CN113134345B - Preparation and application of molecular imprinting composite membrane based on cage-shaped filler - Google Patents

Preparation and application of molecular imprinting composite membrane based on cage-shaped filler Download PDF

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CN113134345B
CN113134345B CN202110437487.XA CN202110437487A CN113134345B CN 113134345 B CN113134345 B CN 113134345B CN 202110437487 A CN202110437487 A CN 202110437487A CN 113134345 B CN113134345 B CN 113134345B
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molecular imprinting
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CN113134345A (en
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李雪琴
赵小宾
程云
高佳齐
魏忠
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Shihezi University
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Abstract

The invention discloses preparation and application of a molecular imprinting composite membrane based on a cage-shaped filler, and relates to the technical field of verbascoside separation. The invention comprises the following steps: the method comprises the following steps: modifying the surface of a polyvinylidene fluoride (PVDF) membrane to form a polydopamine (pDA) thin layer to obtain a pDA modified PVDF membrane; step two: preparation of NH Using pDA modified PVDF Membrane2-POSS @ PVDF film; step three: adding a molecular template and a functional monomer into a solvent to obtain a prepolymerization reaction solution; step four: adding a cross-linking agent and an initiator into the prepolymerization reaction solution to obtain a membrane casting solution; step five: reacting NH2Placing the POSS @ PVDF membrane into the membrane casting solution, deoxidizing, heating, and carrying out polymerization reaction to obtain a blotting membrane; step six: imprinting the composite membraneEluting the template molecules by eluent to obtain the molecular imprinting composite membrane. According to the invention, the phenylethanoid glycosides in cistanche tubulosa is separated and purified through the specific recognition effect of the phenylethanoid glycosides molecularly imprinted composite membrane, so that the separation performance and the stability of the molecularly imprinted membrane are improved.

Description

Preparation and application of molecular imprinting composite membrane based on cage-shaped filler
Technical Field
The invention belongs to the technical field of verbascoside separation, and particularly relates to preparation and application of a molecularly imprinted composite membrane based on a cage-shaped filler.
Background
Cistanche tubulosa is one of the rare tonifying Chinese herbal medicines and is a parasitic plant in desert mainly produced in southern Xinjiang. Research shows that the active components in cistanche tubulosa are mainly phenylethanoid glycosides. Phenylethanoid glycosides have the efficacies of invigorating kidney yang, resisting oxidation, resisting aging, enhancing immunity and the like, and are widely applied to the fields of medicines, health care, foods and the like. Wherein acteoside and echinacoside are index components of phenethyl alcohol glycoside compounds in cistanche tubulosa, and have large molecular weight, complex structure and similarity. Therefore, the separation of pure products of acteoside and echinacoside with single structures is more difficult. In order to obtain a high-purity product, a high-selectivity molecular imprinting composite membrane separation material needs to be designed for a target object.
The molecular imprinting technology is a molecular recognition technology with high selectivity, high efficiency and simple operation, and shows better effect in the separation of active ingredients of natural products. The molecular imprinting membrane has great advantages in the separation of active components of natural products, not only has the advantages of high selectivity and high efficiency of the molecular imprinting technology, but also has the advantages of mild membrane separation conditions, low energy consumption and simple process. However, the currently reported molecularly imprinted membranes have low mechanical strength, and the space for the molecule to recognize the hole is easily deformed during the separation process and the stability of the complementary functional group position is poor.
Disclosure of Invention
The invention aims to provide preparation and application of a molecular imprinting composite membrane based on a cage-shaped filler, and solves the problems in the background art.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a preparation method and application of a molecular imprinting composite membrane based on a cage-shaped filler, which comprises the following steps:
the method comprises the following steps: forming a polydopamine (pDA) thin layer on the surface of a polyvinylidene fluoride (PVDF) membrane to obtain a pDA modified PVDF membrane;
step two: preparation of NH Using pDA modified PVDF Membrane2-POSS @ PVDF film;
step three: adding a molecular template and a functional monomer into a solvent to obtain a prepolymerization reaction solution;
step four: adding a cross-linking agent and an initiator into the prepolymerization reaction solution to obtain a membrane casting solution;
step five: reacting NH2Placing the POSS @ PVDF membrane into the membrane casting solution, deoxidizing, heating, and carrying out polymerization reaction to obtain a blotting membrane;
step six: and eluting the template molecules of the imprinted composite membrane by using eluent to obtain the molecularly imprinted composite membrane.
Preferably, the method for preparing the pDA modified PVDF membrane in the first step comprises the following steps:
firstly, a polyvinylidene fluoride (PVDF) membrane is immersed into 50 mL of 10 mmol of Tris-HC1 aqueous solution for 5 min; then, 100-200 mg of Dopamine (DA) is added into a Tris-HC1 aqueous solution, and the mechanical oscillation is continued for 6-30 h at room temperature to obtain a pDA modified PVDF membrane (pDA @ PVDF);
wherein the pH value of the Tris-HC1 aqueous solution is 8.5.
Preferably, NH is prepared in step two2-the POSS @ PVDF film process comprises the steps of:
firstly, 100-500 mg of amino polyhedral oligomeric silsesquioxane (NH)2POSS) was placed in 50 mL of methanol solution for 30 min to obtain NH2-POSS methanol solution; then a piece of pDA modified PVDF membrane was placed in a hydrothermal reaction kettle, while 50 mL of NH was added2Adding a POSS methanol solution into a hydrothermal kettle, reacting at the temperature of 70 ℃ for 24 hours, and repeatedly washing an obtained product by using methanol and ethanol; finally, drying the cleaned product to constant weight to obtain the productNH2-POSS @ PVDF film.
Preferably, in the third step, the template molecule is acteoside, the functional monomer is 4-vinylpyridine, and the solvent comprises methanol, acetonitrile and DMF;
wherein the volume ratio of acetonitrile to DMF is 1: 1.5;
the preparation method of the prepolymerization reaction solution comprises the following steps:
adding 0.2 mmol of template molecules and 6 mmol of functional monomers into a solvent, mixing, performing ultrasonic treatment, putting into a constant-temperature oscillator, and performing prepolymerization for 2 hours to obtain a prepolymerization solution;
wherein the temperature of the constant temperature oscillator is 30 ℃, and the oscillation rotating speed is 150 rpm.
Preferably, the crosslinking agent is ethylene glycol dimethacrylate, and the initiator is azobisisobutyronitrile;
the preparation method of the membrane casting solution in the fourth step comprises the following steps:
respectively adding 6 mmol of cross-linking agent and 0.1 mmol of initiator into the prepolymerization reaction solution, uniformly mixing, and performing ultrasonic treatment for 10 min to obtain a membrane casting solution.
Preferably, the preparation method of the blotting membrane in the fifth step specifically comprises the following steps:
first NH2And putting the POSS @ PVDF membrane into the membrane casting solution, deoxidizing, and carrying out polymerization reaction for 24 hours at the temperature of 60-68 ℃ to obtain the imprinting membrane.
Preferably, the eluent in the sixth step comprises methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is 9: 1.
The invention has the following beneficial effects:
1. according to the invention, the phenylethanoid glycosides in cistanche tubulosa is separated and purified through the specificity recognition effect of the phenylethanoid glycosides molecularly imprinted composite membrane, so that the separation performance and the stability of the molecularly imprinted membrane are improved, and a new method is provided for efficiently separating the phenylethanoid glycosides in active ingredients of natural products.
2. The method disclosed by the invention has the advantages of high separation and purification efficiency, simplicity in operation, low energy consumption and the like.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method and application of a molecular imprinting composite membrane based on a cage-shaped filler, which comprises the following steps:
the method comprises the following steps: forming a polydopamine (pDA) thin layer on the surface of a polyvinylidene fluoride (PVDF) membrane to obtain a pDA modified PVDF membrane;
step two: preparation of NH Using pDA modified PVDF Membrane2-POSS @ PVDF film;
step three: adding a molecular template and a functional monomer into a solvent to obtain a prepolymerization reaction solution;
step four: adding a cross-linking agent and an initiator into the prepolymerization reaction solution to obtain a membrane casting solution;
step five: reacting NH2Placing the POSS @ PVDF membrane into the membrane casting solution, deoxidizing, heating, and carrying out polymerization reaction to obtain a blotting membrane;
step six: and eluting the template molecules of the imprinted composite membrane by using eluent to obtain the molecularly imprinted composite membrane.
Wherein the method for preparing the pDA modified PVDF membrane in the first step comprises the following steps:
firstly, a polyvinylidene fluoride (PVDF) membrane is immersed into 50 mL of 10 mmol of Tris-HC1 aqueous solution for 5 min; then, 100-200 mg of Dopamine (DA) is added into a Tris-HC1 aqueous solution, and the mechanical oscillation is continued for 6-30 h at room temperature to obtain a pDA modified PVDF membrane (pDA @ PVDF);
wherein the pH value of the Tris-HCl aqueous solution is 8.5.
Wherein, NH is prepared in the second step2-the POSS @ PVDF film process comprises the steps of:
firstly, 100-500 mg of amino polyhedral oligomeric silsesquioxane (NH)2POSS) was placed in 50 mL of methanol solution for 30 min to obtain NH2-POSS methanol solution; then a piece of pDA modified PVDF membrane was placed in a hydrothermal reaction kettle, while 50 mL of NH was added2Adding a POSS methanol solution into a hydrothermal kettle, reacting at the temperature of 70 ℃ for 24 hours, and repeatedly washing an obtained product by using methanol and ethanol; finally, drying the cleaned product to constant weight to prepare NH2-POSS @ PVDF film.
In the third step, the template molecule is acteoside, the functional monomer is 4-vinylpyridine, and the solvent comprises methanol, acetonitrile and DMF;
wherein the volume ratio of acetonitrile to DMF is 1: 1.5;
the preparation method of the prepolymerization reaction solution comprises the following steps:
adding 0.2 mmol of template molecules and 6 mmol of functional monomers into a solvent, mixing, performing ultrasonic treatment, putting into a constant-temperature oscillator, and performing prepolymerization for 2 hours to obtain a prepolymerization solution;
wherein the temperature of the constant temperature oscillator is 30 ℃, and the oscillation rotating speed is 150 rpm.
Wherein the crosslinking agent is ethylene glycol dimethacrylate, and the initiator is azobisisobutyronitrile;
the preparation method of the membrane casting solution in the fourth step comprises the following steps:
respectively adding 6 mmol of cross-linking agent and 0.1 mmol of initiator into the prepolymerization reaction solution, uniformly mixing, and performing ultrasonic treatment for 10 min to obtain a membrane casting solution.
The preparation method of the imprinting mold in the fifth step specifically comprises the following steps:
first NH2And putting the POSS @ PVDF membrane into the membrane casting solution, deoxidizing, and carrying out polymerization reaction for 24 hours at the temperature of 60-68 ℃ to obtain the blotting membrane.
Wherein the eluent in the sixth step comprises methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is 9: 1.
Example 1
The molecular imprinting composite membrane is manufactured by the method disclosed by the invention, and the selective adsorption experiment of the cistanche tubulosa extract comprises the following steps:
wherein 100 mg of Dopamine (DA) is taken, the self-polymerization time of the Dopamine (DA) is 24h, and NH is added2100 mg of POSS;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption amount of 32.63 mg/g, echinacoside has an adsorption amount of 14.14 mg/g, and selectivity of 2.10.
Example 2:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 120 mg of Dopamine (DA);
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption capacity of 32.63 mg/g, echinacoside adsorption capacity of 13.91 mg/g, and selectivity of 2.18.
Example 3:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 140 mg of Dopamine (DA);
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the adsorption amount of purified verbascoside reaches 33.16 mg/g, the adsorption amount of echinacoside reaches 13.78 mg/g, and the selectivity is 2.20.
Example 4:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 160 mg of Dopamine (DA);
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption capacity of 68.19 mg/g, echinacoside has an adsorption capacity of 21.79 mg/g, and selectivity of 2.95.
Example 5:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA);
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the adsorption capacity of purified verbascoside reaches 91.25 mg/g, the adsorption capacity of echinacoside reaches 26.61 mg/g, and the selectivity is 3.25.
Example 6:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 200 mg of Dopamine (DA);
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption amount of 103.59 mg/g, echinacoside adsorption amount of 31.23 mg/g, and selectivity of 3.14.
Example 7:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 6 h;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the adsorption capacity of purified verbascoside reaches 30.57 mg/g, the adsorption capacity of echinacoside reaches 10.72 mg/g, and the selectivity is 2.87.
Example 8:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 12 h;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption capacity of 58.71 mg/g, echinacoside adsorption capacity of 16.98 mg/g, and selectivity of 3.62.
Example 9:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 18 h;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption capacity of 57.98 mg/g, echinacoside adsorption capacity of 18.23 mg/g, and selectivity of 3.32.
Example 10:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 30 h;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Thereafter, the purified verbascoside content was determined by HPLC and found to be: the purified verbascoside has an adsorption capacity of 56.03 mg/g, echinacoside has an adsorption capacity of 23.03 mg/g, and selectivity of 2.51.
Example 11:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 12 h, and the amount of the amino cage polysilsesquioxane is 200 mg;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption amount of 91.87 mg/g, echinacoside has an adsorption amount of 28.70 mg/g, and selectivity of 3.47.
Example 12:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 12 h, and the amount of the amino cage polysilsesquioxane is 300 mg;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption capacity of 95.60 mg/g, echinacoside adsorption capacity of 28.93 mg/g, and selectivity of 3.61.
Example 13:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 12 h, and the amount of the amino cage polysilsesquioxane is 400 mg;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the purified verbascoside has an adsorption capacity of 99.47 mg/g, echinacoside adsorption capacity of 23.78 mg/g, and selectivity of 4.63.
Example 14:
the method disclosed by the invention is used for manufacturing the molecular imprinting composite membrane, and the selective adsorption experiment of the cistanche tubulosa extract is different from the first embodiment in that:
taking 180 mg of Dopamine (DA), wherein the self-polymerization time of the Dopamine (DA) is 12 h, and the amount of the amino cage polysilsesquioxane is 500 mg;
placing the prepared molecular imprinting composite membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a shaker, setting the rotation speed of the shaker to be 150 rpm, and shaking at the temperature of 30 ℃ for 24 h.
Then, the content of purified verbascoside is determined by HPLC, and the determination result is as follows: the adsorption capacity of purified verbascoside reaches 93.09 mg/g, the adsorption capacity of echinacoside reaches 29.27 mg/g, and the selectivity is 3.44.
Example 15:
the molecularly imprinted composite membrane manufactured by the method disclosed by the invention is the same as the molecularly imprinted composite membrane prepared in the embodiment 13, and the permeability selection experiment of the cistanche tubulosa extract solution comprises the following steps:
fixing the prepared molecular imprinting composite membrane (measuring the effective membrane area) in an H-shaped permeation device, adding 50 mL and 0.5 mg/mL mixed solution of verbascoside and echinacoside into one side of a feed liquid pool, adding the same positive ultrapure water into one side of a receiving pool, and placing magnetons at two sides for sealing and stirring;
then, HPLC is adopted to determine the content of purified verbascoside, the experiment is carried out for 24h, and the determination result is as follows: the acteoside has permeability coefficient of 5.13 × 10-7 cm2(s) Echinacoside permeability coefficient of 3.61X 10-6 cm2Per s, the permselectivity factor was 7.02.
Example 16:
this example is a comparative example 1, the difference between the non-molecularly imprinted composite membrane prepared in this example and the molecularly imprinted membrane prepared in example 13 is that verbascoside, which is a template molecule, is not added, and the rest is the same, and the non-molecularly imprinted composite membrane prepared in this example is used for selective adsorption experiment of cistanche tubulosa extract:
placing the non-molecular imprinting membrane in a 50 mL conical flask, adding the extracting solution, sealing and placing on a 150 rpm shaking table, and performing shaking adsorption for 24h at 30 ℃;
thereafter, the purified verbascoside content was determined by HPLC: the purified verbascoside has an adsorption amount of 53.92 mg/g, echinacoside has an adsorption amount of 48.83 mg/g, and selectivity of 1.02.
Example 17:
this example is a comparison example 2, the non-molecularly imprinted composite membrane prepared in this example is the same as the non-molecularly imprinted composite membrane prepared in example 16, and the non-molecularly imprinted composite membrane prepared in this example is used for the osmotic selectivity test of cistanche tubulosa extract:
fixing the membrane (with the effective membrane area measured) in an H-shaped permeation device, adding 50 mL and 0.5 mg/mL mixed solution of verbascoside and echinacoside into one side of a feed liquid pool, adding ultrapure water with the same volume into one side of a receiving pool, and placing magnetons at two sides for sealing and stirring;
then, HPLC is used for measuring the content of the verbascoside on both sides, the experiment is carried out for 24 hours, and the measured result is as follows: the acteoside has permeability coefficient of 5.01 × 10-7 cm2(s) Echinacoside permeability coefficient of 4.84 × 10-7 cm2Per s, the permselectivity factor was 0.96.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (7)

1. A preparation method of a molecular imprinting composite membrane based on a cage-shaped filler is characterized by comprising the following steps:
the method comprises the following steps: modifying the surface of a polyvinylidene fluoride (PVDF) membrane to form a polydopamine (pDA) thin layer to obtain a pDA modified PVDF membrane;
step two: preparation of NH Using pDA modified PVDF Membrane2-POSS @ PVDF membrane, the steps of the membrane preparation method in step two being: firstly 100-500 mg of amino polyhedral oligomeric silsesquioxane (NH)2POSS) was placed in 50 mL of methanol solution for 30 min to obtain NH2-POSS methanol solution; then a piece of pDA modified PVDF membrane was placed in a hydrothermal reaction kettle, while 50 mL of NH was added2Adding a POSS methanol solution into a hydrothermal kettle, reacting at the temperature of 70 ℃ for 24 hours, and repeatedly washing an obtained product by using methanol and ethanol; finally, drying the cleaned product to constant weight to prepare NH2-POSS @ PVDF film;
step three: adding verbascoside and 4-vinylpyridine into a solvent to obtain a prepolymerization reaction solution;
step four: adding ethylene glycol dimethacrylate and azobisisobutyronitrile into the prepolymerization reaction solution to obtain a membrane casting solution;
step five: reacting NH2Placing the POSS @ PVDF film into the film casting solution, deoxidizing, heating, and carrying out polymerization reaction to obtain a composite film;
step six: eluting the composite membrane with eluent to obtain the molecularly imprinted composite membrane.
2. The preparation method of the molecular imprinting composite membrane based on the cage filler, according to claim 1, is characterized in that the method for preparing the pDA modified PVDF membrane in the first step comprises the following steps:
firstly, immersing a polyvinylidene fluoride (PVDF) membrane into 50 mL of 10 mmol Tris-HCl aqueous solution for 5 min; then, 100-200 mg of Dopamine (DA) is added into Tris-HCl aqueous solution, and the mechanical oscillation is continued for 6-30 h at room temperature to obtain a pDA modified PVDF membrane (pDA @ PVDF);
wherein the pH value of the Tris-HCl aqueous solution is 8.5.
3. The preparation method of the molecular imprinting composite membrane based on the cage-shaped filler, according to claim 1, wherein in the third step, the solvent comprises methanol, acetonitrile and DMF;
wherein the volume ratio of acetonitrile to DMF is 1: 1.5;
the preparation method of the prepolymerization reaction solution comprises the following steps:
adding 0.2 mmol of verbascoside and 6 mmol of 4-vinylpyridine into a solvent, mixing, performing ultrasonic treatment, placing into a constant temperature oscillator, and performing prepolymerization for 2 h to obtain a prepolymerization solution;
wherein the temperature of the constant temperature oscillator is 30 ℃, and the oscillation rotating speed is 150 rpm.
4. The preparation method of the molecular imprinting composite membrane based on the cage-shaped filler, according to claim 1, is characterized in that the preparation method of the membrane casting solution in the fourth step is as follows:
respectively adding 6 mmol of ethylene glycol dimethacrylate and 0.1 mmol of azobisisobutyronitrile into the prepolymerization reaction solution, uniformly mixing, and performing ultrasonic treatment for 10 min to obtain a membrane casting solution.
5. The preparation method of the molecular imprinting composite membrane based on the cage-shaped filler, according to claim 1, is characterized in that the preparation method of the composite membrane in the fifth step specifically comprises the following steps:
first NH2Soaking the-POSS @ PVDF membrane in the membrane casting solution, deoxidizing, and carrying out polymerization reaction at the temperature of 60-68 ℃ for 24 hours to obtain the composite membrane.
6. The preparation method of the molecular imprinting composite membrane based on the cage-shaped filler, according to claim 1, wherein the eluent in the sixth step comprises methanol and acetic acid, and the volume ratio of methanol to acetic acid is 9: 1.
7. The application of the molecular imprinting composite membrane based on the cage-shaped filler prepared by the method of claim 1 is used for separating the phenylethanoid glycosides, the adsorption quantity of the molecular imprinting composite membrane on the verbascoside reaches 99.47 mg/g, the adsorption quantity of the echinacoside reaches 23.78 mg/g, and the selectivity is 4.63; in the permselectivity test, the osmotic coefficient of verbascoside is 5.13 × 10-7 cm2(s) Echinacoside permeability coefficient of 3.61X 10-6 cm2Per s, the permselectivity factor was 7.02.
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