CN111072852A - Mesoporous SiO2Preparation method of surface-initiated boron affinity imprinted polymer material and application of surface-initiated boron affinity imprinted polymer material in extraction of shikimic acid - Google Patents
Mesoporous SiO2Preparation method of surface-initiated boron affinity imprinted polymer material and application of surface-initiated boron affinity imprinted polymer material in extraction of shikimic acid Download PDFInfo
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Abstract
The invention belongs to the technical field of resource utilization and chemical separation, and relates to mesoporous SiO2The preparation method of the surface-initiated boron affinity imprinted polymer material comprises the steps of dissolving TEOS and n-amyl alcohol in cyclohexaneFully stirring into a uniform solution, quickly adding CTAB and urea, adding deionized water, carrying out hydrothermal reaction at 80-180 ℃ for 2-6 h, drying, and roasting the prepared silicon material in a tubular furnace at 300-650 ℃ for 4-8 h; then dissolving the silicon material and KH570 in absolute ethyl alcohol, refluxing for 12-48 h at 40-100 ℃, and drying in vacuum to obtain a vinyl modified silicon material; dissolving in acetonitrile solution, adding shikimic acid, VPBA, cross-linking agent EGDMA and initiator AIBN, reacting, and centrifuging to obtain the final product. The material takes a mesoporous silicon material as a substrate, and a double recognition mechanism is introduced to prepare a molecularly imprinted polymer on the surface of the mesoporous silicon material, so that shikimic acid with a cis-dihydroxy structure is enriched on the surface of the material, and the effective separation of the shikimic acid is realized. Has better application prospect in the fields of enriching, separating and purifying natural products with cis-dihydroxy structures.
Description
Technical Field
The invention belongs to the technical field of resource utilization and chemical separation, relates to a material for selectively separating shikimic acid in environmental plant tissues and a preparation method thereof, and particularly relates to mesoporous SiO2A preparation method of a surface-initiated boron affinity imprinted polymer material and application thereof in shikimic acid extraction.
Background
Shikimic Acid (Shikimic Acid) is widely distributed in nature and has high medical value, the chemical structure of the Shikimic Acid is 3,4, 5-trihydroxy-1-cyclohexene-1-carboxylic Acid, the Shikimic Acid content in illicium verum of the family illicaceae is the highest (about 10 percent) and is regarded as the best resource plant for extracting the Shikimic Acid, research shows that the Shikimic Acid has the effects of resisting tumor, thrombus and cerebral ischemia and inflammation, the Shikimic Acid is used as a raw material, the unique weapon for producing the avian influenza virus, namely patent medicine GS4104 (Daphne), China provides 90 percent of illicium verum in the world market, if the illiverum is used as the raw material for producing the Shikimic Acid, good economic benefit and social benefit can be produced, however, the components of the illiverum extracting solution are complex, besides polysaccharide, pigment and protein, a small amount of 2, 4-dihydroxybenzoic Acid, significant farnesin-3-O- β -D-glucopyranoside, kaemferol-3-O- β -D-glucopyranoside, isoshikimic Acid extracting solution, high purity and high purity control impurity extraction and purification of Shikimic Acid, and a variety of high purity and purification problems in scientific research are solved.
At present, the common methods for separating and purifying shikimic acid mainly comprise recrystallization, activated carbon adsorption, silica gel column chromatography and the like. These methods, although each having unique advantages, have their limitations, among which the common disadvantages are strong nonspecific adsorption of the material, small adsorption capacity, poor process selectivity and thus low purity of the product obtained. Therefore, establishing and perfecting a new method for selectively identifying, separating and purifying shikimic acid in the illicium verum extract liquid and effectively increasing the product yield and purity are problems which need to be solved urgently at present.
Molecular Imprinting Technique (MIT) is a Technique for preparing polymers with specific selectivity for a specific target, and the prepared polymers are called Molecular Imprinted Polymers (MIPs). MIP has the characteristics of predetermination, identification, practicability and the like, and has wide application in the field of separation and purification. However, because the components of the shikimic acid extracting solution are complex, the requirement of deep separation and purification is difficult to achieve only by the single recognition capability of the imprinted polymer. Due to the fact that shikimic acid contains a cis-dihydroxy special structure, materials based on boron affinity can be prepared, and effective recognition of shikimic acid is achieved. The introduction of a double recognition mechanism is a reliable guarantee for selectively separating and purifying shikimic acid, and is an effective way for meeting the social demand on high-purity shikimic acid.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, it is an object of the present invention to disclose a method for the preparation of a material for the selective isolation of shikimic acid from plant tissue.
The technical scheme is as follows:
mesoporous SiO2The preparation method of the surface-initiated boron affinity imprinted polymer material comprises the following steps:
a) according to the solid-liquid ratio of 5-30 mmol: 0.5-2.5 mL:30mL, preferably 15 mmol: 1.5mL:30mL, dissolving tetraethyl orthosilicate (TEOS) and n-amyl alcohol in cyclohexane, fully stirring to obtain a uniform solution, quickly adding Cetyl Trimethyl Ammonium Bromide (CTAB) and urea, adding deionized water, and stirring for 30min, wherein the molar volume ratio of CTAB to urea to deionized water is 0.2-1 mmol: 1 mmol: 30mL, preferably 0.6 mmol: 1 mmol: 30mL of the silicon material is transferred to a hydrothermal reaction kettle, the mixture is subjected to a hydrothermal reaction at 80-180 ℃ for 2-6 h, preferably a hydrothermal reaction at 120 ℃ for 4h, naturally cooled to room temperature, centrifuged, washed with acetone and distilled water for three times respectively, dried, and then the prepared silicon material is placed in a tubular furnace to be roasted at 300-650 ℃ for 4-8 h, preferably at 550 ℃ for 6h, and the heating rate is 1 ℃/min;
b) dissolving 0.1g of the prepared silicon material and 0.5-2.5 mL of KH570 in 70mL of absolute ethanol, preferably dissolving 0.1g of the silicon material and 2mL of KH570 in 70mL of absolute ethanol, ultrasonically dispersing for 0.5h, refluxing for 12-48 h at 40-100 ℃ under mechanical stirring, preferably refluxing for 24h at 60 ℃, centrifuging, washing with distilled water, and drying at 30 ℃ in vacuum to obtain the vinyl modified silicon material;
c) weighing 25mg of vinyl modified silicon material, dissolving the vinyl modified silicon material in 25mL of acetonitrile solution, and adding the vinyl modified silicon material into the acetonitrile solution in a mass ratio of 10mg per 25 mL: 2-20 mg: 10-40 mg: 1-10 mg of shikimic acid, 4-vinylphenylboronic acid (VPBA), cross-linking agent Ethylene Glycol Dimethacrylate (EGDMA) and initiator Azobisisobutyronitrile (AIBN), preferably 10mg of the following components are added in each 25mL of acetonitrile solution: 10 mg: 15 mg: 5mg of shikimic acid, VPBA, a cross-linking agent EGDMA and an initiator AIBN, reacting for 6h at 40 ℃ under the protection of nitrogen, reacting for 12-20 h at 65 ℃, aging for 2-6 h at 80 ℃, preferably reacting for 16h at 65 ℃, aging for 4h at 80 ℃, cooling, centrifugally separating, drying, dispersing in methanol/acetic acid mixed solution (8:2v/v) for eluting, centrifugally separating to obtain mesoporous SiO2The surface initiates boron affinity imprinted polymer material.
The mesoporous SiO prepared by the method of the invention2The surface-initiated boron affinity imprinted polymer material is composed of a silicon-based surface imprinted polymer material with the size of about 300 nm, is spherical in shape, and can be applied to extraction of shikimic acid in environmental plants and wastes.
The application experiments were as follows:
adding 0.05g of mesoporous SiO into each 20mL of 1g/L shikimic acid solution2Adjusting the pH of the solution to 5-9.5 by a surface-initiated boron affinity imprinted polymer meter, and adsorbing/enriching shikimic acid in the solution to the surface of the material after stirring and reacting for 4-8 h at 35 ℃; and (4) centrifuging to separate out the reacted materials.
The adsorption quantity Q (mg/g) was calculated according to the formula (1), and an equal amount of the non-imprinted polymer was used as an adsorption control.
In the formula: c0And C (mg/L) is the initial concentration and equilibrium concentration of shikimic acid solution, respectively, V (mL) is the volume of shikimic acid solution, and m (g) is the mass of adsorbent.
For comparison, the procedure for preparing a non-imprinted polymer was the same as that for the imprinted polymer except that no template molecule was added, and this was used as a comparative example.
N-amyl alcohol, cyclohexane, Tetraethoxysilane (TEOS), Cetyl Trimethyl Ammonium Bromide (CTAB), urea, KH570, absolute ethyl alcohol, acetone, acetonitrile, methanol, acetic acid, shikimic acid and a national medicine group chemical reagent company Limited; 4-vinyl phenylboronic acid (VPBA), Ethylene Glycol Dimethacrylate (EGDMA), Azobisisobutyronitrile (AIBN), Shanghai Arlatin Biotech, Inc.
The invention has the characteristics that:
(1) prepared mesoporous SiO2The surface-initiated boron affinity imprinted polymer material has good biocompatibility, convenient preparation and low cost;
(2) the introduction of the molecular imprinting technology has obvious effect on improving the adsorption capacity of shikimic acid;
(3) the material for selectively separating shikimic acid from environmental plant tissues combines a molecular imprinting technology and a boron affinity technology, constructs a binary specificity recognition site of boron affinity and imprinting holes, and provides reliable guarantee for selectively separating and purifying shikimic acid.
Advantageous effects
Existing separation and purificationThe shikimic acid method mainly comprises recrystallization, activated carbon adsorption, silica gel column chromatography, alkali anion exchange resin, macroporous resin method and the like. These processes, although each having unique advantages, have their limitations, among which the common drawbacks are strong nonspecific adsorption of the material, small adsorption capacity, poor process selectivity and low purity of the product obtained. The invention uses mesoporous SiO2The surface-initiated boron affinity imprinted polymer is used as a material for adsorbing/enriching and separating shikimic acid, and the adsorption efficiency of the shikimic acid is improved. The material takes a mesoporous silicon material as a substrate, and a double recognition mechanism is introduced by preparing a molecularly imprinted polymer on the surface of the mesoporous silicon material, so that shikimic acid with a cis-dihydroxy structure is enriched on the surface of the material, and the effective separation of the shikimic acid is realized. The invention has better application prospect in the fields of enrichment, separation and purification of natural products with cis-dihydroxy structures.
Drawings
FIG. 1 is a mesoporous silica SEM;
FIG. 2 is a mesoporous silica TEM;
FIG. 3 is a diagram of mesoporous SiO2Initiating a silicon-based boron affinity imprinted polymer material SEM on the surface;
FIG. 4 is a diagram of mesoporous SiO2Surface initiated silicon-based boron affinity imprinted polymer material TEM.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
Mesoporous SiO2Preparation of surface-initiated boron affinity imprinted polymer materialThe method comprises the following steps:
a) according to the solid-liquid ratio (5 mmol: 0.5 mL:30 mL), TEOS and n-pentanol were dissolved in cyclohexane, stirred well and mixed in a molar ratio (0.2: 1) quickly adding CTAB and urea into the solution, adding 30mL of deionized water, stirring for 30min, transferring to a hydrothermal reaction kettle, placing in an air-blast drying oven at 80 ℃, reacting for 2h, centrifuging, washing with acetone and distilled water for three times respectively, drying, placing the product in a tubular furnace for roasting at the roasting temperature of 300 ℃, the roasting time of 4h and the heating rate of 1 ℃/min;
b) dissolving 0.1g of the prepared silicon material and 0.5mL of KH570 in 70mL of absolute ethanol, ultrasonically dispersing for 0.5h, refluxing for 12h at 40 ℃ under mechanical stirring, centrifuging, washing with distilled water for five times, and drying at 30 ℃ in vacuum to obtain a vinyl modified silicon material;
c) weighing 25mg of vinyl modified silicon material, dissolving the vinyl modified silicon material in 25mL of acetonitrile solution, and adding the vinyl modified silicon material into the acetonitrile solution in a mass ratio of 10mg per 25 mL: 2 mg: 10 mg: 1mg of shikimic acid, VPBA, a cross-linking agent EGDMA and an initiator AIBN, reacting for 6h at 40 ℃ under the condition of nitrogen, reacting for 12h at 65 ℃, finally aging for 2h at 80 ℃, cooling, centrifugally separating, drying, dispersing in methanol/acetic acid mixed solution (8:2v/v), eluting, centrifugally separating to obtain mesoporous SiO2The surface initiates boron affinity imprinted polymer material.
The adsorption amount of the prepared adsorbent to shikimic acid reaches 8-12 mg/g; for comparison, the adsorption amount of the same amount of non-imprinted polymer to shikimic acid under the same condition is 5-7.5 mg/g.
Example 2
Mesoporous SiO2The preparation method of the surface-initiated boron affinity imprinted polymer material comprises the following steps:
a) according to the solid-liquid ratio (12 mmol: 2mL of: 30mL), TEOS and n-pentanol were dissolved in cyclohexane, stirred well and mixed in a molar ratio (0.4: 1) adding CTAB and urea into the solution quickly, adding 30mL of deionized water, stirring for 30min, transferring to a hydrothermal reaction kettle, placing in a blast drying oven at 100 ℃, reacting for 6h, centrifuging, washing with acetone and distilled water for three times respectively, drying, placing the product in a tubular furnace for roasting at the roasting temperature of 400 ℃, the roasting time of 5h and the heating rate of 1 ℃/min;
b) dissolving 0.1g of the prepared silicon material and 2mL of KH570 in 70mL of absolute ethanol, refluxing for 15h at 75 ℃ under mechanical stirring, centrifuging, washing with distilled water for five times, and drying at 30 ℃ in vacuum to obtain a vinyl modified silicon material;
c) weighing 25mg of vinyl modified silicon material, dissolving the vinyl modified silicon material in 25mL of acetonitrile solution, and adding the vinyl modified silicon material into the acetonitrile solution in a mass ratio of 10mg per 25 mL: 8 mg: 12 mg: 4mg of shikimic acid, VPBA, a cross-linking agent EGDMA and an initiator AIBN, react for 6 hours at 40 ℃ under the condition of nitrogen, react for 18 hours at 65 ℃, finally age for 5 hours at 80 ℃, are cooled, centrifugally separated, dried, dispersed in methanol/acetic acid mixed solution (8:2v/v) for elution and centrifugally separated to obtain mesoporous SiO2The surface initiates boron affinity imprinted polymer material.
The adsorption amount of the prepared adsorbent to shikimic acid reaches 14-18 mg/g; for comparison, the adsorption amount of the same amount of non-imprinted polymer to shikimic acid under the same condition is 8-11.5 mg/g.
Example 3
Mesoporous SiO2The preparation method of the surface-initiated boron affinity imprinted polymer material comprises the following steps:
a) according to the solid-liquid ratio (15 mmol: 1.5mL:30 mL), TEOS and n-pentanol were dissolved in cyclohexane, stirred well and mixed in a molar ratio (0.6: 1) adding CTAB and urea into the solution quickly, adding 30mL of deionized water, stirring for 30min, transferring to a hydrothermal reaction kettle, placing in a blast drying oven at 120 ℃, reacting for 4h, centrifuging, washing with acetone and distilled water for three times respectively, drying, placing the product in a tubular furnace for roasting at the roasting temperature of 550 ℃, the roasting time of 6h and the heating rate of 1 ℃/min;
b) dissolving 0.1g of the prepared silicon material and 2mL of KH570 in 70mL of absolute ethanol, refluxing for 24h at 60 ℃ under mechanical stirring, centrifuging, washing with distilled water for five times, and drying at 30 ℃ in vacuum to obtain a vinyl modified silicon material;
c) weighing 25mg of vinyl modified silicon material, dissolving the vinyl modified silicon material in 25mL of acetonitrile solution, and adding the vinyl modified silicon material into the acetonitrile solution in a mass ratio of 10mg per 25 mL: 10 mg: 15 mg: 5mg shikimic acid, VPBA, cross-linking agent EGDMA and initiator AIBN, reacting for 6h at 40 ℃ under the condition of nitrogen, reacting for 16h at 65 ℃, finally aging for 4h at 80 ℃, cooling, centrifugally separating, drying, dispersing in methanol/acetic acid mixed solution (8:2v/v), eluting, centrifugally separating to obtain mesoporous SiO2The surface initiates boron affinity imprinted polymer material.
The adsorption capacity of the prepared adsorbent to shikimic acid reaches 30-35 mg/g; for comparison, the adsorption amount of the same amount of non-imprinted polymer to shikimic acid under the same condition is 12-15 mg/g.
On the basis of the proportion, the prepared polymer material is subjected to morphology characterization, and accompanying figures 1 and 2 are SEM and TEM images of substrate mesoporous silica, so that the material size is 300-400 nm, the material has good monodispersity and uniform spherical morphology, and a unique fibrous morphology is formed. After imprinting, an imprinting layer with a thickness of about 30nm is formed on the surface of the material (FIG. 4. silicon-based boron affinity imprinted polymer material TEM), and it can also be seen from FIG. 3 that a layer of polymer is formed on the mesoporous silicon substrate.
Example 4
Mesoporous SiO2The preparation method of the surface-initiated boron affinity imprinted polymer material comprises the following steps:
a) according to the solid-liquid ratio (15 mmol: 1.2 mL:30 mL), TEOS and n-pentanol were dissolved in cyclohexane, stirred well and mixed in a molar ratio (0.8: 1) adding CTAB and urea into the solution quickly, adding 30mL of deionized water, stirring for 30min, transferring to a hydrothermal reaction kettle, placing in a 150 ℃ blast drying oven, reacting for 4h, centrifuging, washing with acetone and distilled water for three times respectively, drying, placing the product in a tubular furnace, roasting at the roasting temperature of 450 ℃, roasting time of 8h, and heating at the temperature rising speed of 1 ℃/min;
b) dissolving 0.1g of the prepared silicon material and 1.5mL of KH570 in 70mL of absolute ethanol, refluxing for 36h at 85 ℃ under mechanical stirring, centrifuging, washing with distilled water for five times, and drying at 30 ℃ in vacuum to obtain a vinyl modified silicon material; (ii) a
c) Weighing 25mg of vinyl modified silicon material, dissolving the vinyl modified silicon material in 25mL of acetonitrile solution, and adding the vinyl modified silicon material into the acetonitrile solution per 25mL of the acetonitrile solution according to the mass ratio10 mg: 15 mg: 30 mg: 5mg of shikimic acid, VPBA, a cross-linking agent EGDMA and an initiator AIBN, reacting for 6h at 40 ℃ under the condition of nitrogen, reacting for 12h at 65 ℃, finally aging for 6h at 80 ℃, cooling, centrifugally separating, drying, dispersing in methanol/acetic acid mixed solution (8:2v/v), eluting, centrifugally separating to obtain mesoporous SiO2The surface initiates boron affinity imprinted polymer material.
The adsorption capacity of the prepared adsorbent to shikimic acid reaches 20-23 mg/g; for comparison, the adsorption amount of the same amount of non-imprinted polymer to shikimic acid under the same condition is 8-10 mg/g.
Example 5
Mesoporous SiO2The preparation method of the surface-initiated boron affinity imprinted polymer material comprises the following steps:
a) according to the solid-liquid ratio (30 mmol: 2.5 mL:30 mL), TEOS and n-pentanol were dissolved in cyclohexane, stirred well and mixed in a molar ratio of (1: 1) quickly adding CTAB and urea into the solution, adding 30mL of deionized water, stirring for 30min, transferring to a hydrothermal reaction kettle, placing in a forced air drying oven at 180 ℃, reacting for 6h, centrifuging, washing with acetone and distilled water for three times respectively, drying, placing the product in a tubular furnace for roasting at the roasting temperature of 650 ℃, the roasting time of 8h and the heating rate of 1 ℃/min;
b) dissolving 0.1g of the prepared silicon material and 2.5mL of KH570 in 70mL of absolute ethanol, refluxing for 48h at 100 ℃ under mechanical stirring, centrifuging, washing with distilled water for five times, and drying at 30 ℃ in vacuum to obtain a vinyl modified silicon material;
c) weighing 25mg of vinyl modified silicon material, dissolving the vinyl modified silicon material in 25mL of acetonitrile solution, and adding the vinyl modified silicon material into the acetonitrile solution in a mass ratio of 10mg per 25 mL: 20 mg: 40 mg: 10mg of shikimic acid, VPBA, a cross-linking agent EGDMA and an initiator AIBN, react for 6 hours at 40 ℃ under the condition of nitrogen, react for 20 hours at 65 ℃, finally age for 6 hours at 80 ℃, are cooled, centrifugally separated, dried, dispersed in methanol/acetic acid mixed solution (8:2v/v) for elution and centrifugally separated to obtain mesoporous SiO2The surface initiates boron affinity imprinted polymer material.
The adsorption amount of the prepared adsorbent to shikimic acid reaches 18-22 mg/g; for comparison, the adsorption amount of the same amount of non-imprinted polymer to shikimic acid under the same condition is 7.5-10 mg/g.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. Mesoporous SiO2The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps of:
a) according to the solid-liquid ratio of 5-30 mmol: 0.5-2.5 mL:30mL, dissolving ethyl orthosilicate and n-amyl alcohol in cyclohexane, fully stirring into a uniform solution, quickly adding Cetyl Trimethyl Ammonium Bromide (CTAB) and urea, adding deionized water, and stirring for 30min, wherein the molar volume ratio of CTAB to urea to deionized water is 0.2-1 mmol: 1 mmol: 30mL of the silicon material is transferred to a hydrothermal reaction kettle, reacted at the temperature of 80-180 ℃ for 2-6 hours, naturally cooled to room temperature, centrifuged, washed with acetone and distilled water for three times respectively, dried, and then roasted in a tubular furnace at the temperature of 300-650 ℃ for 4-8 hours at the heating rate of 1 ℃/min;
b) dissolving 0.1g of the prepared silicon material and 0.5-2.5 mL of KH570 in 70mL of absolute ethyl alcohol, ultrasonically dispersing for 0.5h, mechanically stirring, refluxing at 40-100 ℃ for 12-48 h, centrifuging, washing with distilled water, and drying at 30 ℃ in vacuum to obtain a vinyl modified silicon material;
c) weighing 25mg of vinyl modified silicon material, dissolving the vinyl modified silicon material in 25mL of acetonitrile solution, and adding the vinyl modified silicon material into the acetonitrile solution in a mass ratio of 10mg per 25 mL: 2-20 mg: 10-40 mg: 1-10 mg of shikimic acid, 4-vinylphenylboronic acid VPBA, a cross-linking agent ethylene glycol dimethacrylate EGDMA, an initiator azobisisobutyronitrile AIBN, reacting for 6h at 40 ℃ under the protection of nitrogen, reacting for 12-20 h at 65 ℃ → aging for 2-6 h at 80 ℃, cooling, centrifugally separating, drying, dispersing in methanol/acetic acid mixed solution for eluting, centrifugally separating to obtain mesoporous SiO2The surface initiates boron affinity imprinted polymer material.
2. The mesoporous SiO of claim 12The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps: in the step a), according to the solid-liquid ratio of 15 mmol: 1.5mL:30mL, and ethyl orthosilicate and n-pentanol were dissolved in cyclohexane.
3. The mesoporous SiO of claim 12The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps: the molar volume ratio of CTAB, urea and deionized water in step a) is 0.6 mmol: 1 mmol: 30 mL.
4. The mesoporous SiO of claim 12The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps: transferring the mixture to a hydrothermal reaction kettle in the step a), and carrying out hydrothermal reaction for 4 hours at the temperature of 120 ℃.
5. The mesoporous SiO of claim 12The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps: after drying in the step a), placing the prepared silicon material in a tubular furnace for roasting at 550 ℃ for 6h, wherein the heating speed is 1 ℃/min.
6. The mesoporous SiO of claim 12The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps: in step b), 0.1g of the above-mentioned silica material and 2mL of KH570 were dissolved in 70mL of absolute ethanol.
7. The mesoporous SiO of claim 12The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps: refluxing at 60 ℃ for 24h in step b) under mechanical stirring.
8. The mesoporous SiO of claim 12The preparation method of the surface-initiated boron affinity imprinted polymer material is characterized by comprising the following steps: adding 10mg of acetonitrile solution per 25mL in the step c): 10 mg: 15 mg: 5mg shikimic acid, VPBA, crosslinking agent EGDMA, initiator AIBN; reacting at 40 ℃ for 6h under the protection of nitrogen, then reacting at 65 ℃ for 16h → aging at 80 ℃ for 4 h; the methanol/acetic acid mixed solution is 8:2 v/v.
9. Mesoporous SiO prepared by the method of any of claims 1-82The surface-initiated boron affinity imprinted polymer material is composed of a silicon-based surface imprinted polymer material with the size of about 300 nm, and the morphology of the material is spherical.
10. The mesoporous SiO of claim 92The application of the surface-initiated boron affinity imprinted polymer material is characterized in that: it is used for extracting shikimic acid.
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