CN111909311A

CN111909311A - Zearalenone functionalized graphene surface molecularly imprinted material and preparation method thereof

Info

Publication number: CN111909311A
Application number: CN202010641149.3A
Authority: CN
Inventors: 韩杨莹; 孙长坡; 王峻; 常晓娇
Original assignee: Academy of National Food and Strategic Reserves Administration
Current assignee: Academy of National Food and Strategic Reserves Administration
Priority date: 2020-07-06
Filing date: 2020-07-06
Publication date: 2020-11-10
Anticipated expiration: 2040-07-06
Also published as: CN111909311B

Abstract

The embodiment of the invention discloses a zearalenone functionalized graphene surface molecularly imprinted material and a preparation method thereof, and belongs to the technical field of molecularly imprinted materials. The zearalenone functionalized graphene surface molecularly imprinted material takes RGO as a carrier, CDHB as a template molecule, 1-ALPP as a functional monomer, TRIM as a cross-linking agent, AIBN as an initiator and acetonitrile as a pore-forming agent. Static and selective adsorption experiments show that the zearalenone functionalized graphene surface molecularly imprinted material prepared by the invention has higher adsorption capacity and good selectivity on ZEN, can be used for separating and removing ZEN, and has wide application prospects.

Description

Zearalenone functionalized graphene surface molecularly imprinted material and preparation method thereof

Technical Field

The embodiment of the invention relates to the technical field of molecular imprinting materials, and particularly relates to a zearalenone functionalized graphene surface molecular imprinting material and a preparation method thereof.

Background

Zearalenone (ZEN), the most widely distributed one of the fusariins in the world, occurs in cereals and agricultural byproducts in asia, europe and america alike. ZEN occurs mainly on starch-rich cereal seeds and enters the food chain in the form of feed, food processing raw materials, causing accumulation in the human or animal body. It produces estrogen effect syndrome in body, and causes excessive estrogen in body, and has carcinogenicity and toxic action to kidney and liver of body.

At present, the main spectrum technology of the ZEN detection method, such as HPLC, GC-MS, LC-MS and the like, has the defects of time consumption, high cost and the like, so that the establishment of an economical, rapid and high-sensitivity ZEN detection method has great significance.

The molecular imprinting technology is a technology for preparing a polymer with a specific binding effect on a specific target object on a spatial structure and a binding site by adopting a chemical method by simulating biological recognition systems such as antigen-antibody, enzyme and the like. Preparing a molecularly imprinted polymer with a three-dimensional structure with fixed hole size and fixed arrangement functional groups by taking a target analyte (or a structural analogue thereof) as a template molecule; when the template molecule is removed, holes which are similar to the spatial structure, the size and the size of the template molecule and are complementary to the binding sites are left in the imprinted polymer, so that high-degree specific recognition of the target molecule is realized.

The preparation process of the molecularly imprinted polymer mainly comprises three steps, namely preassembly, polymerization and template elution. According to the position of the recognition site, the preparation method of the molecular imprinting polymer mainly comprises two main types, namely an embedding method and a surface molecular imprinting method.

Most of the molecularly imprinted polymer recognition sites prepared by the embedding method are distributed in the polymer, the sites on the surface of the polymer are distributed less, and the problems that template molecules are difficult to remove, the mass transfer resistance in the imprinted polymer is large, the effective size is small and the like exist in practical application. The surface imprinting method refers to a imprinted polymer preparation technology for performing polymerization reaction on the surface of a specific carrier (or substrate) and controlling imprinted recognition sites to be distributed on the surface of a polymer or the surface of the carrier (substrate). The imprinted polymer prepared by the technology has the advantages of uniform particle size distribution, controllable morphology through selecting different carriers, controllable thickness of the imprinted polymer, easy elution of template molecules and the like.

Therefore, the establishment of a molecularly imprinted polymer prepared based on a surface molecular imprinting method is necessary for accurate, rapid and high-sensitivity detection of ZEN.

Disclosure of Invention

Therefore, the embodiment of the invention provides a zearalenone functionalized graphene surface molecularly imprinted material and a preparation method thereof.

In order to achieve the above object, the embodiments of the present invention provide the following technical solutions:

according to a first aspect of the embodiments of the present invention, an embodiment of the present invention provides a zearalenone functionalized graphene surface molecularly imprinted material, which uses RGO (reduced graphene oxide) as a carrier, CDHB (2, 4-dihydroxy dodecyl benzoate) as a template molecule, 1-ALPP (1-allylpiperazine) as a functional monomer, TRIM (trimethylolpropane triacrylate) as a cross-linking agent, AIBN (azobisisobutyronitrile) as an initiator, and acetonitrile as a pore-forming agent.

According to a second aspect of the embodiment of the invention, the embodiment of the invention provides a preparation method of the zearalenone functionalized graphene surface molecularly imprinted material.

In one embodiment, the method comprises the steps of:

sequentially adding RGO, CDHB, 1-ALPP, TRIM, AIBN and acetonitrile into a solvent, uniformly mixing, filling nitrogen to remove oxygen, sealing, and carrying out constant-temperature reaction in a water bath at 24h or 60 ℃ for 24h under ultraviolet irradiation to obtain a functionalized graphene surface molecularly imprinted polymer;

grinding the functionalized graphene surface molecularly imprinted polymer, sieving with a 100-200-mesh sieve, removing CDHB by using an eluent, and drying at 40 ℃ overnight to obtain the zearalenone functionalized graphene surface molecularly imprinted material.

In another embodiment, the method comprises the steps of:

sequentially adding CDHB, 1-ALPP, TRIM, AIBN and acetonitrile into a solvent, uniformly mixing, filling nitrogen to remove oxygen, sealing, and carrying out constant-temperature reaction in a water bath at 24h or 60 ℃ for 24h under ultraviolet irradiation to prepare a molecularly imprinted polymer;

grinding the molecularly imprinted polymer, sieving the ground molecularly imprinted polymer with a sieve of 100-200 meshes, removing CDHB by using eluent, and drying the product overnight at 40 ℃ to obtain the molecularly imprinted polymer with the template removed;

and preparing the zearalenone functionalized graphene surface molecularly imprinted material by using GO and the molecularly imprinted polymer without the template through a water bath method.

Of the above two methods, CDHB: 1-ALPP: the molar ratio of TRIM is 1: 4-8: 20.

AIBN is an initiator for initiating thermal polymerization or photopolymerization. Preferably, in the embodiment of the present invention, the AIBN is added in an amount of 10 to 20% by weight based on 1-ALPP.

Acetonitrile is used as a pore-forming agent for forming pores in the material. When the amount of the pore-forming agent is small, the obtained material is hard and not easy to grind, and adsorption sites on the surface cannot be completely exposed, so that the adsorption effect is influenced; when the amount of the pore-forming agent is large, the obtained material is soft, adsorption sites on the surface of the material are easy to collapse, and the adsorption effect is also influenced. Preferably, in the embodiment of the present invention, the molar weight to volume ratio of CDHB to acetonitrile is 1 mol: 10-30 mL.

DMF is a solvent, and raw materials can be well dispersed in the solvent during polymerization reaction, so that a polymer with uniform distribution can be obtained.

The volume ratio of the adopted eluent is 96: 4, and acetic acid.

In another embodiment, preferably, the GO is dispersed in water or DMF, the molecularly imprinted polymer with the template removed is added, the mixture is uniformly mixed by ultrasonic, hydrazine hydrate is added, the obtained mixed solution is heated in a water bath at 90-95 ℃ for 4-6 hours, the mixture is cooled to room temperature, powder is obtained by filtration, and then the powder is sequentially washed with water and ethanol for multiple times, and dried at 60 ℃ for 1-2 hours, so that the zearalenone functionalized graphene surface molecularly imprinted material is obtained.

Preferably, the addition amount of GO is 0.1 to 0.5%, and more preferably 0.3% of the weight of the molecularly imprinted polymer excluding the template. The concentration of hydrazine hydrate is 1-10%, and the ratio of the addition amount of hydrazine hydrate to the volume and weight of GO is 1-2 μ L: 1 mg.

RO and RGO used in the present invention are prepared by the following methods, respectively.

Method for the laboratory preparation of GO, modified Hummers method: graphite powder and sodium nitrate were added to concentrated sulfuric acid in this order with vigorous stirring at room temperature to form a mixed solution, and then the mixture was cooled to 0 ℃ in an ice bath. Keeping the temperature of the suspension below 20 ℃, slowly adding potassium permanganate into the mixture under the condition of vigorous stirring, and transferring the reaction system into a water bath at 35-40 ℃ for about half an hour to form a thick paste substance. Deionized water is added into the substances, the formed new solution is continuously stirred for 15min, and then 30% hydrogen peroxide is slowly added, so that the color of the solution is changed from brown to yellow. The metal ions in the solution were removed by filtration and washing with 10% aqueous HCl, and then the excess acid was removed by repeated water washing and centrifugation. Finally, re-dispersing the obtained solid in water, and performing ultrasonic treatment, centrifugation, dialysis and purification to obtain a uniform GO aqueous solution. Wherein, graphite powder: sodium nitrate: the weight ratio of potassium permanganate is 1:0.5: 3; the mass fraction of the graphite powder in the concentrated sulfuric acid is 5 percent; the volume of the hydrogen peroxide solution is 2.5 percent of the total volume of the solution.

Method for preparing RGO in laboratory: adding hydrazine hydrate (the mass ratio of hydrazine hydrate to GO is 0.008-0.01: 1) into the uniform GO aqueous solution dropwise, stirring for 1h, transferring the solution into a 50mL reaction kettle, heating at 180 ℃ for 12h, and cooling to room temperature. The color change from brown for GO to black for RGO indicates the reduction of GO to RGO. This dispersion was then centrifuged, the resulting precipitate was washed sequentially with deionized water and ethanol, and finally the sample was dried overnight at 60 ℃ to give an RGO solid.

The CDHB adopts the following synthesis steps:

accurately weighing 1.6202g N, N' -Carbonyldiimidazole (CDI) and 1.5409g of 2, 4-dihydroxybenzoic acid, placing the materials in a 250mL round-bottom flask, adding 20mL of anhydrous N, N-Dimethylformamide (DMF) to dissolve the materials, magnetically stirring the materials in a 40 ℃ water bath for 1h, adding 2.2108g of cyclododecanol and 1.8214g of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) to the solution, continuing stirring the solution at 40 ℃ for 22h, adding 20mL of water and 20mL of dichloromethane to fully mix the solution after the reaction is finished, taking a lower organic phase after standing and layering, respectively washing the organic phase by respectively repeating 3 times with 30mL of 10% (v/v) hydrochloric acid, water and saturated sodium bicarbonate solution, drying the organic phase over night with anhydrous sodium sulfate, centrifuging the upper oil phase, transferring the upper oil phase flask product to a 50mL round-bottom, the solvent such as methylene chloride is removed by rotary evaporation under reduced pressure at 40 ℃ to obtain a crude product in a light yellow solid state.

In the prior art, silica gel column chromatography is adopted for purification, and an eluent is prepared from petroleum ether: ethyl acetate 32: 1(v/v) slowly increasing its polarity to petroleum ether: ethyl acetate 16: 1(v/v), this method has the drawback of low yield (about 60%) and not high purity (80% by HPLC).

The invention adopts high performance counter current chromatography and preparative liquid chromatography for purification, and can effectively solve the problems. The high-efficiency counter-current chromatography selects a solvent system of n-hexane, ethyl acetate, methanol and water for mixing and separation, the upper phase is an HSCCC mobile phase, the lower phase is a stationary phase, and after experiments with different solvent ratios are set, n-hexane is selected: ethyl acetate: methanol: water 1: 0.2: 1: 0.2 (volume ratio), the speed of a mobile phase is 2mL/min, the rotating speed is 800r/min, the loading amount is 10mL, the loading mass concentration is 20mg/mL, the detection wavelength is 254nm, the yield is 70%, and the purity is 95% by HPLC (high performance liquid chromatography).

The preparation liquid phase method comprises the following steps of (1) preparing a liquid phase by a volume ratio of 40: the mixed liquid of 60 water and acetonitrile is used as a mobile phase, the detection wavelength is 254nm, the flow rate is 16ml/min, the yield is 72 percent, and the purity is 97 percent by HPLC detection.

The graphene is formed by sp²The two-dimensional planar carbon material formed by hybridization and connection has large specific surface area, mechanical strength and excellent electric conduction and heat conduction performance, so that the graphene can be used as a good carrier for preparing the molecular imprinting material. The molecularly imprinted polymer with graphene as a carrier is formed on the surface of a graphene sheet layer, has a large specific surface area and is thin, so that the embedding phenomenon is reduced, and the imprinting process on the surface of the graphene is also favorable for eluting and identifying template molecules; the graphene has good conductivity, and the molecularly imprinted electrochemical sensor using the graphene as a carrier can realize high sensitivity and low detection limit; the good thermal property and mechanical property of the graphene can improve the stability and reproducibility of the molecularly imprinted membrane.

The embodiment of the invention has the following advantages:

the zearalenone functionalized graphene surface molecularly imprinted material disclosed by the invention has the advantages that RGO is used as a carrier, CDHB is used as a template molecule, 1-ALPP is used as a functional monomer, TRIM is used as a cross-linking agent, AIBN is used as an initiator, and acetonitrile is used as a pore-forming agent, and static and selective adsorption experiments show that the zearalenone functionalized graphene surface molecularly imprinted material has higher adsorption capacity and good selectivity on ZEN, can be used for separation and purification of ZEN, and has a wide application prospect.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.

FIG. 1 is a Scanning Electron Microscope (SEM) of the template-removed molecularly imprinted polymer (denoted as MIP) obtained in the second step of example 3;

FIG. 2 is a Scanning Electron Microscope (SEM) of a zearalenone functionalized graphene surface molecularly imprinted material (denoted as RGO-MIP) prepared in example 3;

FIG. 3 is X-ray photoelectron Spectroscopy (XPS) of MIP and RGO-MIP, which has a higher C/O ratio than MIP, indicating that functionalized graphene does exist in RGO-MIP. Compared with the MIP, the appearance of C ═ O and the increase of C-C, C-O (epoxy group) and C-OH of the RGO-MIP indicate that the functionalized graphene is successfully introduced into the MIP, and the O-C ═ O disappears under the reduction action of hydrazine hydrate, so that GO is reduced into RGO;

FIG. 4 is a comparison of adsorption performance of three polymers on ZEN at different adsorption times;

fig. 5 is an adsorption kinetics model of a zearalenone functionalized graphene surface molecularly imprinted material provided by an embodiment of the present invention.

Detailed Description

The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. 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 examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.

Example 1

The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material comprises the following steps:

ultrasonically dispersing 20.0mg of RGO into 20mL of DMF, adding 4.0mg of N-vinylcarbazole into the DMF, ultrasonically mixing the mixture for 2h, then adding 320.0mg of CDHB, 504.8mg of 1-ALPP and 10mL of acetonitrile, keeping the mixed solution for 15min, then adding 5.9264g of TRIM and 77.2mg of AIBN, uniformly mixing the mixture, introducing nitrogen into a system for 30min, and placing a sealed reaction container under ultraviolet light (lambda-254 nm) for irradiating for 24h to prepare the functionalized graphene surface molecularly imprinted polymer (in a gray black hard state);

and (3) grinding the obtained polymer in a mortar, sieving the ground polymer by using a 200-mesh sieve, refluxing the ground polymer for multiple times by using a mixed solution of methanol/acetic acid (96/4 (v/v)) as an eluent to remove CDHB, and finally drying the washed polymer in an oven at 40 ℃ overnight to obtain the zearalenone functionalized graphene surface molecularly imprinted material.

Example 2

ultrasonically dispersing 20.0mg of RGO into 20mL of DMF, adding 4.0mg of N-vinylcarbazole into the DMF, ultrasonically mixing the mixture for 2h, then adding 320.0mg of CDHB, 757.2mg of 1-ALPP and 10mL of acetonitrile, keeping the mixed solution for 15min, then adding 5.9264g of TRIM and 77.2mg of AIBN, uniformly mixing the mixture, introducing nitrogen into a system for 30min, placing a sealed reaction container in a water bath at 60 ℃ for constant-temperature reaction for 24h, and preparing the functionalized graphene surface molecularly imprinted polymer (in a gray black hard state);

and (3) grinding the obtained polymer in a mortar, sieving the ground polymer by using a 200-mesh sieve, refluxing the ground polymer for multiple times by using a mixed solution of methanol/acetic acid (96/4 (v/v)) as an eluent, removing CDHB, and drying the washed polymer in an oven at 40 ℃ overnight to obtain the zearalenone functionalized graphene surface molecularly imprinted material.

Example 3

320.0mg of CDHB, 504.8mg of 1-ALPP and 10mL of acetonitrile are sequentially added into 20mL of DMF, after the mixed solution is kept for 15min, 5.9264g of TRIM and 77.2mg of AIBN are added, nitrogen is introduced into the system for 30min after uniform mixing, and the sealed reaction vessel is placed under ultraviolet light (lambda is 254nm) for irradiation for 24h to prepare a molecularly imprinted polymer (which is gray black and hard);

grinding the obtained polymer in a mortar, sieving the ground polymer by a 200-mesh sieve, taking a mixed solution of methanol/acetic acid (96/4 (v/v)) as an eluent, refluxing for multiple times to remove CDHB, and finally drying in an oven at 40 ℃ overnight to obtain the molecularly imprinted polymer with the template removed;

adding 50mg of template-removed molecularly imprinted polymer and 0.15mg of GO into 50mL of water, carrying out ultrasonic treatment for 1h, uniformly mixing, adding 20 mu L of 1% hydrazine hydrate, heating in a water bath at 95 ℃ for 4h, cooling to room temperature, filtering to obtain powder, sequentially washing with water and ethanol for multiple times, and drying in an oven at 60 ℃ for 2h to obtain the zearalenone functionalized graphene surface molecularly imprinted material.

Example 4

320.0mg CDHB, 1009.6mg 1-ALPP and 10mL acetonitrile are sequentially added into 20mL DMF, after the mixed solution is kept for 15min, 5.9264g TRIM and 77.2mg AIBN are added, nitrogen is introduced into the system for 30min after uniform mixing, and the sealed reaction vessel is placed in a water bath at 60 ℃ for constant temperature reaction for 24h to prepare the molecularly imprinted polymer (which is gray black hard);

grinding the obtained polymer in a mortar, sieving the ground polymer by a 200-mesh sieve, taking a mixed solution of methanol/acetic acid (96/4 (v/v)) as an eluent, refluxing for many times to remove CDHB, and finally drying in an oven at 40 ℃ overnight to obtain the molecularly imprinted polymer with the template removed;

adding 50mg of template-removed molecularly imprinted polymer and 0.15mg of GO into 50mL of DMF, carrying out ultrasonic treatment for 1h, uniformly mixing, adding 20 mu L of 1% hydrazine hydrate, heating in a water bath at 95 ℃ for 6h, cooling to room temperature, filtering to obtain powder, sequentially washing with water and ethanol for multiple times, and drying in an oven at 60 ℃ for 2h to obtain the zearalenone functionalized graphene surface molecularly imprinted material.

Example 5

The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material of the embodiment is different from that of the embodiment 3 only in that: the addition amount of GO is 0.05 mg.

Example 6

The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material of the embodiment is different from that of the embodiment 3 only in that: the addition amount of GO is 0.25 mg.

Comparative example 1

The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material of the comparative example is different from that of example 3 only in that: mu.L of 1% hydrazine hydrate was replaced with 6.25mg of ascorbic acid.

Comparative example 2

The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material of the embodiment is different from that of the embodiment 3 only in that: hydrazine hydrate was not added as a reducing agent.

Test example 1

Adsorption capacity of zearalenone functionalized graphene surface molecularly imprinted materials prepared in examples 1-6 and comparative examples 1-2 on ZEN was tested.

And taking 8 parts of 5mL of 0.5ppm ZEN acetonitrile solution, adding the same amount of the materials respectively, ultrasonically stirring until the adsorption is balanced, and observing the influence of different modification modes on the adsorption capacity.

The adsorption capacity was determined by the adsorption ratio (Q), Q ═ C₀-C_t)/C₀100% of C₀And C_tRespectively representing the initial concentration and the concentration of adsorption equilibrium (mg. L) of ZEN^-1). The results are shown in Table 1.

TABLE 1

The results show that: the adsorption capacity of RGO-MIP is improved with the increase of RGO content, and when the RGO content is 0.3%, the prepared RGO-MIP has the best adsorption effect, and the adsorption capacity is reduced on the contrary by continuously increasing the proportion of RGO. The adsorption capacity is improved as the content of RGO increases because the surface ductility of RGO increases the contact area between the MIP and the target molecule, but when the content of RGO is too large, the specific binding site on the surface of the MIP is covered, and the specific binding with the target molecule is adversely affected, so that the optimal proportion of RGO is 0.3%.

The ascorbic acid used in comparative example 1 has a weak reducing effect, cannot completely reduce GO, affects the adsorption effect, and the hydroxyl group thereof inhibits the adsorption of ZEN by the material considering that there may be residual ascorbic acid on the surface of the material.

While GO and RGO have the same surface ductility that increases the contact area between MIP and target molecule, exposing more binding sites, and meanwhile, functional groups such as carboxyl and hydroxyl on GO surface can also bind with target molecule through hydrogen bond interaction or electrostatic interaction, so comparative example 2 also shows good adsorption effect in the case of single target molecule (ZEN).

Test example 2

The zearalenone functionalized graphene surface molecularly imprinted material prepared in example 1, example 3 and comparative example 2 is tested for the specific adsorption capacity of ZEN.

A mixed solution of ZEN and DON (both containing 0.5ppm) with certain concentration is prepared, and the same amount of GO-MIP and RGO-MIP are added respectively, and 10mg is added. The adsorption capacity was determined by the adsorption ratio (Q), Q ═ C₀-C_t)/C₀100% of C₀And C_tRespectively representing the initial concentration and the concentration of adsorption equilibrium (mg. L) of ZEN^-1). The results are shown in Table 2.

TABLE 2

The results show that: the specific adsorption capacity of the molecular imprinting material of comparative example 2 on ZEN is weak, which shows that the zearalenone functionalized graphene surface molecular imprinting material of the invention has strong specific adsorption capacity on ZEN.

GO has oxygen-containing functional groups on the surface, can indiscriminately adsorb compounds with hydroxyl functional groups such as ZEN, DON, etc., and the oxygen-containing functional groups can be reduced or disappear after being reduced into RGO, and mainly exert adsorption effect by a molecular imprinting material, thereby improving the specific adsorption capacity to ZEN.

Test example 3

Preparing a ZEN solution with a certain concentration, taking 10mg of the example3 (marked as RGO-MIP) (shown in a Scanning Electron Microscope (SEM) in figure 2), the template-removed molecularly imprinted polymer (marked as MIP) (shown in a Scanning Electron Microscope (SEM) in figure 1) prepared in the second step in the example 3 and NIP (namely blank control without adding CDHB during synthesis) are respectively added into 100mLZEN solution (0.5ppm), ultrasonic stirring and adsorption are carried out for 5h, sampling is carried out every 1h, liquid inlet phase detection is carried out, and the adsorption capacity (q) of the polymer to ZEN is calculated (q is obtained by liquid inlet phase detection)_e)。q_eCalculated according to the following formula:

q_e＝(C₀-C_t)V/m

wherein C is₀And C_tRespectively representing the initial concentration of ZEN and the concentration (mg. L) of adsorption equilibrium at a certain time^-1) V represents the volume of the solution (L) and m represents the mass of the adsorbent (g).

Figure 4 is a comparison of adsorption performance of three polymers on ZEN at different adsorption times.

In order to further study the adsorption mechanism of the zearalenone functionalized graphene surface molecularly imprinted material in the embodiment of the invention, a quasi-first-level model and a quasi-second-level model are respectively adopted for fitting, and as can be seen from fig. 5, the adsorption kinetics is closer to the quasi-second-level kinetic model.

According to the formation principle of a molecularly imprinted polymer, after CDHB is added, the CDHB and a functional monomer are combined under the action of a hydrogen bond, then the polymer is formed by ultraviolet light under the action of a cross-linking agent and an initiator, and when the CDHB is eluted out of the polymer in a solution, a cavity site similar to a ZEN structure is formed on the surface of the polymer, so that the ZEN can be effectively combined with the cavity on the surface of the polymer; and the adsorption performance of the RGO-MIP is superior to that of the MIP, which shows that the introduced graphene plays a role, according to the self-network structure of the graphene, when CDHB and a graphene solution are mixed, CDHB is introduced to the graphene substrate, and meanwhile, hydrogen bonding is combined with a functional monomer, so that a polymer is further formed on the surface of the graphene, the polymer is more spread on the surface of a carrier due to the structure, and more hole sites are exposed after the template is eluted, so that under the same condition, the RGO-MIP can adsorb more ZEN molecules.

Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. A zearalenone functionalized graphene surface molecularly imprinted material is characterized in that RGO is used as a carrier, CDHB is used as a template molecule, 1-ALPP is used as a functional monomer, TRIM is used as a cross-linking agent, AIBN is used as an initiator, and acetonitrile is used as a pore-forming agent.

2. A method for preparing zearalenone functionalized graphene surface molecularly imprinted material according to claim 1, wherein the method comprises the following steps:

3. A method for preparing zearalenone functionalized graphene surface molecularly imprinted material according to claim 1, wherein the method comprises the following steps:

4. The production method according to claim 2 or 3, wherein the ratio of CDHB: 1-ALPP: the molar ratio of TRIM is 1: 4-8: 20, the addition amount of AIBN is 10-20% of the weight of 1-ALPP, and the molar weight-volume ratio of CDHB to acetonitrile is 1 mol: 10-30 mL, and the mass concentration of RGO is 0.3-0.8 mg/mL.

5. The method of claim 2 or 3, wherein the solvent is DMF.

6. The method according to claim 2 or 3, wherein the eluent is a mixture of 96: 4, and acetic acid.

7. The preparation method of claim 3, wherein the GO is dispersed in water or DMF, the molecularly imprinted polymer with the template removed is added, after uniform ultrasonic mixing, hydrazine hydrate is added, the obtained mixed solution is heated in a water bath at 90-95 ℃ for 4-6 hours, cooled to room temperature, filtered to obtain powder, and then washed with water and ethanol for multiple times in sequence, and dried at 60 ℃ for 1-2 hours to obtain the zearalenone functionalized graphene surface molecularly imprinted material.

8. The preparation method of claim 7, wherein the addition amount of GO is 0.1-0.5% of the weight of the template-removed molecularly imprinted polymer, the concentration of hydrazine hydrate is 1-10%, and the volume-to-weight ratio of the addition amount of hydrazine hydrate to GO is 1-2 μ L: 1 mg.

9. The method of producing according to claim 2 or 3, wherein the method of producing CDHB comprises the steps of:

taking 2, 4-dihydroxy benzoic acid and cyclododecanol as raw materials, CDI as an activating agent, DBU as a catalyst and DMF as a solvent, reacting for 18-24 h at 40-60 ℃, separating an organic phase, drying, and evaporating the solvent under reduced pressure to obtain a crude product in a light yellow solid state;

purifying the crude product by high performance counter current chromatography or preparative liquid chromatography, wherein the high performance counter current chromatography is performed by selecting a solvent with a volume ratio of 1: 0.2: 1: 0.2 of mixed solution of n-hexane, ethyl acetate, methanol and water is a mobile phase, the speed of the mobile phase is 2mL/min, the rotating speed is 800r/min, the loading amount is 10mL, the loading mass concentration is 20mg/mL, and the detection wavelength is 254 nm; the preparation liquid phase method comprises the following steps of (1) preparing a liquid phase by a volume ratio of 40: 60 of water and acetonitrile is used as a mobile phase, the detection wavelength is 254nm, and the flow rate is 16 ml/min.