CN110560016A - Preparation method of patulin molecularly imprinted nanofiber membrane - Google Patents
Preparation method of patulin molecularly imprinted nanofiber membrane Download PDFInfo
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- CN110560016A CN110560016A CN201910905475.8A CN201910905475A CN110560016A CN 110560016 A CN110560016 A CN 110560016A CN 201910905475 A CN201910905475 A CN 201910905475A CN 110560016 A CN110560016 A CN 110560016A
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- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
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- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
- B01J20/28038—Membranes or mats made from fibers or filaments
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Abstract
The invention discloses a preparation method of a patulin molecular imprinting nanofiber membrane, which is characterized in that a molecularly imprinted polymer is prepared and an electrostatic spinning technology is combined to obtain the molecularly imprinted nanofiber membrane, 2-indolone and 6-hydroxynicotinic acid are used as virtual template molecules, and the molecularly imprinted nanofiber membrane obtained by combining a sol-gel technology and the electrostatic spinning technology has good specific adsorption and reutilization on patulin, and can realize the specific adsorption on the patulin through the application of specific identification, efficient separation and enrichment on the patulin.
Description
Technical Field
The invention relates to the technical field of molecular imprinting technology and electrostatic spinning, in particular to a preparation method of a patulin molecular imprinting nanofiber membrane.
Background
The molecular imprinting sol-gel technology is characterized in that imprinting molecules are introduced into inorganic and inorganic-organic network structures through a sol-gel process to obtain an imprinting polymer with high stability, and the polymer shows good affinity. The obtained polymer has the characteristics of small particle size, large specific surface area, specific selectivity and the like, and the three-dimensional network space structure of the polymer has good adsorption performance. The molecular imprinting sol-gel technology gives consideration to the advantages of both sol-gel and molecular imprinting, and the defects of poor mechanical stability and easy swelling of the organic high molecular polymer are well solved in the technology. Electrospinning techniques utilize electrostatic forces to produce fine fibers from a spinning solution, which produces fibers that are finer in diameter than conventional spinning processes, and have a larger surface area and higher porosity. The electrostatic spinning technology is combined with the molecular imprinting technology, so that the specific adsorption capacity of the electrostatic spinning membrane is endowed, the specific surface area of the molecular imprinting polymer is increased, and the adsorption capacity and the mass transfer rate are improved. Therefore, the invention combines the three processes to successfully prepare the molecularly imprinted nanofiber membrane, has the advantages of large specific surface area, high porosity, good flexibility, mechanical strength, reusability and the like, has easy separation from a sample to be detected, higher mass transfer rate and binding capacity compared with MIPs, and improves the non-specific adsorption capacity of the electrostatic spinning fiber membrane; meanwhile, the method establishes the extraction and enrichment procedures of the patulin, saves a solid phase extraction device, simplifies the operation steps, and can be used for extracting and enriching the patulin in the actual sample. In view of the above, the present invention is particularly proposed.
disclosure of Invention
The invention aims to provide a preparation method of a patulin molecular imprinting nanofiber membrane.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
The invention comprises the following steps:
Preparation of patulin polymer: mixing a 2-indolone standard substance and a 6-hydroxynicotinic acid standard substance according to a molar ratio of 1: 1-4 is dissolved in methanol, then 3-aminopropyltriethoxysilane is added for magnetic stirring for prepolymerization for 10-50min, tetraethoxysilane is added and 1-10mL of ammonia water is dripped, after magnetic stirring for 15-90min, the reactant is placed in a 30-80 ℃ water bath for incubation reaction for 4-24h to obtain a polymer solid, wherein the template molecules are 2-indolone and 6-hydroxynicotinic acid.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
B eluting polymer solids: washing the polymer solid with methanol for 2-5 times, drying and aging in vacuum at 40-80 ℃ for 4-24h, putting the dried polymer into a 100mL round-bottom flask, adding a primary organic solvent for pre-elution, magnetically stirring for 2-8h, washing with methanol, drying in vacuum at 40-80 ℃ for 4-12h, and eluting the polymer solid with a secondary organic solvent until the template molecule cannot be detected by an ultraviolet spectrophotometer.
C, preparing a molecularly imprinted nanofiber membrane: carrying out electrostatic spinning on a 4-10% polyvinyl alcohol (PVA) spinning solution containing a Molecularly Imprinted Polymer (MIP), wherein the MIP accounts for 10-40% of the mass fraction of the PVA, under the conditions that the spinning voltage is 8-23kv, the spinning distance is 8-20cm, the flow speed is 10-40 mu L/min and the relative humidity is 40-50%, and obtaining the molecularly imprinted nanofiber membrane after the spinning is finished. Non-imprinted nanofiber membranes (NINFMs) were prepared in the same manner.
d, crosslinking of the electrostatic spinning fiber membrane: soaking MINFMs (or NINFMs) prepared under the optimal conditions in 1-6% Glutaraldehyde (GA) aqueous solution (wherein the concentration of sulfuric acid is 1-8%, and sodium sulfate is saturated), crosslinking for 10-60min, drying the molecularly imprinted nanofiber membrane in vacuum for 8-24h, and sealing to obtain the patulin molecularly imprinted nanofiber membrane.
specifically, the primary organic solvent is acetic acid and methanol, the volume ratio of the acetic acid to the methanol is 1-5:7, the secondary organic solvent is acetic acid and methanol, and the volume ratio of the acetic acid to the methanol is 1-4: 9.
specifically, the 3-aminopropyltriethoxysilane is a functional monomer, and the molar ratio of the 3-aminopropyltriethoxysilane to the template molecule is 2-15: 1.
Specifically, the tetraethoxysilane is a cross-linking agent, and the molar ratio of the tetraethoxysilane to the template molecule is 2-20: 1.
Specifically, the ammonia water is used as a catalyst, and the concentration is 0.05-2 mol/L.
Specifically, the polyvinyl alcohol (PVA) spinning solution comprises polyvinyl alcohol, ultrapure water, methanol and polymer solid powder, wherein the polymer solid powder is uniformly dispersed in the methanol by ultrasonic, and the mass ratio of the polyvinyl alcohol to the ultrapure water is 1: 10-25, heating and stirring at 90 ℃ until the polymer methanol dispersion liquid is completely dissolved, cooling to room temperature, and mixing the polymer methanol dispersion liquid and the polyvinyl alcohol solution according to a volume ratio of 1:2-4, wherein the molecularly imprinted polymer accounts for 10% -40% of the polyvinyl alcohol by mass fraction, and the polyvinyl alcohol (PVA) spinning solution is obtained by uniformly mixing with ultrasonic waves.
specifically, the electrostatic spinning time is 0.5h-10 h.
The application of the patulin molecular imprinting nanofiber membrane in the adsorption of patulin.
The invention has the beneficial effects that:
The invention can realize the application of specific recognition, high-efficiency separation and enrichment of patulin in agricultural products by a molecular imprinting recognition technology, has good adsorption and separation performance, and can realize the specific adsorption of patulin.
Drawings
FIG. 1 is a schematic view of a scanning electron microscope of the patulin molecularly imprinted polymer of the present invention;
FIG. 2 is a schematic view of a scanning electron microscope of the patulin molecularly imprinted nanofiber membrane of the present invention;
Detailed Description
The invention will be further described with reference to the accompanying drawings in which:
In this example, a polymer of patulin molecular imprinting was prepared
weighing a certain amount of 2-indolone standard substance and 6-hydroxynicotinic acid standard substance into a 100mL round-bottom flask, adding 2-10mL methanol, adding 3-aminopropyltriethoxysilane (the molar ratio of the 3-aminopropyltriethoxysilane to template molecules is 2-15:1) after the template molecules are dissolved, and magnetically stirring for 10-50min for prepolymerization. Adding tetraethoxysilane (the molar ratio of tetraethoxysilane to template molecules is 2-20:1) and magnetically stirring for 10-60min, adding 1-10mL of ammonia water (0.05-2mol/L) and magnetically stirring for 5-30min, sealing by using a sealing film with a pinhole, and then putting into a water bath kettle with the temperature of 30-80 ℃ for incubation and reaction for 4-24 h. After the reaction is finished, the obtained solid is taken out, washed by methanol for 2-5 times, dried and aged for 4-24h under vacuum at the temperature of 40-80 ℃. The dried polymer was placed in a 100mL round bottom flask and 10-100mL acetic acid: methanol (1-5:7, v/v), magnetically stirring for 2-8h, washing with methanol several times, and vacuum drying at 40-80 deg.C for 4-12 h. Finally the polymer was placed in a soxhlet, washed with acetic acid: the template was eluted with methanol (1-4:9, v/v) until no template molecules were detected by UV spectrophotometer.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
Preparation of patulin molecularly imprinted nanofiber membranes (MINFMs)
Preparing a spinning solution: accurately weighing a certain mass of PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature, weighing a certain mass of properly sieved MIPs powder, and selecting small-particle polymers to be ultrasonically dispersed uniformly in methanol (the mass of the MIPs accounts for 10-40% of the mass of the PVA). And finally, transferring a certain volume of the MIPs-containing methanol dispersion liquid into a certain volume of PVA solution (the volume ratio of the MIPs to the PVA solution is 1:2-4), uniformly mixing, and preparing 4-10% of the molecular imprinting nano-fiber membrane PVA spinning solution. 4-10% non-imprinted nanofiber membrane (NINFMs) PVA spinning solution is prepared according to the same method.
Preparing an electrostatic spinning fiber membrane: adding the prepared PVA spinning solution (the concentration is 4-10%) into an injector, and performing under the conditions that the spinning voltage is 8-23kv, the spinning distance is 8-20cm, the flow rate is 10-40 mu L/min and the relative humidity is 40-50%, wherein the obtained MINFMs have good fiber morphology. Non-imprinted nanofiber membranes NINFMs were prepared in the same manner.
Crosslinking of the electrospun fiber membrane: soaking MINFMs (or NINFMs) prepared under optimal conditions in 1-6% glutaraldehyde water solution (with sulfuric acid concentration of 1-8% and sodium sulfate saturated), crosslinking for 10-60min, vacuum drying the crosslinked membrane for 8-24h, and packaging into sealed bag.
Extraction and enrichment of patulin
Weighing a certain amount of MINFMMs in 1-5mL of patulin acetonitrile solution, carrying out shaking adsorption for 0.5-4h, then simply washing off the solution with methanol, eluting with an eluent methanol-acetic acid solution (3-9:1, v/v) for 0.5-4h, and measuring the free concentration of the patulin in the eluent, wherein the recovery rate can reach 98%.
example 1:
(1) Preparation of patulin molecularly imprinted polymer: mixing a 2-indolone standard substance and a 6-hydroxynicotinic acid standard substance according to a molar ratio of 1: 1 is dissolved in methanol, then 3-aminopropyltriethoxysilane (the molar ratio of the 3-aminopropyltriethoxysilane to template molecules is 2:1) is added for magnetic stirring and prepolymerization for 10min, tetraethoxysilane (the molar ratio of the tetraethoxysilane to the template molecules is 4:1) is added, magnetic stirring is carried out for 20min, 1ml of 0.05mol/L ammonia water is added dropwise, after magnetic stirring is carried out for 5min, the reactant is placed into a 30 ℃ water bath for incubation and reaction for 5h to obtain polymer solid, wherein the template molecules are 2-indolone and 6-hydroxynicotinic acid.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
(2) Eluting the polymer solids: after washing the polymer solid 3 times with methanol, after drying and aging under vacuum at 40 ℃ for 6h, the dried polymer was placed in a 100mL round bottom flask, 20mL acetic acid: methanol (1: 5, v/v), magnetic stirring for 3h, washing several times with methanol, washing with methanol, vacuum drying at 40 ℃ for 6h, finally placing the polymer in a soxhlet, washing with acetic acid: the template was eluted with methanol (1: 8, v/v) until no template molecules were detected by UV spectrophotometer.
(3) Preparing a spinning solution: accurately weighing a certain mass of PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature, preparing a PVA solution, weighing a certain mass of properly sieved MIPs powder (accounting for 30% of the mass of the PVA), and ultrasonically dispersing small-particle polymers in methanol uniformly. Finally, the methanol dispersion liquid of MIP and PVA solution are mixed ultrasonically (the volume ratio of the two is 1:2) to obtain 5% PVA spinning solution, and 5% PVA spinning solution of non-imprinted nanofiber membranes (NINFMs) is prepared according to the same method.
(4) preparing an electrostatic spinning fiber membrane: adding the prepared PVA spinning solution into an injector, and performing under the conditions that the concentration of the spinning solution is 5%, the spinning voltage is 8kv, the spinning distance is 10cm, the flow rate is 20 mu L/min, and the relative humidity is 40-50% to obtain the MINFMs. Non-imprinted nanofiber membranes (NINFMs) were prepared in the same manner.
(5) Crosslinking of the electrospun fiber membrane: soaking the prepared MINFMs (or NINFMs) in 2% GA water solution (sulfuric acid concentration is 2%, sodium sulfate is saturated), crosslinking for 10min, vacuum drying the crosslinked film for 10h, and packaging into sealed bags.
Example 2:
(1) Preparation of patulin molecularly imprinted polymer: mixing a 2-indolone standard substance and a 6-hydroxynicotinic acid standard substance according to a molar ratio of 1:2, dissolving in methanol, then adding 3-aminopropyltriethoxysilane (the molar ratio of the 3-aminopropyltriethoxysilane to the template molecule is 4:1) to perform magnetic stirring and prepolymerization for 10min, adding tetraethoxysilane (the molar ratio of the tetraethoxysilane to the template molecule is 6:1), performing magnetic stirring for 20min, dropwise adding 2mL of 0.05mol/L ammonia water, performing magnetic stirring for 10min, and then placing reactants into a 60 ℃ water bath to perform incubation reaction for 12h to obtain a polymer solid, wherein the template molecules are 2-indolone and 6-hydroxynicotinic acid.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
(2) Eluting the polymer solids: after washing the polymer solid 3 times with methanol, after drying and aging under vacuum at 40 ℃ for 6h, the dried polymer was placed in a 100mL round bottom flask, 20mL acetic acid: methanol (1: 5, v/v), magnetic stirring for 3h, washing several times with methanol, washing with methanol, vacuum drying at 40 ℃ for 6h, finally placing the polymer in a soxhlet, washing with acetic acid: the template was eluted with methanol (1: 8, v/v) until no template molecules were detected by UV spectrophotometer.
(3) Preparing a spinning solution: accurately weighing a certain mass of PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature, preparing a PVA solution, weighing a certain mass of properly sieved MIPs powder (accounting for 30% of the mass of the PVA), and ultrasonically dispersing small-particle polymers in methanol uniformly. Finally, the methanol dispersion liquid of MIP and PVA solution are mixed ultrasonically (the volume ratio of the two is 1:2) to obtain 5% PVA spinning solution, and 5% PVA spinning solution of non-imprinted nanofiber membranes (NINFMs) is prepared according to the same method.
(4) Preparing an electrostatic spinning fiber membrane: adding the prepared PVA spinning solution into an injector, and performing under the conditions that the concentration of the spinning solution is 5%, the spinning voltage is 8kv, the spinning distance is 10cm, the flow rate is 20 mu L/min, and the relative humidity is 40-50% to obtain the MINFMs. Non-imprinted nanofiber membranes (NINFMs) were prepared in the same manner.
(5) Crosslinking of the electrospun fiber membrane: soaking the prepared MINFMs (or NINFMs) in 2% GA water solution (sulfuric acid concentration is 2%, sodium sulfate is saturated), crosslinking for 10min, vacuum drying the crosslinked film for 10h, and packaging into sealed bags.
Example 3:
(1) Preparation of patulin molecularly imprinted polymer: mixing a 2-indolone standard substance and a 6-hydroxynicotinic acid standard substance according to a molar ratio of 1: 1 is dissolved in methanol, then 3-aminopropyltriethoxysilane (molar ratio of 4:1 to template molecules) is added for magnetic stirring and prepolymerization for 30min, tetraethoxysilane (molar ratio of 4:1 to template molecules) is added for magnetic stirring for 20min, 1mL of 0.05mol/L ammonia water is added dropwise, after 10min of magnetic stirring, the reactant is put into a 60 ℃ water bath for incubation and reaction for 12h to obtain polymer solid, wherein the template molecules are 2-indolone and 6-hydroxynicotinic acid.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
(2) Eluting the polymer solids: after washing the polymer solid 3 times with methanol, after drying and aging under vacuum at 70 ℃ for 6h, the dried polymer was placed in a 100mL round bottom flask, 40mL acetic acid: methanol (1: 5, v/v), magnetic stirring for 4h, washing several times with methanol, washing with methanol, vacuum drying at 60 ℃ for 8h, finally placing the polymer in a soxhlet, washing with acetic acid: the template was eluted with methanol (1: 8, v/v) until no template molecules were detected by UV spectrophotometer.
(3) Preparing a spinning solution: accurately weighing a certain mass of PVA in ultrapure water, heating and stirring at 90 ℃ until the PVA is completely dissolved, cooling to room temperature, preparing a PVA solution, weighing a certain mass of properly sieved MIPs powder (accounting for 30% of the mass of the PVA), and ultrasonically dispersing small-particle polymers in methanol uniformly. Finally, the methanol dispersion liquid of MIP and PVA solution are mixed ultrasonically (the volume ratio of the two is 1:4) to obtain 6% PVA spinning solution, and 5% PVA spinning solution of non-imprinted nanofiber membranes (NINFMs) is prepared according to the same method.
(4) Preparing an electrostatic spinning fiber membrane: adding the prepared PVA spinning solution into an injector, and performing under the conditions that the concentration of the spinning solution is 6%, the spinning voltage is 15kv, the spinning distance is 15cm, the flow rate is 20 mu L/min, and the relative humidity is 40-50% to obtain the MINFMs. Non-imprinted nanofiber membranes (NINFMs) were prepared in the same manner.
(5) Crosslinking of the electrospun fiber membrane: soaking the prepared MINFMs (or NINFMs) in 3% GA water solution (sulfuric acid concentration is 5%, sodium sulfate is saturated), crosslinking for 20min, vacuum drying the crosslinked film for 10h, and packaging into sealed bags.
FIG. 1 is a schematic view of a scanning electron microscope of the patulin molecularly imprinted polymer of the present invention, wherein the polymer particles are uniform and have more wrinkles;
FIG. 2 is a schematic view of a scanning electron microscope of the patulin molecularly imprinted nanofiber membrane of the present invention, in which the fibers are in good condition and have uniform diameter, and the polymer is uniformly dispersed in the nanofibers;
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of patulin molecular imprinting nanofiber membrane is characterized by comprising the following steps:
Comprises the following steps
Preparation of patulin molecularly imprinted polymer: mixing a 2-indolone standard substance and a 6-hydroxynicotinic acid standard substance according to a molar ratio of 1: 1-4 is dissolved in methanol, then 3-aminopropyltriethoxysilane is added for magnetic stirring for prepolymerization for 10-50min, tetraethoxysilane is added and 1-10mL of ammonia water is dripped, after magnetic stirring for 15-90min, the reactant is placed in a 30-80 ℃ water bath for incubation reaction for 4-24h to obtain a polymer solid, wherein the template molecules are 2-indolone and 6-hydroxynicotinic acid.
Preparation of non-molecularly imprinted polymers (NIP) the procedure was the same as for Molecularly Imprinted Polymers (MIP) except that no template was added.
B eluting polymer solids: washing the polymer solid with methanol for 2-5 times, drying and aging in vacuum at 40-80 ℃ for 4-24h, putting the dried polymer into a round-bottom flask, adding a primary organic solvent for pre-elution, magnetically stirring for 2-8h, washing with methanol, putting at 40-80 ℃ for vacuum drying for 4-12h, and eluting the template from the polymer solid with a secondary organic solvent until the template molecule cannot be detected by an ultraviolet spectrophotometer.
c, preparing a molecularly imprinted nanofiber membrane: carrying out electrostatic spinning on a 4-10% polyvinyl alcohol (PVA) spinning solution containing a Molecularly Imprinted Polymer (MIP), wherein the MIP accounts for 10-40% of the mass fraction of the PVA, under the conditions that the spinning voltage is 8-23kv, the spinning distance is 8-20cm, the flow rate is 10-40 mu L/min and the relative humidity is 40-50%, obtaining a molecularly imprinted nanofiber membrane after the spinning is finished, and preparing non-imprinted nanofiber membranes (NINFMs) according to the same method.
D, crosslinking of the electrostatic spinning fiber membrane: soaking MINFMs (or NINFMs) prepared under the optimal conditions in 1-6% Glutaraldehyde (GA) aqueous solution (wherein the concentration of sulfuric acid is 1-8%, and sodium sulfate is saturated), crosslinking for 10-60min, drying the molecularly imprinted nanofiber membrane in vacuum for 8-24h, and sealing to obtain the patulin molecularly imprinted nanofiber membrane.
2. The method for preparing the patulin molecular imprinting nano-fiber membrane as claimed in claim 1, wherein the primary organic solvent is acetic acid and methanol, the volume ratio of the acetic acid to the methanol is 1-5:7, the secondary organic solvent is acetic acid and methanol, and the volume ratio of the acetic acid to the methanol is 1-4: 9.
3. The method for preparing patulin molecular engram nanofiber membrane as claimed in claim 1, wherein the molar ratio of 3-aminopropyltriethoxysilane as functional monomer to the template molecule is 2-15: 1.
4. The method for preparing the patulin molecular imprinting nano-fiber membrane as claimed in claim 1, wherein the tetraethoxysilane is a cross-linking agent, and the molar ratio of the tetraethoxysilane to the template molecule is 2-20: 1.
5. the method for preparing patulin molecular engram nanofiber membrane as claimed in claim 1, wherein the ammonia water is used as catalyst, and the concentration is 0.05-2 mol/L.
6. The preparation method of the patulin molecular imprinting nanofiber membrane as claimed in claim 1, wherein the polyvinyl alcohol PVA spinning solution comprises polyvinyl alcohol, ultrapure water, methanol and polymer solid powder, the polymer solid powder is dispersed in the methanol by ultrasound, the polyvinyl alcohol is heated and stirred in pure water at 90 ℃ until the polyvinyl alcohol is completely dissolved, then the solution is cooled to room temperature, and the polymer methanol dispersion solution and the polyvinyl alcohol solution are mixed according to a volume ratio of 1:2-4, wherein the molecularly imprinted polymer accounts for 10-40% of the polyvinyl alcohol by mass fraction, and the polyvinyl alcohol (PVA) spinning solution with the concentration of 4-10% is obtained by ultrasonic mixing.
7. The method for preparing patulin molecularly imprinted nanofiber membrane according to claim 1, wherein the electrospinning time is 0.5h to 10 h.
8. the use of the patulin molecularly imprinted nanofiber membrane of claim 1 for adsorbing patulin.
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| CN113846418A (en) * | 2021-06-28 | 2021-12-28 | 南通大学 | Flexible porous SiO with high specific surface area and large aperture2Preparation method of nanofiber membrane |
| CN113893833A (en) * | 2021-11-29 | 2022-01-07 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method and application of molecularly imprinted composite two-dimensional material for high-throughput identification of aflatoxin |
| CN114653347A (en) * | 2021-12-16 | 2022-06-24 | 四川省乾启生物科技有限公司 | Molecularly imprinted magnetic nanofiber membrane and preparation method and application thereof |
| CN114875507A (en) * | 2022-04-28 | 2022-08-09 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of pyrethroid molecular imprinting electrostatic spinning membrane |
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| CN113893833B (en) * | 2021-11-29 | 2024-03-05 | 北京普析通用仪器有限责任公司 | Preparation method and application of molecular imprinting composite two-dimensional material for high-throughput identification of aflatoxin |
| CN114653347A (en) * | 2021-12-16 | 2022-06-24 | 四川省乾启生物科技有限公司 | Molecularly imprinted magnetic nanofiber membrane and preparation method and application thereof |
| CN114875507A (en) * | 2022-04-28 | 2022-08-09 | 中国农业科学院农业质量标准与检测技术研究所 | Preparation method of pyrethroid molecular imprinting electrostatic spinning membrane |
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| NL2026536A (en) | 2021-05-18 |
| CN110560016B (en) | 2022-09-16 |
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