Synthesis and application of a nanomaterial for removal of patulin

Abstract

The present disclosure belongs to the technical field of analytical chemistry, in particular to synthesis and application of a nanomaterial for removal of patulin (Pat). The present disclosure adopts 2-Oxin as a substitute template, AM as a functional monomer, and synthetic Fe.sub.3O4@SiO.sub.2@CS-GO magnetic nanoparticles as a carrier, for preparing a magnetic MIP specific for Pat adsorption by surface imprinting. The addition of Fe.sub.3O.sub.4 makes the finally prepared molecular imprinted adsorbent material magnetic, thereby facilitating separation of a material from a matrix, eliminating complicated operation steps such as filtration and centrifugation, and facilitating recovery of materials.

Claims

1. A synthesis method of a nanomaterial, comprising the following steps: preparing Fe.sub.3O.sub.4 magnetic cores; preparing a dispersion of Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles; performing amination of the Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles to obtain a dispersion of aminated Fe.sub.3O.sub.4@SiO.sub.2, and performing synthesis of Fe.sub.3O.sub.4@SiO.sub.2@ chitosan (Fe.sub.3O.sub.4@SiO.sub.2CS) nanoparticles; binding of graphene oxide (GO) carriers to the Fe.sub.3O.sub.4@SiO.sub.2@CS nanoparticles to obtain Fe.sub.3O.sub.4@SiO.sub.2@CS-GO; and performing synthesis of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@Molecular Imprinted Polymer (Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP) by surface imprinting; wherein the synthesis of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP uses 2-oxindole as a substitute template, acrylamide as a functional monomer, and Fe.sub.3O.sub.4@SiO.sub.2@CS-GO as a carrier.

2. The synthesis method according to claim 1, wherein preparing the Fe.sub.3O.sub.4 magnetic cores is as follows: dissolving FeCl.sub.3⋅6H.sub.2O in ethylene glycol, adding anhydrous sodium acetate and trisodium citrate, continuously stirring for 0.5 to 2 h, and allowing the reaction liquid to react at 160 to 250° C. for 2 to 5 hours to obtain a Fe.sub.3O.sub.4 mother liquid comprising Fe.sub.3O.sub.4 magnetic cores.

3. The synthesis method according to claim 1, wherein preparing the Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles is as follows: adding the Fe.sub.3O.sub.4 magnetic cores to anhydrous ethanol, adding ammonia water dropwise, reacting for 30 minutes, then, adding tetraethyl orthosilicate dropwise, and reacting for 2 to 5 hours to obtain the dispersion of Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles.

4. The synthesis method according to claim 1, wherein the performing amination of the Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles is as follows: adding 3-aminopropyltrimethoxysilane dropwise to the dispersion of Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles and stirring for 1 to 3 hours to obtain aminated Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles.

5. The synthesis method according to claim 1, wherein the performing synthesis of the Fe.sub.3O.sub.4@SiO.sub.2@CS nanoparticles comprises: preparing a CS acetic acid solution by placing CS powder in 2% acetic acid, and performing heating and stirring to dissolve the CS powder to obtain the CS acetic acid solution having a concentration of 8 to 15 g/L; mixing the dispersion of aminated Fe.sub.3O.sub.4@SiO.sub.2 with the CS acetic acid solution, performing stirring at 45 to 60° C. for 0.5 to 2 hours to obtain a solution of the Fe.sub.3O.sub.4@SiO.sub.2@CS nanoparticles.

6. The synthesis method according to claim 5, wherein the preparation of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO nanoparticle is as follows: adding a GO dispersion to the solution of the Fe.sub.3O.sub.4@SiO.sub.2@CS nanoparticles and continuing stirring for 0.5 to 2 hours, raising the temperature to 70 to 90° C., and dropwise adding a glutaraldehyde solution with a mass fraction of 5% to obtain the Fe.sub.3O.sub.4@SiO.sub.2@CS-GO nanoparticles.

7. The synthesis method according to claim 1, wherein the synthesis of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP comprises: performing preparation of a pre-assembly liquid of template molecules and functional monomers as follows: adding 2-oxindole and acrylamide to a mixed solution of acetonitrile and toluene, and performing stirring to obtain the pre-assembly liquid of template molecules and functional monomers; adding Fe.sub.3O.sub.4@SiO.sub.2@CS-GO modified with vinyl to the pre-assembly liquid for dispersion, then, sequentially adding a cross-linking agent ethylene glycol dimethacrylate and an initiator azobisisobutyronitrile, and reacting at 60° C. for 24 hours to obtain Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP.

Description

BRIEF DESCRIPTION OF FIGURES

(1) FIG. 1 is a TEM diagram of the nanoparticles in Example 1: (A, F) Fe.sub.3O.sub.4; (B, G) Fe.sub.3O.sub.4@SiO.sub.2; (C, H) Fe.sub.3O.sub.4@SiO.sub.2@CS; (D, I) Fe.sub.3O.sub.4@SiO.sub.2@CS-GO; (E, J) Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP; (ruler: A, B, C: 200 nm; D, E, F, G, H: 500 nm; I, J: 1 μm).

(2) FIG. 2 is an infra-red spectrogram of the nanoparticles in Example 1: (a) Fe.sub.3O.sub.4, (b) Fe.sub.3O.sub.4@SiO.sub.2, (c) Fe.sub.3O.sub.4@SiO.sub.2@CS, (d) Fe.sub.3O.sub.4@SiO.sub.2@CS-GO, (e) Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP.

(3) FIG. 3(A) is a N.sub.2 adsorption-desorption isothermal diagram of Fe.sub.3O.sub.4 and Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP in Example 1; FIG. 3(B) is a pore diameter distribution diagram of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP.

(4) FIG. 4 is an adsorption kinetics curve of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP and Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP on Pat in Example 2.

(5) FIG. 5 is an isothermal adsorption curve of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP on Pat in Example 2.

(6) FIG. 6 is a chromatogram of Pat and 5-hydroxymethyl furfural (5-HMF) in Example 2.

(7) FIG. 7 is a standard curve of Pat and 5-HMF in Example 2.

(8) FIG. 8 is an adsorption quantity diagram of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP and Fe.sub.3O.sub.4@SiO.sub.2 @CS-GO@NIP on Pat and 5-HMF in Example 2.

(9) FIG. 9 is a diagram showing the relationship between the adsorption rate of Pat and the number of times of reuse of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP in Example 2.

DETAILED DESCRIPTION

(10) The graphene oxide (GO) dispersion in the present disclosure was purchased from Xianfeng Nano Materials Co., Ltd.

(11) CS in the present disclosure refers to chitosan.

(12) Those which are not specified with specific conditions in the examples are carried out according to conventional conditions or conditions recommended by manufacturers. Any reagents or instruments that are not indicated with the manufacturers are commercially available products.

EXAMPLE 1

1. Preparation of Fe3O4 Nanoparticles

(13) 0.81 g of FeCl.sub.3.6H.sub.2O was weighed and placed in 35 mL of ethylene glycol (EG), magnetic stirring was performed until the FeCl.sub.3.6H.sub.2O solid particles were completely dissolved, then 2 g of anhydrous sodium acetate and 0.75 g of trisodium citrate were added, and stirring was performed continuously for 1 h to obtain a brown yellow reaction liquid. The reaction liquid was transferred and sealed in a 50 mL polytetrafluoroethylene reactor, and reacted at 200° C. for 4 h. After cooling at room temperature, a Fe.sub.3O.sub.4 mother liquid was obtained. A magnet was additionally added to the Fe.sub.3O.sub.4 mother liquid to separate the black Fe.sub.3O.sub.4 nanoparticles from the mother liquid, and then the Fe.sub.3O.sub.4 nanoparticles were washed with ultrapure water and absolute ethanol three times, and finally dispersed in ultrapure water for later use.

2. Preparation of Fe.SUB.3.O.SUB.4.@SiO.SUB.2

(14) 10 mL of the Fe.sub.3O.sub.4 magnetic liquid (having a Fe.sub.3O.sub.4 concentration of 20 mg/mL) was taken, and added to 100 mL of absolute ethanol. The nanoparticles were dispersed evenly with a mechanical stirrer, 1 mL of NH.sub.3.H.sub.2O was added dropwise, and reaction was continued for 30 min. Then, while maintaining vigorous stirring, 0.5 mL of TEOS was added dropwise, and reaction was continued for 4 h to obtain a Fe.sub.3O.sub.4@SiO.sub.2 core-shell nanoparticle dispersion.

3. Preparation of Fe.SUB.3.O.SUB.4.@SiO.SUB.2.@CS-GO

(15) (1). Amination of Fe.sub.3O.sub.4@SiO.sub.2

(16) 20 μL of 3-aminopropyltrimethoxysilane (APTMS) was added dropwise to the Fe.sub.3O.sub.4@SiO.sub.2 dispersion and stirring was performed for 2 h to obtain aminated Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles. A magnet was additionally added to collect the Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles, and the Fe.sub.3O.sub.4@SiO.sub.2 nanoparticles were washed with ultrapure water and absolute ethanol, and dispersed in ultrapure water.

(17) (2). Preparation of CS Acetic Acid Solution

(18) 1 g of chitosan (CS) powder was weighed and placed in 100 mL of 2% acetic acid. Heating and stirring were performed to dissolve the CS powder to obtain a CS acetic acid solution.

(19) (3). Synthesis of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO

(20) 20 mL of the aminated Fe.sub.3O.sub.4@SiO.sub.2 dispersion (having a Fe.sub.3O.sub.4@SiO.sub.2 concentration of 16 mg/mL) and 20 mL of the CS acetic acid solution were mixed, and heating and stirring were performed in a constant temperature water bath at 50° C. for 1 h. Then 1.7 mL of a graphene oxide (GO) dispersion was added, and stirring was continued for 1 h. Finally, the temperature was raised to 80° C., and 20 mL of a glutaraldehyde solution having a mass fraction of 5% was added dropwise. The obtained Fe.sub.3O.sub.4@SiO.sub.2@CS-GO nanoparticles were washed by ultrapure water and absolute ethanol and then dispersed in absolute ethanol.

4. Preparation of Fe.SUB.3.O.SUB.4.@SiO.SUB.2.@CS-GO@MIP

(21) (1). Preparation of Pre-Assembly Liquid of Template Molecules and Functional Monomers

(22) 0.133 g of 2-oxindole (2-Oxin) and 0.517 g of acrylamide (AM) were weighed and added to 50 mL of a mixed solution of acetonitrile and toluene (4:1), and magnetic stirring was performed for 2 h to obtain the pre-assembly liquid of template molecules and functional monomers for later use.

(23) (2). Acrylic Acid Modified Fe.sub.3O.sub.4@SiO.sub.2@CS-GO Magnetic Carrier

(24) To stably synthesize MIP on a carrier matrix, modification of the surface of the carrier has become a key step in surface imprinting. 20 mL of a Fe.sub.3O.sub.4@SiO.sub.2@CS-GO absolute ethanol dispersion (with a Fe.sub.3O.sub.4@SiO.sub.2@CS-GO concentration of 16 mg/mL) was taken, 1 mL of acrylic acid (AA) was added to the system while ultrasonic dispersion was performed, reaction was continued for 2 h, and finally the system was dispersed with 10 mL of an acetonitrile and toluene (4:1) solution.

(25) (3). Polymerization of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP

(26) 10 mL of a Fe.sub.3O.sub.4@SiO.sub.2@CS-GO dispersion modified with vinyl (with a Fe.sub.3O.sub.4@SiO.sub.2@CS-GO concentration of 10 mg/mL) was added to the pre-assembly liquid to perform ultrasonic dispersion, and then 10 mmol of a cross-linking agent ethylene glycol dimethacrylate (EGDMA) and 25 mg of an initiator azodiisobutyronitrile (AIBN) were sequentially added. The whole reaction system was sealed, degassed by nitrogen for 15 min, and finally heated in a water bath at 60° C. for 24 h. After washing, grey black magnetic MIP was obtained by freeze drying.

(27) (4). Elution of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP Template Molecules

(28) The template molecules were eluted by Soxhlet extraction. A mix solution of methanol and acetic acid (9:1) is used as the eluent. The freeze-dried magnetic MIP was placed in a Soxhlet extraction apparatus, and 200 mL of the eluent was prepared and added to a round bottom flask. Soxhlet extraction was performed at a temperature of 80° C., the eluent was replaced once every 12 h, and elution was continued for 48 h until no 2-Oxin was detected in the extract.

(29) FIG. 1 shows the TEM characterization results of five types of nanoparticles: Fe.sub.3O.sub.4, Fe.sub.3O.sub.4@SiO.sub.2, Fe.sub.3O.sub.4@SiO.sub.2@CS, Fe.sub.3O.sub.4@SiO.sub.2@CS-GO, and Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP in the synthesis process. As shown in FIG. 1(A) and (F), Fe.sub.3O.sub.4 has a black spherical structure and a particle diameter of approximately 269 nm. After SiO.sub.2 was coated, the appearance is shown in FIGS. 1(B) and (G). The presence of the SiO.sub.2 shell layer can be clearly observed from the figure, and the particle diameter is increased to about 351 nm. FIGS. 1(C) and (H) are the TEM characterization diagrams of Fe.sub.3O.sub.4@SiO.sub.2@CS. It can be seen from the Figures that after CS is coated, the shell layer is thickened, the particle diameter is further increased to about 397 nm, and the edge of the CS coated layer is not as regular as that of the SiO.sub.2 coated layer. Because CS has viscosity, as shown in FIG. 1(H), the Fe.sub.3O.sub.4@SiO.sub.2@CS nanoparticles adhere to each other and are closely arranged. It is also because of rich reactive groups and viscosity of the CS that make the Fe.sub.3O.sub.4@SiO.sub.2@CS more easily bound to GO. The appearance of the Fe.sub.3O.sub.4@SiO.sub.2@CS-GO is shown in FIGS. 1(D) and (I). It can be observed from the figures that the Fe.sub.3O.sub.4@SiO.sub.2@CS nanoparticles exist in the GO sheet structure, which proves that the two are successfully bound. FIGS. 1(E) and (J) are TEM diagrams of the Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP, and it can be found that a specific pore structure is formed in the magnetic MIP from the edges in the figures.

(30) FIG. 2 is an infra-red spectrogram of (a) Fe.sub.3O.sub.4, (b) Fe.sub.3O.sub.4@SiO.sub.2, (c) Fe.sub.3O.sub.4@SiO.sub.2@CS, (d) Fe.sub.3O.sub.4@SiO.sub.2@CS-GO, and (e) Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP in the synthesis process. Observing FIGS. 2(a) to (e), all samples have a strong absorption peak at the wave number of 597 cm.sup.−1, and the absorption peak is the characteristic absorption peak of the Fe—O group, indicating that Fe.sub.3O.sub.4 is always present throughout the reaction process and keeps the nanoparticles magnetic. Compared with FIG. 2(a), FIGS. 2(b) to (e) have the characteristic absorption peak of SiO.sub.2 at 1091 cm.sup.−1, which represents the Si—O—Si stretching vibration, proving that the SiO.sub.2 shell coating was successful. In FIGS. 2(c) to (e), the characteristic absorption peak of the CS-NH2 group is at 1556 cm.sup.−1 and 1625 cm.sup.−1, which is the NH.sub.3+ bending vibration peak, indicating smooth coating of the CS layer. Comparing FIG. 2(d) with FIG. 2(c), it is found that FIG. 2(d) has a C═O stretching vibration peak at 1734 cm.sup.−1, which is derived from the —COOH group in GO, confirming the successful binding of Fe.sub.3O.sub.4@SiO.sub.2@CS nanoparticles to the GO carriers. In the infrared spectrum of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP (as shown in FIG. 2(e)), the C—O symmetric and asymmetric stretching vibration peaks of the cross-linking agent EGDMA are shown at 1249 cm.sup.−1 and 1302 cm.sup.−1, and the C—H stretching vibration peaks in CH.sub.2 and CH.sub.3 are reflected at 2850 cm.sup.−1 and 2906 cm.sup.−1. In addition, the N—H and O—H stretching vibration peaks between 3000 cm.sup.−1 and 3600 cm.sup.−1 are broadened and become dull, indicating that intermolecular hydrogen bonds were formed during polymerization of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP, and also proving successful synthesis of magnetic MIP.

(31) The N.sub.2 adsorption-desorption isotherms of Fe.sub.3O.sub.4 and Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP are shown in FIG. 3(A), and the pore diameter distribution of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP is shown in FIG. 3(B). Compared to Fe.sub.3O.sub.4, Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP has a larger specific surface area and a larger pore volume (as shown in Table 1). According to the analysis and calculation of a BJH model, the mesoporous pore diameter of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP is mostly distributed around 11.5 nm, which is beneficial to the adsorption of target molecule Pat by magnetic MIP.

(32) TABLE-US-00001 TABLE 1 Specific surface area and total pore volume Specific surface area Total pore Sample name (m.sup.2/g) volume (cm.sup.3/g) Fe.sub.3O.sub.4 43.5 0.175 Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP 279.6 0.476

Comparative Example 1

(33) The preparation method of a magnetic non-molecular imprinted polymer Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP is consistent with the preparation method of the magnetic molecular imprinted polymer Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP, except that the template molecules 2-Oxin were not added.

EXAMPLE 2

1. Detection Method of Patulin

(34) The content of Pat was measured by HPLC. 25 mg of a Pat standard was dissolved in 4 mL of acetonitrile to obtain a Pat mother liquid with a concentration of 6250 mg/L. Pat standard addition apple juice (with a PAT concentration of 100 mg/L) and a group of 10 mg/L, 50 mg/L, 100 mg/L, 150 mg/L, 200 mg/L and 250 mg/L standard working solutions were prepared.

(35) Pretreatment method of samples: A magnet was additionally added to separate magnetic MIP from the apple juice solution. The apple juice clear liquid was poured into a 50 mL test tube with a stopper, 10 mL of ethyl acetate was added, vortex oscillation was performed for 1 min, and then the solution was allowed to stand and layer. The upper organic phase was taken into another test tube, and the above extraction operation was repeated three times. The organic phases were combined, and then the extract was purified by adding 5 mL of a 2% anhydrous sodium carbonate solution. The extract was dehydrated and filtered by weighing 1 g of anhydrous sodium sulfate. The filtrate was immersed in a water bath at 40° C., blow-dried with N.sub.2 slowly and re-dissolved with acetonitrile.

(36) Liquid chromatography conditions: The chromatographic column was a C18 reverse phase column (Agilent), the mobile phase was a 20% aqueous solution of acetonitrile containing 0.1% acetic acid, the detector was a UV detector, the detection wavelength was 275 nm, the column temperature was 30° C., the injection volume was 5 μL, the retention time of Pat was 6.427 min, and an external standard peak area method was adopted for quantification.

2. Kinetic Adsorption Experiment

(37) 7 groups of 100 mg of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP and 100 mg of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP adsorbent materials were accurately weighed, and placed in a 25 mL conical flask with a stopper respectively. 10 mL of a Pat apple juice solution with a Pat concentration of 100 mg/L was added, and oscillated and adsorbed in a constant temperature water bath at 25° C. Corresponding samples were selected at different time points (4 h, 8 h, 12 h, 16 h, 20 h, 24 h, 28 h). After pretreatment, the content of Pat in the supernatant was determined by HPLC.

(38) As shown in FIG. 4, as the adsorption time is prolonged, the adsorption quantity of Pat of both Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP and Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP is gradually increasing, and there was no significant change in the adsorption quantity until 24 h of adsorption. In contrast, the magnetic MIP with template molecules added during polymerization exhibited better adsorption effect than the magnetic NIP without template molecules. At room temperature of 25° C., the saturated adsorption capacity of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP is 3.5 times that of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP. This depends on the specific adsorption site formed in Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP.

3. Isothermal Adsorption Experiment

(39) 3 groups (8 parts in each group) of 100 mg of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP adsorbent materials were accurately weighed, and placed in a 25 mL conical flask with a stopper respectively. 10 mL of Pat standard addition fruit juice with different concentrations (30 mg/L, 50 mg/L, 70 mg/L, 90 mg/L, 100 mg/L, 110 mg/L, 120 mg/L and 130 mg/L) were added, and oscillated and adsorbed in a constant temperature water bath at different temperatures (25° C., 35° C. and 45° C.) for 24 h. The corresponding samples were selected, and after pretreatment, the content of Pat in the supernatant was measured by HPLC.

(40) FIG. 5 is an isothermal adsorption curve of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP on Pat at 25° C., 35° C., and 45° C. It can be seen from FIG. 5 that the equilibrium adsorption quantity of the magnetic MIP increases with the initial concentration of the Pat and the temperature, indicating that the adsorption process is an endothermic reaction.

4. Selective Adsorption Experiment

(41) Standard solutions (with concentration gradients of 10 mg/L, 50 mg/L, 100 mg/L, 150 mg/L, 200 mg/L, and 250 mg/L) of Pat and 5-hydroxymethyl furfural (5-HMF) were prepared. The standard curves of Pat and 5-HMF were plotted using the obtained chromatogram information, as shown in FIGS. 6 and 7. 100 mg of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP and 100 mg of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP adsorbent materials were accurately weighed, and placed in a 25 mL conical flask with a stopper respectively. 10 mL of apple juice mixed solutions containing Pat and 5-HMF (with concentrations of 100 mg/L respectively) were added, and oscillated and adsorbed in a constant temperature water bath for 24 h at room temperature of 25° C. The corresponding samples were selected, and after pretreatment, the content of Pat in the supernatant was measured by HPLC.

(42) As shown in FIG. 8, since Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP has specific binding sites for Pat on the surface, its adsorption quantity of Pat is significantly higher than that of 5-HMF. While, since Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP does not form specific adsorption pores for Pat on the surface, the adsorption quantity of Pat is low, which is similar to that of 5-HMF.

5. Reuse Experiment

(43) 100 mg of Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP adsorbent material was accurately weighed, and placed in a 25 mL conical flask with a stopper. 10 mL of a Pat apple juice solution with a Pat concentration of 100 mg/L was added, and oscillated and adsorbed in a constant temperature water bath at 25° C. for 24 h. A magnet was additionally added to recover the material, and the material was eluted and placed in a new Pat standard addition juice solution. The above adsorption and elution process was repeated 5 times. The supernatant of each sample was taken, and after pretreatment, the Pat content was measured by HPLC.

(44) As shown in FIG. 9, the Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@MIP magnetic molecular imprinted adsorbent material can maintain good adsorption characteristics after reuse twice. After reuse 5 times, the adsorption rate of Pat by the magnetic molecular imprinting material decreases slightly, and the adsorption rate decreases by 23.93% compared with the initial use. This may be due to an incomplete elution process, resulting in residual template molecules, and affecting the adsorption effect. It may also be because multiple adsorption oscillations and elution extractions have a certain effect on the magnetic MIP spatial structure, and the specific binding sites suffers from regional damage. However, compared to the non-molecular imprinted polymer Fe.sub.3O.sub.4@SiO.sub.2@CS-GO@NIP, Fe.sub.3O.sub.4@SiO.sub.22@CS-GO@MIP still exhibits excellent adsorption characteristics for Pat.

Comparative Example 2

(45) Referring to Example 1, the carrier Fe.sub.3O.sub.4@SiO.sub.2@CS-GO was replaced with activated silicon spheres prepared by the following method, and the other conditions were unchanged to prepare the molecular imprinted adsorbent material SiO.sub.2@MIP.

(46) Preparation of activated silicon: Silicon spheres (mesh) were accurately weighed and put in a three-necked flask, the aqueous solution of methanesulfonic acid was added, and magnetic stirring was performed for reflux reaction. After cooling, the solid matter was filtered off, and the filtered matter was repeatedly washed with secondary deionized water until the washed aqueous solution was neutral. The obtained filtered solid matter was placed in a vacuum oven to be vacuum dried, taken out, and placed in a dry container for later use.

(47) The material obtained in Comparative Example 2 was subjected to an adsorption test with reference to Example 2, and the results are shown in Table 2.

(48) TABLE-US-00002 TABLE 2 Adsorption effects of materials obtained in Example 1 and Comparative Example 2 Adsorbent material Example 1 Comparative Example 2 Kinetic adsorption 7.0 mg/g 3.2 mg/g (24 h adsorption quantity) Isothermal adsorption (25° C.) 8.4 6.1 Reuse (times/adsorption rate) 5 (47%) 3 (32%)