CN108404891B - Bernoulli type hollow single-hole magnetic molecular imprinting adsorbent and preparation method thereof - Google Patents
Bernoulli type hollow single-hole magnetic molecular imprinting adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a Bernoulli type hollow single-hole magnetic molecular imprinting adsorbent and a preparation method thereof, belonging to the technical field of preparation of specific separation functional materials; firstly, preparing a Bernoulli type single-hole hollow silicon ball by utilizing an anisotropic emulsion template method, introducing carboxyl after an amino functional group on the inner surface of the hollow single-hole nano silicon ball reacts with acid anhydride, and chemically bonding the prepared magnetic iron oxide nanoparticles on the carboxyl on the inner surface of the hollow single-hole nano silicon ball through the pyrolysis of ferric acetylacetonate to obtain the magnetic hollow single-hole nano silicon ball; modifying an imprinted polymer of luteolin molecules on the outer surface of the single-hole hollow magnetic silicon ball by utilizing vinyl phenylboronic acid with boron affinity as a functional monomer and luteolin as a template molecule through atom transfer radical polymerization to obtain a Knudus type single-hole hollow magnetic imprinted adsorbent; finally, experiments prove that the material has specific separation performance on luteolin and excellent magnetism.
Description
Technical Field
The invention relates to a method for preparing a hollow single-hole magnetic molecular imprinting adsorbent of a Jacobs type and a preparation method thereof, in particular to a method for preparing the hollow single-hole magnetic molecular imprinting adsorbent of the Jacobs type through an anisotropic emulsion template, high-temperature pyrolysis of ferric acetylacetonate and atom transfer radical imprinting polymerization, and belongs to the technical field of preparation of specific separation functional materials.
Background
The molecular imprinting technology is a method for preparing a polymer with a specific recognition effect on a certain molecule, and the prepared polymer is a Molecular Imprinted Polymer (MIPs). Due to its specific recognition, wide applicability and chemical stability, molecularly imprinted polymers have been widely used in the field of separation and purification. However, conventional MIPs are generally highly cross-linked polymeric networks, and the kinetic performance of elution and re-identification of template molecules is poor. Hollow imprinted polymers (H-MIPs) have unique hollow-core structures, and the small density and high specific surface area of the hollow imprinted polymers can significantly enhance the binding kinetics and the saturated adsorption capacity. The MIPs with the hollow single-hole structure are used as H-MIPs in a special form, a single hole is formed in the original hollow framework structure, and external sample solution or eluent can enter the interior of the MIPs through the single-hole pore channel, so that the binding kinetics performance of the imprinted binding site can be further improved.
Magnetic Molecularly Imprinted Polymers (MMIPs) are coated on superparamagnetic nanoparticles (such as Fe) with imprinted polymer materials3O4And gamma-Fe2O3Etc.) surface obtained magnetic composite material. MMIPs can perform separation operations such as recognition, loading, carrying, unloading and the like on target molecules by utilizing the affinity and specificity of imprinted polymers and by virtue of a magnetic separation device, thereby simplifying the separation and enrichment processes of the target molecules. Because the MMIPs preparation and the hollow single-pore structure design belong to different technical routes, the conventional method introduces superparamagnetic nanoparticles to the surfaces of the hollow single-pore structure MIPs by means of physical dispersion and chemical grafting. This approach will severely occupy the available blot binding sites, resulting in a decrease in adsorption capacity. Therefore, an effective method for simultaneously introducing imprinted polymeric sites and superparamagnetic nanoparticles on the premise of ensuring that binding sites are not embedded and occupied is urgently needed.
The Janus (Janus) nano material can endow the same nano particle with multiple functions due to the double-sided structure. If the bernoulli-type hollow single-hole magnetic MIPs are prepared by adopting a proper method, the problems can be effectively solved. The emulsion template method is one of the important methods for preparing the hollow microsphere nano material. However, no work has been reported for producing bernoulli-type MIPs using this strategy. Luteolin (LTL) is one of natural organic flavonoid drugs, and has medicinal values of antibiosis, anti-inflammation, antivirus, antitumor, antioxidation and the like. At present, the methods for separating and purifying luteolin mainly comprise an acid precipitation method, a thin layer chromatography method, a gradient extraction column, a chromatography method, a macroporous resin adsorption separation method and the like. These conventional methods often involve problems of difficult elution, difficult separation, poor selectivity, and the like. Therefore, the preparation of the bernoulli-type hollow single-hole magnetic MIPs and the application of the bernoulli-type hollow single-hole magnetic MIPs in specific recognition, separation and purification of luteolin have great economic, social and academic values.
Disclosure of Invention
The invention utilizes an anisotropic emulsion template method to prepare the hollow silicon spheres (SHH-Si) with the single holes of the Bernoulli type, and the outer surface and the inner surface of the SHH-Si respectively contain chlorine atoms and amino functional groups; introducing carboxyl (SHH-Si-COOH) after the amino functional group on the inner surface reacts with acid anhydride, chemically bonding the prepared magnetic iron oxide nanoparticles on the carboxyl on the inner surface of the SHH-Si-COOH through the pyrolysis of iron acetylacetonate to obtain a single-hole hollow magnetic silicon sphere (MSHH-Si); imprinting polymerization is initiated on the outer surface of the silicon spheres, vinyl phenylboronic acid with boron affinity is used as a functional monomer, luteolin is used as a template molecule, and an imprinting polymer of the luteolin molecule is modified on the outer surface of the single-hole hollow magnetic silicon spheres through atom transfer radical polymerization, so that the Knudus type single-hole hollow magnetic imprinting adsorbent (SHH-MMPs) is obtained. And finally, the specific separation performance of the SHH-MMIPs on the luteolin is verified by combining a static adsorption experiment and applying the static adsorption experiment to the selective adsorption separation of the luteolin.
The invention firstly provides a Bernoulli type hollow single-hole magnetic molecular imprinting adsorbent, which combines the advantages of a hollow single-hole structure, magnetic separation and molecular imprinting, uses iron acetylacetonate for pyrolysis as an iron source, realizes boric acid group imprinting polymerization by an atom transfer radical polymerization method, is used for the adsorption of luteolin while not influencing the mutual advantages, and protects ferroferric oxide from acid corrosion during the adsorption and desorption process.
The technical scheme adopted by the invention is as follows:
(1) preparing hollow single-hole nano silicon spheres (SHH-Si):
dissolving polyvinylpyrrolidone in n-amyl alcohol, and then adding an ammonia water solution of ethanol and sodium citrate; mixing the above solutions, placing in a three-neck flask, mechanically stirring, and simultaneously adding tetraethyl orthosilicate, gamma-aminopropyltriethoxysilane and chloropropyltrimethoxysilane in sequence; stirring for a period of time, stopping stirring, washing with ethanol and water for several times, and vacuum drying at 40 deg.C to obtain hollow single-hole nano silicon spheres (SHH-Si).
Wherein, the dosage of the polyvinylpyrrolidone and the n-amyl alcohol is 2.0 to 4.0 g: 20-30 mL; the dosage of the ethanol, the sodium citrate and the ammonia water is 2-5 mL: 0.1-0.5 g: 5-10 mL.
The volume ratio of the added tetraethyl orthosilicate, the gamma-aminopropyltriethoxysilane to the chloropropyltrimethoxysilane is 0.10-0.35: 0.02-0.06: 0.01-0.05.
The mechanical stirring time is 2-2.5 h.
(2) Preparation of magnetic hollow single-hole nano silicon spheres (MSHH-Si):
firstly dissolving succinic anhydride in dimethylformamide, then adding hollow single-hole nano silicon spheres and stirring for 24h, washing by the dimethylformamide, carrying out vacuum drying at 40 ℃, then ultrasonically dispersing in N-methylpyrrolidone, heating to 150 ℃ and 200 ℃ under the protection of nitrogen, adding ferric acetylacetonate, stirring by magnetons, cooling to room temperature, washing by ethanol, collecting magnets, and drying in an oven at 40 ℃ to obtain the magnetic hollow single-hole nano silicon spheres (MSHH-Si).
Wherein 50-100mg of the hollow single-hole nano silicon spheres are added into every 0.1g of succinic anhydride.
The succinic anhydride of 0.1-1g is dissolved in the dimethylformamide of 10-100 mL; the dosage of the succinic anhydride, the N-methyl pyrrolidone and the iron acetylacetonate is 0.1-1 g: 20-50 mL: 0.1-0.5 g.
The stirring time of the magnetons is 1-3 h.
(3) Preparation of the hollow magnetic imprinted adsorbents of the model of Janus in a single pore (SHH-MMIPs):
weighing luteolin and 4-vinyl phenylboronic acid, dissolving in a mixed solution of methanol and water, standing in a dark place; respectively adding the magnetic hollow single-hole nano silicon spheres prepared in the step (2), copper chloride dihydrate and N, N, N ' -N ' ' -pentamethyldiethylenetriamine, adding ascorbic acid under the condition of nitrogen, magnetically stirring at room temperature, respectively washing the product with ethanol and water, and then carrying out Soxhlet extraction by taking a mixed solution of methanol and acetic acid as an eluent to remove template molecule luteolin (the volume ratio of the methanol to the acetic acid is 9: 1). The final product SHH-MMIPs are dried in vacuum at 40 ℃ and stored in the dark.
Wherein the mass ratio of the luteolin to the 4-vinylphenylboronic acid is 5-20: 10-25; the volume ratio of the methanol to the water in the mixed solution of the methanol and the water is 1: 1-3.
The dark standing time is 3-8 h.
The amount of the added magnetic hollow single-hole nano silicon spheres is 50-100mg of the magnetic hollow single-hole nano silicon spheres added into every 5mg of luteolin.
The added luteolin, copper chloride dihydrate and N, N, N '' -pentamethyldiethylenetriamine are used in an amount of 5-20 mg: 5-50 mg: 5-20 mL.
The mass ratio of the luteolin to the ascorbic acid is 5-20: 10-30.
The magnetic stirring time of the greenhouse is 2-5 h.
Meanwhile, the preparation of the Bernoulli-type single-hole hollow magnetic non-imprinted adsorbent (SHH-MNIPs) is consistent with the preparation of SHH-MMIPs, except that a template molecule luteolin is not added.
Compared with the prior art, the invention has the following technical advantages:
the invention successfully prepares hollow single-hole magnetic imprinted polymers (SHH-MMIPs) by combining an emulsion template method with magnetic separation and molecular imprinting technologies, and realizes the double-faced property of the Bernoulli particles by adding different silane coupling agents (tetraethyl orthosilicate, gamma-aminopropyl triethoxysilane and chloropropyl trimethoxysilane) in the preparation of the single-hole hollow silicon spheres. The ferric acetylacetonate is decomposed under the high temperature condition, and the problems of unstable input amount, weak binding capacity and subsequent imprinting site coverage caused by non-positional modification when magnetic particles are introduced by the original ultrasonic method are solved. In the imprinting layer modification process, the application of a reverse atom transfer radical polymerization method reduces the addition of metal ions, and is more beneficial to environmental protection. The invention is the method for selectively identifying the luteolin by combining three technologies of an emulsion template method, magnetic separation and molecular imprinting.
Drawings
Fig. 1 is a scanning electron micrograph of the hollow single-pore nano-silica spheres (a), the magnetic hollow single-pore nano-silica spheres (B), and the bernoulli-type single-pore hollow magnetic imprinted adsorbent (C) prepared in example 1.
Fig. 2 is a transmission electron micrograph of the hollow single-pore nano-silica spheres (a), the magnetic hollow single-pore nano-silica spheres (b), and the bernoulli-type single-pore hollow magnetic imprinted adsorbent (c) prepared in example 1.
FIG. 3 is a Fourier infrared spectrum of hollow single-pore nano-silica spheres (SHH-Si), magnetic hollow single-pore nano-silica spheres (MSHH-Si), and Zealand-type single-pore hollow magnetic imprinted adsorbents (SHH-MMIPs) prepared in example 1.
FIG. 4 is a hysteresis loop of hollow single-pore nano-silica spheres (SHH-Si), magnetic hollow single-pore nano-silica spheres (MSHH-Si), and Zealand-type single-pore hollow magnetic imprinted adsorbents (SHH-MMIPs) prepared in example 1.
Fig. 5 shows a dispersion liquid (a) of the bernoulli-type single-hole hollow magnetic imprinted adsorbent before magnetic attraction and a dispersion liquid (b) of the bernoulli-type single-hole hollow magnetic imprinted adsorbent after magnetic attraction.
FIG. 6 is a curve fit of the adsorption kinetics of the single-pore hollow magnetic imprinted adsorbent of the model of Bernoulli obtained in example 1.
FIG. 7 is an adsorption equilibrium isotherm fit of the single-well hollow magnetic imprinted adsorbent of the model of Janus obtained in example 1 (where the left panel is SHH-MMIPs and the right panel is SHH-MNIPs).
FIG. 8 shows the results of selective adsorption experiments on the hollow magnetic imprinted adsorbent of the Jacobs type with a single pore obtained in example 1.
Detailed Description
In order to better enable those skilled in the art to understand the technical scheme of the invention, the invention is further described with reference to the specific embodiments and the attached drawings.
The identification performance evaluation in the embodiment of the invention is carried out according to the following method: the method is completed by utilizing a static adsorption experiment and a selective adsorption experiment. Adding 10mL of luteolin (LTL) solution with a certain concentration into a centrifuge tube, adjusting the pH to be =7.0, adding a certain amount of a Bernoulli type single-hole hollow magnetic imprinting adsorbent (SHH-MMIPs), standing for a plurality of hours in a constant-temperature water bath at 25 ℃, measuring the content of the luteolin (LTL) after adsorption by using an ultraviolet-visible spectrophotometer, and calculating the adsorption capacity according to the result; several hydroxyl compounds with similar structures and properties, such as Quercetin (QRT), hydroquinone, 2,4, 6-Trichlorophenol (TCP) and the like, are selected as competitive adsorbates and participate in the research of the identification performance of the adsorbent.
Example 1:
(1) preparing hollow single-hole nanoparticles:
firstly, 2.0g of polyvinylpyrrolidone is dissolved in 20mL of n-amyl alcohol; the preparation ratio is 2 mL: 0.1 g: 5mL of an ammonia water mixed solution of ethanol and sodium citrate; mixing the two solutions, placing the two solutions in a three-neck flask, mechanically stirring, simultaneously adding 0.1mL of tetraethyl orthosilicate, 0.02mL of gamma-aminopropyltriethoxysilane and 0.01mL of chloropropyltrimethoxysilane, stopping stirring after 2h, respectively washing with ethanol and water for three times, centrifuging and drying in vacuum at 40 ℃. The scanning electron microscope and the transmission electron microscope of the obtained hollow single-hole nano particles are shown in the figure 1A and the figure 2a respectively, and the radius of the hollow single-hole nano material is about 300 nm.
(2) Preparing magnetic hollow single-hole nanoparticles:
dissolving 0.1g succinic anhydride in 10mL dimethylformamide, adding 50mg of the hollow single-hole nanoparticle material prepared in the step (1), stirring for 24h, washing with dimethylformamide for three times, and vacuum-drying at 40 ℃. Then dispersing the mixture in 20mL of N-methylpyrrolidone by ultrasonic waves, heating to 150 ℃ under the protection of nitrogen, adding 0.1g of ferric acetylacetonate, stirring for 1h by magnetons, cooling to room temperature, washing with ethanol for three times, collecting by using a magnet, and drying in an oven at 40 ℃. The scanning electron microscope of the magnetic hollow single-hole nano-particle as shown in figure 1B and the transmission electron microscope as shown in figure 2B realize the modification of the magnetic particle on the inner surface of the hollow single-hole nano-material.
(3) Preparation of magnetic hollow single-hole imprinted polymer:
weighing 5mg of luteolin (LTL) and 10mg of 4-vinylphenylboronic acid, dissolving in a solvent at a volume ratio of 1:1 in a mixed solution of methanol and water, and standing for 3 hours in a dark place. Respectively adding 50mg of MSHH-Si material prepared in the step (2), 5mg of copper chloride dihydrate and 5mL of N, N, N '' -pentamethyldiethylenetriamine, adding 10mg of ascorbic acid under the condition of nitrogen, magnetically stirring for 2h at room temperature, washing with ethanol and water for three times, and finally, drying in vacuum at 40 ℃ and keeping out of the sun. As can be seen from the figure of a scanning electron microscope (shown in figure 1C) and a transmission electron microscope (shown in figure 2C) of the magnetic hollow single-hole imprinted polymer, imprinting modification on the outer surface of the magnetic modified hollow single-hole nano material is realized. As can be seen, the thickness of the shell layer of the obtained adsorbent is (35 + -10) nm, and the size of the opening is (150- & lt 250- & gt) nm. The magnetic particles have uniform particle size and are distributed on the inner surface of the material, so that the advantage of not covering outer surface groups is realized.
Furthermore, the introduction of imprinted polymers during modification is illustrated by means of characterization of fourier-infrared spectroscopy, as shown in fig. 3. The magnetic sizes of the hollow single-hole nano silicon spheres, the magnetic hollow single-hole nano silicon spheres and the bernoulli type single-hole hollow magnetic imprinting adsorbent are respectively 1.82 gauss and 1.29 gauss in the saturation magnetization values of the magnetic hollow single-hole nano particles and the magnetic hollow single-hole imprinting polymer through a magnetic hysteresis loop shown in figure 4. In fig. 5, the dispersion liquid (a) of the bernoulli-type single-hole hollow magnetic imprinted adsorbent before the magnet attraction and the dispersion liquid (b) of the bernoulli-type single-hole hollow magnetic imprinted adsorbent after the magnet attraction are compared, which shows that the material has good magnetism and magnetic separation effect.
Example 2:
(1) preparing hollow single-hole nanoparticles:
firstly, 4.0g of polyvinylpyrrolidone is dissolved in 30mL of n-amyl alcohol; the preparation proportion is 5 mL: 0.5 g: 10mL of mixed solution of ethanol and ammonia water of sodium citrate; mixing the two solutions, placing the two solutions in a three-neck flask, mechanically stirring, simultaneously adding 0.35mL of tetraethyl orthosilicate, 0.06mL of gamma-aminopropyltriethoxysilane and 0.05mL of chloropropyltrimethoxysilane, stopping stirring after 2.5h, washing with ethanol and water three times, centrifuging and drying in vacuum at 40 ℃.
(2) Preparing magnetic hollow single-hole nanoparticles:
1g succinic anhydride was dissolved in 100mL dimethylformamide, and 500mg of the nanomaterial prepared in the above step (1) was added and stirred for 24 hours. Washed three times with dimethylformamide and dried in vacuo at 40 ℃. Then dispersing the mixture in 50mL of N-methylpyrrolidone by ultrasonic waves, heating to 200 ℃ under the protection of nitrogen, adding 0.5g of ferric acetylacetonate, stirring for 3 hours by magnetons, cooling to room temperature, washing with ethanol for three times, collecting by using a magnet, and drying in an oven at 40 ℃.
(3) Preparation of magnetic hollow single-hole imprinted polymer:
20mg of luteolin (LTL) and 25mg of 4-vinylphenylboronic acid were weighed out and dissolved in a volume ratio of 1: 3, standing for 8 hours in a dark place. 200mg of MSHH-Si material prepared in the step (2), 50mg of copper chloride dihydrate and 20mL of N, N, N '' -pentamethyldiethylenetriamine are respectively added, 30mg of ascorbic acid is added under the condition of nitrogen, the mixture is magnetically stirred for 5 hours at room temperature, ethanol and water are respectively washed for three times, and finally the mixture is dried in vacuum at 40 ℃ and kept away from light.
Example 3:
(1) preparing hollow single-hole nanoparticles:
firstly, 3.0g of polyvinylpyrrolidone is dissolved in 25mL of n-amyl alcohol; the preparation ratio is 3 mL: 0.3 g: 8 mL of an ammonia water mixed solution of ethanol and sodium citrate; mixing the two solutions, placing the two solutions in a three-neck flask, mechanically stirring, simultaneously adding 0.25mL of tetraethyl orthosilicate, 0.04mL of gamma-aminopropyltriethoxysilane and 0.03mL of chloropropyltrimethoxysilane, stopping stirring after 2.5h, washing with ethanol and water three times, centrifuging and drying in vacuum at 40 ℃.
(2) Preparing magnetic hollow single-hole nanoparticles:
0.5g succinic anhydride was dissolved in 50mL dimethylformamide, and 250mg of the nanomaterial prepared in the above step (1) was added and stirred for 24 hours. Washed three times with dimethylformamide and dried in vacuo at 40 ℃. Then dispersing the mixture in 35mL of N-methylpyrrolidone by ultrasonic, heating to 180 ℃ under the protection of nitrogen, adding 0.4g of ferric acetylacetonate, stirring for 2 hours by magnetons, cooling to room temperature, washing with ethanol for three times, collecting by a magnet, and drying in an oven at 40 ℃.
(3) Preparation of magnetic hollow single-hole imprinted polymer:
15mg of luteolin (LTL) and 20mg of 4-vinylphenylboronic acid were weighed out and dissolved in 1: 2, standing for 4 hours in a mixed solution of methanol and water in a dark place. 150mg of MSHH-Si material prepared in the step (2), 35mg of copper chloride dihydrate and 15mL of N, N, N '' -pentamethyldiethylenetriamine are respectively added, 20mg of ascorbic acid is added under the condition of nitrogen, the mixture is magnetically stirred for 3 hours at room temperature, ethanol and water are respectively used for washing for three times, and finally the mixture is dried in vacuum at 40 ℃ and is protected from light.
Test example 1:
10mL of luteolin (LTL) solutions with initial concentrations of 20 mg/L, 40 mg/L, 60 mg/L, 80mg/L and 100mg/L are respectively added into a centrifuge tube to form a group, 5mg of the Bernoulli-type single-hole hollow magnetic imprinting adsorbent (SHH-MMPs) in the embodiment 1 is respectively added, the three groups of test solutions are respectively placed in water baths with the temperature of 25 ℃, 35 ℃ and 45 ℃ for standing for 6 hours, collecting supernatant after magnet separation, measuring unadsorbed LTL molecule concentration with ultraviolet-visible spectrophotometer, with adsorption isotherm as shown in FIG. 7, the adsorption capacity was calculated from the results, which revealed that, when the initial concentration was 80mg/L, adsorption of the hollow magnetic imprinting adsorbent (SHH-MMIPs) in the model of the Yannus is balanced, and the maximum adsorption amount is 187.2 mu mol/g.
Test example 2:
adding 10mL of luteolin (LTL) solution with initial concentration of 100mg/L into a centrifuge tube, respectively adding 5mg of the Bernoulli-type single-hole hollow magnetic imprinting adsorbent (SHH-MMIPs) in example 1, placing the test solution in a constant temperature water bath at 25 deg.C, and taking out at 5min, 15min, 30min, 60min, 120min, 240min, 360min and 720 min; the blot adsorbent was separated from the solution by a magnet. The LC concentration in the filtrate is calculated and measured by an ultraviolet spectrophotometer under the wavelength of 353nm, and the adsorption capacity is calculated according to the result; the adsorption kinetics are shown in FIG. 6, and the results show that the adsorption process of the SHH-MMIPs can be divided into a fast stage (first 60 min) and a slow stage, while the adsorption capacity of the SHH-MMIPs in the fast stage reaches 80% of the equilibrium capacity, and then slowly increases until the equilibrium, thus proving the influence of the binding site of the boric acid on the adsorption, and the adsorption behavior belongs to monolayer adsorption, furthermore, the imprinted molecules have large adsorption equilibrium capacity and fast adsorption rate, the adsorption reaches 89.58% in 60min, and the adsorption is completed in 120 min.
Test example 3:
2,4, 6-Trichlorophenol (TCP), Quercetin (QRT) and Hydroquinone (HDQ) are selected as hydroxyl compounds for competitive adsorption, and solutions of the three compounds are respectively prepared, wherein the concentration is 100 mg/L. 10mL of the test solution was added to a centrifuge tube, 5mg of the blotting adsorbent and the non-blotting adsorbent prepared in example 1 were added, respectively, and the test solution was placed in a 25 ℃ water bath shaker for 12 hours, followed by magnetic separation to obtain a supernatant. The concentrations of TCP, QRT and HDQ solutions in the supernatant are respectively calculated and determined by an ultraviolet spectrophotometer under the wavelengths of 291 nm, 291 nm and 275 nm, and the adsorption capacity is calculated according to the results. The adsorption selectivity is shown in FIG. 8, and the results show that the maximum adsorption capacity of SHH-MMIPs for TCP, QRT, HDQ is smaller. Indicating that SHH-MMIPs have specific adsorption and selectivity for LTL relative to TCP, QRT and HDQ.
Claims (10)
1. A kind of bernoulli type hollow single-hole magnetic molecular engram adsorbent, the said adsorbent is prepared on the basis of the hollow single-hole nanoparticle, possess magnetism; firstly, chemically bonding the prepared magnetic iron oxide nanoparticles on carboxyl on the inner surface of a hollow silicon sphere (SHH-Si-COOH) introduced with carboxyl through the pyrolysis of acetylacetone iron to obtain a single-hole hollow magnetic silicon sphere (MSHH-Si); imprinting polymerization is initiated on the outer surface of the silicon ball, vinyl phenylboronic acid with boron affinity is used as a functional monomer, luteolin is used as a template molecule, and an imprinting polymer of the luteolin molecule is modified on the outer surface of the single-hole hollow magnetic silicon ball through atom transfer radical polymerization, so that the bernoulli type single-hole hollow magnetic imprinting adsorbent is obtained.
2. The method for preparing the bernoulli-type hollow single-hole magnetic molecular imprinting adsorbent as claimed in claim 1, which is characterized by comprising the following steps:
(1) preparing hollow single-hole nano silicon spheres:
dissolving polyvinylpyrrolidone in n-amyl alcohol, and then adding an ammonia water solution of ethanol and sodium citrate; mixing the above solutions, placing in a three-neck flask, mechanically stirring, and simultaneously adding tetraethyl orthosilicate, gamma-aminopropyltriethoxysilane and chloropropyltrimethoxysilane in sequence; stirring for a period of time, stopping stirring, washing with ethanol and water in sequence, and performing vacuum drying to obtain hollow single-hole nano silicon spheres;
(2) preparing magnetic hollow single-hole nano silicon spheres:
firstly, dissolving succinic anhydride in dimethylformamide, adding hollow single-hole nano-silica spheres for stirring, washing by the dimethylformamide, then drying in vacuum, ultrasonically dispersing in N-methylpyrrolidone, heating to a preset temperature under the protection of nitrogen, adding ferric acetylacetonate, stirring by magnetons, cooling to room temperature, washing by ethanol, collecting by a magnet, and drying in an oven to obtain the magnetic hollow single-hole nano-silica spheres;
(3) preparing a bernoulli type single-hole hollow magnetic imprinting adsorbent:
weighing luteolin and 4-vinyl phenylboronic acid, dissolving in a mixed solution of methanol and water, standing in a dark place; respectively adding the magnetic hollow single-hole nano silicon spheres prepared in the step (2), copper chloride dihydrate and N, N, N' -pentamethyldiethylenetriamine, adding ascorbic acid under the condition of nitrogen, magnetically stirring at room temperature, respectively washing the product with ethanol and water, and then carrying out Soxhlet extraction by taking a mixed solution of methanol and acetic acid as an eluent to remove template molecule luteolin; the final product was vacuum dried and stored in the dark.
3. The method for preparing the hollow and single-hole magnetic molecular imprinting adsorbent of the bernoulli type according to claim 2, wherein the dosage of the polyvinylpyrrolidone and the n-pentanol in the step (1) is 2.0 to 4.0 g: 20-30 mL; the dosage of the ethanol, the sodium citrate and the ammonia water is 2-5 mL: 0.1-0.5 g: 5-10 mL; the volume ratio of the added tetraethyl orthosilicate, the gamma-aminopropyltriethoxysilane to the chloropropyltrimethoxysilane is 0.10-0.35: 0.02-0.06: 0.01-0.05.
4. The method for preparing the bernoulli-type hollow single-hole magnetic molecular imprinting adsorbent according to claim 2, wherein the hollow single-hole nano silicon spheres are added in the step (2) and then stirred for 24 hours, and the mechanical stirring time is 2-2.5 hours.
5. The method for preparing the bernoulli-type hollow single-hole magnetic molecular imprinting adsorbent according to claim 2, wherein 50-100mg of hollow single-hole nano silicon spheres are added in every 0.1g of succinic anhydride in the step (2); 0.1-1g succinic anhydride is dissolved in 10-100mL dimethylformamide; the dosage of the succinic anhydride, the N-methyl pyrrolidone and the iron acetylacetonate is 0.1-1 g: 20-50 mL: 0.1-0.5 g.
6. The method for preparing the hollow-core and single-hole magnetic molecular imprinting adsorbent as claimed in claim 2, wherein the temperature in step (2) is raised to 150-200 ℃ under the protection of nitrogen; the stirring time of the magnetons is 1-3 h.
7. The method for preparing a hollow and single-hole magnetic molecular imprinting adsorbent of the bernoulli type according to claim 2, wherein the mass ratio of luteolin to 4-vinylphenylboronic acid in step (3) is 5-20: 10-25; the volume ratio of the methanol to the water in the mixed solution of the methanol and the water is 1: 1-3; the dark standing time is 3-8 h.
8. The preparation method of the bernoulli-type hollow single-hole magnetic molecular imprinting adsorbent according to claim 2, wherein the amount of the added magnetic hollow single-hole nano-silicon spheres in the step (3) is 50-100mg per 5mg of luteolin; the added luteolin, copper chloride dihydrate and N, N, N '' -pentamethyldiethylenetriamine are used in an amount of 5-20 mg: 5-50 mg: 5-20 mL.
9. The preparation method of the bernoulli-type hollow single-hole magnetic molecular imprinting adsorbent according to claim 2
The method is characterized in that the mass ratio of the luteolin to the ascorbic acid in the step (3) is 5-20: 10-30 parts of; the room temperature magnetic stirring time is 2-5 h.
10. The use of the hollow, single-pore magnetic molecular imprinting adsorbent of claim 1 for selective recognition of luteolin.
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