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    • 专利摘要:
    The present invention discloses a method of preparing patulin molecularly imprinted nanofiber membranes (MINFMs). The present invention obtains MINFMs through preparation of molecularly imprinted polymers (MIPs) and electrospinning technology. The MINFMs are obtained with sol-gel technology and electrospinning technology using 2-indolinone and 6-hydroxynicotinic acid as virtual template molecules. The MINFMs of the present invention show excellent specific adsorption of patulin and reusability. The present invention enables specific recognition, efficient separation and enrichment of patulin and achieves specific adsorption of patulin.
    公开号:NL2026536A
    申请号:NL2026536
    申请日:2020-09-24
    公开日:2021-05-18
    发明作者:Shao Hua；She Yongxin；Zhao Minjuan；Wang Jing；Jin Fen；Jin Maojun；Wang Shanshan；Wang Miao；Cao Zhen
    申请人:Institute Of Quality Standard And Testing Tech Foragro Products Chinese Academy Of Agricultural Scie；
    IPC主号:
    专利说明:

    METHOD OF PREPARING PATULIN MOLECULARLY IMPRINTED NANOFIBERMEMBRANES
    TECHNICAL FIELD The present invention relates to fields of molecular imprinting technology (MIT) and electrospinning technology, and in particular to a method of preparing patulin molecularly imprinted nanofiber membranes (MINFMs).
    BACKGROUND Molecularly imprinted sol-gel (MISG) technology introduces imprint molecules into inorganic or inorganic-organic network structures through a sol-gel process to obtain imprinted IO polymers with relatively high stability and excellent affinity. The obtained polymers have a small particle size, a large specific surface area, a specific selectivity and other features, and spatial structures of three-dimensional networks thereof lead to excellent adsorption performance. The MISG technology combines advantages with both sol-gel and molecular imprinting. The disadvantages of poor mechanical stability and easy swelling of organic macromolecule polymers are well solved by this technology. The electrospinning technology uses electrostatic force to produce fine fibers from a spinning solution. This method generates fibers with a smaller diameter, a larger surface area and higher porosity compared with a traditional spinning process. Combination of the electrospinning technology and the MIT can produce electrospun membranes having a specific adsorption capacity, and at the same time increase the specific surface area of molecularly imprinted polymers (MIPs), improving an adsorption capacity and a mass transfer rate. Therefore, the present invention combines the three processes and successfully prepares MINFMs, which not only have a large specific surface area and high porosity, but also have excellent flexibility, mechanical strength and reusability and other advantages. Compared with MIPs, the present invention also has advantages of easy separation from a test sample, relatively high mass transfer rate and binding capacity. Moreover, the present invention addresses the problem that an electrospun fiber membrane has no specific adsorption capacity. Furthermore, the present invention establishes a patulin extraction and enrichment procedure which eliminates the need for a solid phase extraction device, thereby simplifying operation steps. The present invention can be used for the extraction and enrichment of patulin in practical samples. In view of this, the present invention is specifically proposed.
    SUMMARY An objective of the present invention is to provide a method of preparing patulin MINFMs. To achieve the above objective, the present invention adopts the following technical solutions: The present invention includes the following steps: Step A. Preparation of patulin polymers: dissolving a 2-indolinone standard and a 6-hydroxynicotinic acid standard in a molar ratio of 1:(1-4) in methanol, then adding S 3-aminopropyltriethoxysilane, magnetically stirring for pre-polymerization for 10-50 min, adding tetraethoxysilane, adding 1-10 mL ammonia water dropwise, magnetically stirring for 15-90 min, incubating reactants with a 30-80°C water bath for reaction for 4-24 h to obtain polymer solids, where template molecules are 2-imdolinone and 6-hydroxynicotinic acid, preparing non-molecularly imprinted polymers (NIPs) by a method the same as that of MIPs except that no template is added.
    Step B. Elution of polymer solids: washing the polymer solids with methanol for 2-5 times, vacuum drying and aging at 40-80°C for 4-24 h, adding dried polymers into a 100 mL round bottom flask, adding a first organic solvent for pre-elution, magnetically stirring for 2-8 h, rinsing with methanol, vacuum drying at 40-80°C for 4-12 h, eluting templates from the polymer solids with a second organic solvent until no template molecule is detected by an ultraviolet spectrophotometer.
    Step C. Preparation of MINFMs: electrospinning with a 4-10% polyvinyl alcohol (PVA) spinning solution containing the MIPs (where the MIPs takes up 10-40% of the mass fraction of the PVA) at a voltage of 8-23 kV, a spinning distance of 8-20 cm, a flow rate of 10-40 pL/min and a relative humidity of 40-50% to obtain the MINFMs; preparing non-imprinted nanofiber membranes (NINFMs) by the same method.
    Step D. Crosslink of electrospun fiber membranes: immersing the MINFMs (or NINFMs) prepared under optimal conditions in a 1-6% glutaraldehyde (GA) aqueous solution (where sulfuric acid has a concentration of 1-8%, sodium sulfate is saturated), crosslinking for 10-60 min, vacuum drying the MINFMs for 8-24 h and sealing to obtain the patulin MINFMs.
    Specifically, the first organic solvent is acetic acid and methanol in a volume ratio of (1-5):7, the second organic solvent is acetic acid and methanol in a volume ratio of (1-4):9.
    Specifically, the 3-aminopropyltriethoxysilane 1s a functional monomer, and a molar ratio thereof to the template molecule is (2-15):1.
    Specifically, the tetraethoxysilane is a crosslinking agent, and a molar ratio thereof to the template molecules is (2-20): 1.
    Specifically, the ammonia water is a catalyst having a concentration of 0.05-2 mol/L.
    Specifically, the PVA spinning solution includes PVA, ultrapure water, methanol and polymer solid powders. The PVA spinning solution is obtained by dispersing the polymer solid powders uniformly in the methanol by ultrasound, heating the PVA and the ultrapure water in a mass ratio of 1:(10-25) at 90°C under stirring until complete dissolution is achieved, cooling to room temperature, mixing a dispersion of the polymers in methanol with a PVA solution in which the MIPs take up 10-40% of mass fraction of the PVA in a volume ratio of 1:(2-4) uniformly by ultrasound to obtain the PVA spinning solution. Specifically, the electrospinning is carried out for 0.5-10 h.
    Use of patulin MINFMs in adsorption of patulin.
    The present invention has the following beneficial effects: The present invention can enable specific recognition, efficient separation and enrichment of patulin in agricultural products through molecular imprinting recognition technology. The present invention has excellent adsorption and separation performances, and can achieve specific adsorption of patulin.
    BRIEF DESCRIPTION OF DRAWINGS FIG 1 shows a scanning electron microscopy (SEM) image of the patulin MIPs of the present invention; FIG 2 shows an SEM image of the patulin MINFMs of the present invention.
    DETAILED DESCRIPTION The present invention will be explained in detail with reference to the accompanying drawings. In the present example, patulin MIPs are prepared.
    2-indolinone standard and a 6-hydroxynicotinic acid standard are placed in a 100 mL round bottom flask. 2-10 mL of methanol is added. After dissolution of the template molecules, 3-aminopropyltriethoxysilane (in a molar ratio to the template molecules of (2-15).1) 1s added and magnetically stirred for 10-50 min for pre-polymerization. Tetraethoxysilane (in a molar ratio to the template molecules of (2-20):1) is added and magnetically stirred for 10-60 min.
    1-10 mL ammonia water (0.05-2 mol/L) is added and magnetically stirred for 5-30 min. The opening is sealed with a sealing film having pinholes. A 30-80°C water bath is used to incubate the reaction for 4-24 h. After the reaction is completed, the obtained solids are washed with methanol for 2-5 times, and vacuum dried at 40-80°C for aging for 4-24 h. The dried polymers are put into a 100 mL round bottom flask, added with 10-100 mL of acetic acid: methanol ((1-5):7, v/v), magnetically stirred for 2-8 h, rinsed with methanol for several times, and vacuum dried at 40-80°C for 4-12 h. Finally, the polymers are placed in a Soxhlet extractor. The templates are eluted with an acetic acid: methanol ((1-4):9, v/v) solution until no template molecule 1s detected by an ultraviolet spectrophotometer.
    Preparation of NIPs is the same as that of the MIPs except that no template is added.
    Preparation of patulin MINFMs
    Preparation of a spinning solution: a certain amount of PVA is accurately weighed, added to ultrapure water, heated at 90°C under stirring until complete dissolution is achieved, and then cooled to room temperature. A certain amount of MIP powders screened appropriately is weighed, and small polymer particles are selected and dispersed in methanol uniformly by ultrasound (the mass of MIPs taking up 10-40% of the mass of PVA). Finally, a certain volume of the dispersion of the MIPs in methanol is added to a certain volume of PVA solution (in a volume ratio of 1:(2-4)) and mixed well to prepare a PVA spinning solution containing 4-10% MINFMs. A PVA spinning solution containing 4-10% NINFMs is prepared by the same method.
    Preparation of electrospun fiber membranes: the prepared PVA spinning solution (with a concentration of 4-10%) is added into a syringe. MINFMs have relatively desired morphology when prepared at a spinning voltage of 8-23 kV, a spinning distance of 8-20 cm, a flow rate of 10-40 uL/min and a relative humidity of 40-50%. NINFMs are prepared in the same way.
    Crosslink of electrospun fiber membranes: the MINFMs (or NINFMs) prepared under optimal conditions are immersed in a 1-6% GA aqueous solution (where sulfuric acid has a concentration of 1-8%, and sodium sulfate is saturated) and allowed to crosslink for 10-60 min. The crosslinked membranes are vacuum dried for 8-24 h and sealed in bags for use. Extraction and enrichment of patulin A certain amount of MINFMs is added to 1-5 mL of patulin in acetonitrile, shaken for adsorption for 0.5-4 h. The upper solution is washed off simply with methanol. Elution is carried out with a methanol-acetic acid solution ((3-9):1, v/v) for 0.5-4 h. The concentration of free patulin in the eluate 1s determined, and the recovery rate can reach 98%.
    Example 1 (1) Preparation of patulin MIPs: a 2-indolinone standard and a 6-hydroxynicotinic acid standard in a molar ratio of 1:1 were dissolved in methanol, then added with 3-aminopropyltriethoxysilane (in a molar ratio to template molecules of 2:1), magnetically stirred for pre-polymerization for 10 min. Tetraethoxysilane (in a molar ratio to the template molecules of 4:1) was added and magnetically stirred for 20 min. 1 mL of 0.05 mol/L ammonia water was added dropwise, and magnetically stirred for 5 min. Then reactants were incubated with a 30°C water bath for reaction for 5 h to obtain polymer solids. The template molecules were 2-indolinone and 6-hydroxynicotinic acid.
    Preparation of NIPs was the same as that of the MIPs except that no template was added. Elution of polymer solids: the polymer solids were washed with methanol for 3 times, vacuum dried and aged at 40°C for 6 h. The dried polymers were added to a 100 mL round bottom flask. 20 mL acetic acid: methanol (1:5, v/v) was added and magnetically stirred for 3 h. Rinsing was carried out with methanol for several times, and then vacuum drying was carried out at 40°C for 6 h. Finally, the polymers were added to a Soxhlet extractor, and the templates were eluted with an acetic acid: methanol (1:8, v/v) solution until no template molecule was detected by an ultraviolet spectrophotometer.
    5 (3) Preparation of a spinning solution: a certain amount of PVA was accurately weighed, added to ultrapure water, heated at 90°C under stirring until complete dissolution was achieved, and then cooled to room temperature to prepare a PVA solution. A certain amount of MIP powders screened appropriately (taking up 30% of the mass of PVA) was weighed, and small polymer particles were dispersed in methanol uniformly by ultrasound. Finally, the dispersion of the MIPs in methanol was mixed with the PVA solution (in a volume ratio of 1:2) by ultrasound to obtain a 5% PVA spinning solution. The same method was used to prepare a 5% PVA spinning solution of NINFMs.
    (4) Preparation of electrospun fiber membranes: the prepared PVA spinning solution was added into a syringe. MINFMs were prepared with the 5% spinning solution at a spinning voltage of 8 kV, a spinning distance of 10 cm, a flow rate of 20 uL/min and a relative humidity of 40-50%. NINFMs were prepared by the same method.
    (5) Crosslink of electrospun fiber membranes: the prepared MINFMs (or NINFMs) were immersed in a 2% GA aqueous solution (where sulfuric acid had a concentration of 2%, and sodium sulfate was saturated) and allowed to crosslink for 10 min. The crosslinked membranes were vacuum dried for 10 h and sealed in bags for use.
    Example 2 (1) Preparation of patulin MIPs: a 2-indolinone standard and a 6-hydroxynicotinic acid standard in a molar ratio of 1:2 were dissolved in methanol, then added with 3-aminopropyltriethoxysilane (in a molar ratio to template molecules of 4:1), magnetically stirred for pre-polymerization for 10 min. Tetraethoxysilane (in a molar ratio to the template molecules of 6:1) was added and magnetically stirred for 20 min. 2 mL of 0.05 mol/L ammonia water was added dropwise, and magnetically stirred for 10 min. Then reactants were incubated with a 60°C water bath for reaction for 12 h to obtain polymer solids. The template molecules were 2-indolinone and 6-hydroxynicotinic acid.
    Preparation of NIPs was the same as that of the MIPs except that no template was added.
    (2) Elution of polymer solids: the polymer solids were washed with methanol for 3 times, vacuum dried and aged at 40°C for 6 h. The dried polymers were added to a 100 mL round bottom flask. 20 mL acetic acid: methanol (1:5, v/v) was added and magnetically stirred for 3 h. Rinsing was carried out with methanol for several times, and then vacuum drying was carried out at 40°C for 6 h. Finally, the polymers were added to a Soxhlet extractor, and the templates were eluted with an acetic acid: methanol (1:8, v/v) solution until no template molecule was detected by the ultraviolet spectrophotometer.
    (3) Preparation of a spinning solution: a certain amount of PVA was accurately weighed, added to ultrapure water, heated at 90°C under stirring until complete dissolution was achieved, and then cooled to room temperature to prepare a PVA solution. A certain amount of MIP powders screened appropriately (taking up 30% of the mass of PVA) was weighed, and small polymer particles were dispersed in methanol uniformly by ultrasound. Finally, the dispersion of the MIPs in methanol was mixed with the PVA solution (in a volume ratio of 1:2) by ultrasound to obtain a 5% PVA spinning solution. The same method was used to prepare a 5% PVA spinning solution of NINFMs.
    (4) Preparation of electrospun fiber membranes: the prepared PVA spinning solution was added into a syringe. MINFMs were prepared with the 5% spinning solution at a spinning voltage of 8 kV, a spinning distance of 10 cm, a flow rate of 20 pL/min and a relative humidity of 40-50%. NINFMs were prepared by the same method.
    (5) Crosslink of electrospun fiber membranes: the prepared MINFMs (or NINFMs) were immersed in a 2% GA aqueous solution (where sulfuric acid had a concentration of 2%, and sodium sulfate was saturated) and allowed to crosslink for 10 min. The crosslinked membranes were vacuum dried for 10 h and sealed in bags for use.
    Example 3 (1) Preparation of patulin MIPs: a 2-indolinone standard and a 6-hydroxynicotinic acid standard in a molar ratio of 1:1 were dissolved in methanol, then added with 3-aminopropyltriethoxysilane (in a molar ratio to the template molecules of 4:1), magnetically stirred for pre-polymerization for 30 min. Tetraethoxysilane (in a molar ratio to template molecules of 4:1) was added and magnetically stirred for 20 min. 1 mL of 0.05 mol/L ammonia water was added dropwise, and magnetically stirred for 10 min. Then reactants were incubated with a 60°C water bath for reaction for 12 h to obtain polymer solids. The template molecules were 2-indolinone and 6-hydroxynicotinic acid.
    Preparation of NIPs was the same as that of the MIPs except that no template was added.
    (2) Elution of polymer solids: the polymer solids were washed with methanol for 3 times, vacuum dried and aged at 70°C for 6 h. The dried polymers were added to a 100 mL round bottom flask. 40 mL acetic acid: methanol (1:5, v/v) was added and magnetically stirred for 4 h. Rinsing was carried out with methanol for several times, and then vacuum drying was carried out at 60°C for 8 h. Finally, the polymers were added to a Soxhlet extractor, and the templates were eluted with an acetic acid: methanol (1:8, v/v) solution until no template molecule was detected by the ultraviolet spectrophotometer.
    (3) Preparation of a spinning solution: a certain amount of PVA was accurately weighed, added to ultrapure water, heated at 90°C under stirring until complete dissolution was achieved, and then cooled to room temperature to prepare a PVA solution. A certain amount of MIP powders screened appropriately (taking up 30% of the mass of PVA) was weighed, and small polymer particles were dispersed in methanol uniformly by ultrasound. Finally, the dispersion of the MIPs in methanol was mixed with the PVA solution (in a volume ratio of 1:4) by ultrasound to obtain a 6% PVA spinning solution. The same method was used to prepare a 5% PVA spinning solution of NINFMs.
    (4) Preparation of electrospun fiber membranes: the prepared PVA spinning solution was added into a syringe. MINFMs were prepared with the 6% spinning solution at a spinning voltage of 15 kV, a spinning distance of 15 cm, a flow rate of 20 pL/min and a relative humidity of 40-50%. NINFMs were prepared by the same method.
    (5) Crosslink of electrospun fiber membranes: the prepared MINFMs (or NINFMs) were immersed in a 3% GA aqueous solution (where sulfuric acid had a concentration of 5%, and sodium sulfate was saturated) and allowed to crosslink for 20 min. The crosslinked membranes were vacuum dried for 10 h and sealed in bags for use.
    FIG 1 showed an SEM image of the patulin MIPs of the present invention, where the polymer particles were uniform with many wrinkles.
    FIG 2 showed an SEM image of the patulin MINFMs of the present invention, where the fibers were at a desired state with a uniform diameter and the polymers were dispersed uniformly inside the nanofibers.
    The above descriptions are merely preferred examples of the present invention, and are not intended to limit the present invention. Any modification, equivalent substitute and improvement without departing from the spirit and principle of the present invention shall be included within the protection scope of the present invention.
    权利要求:
    Claims (8)
    [1]
    1. A method for preparing patulin molecularly printed nanofiber membranes (MINFMs}, comprising the following steps: Step A. Preparation of patulin molecularly printed polymers (MIPs): dissolving a 2-indolinone standard and a 6-hydroxynicotinic acid standard in a molar ratio of 1:{1-4) in methanol, then addition of 3-aminopropyltriethoxysilane, magnetic stirring for pre-polymerization for 10-50 min, addition of tetraethoxysilane, dropwise addition of 1-10 ml of ammonia water, magnetic stirring for 15-90 min, incubating reactants with a 30-80°C reaction water bath for 4-24 hours to obtain solid polymers, wherein template molecules are 2-indolinone and 6-hydroxynicotinic acid; preparing non-molecularly imprinted polymers (NIPs) by a method similar to that of MIPs, except that no template is added; Step B. Elution of polymer solids: washing the polymer solids 2-5 times with methanol, vacuum drying and aging at 40-80°C for 4-24 hours, adding dried polymers to a round bottom flask, adding a first organic solvent for pre-elution, magnetic stirring for 2-8 hours, rinsing with methanol, vacuum drying at 40-80°C for 4-12 hours, eluting templates from the solid polymers with a second organic solvent until no template molecule is formed detected by an ultraviolet spectrophotometer; Step C. Preparation of MINFMs: Electrospinning with a 4-10% polyvinyl alcohol (PVA) spinning solution containing the MIPs (with the MIPs occupying 10-40% of the mass fraction of the PVA) at a voltage of 8-23 kV , a spinning distance of 8-20 cm, a flow rate of 10-40 µL/min and a relative humidity of 40-50% to obtain the MINFMs; preparing non-molecularly printed nanofiber membranes (NINFMs) by the same method; Step D. Crosslinking of Electrospun Fiber Membranes: Immersing the MINFMs (or NINFMs) prepared under optimal conditions in a 1-6% glutaraldehyde (GA) aqueous solution (where sulfuric acid has a concentration of 1-8%, sodium sulfate is saturated }, crosslinking for 10-60 min, vacuum drying the MINFMs for 8-24 hours and sealing to obtain the patulin MINFMs.
    [2]
    The method for preparing MINFMs according to claim 1, wherein the first organic solvent is acetic acid and methanol in a volume ratio of (1-5):7, and the second organic solvent is acetic acid and methanol in a volume ratio of (1-4). ):9.
    [3]
    The method for preparing MINFMs according to claim 1, wherein the 3-aminopropyltriethoxysilane is a functional monomer and a molar ratio thereof to the template molecules is (2-15):1.
    [4]
    The method for preparing MINFMs according to claim 1, wherein the tetraethoxysilane is a crosslinking agent and a molar ratio thereof to the template molecules is (2-20):1.
    [5]
    The method for preparing MINFMs according to claim 1, wherein the ammonia water is a catalyst having a concentration of 0.05-2 mol/l.
    [6]
    The method for preparing MINFMs according to claim 1, wherein the PVA spinning solution comprises PVA, ultrapure water, methanol and solid polymeric powders, and the 4-10% PVA spinning solution is obtained by uniformly dispersing the polymeric solid powders in the methanol by ultrasound, heating the PVA and ultrapure water to 90°C with stirring until complete dissolution is reached, cooling to room temperature, evenly sonicating a dispersion of the polymers in methanol with a PVA solution containing MIPs occupy 10-40% of the mass fraction of the PVA in a volume ratio of 1:(2-4).
    [7]
    The method for preparing MINFMs according to claim 1, wherein the electrospinning is performed for 0.5-10 hours.
    [8]
    Use of the patulin MINFMs prepared according to the method of claim 1 in the adsorption of patulin.
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    CN201910905475.8A|CN110560016A|2019-09-24|2019-09-24|Preparation method of patulin molecularly imprinted nanofiber membrane|
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