging at the rotating speed of 4250rpm for 15min, taking supernatant, carrying out vacuum filtration on the surface of the dopamine modified basement membrane obtained in S1 on 0.4mL of supernatant, drying, carrying out vacuum filtration on the other surface of the basement membrane on 0.1mL of diluent, and drying again to obtain the double-sided carbon nano tube supported membrane.
Preparing a S3 and KH570 modified double-sided carbon nanotube loaded film:
and dispersing the double-sided carbon nanotube supported membrane prepared in the S2 into a mixed solution containing 80mL of ethanol and 20mL of water, adding 1mL of 3- (methacryloyloxy) propyl trimethoxy silane, refluxing at 60 ℃ for 12h, and washing with alcohol and drying to obtain the KH570 modified double-sided carbon nanotube supported membrane.
S4, preparing a pyrimethamine molecularly imprinted composite membrane:
dissolving 0.5mmol of pyrimethamine in a mixed solution containing 75mL of ethanol and 5mL of dimethyl sulfoxide, respectively adding 4mmol of methacrylic acid, 1mmol of dipentaerythritol penta-/hexa-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 10mg of 2, 2-dimethoxy-2-phenylacetophenone after uniform mixing, adding the KH570 modified double-sided carbon nanotube supported 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 template molecules by using a mixed solution (v/v ═ 95:5) of methanol and acetic acid, washing with alcohol, washing with water, and drying to obtain the pyrimethamine molecularly imprinted composite membrane.
Fig. 1(a) is an isothermal adsorption curve of the prepared pyrimethamine molecularly imprinted composite membrane, which has adsorption amounts of pyrimethamine, fenarimol, bisphenol a, and sulfadiazine for 180min in mixed solutions having concentrations of 5, 10, 25, 50, 75, 100, 150, and 200mg/L as shown in table 1 (a). The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has higher adsorption capacity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine in a mixed solution with the concentration of 5-200 mg/L, namely has the effect of selective adsorption and separation on pyrimethamine.
TABLE 1(a) isothermal adsorption data for pyrimethamine molecularly imprinted composite membranes
FIG. 1(b) is a kinetic adsorption curve of the prepared pyrimethamine molecularly imprinted composite membrane, which has adsorption amounts of pyrimethamine, fenaminoxidil, bisphenol A and sulfadiazine of 0, 5, 10, 15, 30, 60, 90, 120 and 180min in a mixed solution having a concentration of 50mg/L as shown in Table 1 (b). The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has higher adsorption capacity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine before reaching the equilibrium adsorption capacity, namely has the effect of selective adsorption and separation on pyrimethamine.
TABLE 1(b) kinetics adsorption data of pyrimethamine molecularly imprinted composite membranes
Fig. 1(c) is a concentration curve of the permeate obtained from the prepared pyrimethamine molecularly imprinted composite membrane in the selective permeation experiment, wherein the concentrations of pyrimethamine, fenaminoxidil, bisphenol a and sulfadiazine in the permeate at 0, 5, 10, 15, 30, 60, 90, 120, 180, 360 and 720min are shown in table 1(c) by using the mixed solution with the concentration of 50mg/L as the stock solution and the prepared pyrimethamine molecularly imprinted composite membrane as the permeation medium. The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has lower permeation quantity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine, namely has a selective separation effect on pyrimethamine.
TABLE 1(c) selective permeation data for pyrimethamine molecularly imprinted composite membranes
Example 2:
s1, preparation of dopamine modified basement membrane:
0.1211g of tris (hydroxymethyl) aminomethane hydrochloride 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 a dilute solution of hydrochloric acid and sodium hydroxide, a basement membrane (the diameter of 25mm) is immersed in the mixed solution, the mixed solution is shaken for 6h at room temperature, and the basement membrane is washed and dried to obtain the dopamine modified basement membrane.
S2, preparing a double-sided carbon nanotube loaded film:
mixing 0.12g of carbon nano tube, 0.42g of N, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt and 4mL of glycerol, grinding for 20min, adding 4mL of aqueous solution containing 0.01g of kappa-carrageenan, continuously grinding for 40min, centrifuging at the rotating speed of 4250rpm for 15min, taking supernatant, diluting the supernatant to 1/20 of the original concentration by using water, carrying out vacuum filtration on the surface of the dopamine modified basement membrane obtained in the S1, drying, carrying out vacuum filtration on 0.4mL of diluent on the other surface of the basement membrane, and drying again to obtain the double-sided carbon nano tube supported membrane.
Preparing a S3 and KH570 modified double-sided carbon nanotube loaded film:
and dispersing the double-sided carbon nanotube loaded membrane prepared in the S2 into a mixed solution containing 80mL of ethanol and 20mL of water, adding 3mL of 3- (methacryloyloxy) propyl trimethoxy silane, refluxing for 16h at 80 ℃, and washing and drying by alcohol to obtain the KH570 modified double-sided carbon nanotube loaded membrane.
S4, preparing a pyrimethamine molecularly imprinted composite membrane:
dissolving 1mmol of pyrimethamine in a mixed solution containing 75mL of ethanol and 10mL of dimethyl sulfoxide, respectively adding 4mmol of methacrylic acid, 1mmol of dipentaerythritol penta-/hexa-acrylic acid, 2mmol of tetra (3-mercaptopropionic acid) pentaerythritol ester and 20mg of 2, 2-dimethoxy-2-phenylacetophenone after uniform mixing, adding the KH570 modified double-sided carbon nanotube supported membrane prepared by S3, purifying by using nitrogen, sealing, reacting for 4 hours under 365nm ultraviolet light, washing with alcohol, drying to obtain an imprinted polymeric membrane, eluting template molecules 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 pyrimethamine molecularly imprinted composite membrane.
Fig. 2(a) is an isothermal adsorption curve of the prepared pyrimethamine molecularly imprinted composite membrane, which has adsorption amounts of pyrimethamine, fenarimol, bisphenol a, and sulfadiazine for 180min in mixed solutions having concentrations of 5, 10, 25, 50, 75, 100, 150, and 200mg/L as shown in table 2 (a). The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has higher adsorption capacity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine in a mixed solution with the concentration of 5-200 mg/L, namely has the effect of selective adsorption and separation on pyrimethamine.
TABLE 2(a) isothermal adsorption data for pyrimethamine molecularly imprinted composite membranes
Fig. 2(b) is a kinetic adsorption curve of the prepared pyrimethamine molecularly imprinted composite membrane, which has adsorption amounts of pyrimethamine, fenaminoxidil, bisphenol a and sulfadiazine of 0, 5, 10, 15, 30, 60, 90, 120 and 180min in a mixed solution having a concentration of 50mg/L as shown in table 2 (b). The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has higher adsorption capacity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine before reaching the equilibrium adsorption capacity, namely has the effect of selective adsorption and separation on pyrimethamine.
TABLE 2(b) kinetics adsorption data of pyrimethamine molecularly imprinted composite membranes
Fig. 2(c) is a concentration curve of the permeate obtained from the prepared pyrimethamine molecularly imprinted composite membrane in the selective permeation experiment, wherein the concentrations of pyrimethamine, fenaminoxidil, bisphenol a and sulfadiazine in the permeate at 0, 5, 10, 15, 30, 60, 90, 120, 180, 360 and 720min are shown in table 2(c) by using the mixed solution with the concentration of 50mg/L as the stock solution and the prepared pyrimethamine molecularly imprinted composite membrane as the permeation medium. The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has lower permeation quantity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine, namely has a selective separation effect on pyrimethamine.
TABLE 2(c) selective permeation data for pyrimethamine molecularly imprinted composite membranes
Example 3:
s1, preparation of dopamine modified basement membrane:
0.1211g of tris (hydroxymethyl) aminomethane hydrochloride 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 a dilute solution of hydrochloric acid and sodium hydroxide, a basement membrane (the diameter of 25mm) is immersed in the mixed solution, the mixed solution is shaken for 24h at room temperature, and the basement membrane is washed and dried to obtain the dopamine modified basement membrane.
S2, preparing a double-sided carbon nanotube loaded film:
mixing 0.50g of carbon nano tube, 0.42g of N, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt and 4mL of glycerol, grinding for 30min, adding 4mL of aqueous solution containing 0.01g of kappa-carrageenan, continuously grinding for 60min, centrifuging at the rotating speed of 4250rpm for 15min, taking supernatant, diluting the supernatant to 1/40 of the original concentration by using water, carrying out vacuum filtration on the surface of the dopamine modified basement membrane obtained in the S1, drying, carrying out vacuum filtration on 5.0mL of diluent on the other surface of the basement membrane, and drying again to obtain the double-sided carbon nano tube supported membrane.
Preparing a S3 and KH570 modified double-sided carbon nanotube loaded film:
and dispersing the double-sided carbon nanotube supported membrane prepared in the S2 into a mixed solution containing 80mL of ethanol and 20mL of water, adding 5mL of 3- (methacryloyloxy) propyl trimethoxy silane, refluxing at 120 ℃ for 24h, and washing with alcohol and drying to obtain the KH570 modified double-sided carbon nanotube supported membrane.
S4, preparing a pyrimethamine molecularly imprinted composite membrane:
dissolving 4mmol pyrimethamine in a mixed solution containing 75mL of ethanol and 30mL of dimethyl sulfoxide, respectively adding 4mmol methacrylic acid, 1mmol dipentaerythritol penta-/hexan-acrylic acid, 2mmol tetra (3-mercaptopropionic acid) pentaerythritol ester and 80mg 2, 2-dimethoxy-2-phenylacetophenone after uniformly mixing, adding the KH570 modified double-sided carbon nanotube supported membrane prepared by S3, purifying by using nitrogen, sealing, reacting for 12h under 365nm ultraviolet light, washing by using alcohol, drying to obtain an imprinted polymeric membrane, eluting template molecules 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 pyrimethamine molecularly imprinted composite membrane.
Fig. 3(a) is an isothermal adsorption curve of the prepared pyrimethamine molecularly imprinted composite membrane, which shows 180min adsorption amounts of pyrimethamine, fenarimol, bisphenol a, and sulfadiazine in mixed solutions having concentrations of 5, 10, 25, 50, 75, 100, 150, and 200mg/L as shown in table 3 (a). The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has higher adsorption capacity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine in a mixed solution with the concentration of 5-200 mg/L, namely has the effect of selective adsorption and separation on pyrimethamine.
TABLE 3(a) isothermal adsorption data for pyrimethamine molecularly imprinted composite membranes
FIG. 3(b) is a kinetic adsorption curve of the prepared pyrimethamine molecularly imprinted composite membrane, which has adsorption amounts of pyrimethamine, fenaminoxidil, bisphenol A and sulfadiazine of 0, 5, 10, 15, 30, 60, 90, 120 and 180min in a mixed solution having a concentration of 50mg/L as shown in Table 3 (b). The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has higher adsorption capacity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine before reaching the equilibrium adsorption capacity, namely has the effect of selective adsorption and separation on pyrimethamine.
TABLE 3(b) kinetics adsorption data of pyrimethamine molecularly imprinted composite membranes
Fig. 3(c) is a concentration curve of the permeate obtained from the prepared pyrimethamine molecularly imprinted composite membrane in the selective permeation experiment, wherein the concentrations of pyrimethamine, fenaminoxidil, bisphenol a and sulfadiazine in the permeate at 0, 5, 10, 15, 30, 60, 90, 120, 180, 360 and 720min are shown in table 3(c) by using the mixed solution with the concentration of 50mg/L as the stock solution and the prepared pyrimethamine molecularly imprinted composite membrane as the permeation medium. The experimental result shows that the prepared pyrimethamine molecularly imprinted composite membrane has lower permeation quantity to pyrimethamine than that of dimethachlon, bisphenol A and sulfadiazine, namely has a selective separation effect on pyrimethamine.
TABLE 3(c) selective permeation data for pyrimethamine molecularly imprinted composite membranes
As can be seen from the isothermal adsorption curve and the kinetic adsorption curve of the pyrimethamine molecularly imprinted composite membrane on pyrimethamine in figures 1 to 3, the pyrimethamine molecularly imprinted composite membrane prepared by the invention has higher adsorption selectivity on pyrimethamine in a mixed solution of pyrimethamine and structural analogues thereof, and can realize effective separation of pyrimethamine from analogues in a 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 pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading is characterized by comprising the following steps:
s1, preparing and obtaining a dopamine modified basement membrane;
s2, mixing the carbon nano tube, the N, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt and the glycerol, grinding for the first time, adding a kappa-carrageenan aqueous solution, and grinding for the second time; centrifuging to obtain supernatant, and diluting the supernatant with water to obtain diluent; vacuum-filtering a certain volume of diluent on the upper surface of the dopamine modified basement membrane prepared in S1, drying, vacuum-filtering the diluent on the lower surface of the dopamine modified basement membrane again, and drying to obtain the double-sided carbon nanotube supported membrane;
s3, firstly, preparing a mixed solution of ethanol and water, then adding the double-sided carbon nanotube load film prepared in the 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 double-sided carbon nanotube load film;
s4, mixing ethanol and dimethyl sulfoxide, adding pyrimethamine, uniformly mixing, adding methacrylic acid, dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenyl acetophenone to obtain a mixed solution, finally immersing the KH570 modified double-sided carbon nanotube load membrane prepared in S3 into the mixed solution, purifying by using nitrogen, sealing, carrying out imprinting polymerization reaction under ultraviolet irradiation, washing by using alcohol, drying to obtain an imprinting polymerization membrane, eluting template molecules by using eluent, washing by using alcohol, washing by using water, and drying to obtain the pyrimethamine molecular imprinting composite membrane.
2. The preparation method of the pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading according to claim 1, wherein the amount ratio of the carbon nanotubes, the N, N-dimethyl-N- (3-sulfopropyl) -1-octadecamonium inner salt, the glycerol and the kappa-carrageenan in the step S2 is 0.01-0.50 g: 0.42 g: 4mL of: 0.01 g.
3. The preparation method of the pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading according to claim 1, wherein preferably, in the step S2, the first grinding time is 0-30 min; the second grinding time is 0-60 min; the rotation speed of the centrifugation is 4250rpm, and the time is 15 min; and the dilution multiple of the supernatant diluted by water is 1-40 times.
4. The preparation method of the pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading according to claim 1, wherein the ratio of the diameter of the upper surface and the lower surface of the dopamine modified basement membrane to the volume of the suction filtration diluent is 25 mm: (0.1-5.0) mL.
5. The preparation method of the click chemistry double-sided loaded pyrimethamine molecularly imprinted composite membrane according to claim 1, wherein in step S3, the volume ratio of ethanol to water in the mixed solution is 4: 1; the volume ratio of the 3- (methacryloyloxy) propyl trimethoxy silane to the mixed solution is (1-5): 100.
6. the preparation method of the click chemistry double-sided loaded pyrimethamine molecularly imprinted composite membrane based on claim 1, wherein in the step S3, the heating reflux temperature is 60-120 ℃, and the reflux time is 12-24 h.
7. The preparation method of the pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading according to claim 1, wherein in step S4, the dosage ratio of pyrimethamine, ethanol and dimethyl sulfoxide is 0.5-4 mmol: 75mL of: 5-30 mL; the dosage ratio of pyrimethamine, methacrylic acid, dipentaerythritol penta-/hexa-acrylic acid, tetra (3-mercaptopropionic acid) pentaerythritol ester and 2, 2-dimethoxy-2-phenylacetophenone is 0.5-4 mmol: 4 mmol: 1 mmol: 2 mmol: 10-80 mg.
8. The preparation method of the pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading according to claim 1, wherein in step S4, the wavelength of the ultraviolet light is 365 nm; the time of the imprinting polymerization reaction is 1-12 h.
9. The preparation method of the pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading according to claim 1, wherein in step S4, the sealing manner is to seal with a vacuum plug, a degreasing tape and a preservative film; the eluent is a mixed solution composed of methanol and acetic acid according to a volume ratio of 95: 5; the elution mode is as follows: the elution was repeated every 3 hours with shaking at room temperature for 3 days.
10. The composite membrane prepared by the preparation method according to any one of claims 1 to 9 is applied to selective adsorption and separation of pyrimethamine in a mixed solution of pyrimethamine, fenaminoxidil, bisphenol A and sulfadiazine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811542607.7A CN109772178B (en) | 2018-12-17 | 2018-12-17 | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811542607.7A CN109772178B (en) | 2018-12-17 | 2018-12-17 | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109772178A CN109772178A (en) | 2019-05-21 |
| CN109772178B true CN109772178B (en) | 2021-05-25 |
Family
ID=66497128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811542607.7A Active CN109772178B (en) | 2018-12-17 | 2018-12-17 | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109772178B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110193290B (en) * | 2019-05-30 | 2021-10-12 | 江苏大学 | Preparation method and application of click chemistry imprinting-based lincomycin molecular composite membrane |
| CN110501402B (en) * | 2019-09-24 | 2020-04-28 | 山东农业大学 | Electrochemical sensor for ultrasensitive detection of sulfathiazole and detection method thereof |
| CN111440354B (en) * | 2020-03-27 | 2022-04-26 | 江苏大学 | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure |
| CN113318602B (en) * | 2021-05-17 | 2022-04-26 | 江苏大学 | Preparation method and application of three-dimensional macroporous PVDF (polyvinylidene fluoride) -based anti-fouling molecular imprinting membrane |
| CN113368706B (en) * | 2021-06-02 | 2022-05-20 | 江苏大学 | Preparation method and application of bionic suction filtration type double-layer molecularly imprinted nanofiber composite membrane based on poly-dopamine imprinting strategy |
| CN113368708B (en) * | 2021-06-02 | 2022-04-26 | 江苏大学 | Preparation method and application of suction filtration type double-layer molecular imprinting nano composite membrane based on multiple nano composite imprinting system |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6606974B2 (en) * | 2015-10-28 | 2019-11-20 | 日立化成株式会社 | Separating material and method for producing the same |
| CN105693959B (en) * | 2016-01-29 | 2018-05-08 | 华南师范大学 | The preparation method of magnetic molecularly imprinted polymer with hydrogen bond array |
| CN106008856B (en) * | 2016-06-30 | 2018-10-26 | 佛山科学技术学院 | The preparation method of molecularly imprinted polymer based on click chemistry |
| CN106117558B (en) * | 2016-06-30 | 2018-08-28 | 佛山科学技术学院 | A kind of method for separating and detecting of pyrimethamine |
| CN106902654B (en) * | 2017-03-30 | 2020-10-02 | 吉林师范大学 | Preparation method and application of lithium ion imprinted polyether sulfone composite membrane |
| CN107344095A (en) * | 2017-08-29 | 2017-11-14 | 江苏大学 | A kind of lithium ion Blot PVDF Membrane and preparation method and its usage |
| CN108201795B (en) * | 2017-12-22 | 2019-12-03 | 江苏大学 | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material |
-
2018
- 2018-12-17 CN CN201811542607.7A patent/CN109772178B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109772178A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109772178B (en) | Preparation method and application of pyrimethamine molecularly imprinted composite membrane based on click chemistry double-sided loading | |
| Liu et al. | A review on the use of ionic liquids in preparation of molecularly imprinted polymers for applications in solid-phase extraction | |
| CN107469653B (en) | Synthesis method of molecular imprinting composite membrane for enriching and separating norfloxacin | |
| CN111004411B (en) | Preparation method of biomass-based molecularly imprinted composite membrane for selectively separating tetracycline | |
| CN105131178B (en) | Preparation method of molecularly imprinted composite material for enriching and separating glycoprotein | |
| CN109174023A (en) | A kind of nano-cellulose cross-linked graphene/chitosan aeroge and preparation method thereof, application | |
| CN108201795A (en) | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material | |
| Zheng et al. | Specific enrichment of glycoproteins with polymer monolith functionalized with glycocluster grafted β-cyclodextrin | |
| CN110559868B (en) | Preparation method and application of click chemical imprinting-based o-cloxacillin molecular composite membrane | |
| CN113398776B (en) | Preparation method and application of bionic MOFs (metal organic frameworks) -based double-layer molecular imprinting nano composite membrane based on dual continuous imprinting system | |
| CN107413317B (en) | Chitosan modified GMA/MAA polymer adsorbent and method and application thereof | |
| An et al. | Zipper-like thermosensitive molecularly imprinted polymers based on konjac glucomannan for metformin hydrochloride | |
| CN110193290B (en) | Preparation method and application of click chemistry imprinting-based lincomycin molecular composite membrane | |
| CN111604030B (en) | Graphene oxide-covalent organic framework material composite material, capillary electrochromatography column and preparation method | |
| CN111440354B (en) | Preparation method and application of bisphenol A molecularly imprinted composite membrane with through hierarchical pore structure | |
| CN112979893A (en) | Preparation of magnetic fluorescent material @ molecularly imprinted particle and method for preparing composite membrane by using same | |
| CN103111260B (en) | Preparation method of dumbbell-shaped molecular imprinting stirring rod | |
| CN113368708B (en) | Preparation method and application of suction filtration type double-layer molecular imprinting nano composite membrane based on multiple nano composite imprinting system | |
| CN111944195A (en) | Cellulose aerogel modified by polyion liquid as well as preparation method and application thereof | |
| CN108927113B (en) | Nano-hydroxyapatite functionalized solid phase extraction monolithic column | |
| CN109012587B (en) | Preparation method of tetracycline hydrophilic carbon composite adsorbent | |
| CN113368706B (en) | Preparation method and application of bionic suction filtration type double-layer molecularly imprinted nanofiber composite membrane based on poly-dopamine imprinting strategy | |
| CN113368707B (en) | Preparation method and application of three-dimensional porous MOFs/poly dopamine-based polycarbonate track etching imprinted membrane | |
| CN104772127B (en) | A kind of preparation method for being directed to the carbon cloth surface molecule print passive sampling film of organic pollution in water environment | |
| CN113368705A (en) | Preparation method and application of functionalized double-layer molecularly imprinted nanofiber composite membrane based on double-synergistic imprinting strategy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |