CN111909311B - Corn gibberellin ketone functionalized graphene surface molecularly imprinted material and preparation method thereof - Google Patents

Corn gibberellin ketone functionalized graphene surface molecularly imprinted material and preparation method thereof Download PDF

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CN111909311B
CN111909311B CN202010641149.3A CN202010641149A CN111909311B CN 111909311 B CN111909311 B CN 111909311B CN 202010641149 A CN202010641149 A CN 202010641149A CN 111909311 B CN111909311 B CN 111909311B
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zearalenone
cdhb
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CN111909311A (en
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韩杨莹
孙长坡
王峻
常晓娇
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Academy of National Food and Strategic Reserves Administration
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Abstract

The embodiment of the invention discloses a zearalenone functionalized graphene surface molecularly imprinted material and a preparation method thereof, belonging to the technical field of molecularly imprinted materials. The zearalenone functionalized graphene surface molecularly imprinted material uses 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. The corn gibberellin ketone functionalized graphene surface molecularly imprinted material prepared by the method has higher adsorption capacity and good selectivity to ZEN, can be used for separating and removing ZEN, and has wide application prospect.

Description

Corn gibberellin ketone functionalized graphene surface molecularly imprinted material and preparation method thereof
Technical Field
The embodiment of the invention relates to the technical field of molecularly imprinted materials, in particular to a zearalenone functionalized graphene surface molecularly imprinted material and a preparation method thereof.
Background
Zearalenone (ZEN) is one of the most widely distributed fusarium in the world, occurring in cereals and agricultural by-products in asia, europe and america. ZEN occurs mainly on cereal seeds rich in starch, enters the food chain in the form of feed, food processing materials, and causes accumulation in the human or animal body. It produces estrogen effect syndrome in organism, causes excessive estrogen in animal body, has carcinogenicity, and can produce toxic action on kidney and liver of animal body.
The existing detection method of ZEN mainly has the defects of time consumption, high cost and the like in chromatographic techniques such as HPLC, GC-MS, LC-MS and the like, so that the establishment of the detection method of ZEN with economy, rapidness and good sensitivity has great significance.
The molecular imprinting technology refers to a polymer technology for simulating biological recognition systems such as antigen-antibody, enzyme and the like and adopting a chemical method to prepare a polymer with specific binding effect on specific targets on a space structure and a binding site. Preparing a molecularly imprinted polymer with a three-dimensional structure with a fixed hole size and a fixed arrangement functional group by taking a target analyte (or a structural analogue thereof) as a template molecule; after the template molecules are removed, holes which are complementary to the space structures, the sizes and the sizes of the template molecules and the binding sites of the template molecules are left in the imprinted polymer, so that the target molecules are identified with high specificity.
The preparation process of the molecularly imprinted polymer mainly comprises three steps, namely pre-assembly, polymerization and template elution. According to the different positions of recognition sites, the preparation methods of the molecularly imprinted polymer mainly comprise two main types, namely an embedding method and a surface molecularly imprinted method.
The molecular imprinting polymer prepared by the embedding method has the advantages that the recognition sites are mostly distributed in the polymer, the distribution of sites on the surface of the polymer is less, and the problems that template molecules are difficult to remove, the mass transfer resistance in the imprinting polymer is large, the effective size is small and the like can exist in practical application. Surface blotting refers to a technique for preparing a blotting polymer by performing polymerization reaction on the surface of a specific carrier (or substrate) and controlling the distribution of blotting recognition sites on the surface of the 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 by selecting different carriers, controllable thickness of the imprinted polymer, easy elution of template molecules and the like.
Therefore, it is necessary to establish a molecularly imprinted polymer based on a surface molecularly imprinted method 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 embodiment of the present invention provides the following technical solutions:
according to a first aspect of the embodiment of the invention, the embodiment of the invention provides a zearalenone functionalized graphene surface molecularly imprinted material, which takes RGO (reduced graphene oxide) as a carrier, CDHB (2, 4-dihydroxybenzoic acid cyclododecyl ester) 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, deoxidizing, sealing, and carrying out constant-temperature reaction for 24 hours in a water bath at the temperature of 24 hours or 60 ℃ under ultraviolet irradiation to prepare 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, deoxidizing, sealing, and carrying out a water bath constant temperature reaction for 24 hours at the temperature of 24 hours or 60 ℃ under ultraviolet irradiation to prepare a molecular imprinting polymer;
grinding the molecularly imprinted polymer, sieving with a 100-200 mesh sieve, removing CDHB by using an eluent, and drying 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 the GO and the molecularly imprinted polymer with the template removed through a water bath method.
Of the above two methods, CDHB is preferable: 1-ALPP: the molar ratio of TRIM is 1: 4-8: 20.
AIBN is an initiator for initiating thermal or photopolymerization. Preferably, in the embodiment of the invention, the addition amount of AIBN is 10 to 20 percent of the weight of 1-ALPP.
Acetonitrile is a porogen used to pore-form within a material. When the consumption of the pore-forming agent is small, the obtained material is hard and not easy to grind, and the surface adsorption sites cannot be completely exposed, so that the adsorption effect is affected; when the consumption 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 examples of the present invention, the molar amount to volume ratio of CDHB to acetonitrile is 1mol: 10-30 mL.
DMF is used as a solvent, and raw materials can be well dispersed in the solvent during polymerization reaction, so that a polymer with uniform distribution is obtained.
The volume ratio of the adopted eluent is 96:4 with 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 mixed uniformly by ultrasound, 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, washed with water and ethanol for multiple times in sequence, and dried at 60 ℃ for 1-2 hours, so as to obtain the zearalenone functionalized graphene surface molecularly imprinted material.
Preferably, the addition amount of GO is 0.1 to 0.5% by weight, more preferably 0.3% by weight of the molecularly imprinted polymer from which the template is removed. The concentration of the hydrazine hydrate is 1-10%, and the ratio of the adding amount of the hydrazine hydrate to the volume and the weight of GO is 1-2 mu L:1mg.
The RO and RGO used in the present invention are each produced according to the following method.
The method of laboratory preparation of GO, i.e. modified Hummers method: graphite powder and sodium nitrate were added to concentrated sulfuric acid with vigorous stirring at room temperature in order to form a mixed solution, and then the mixture was cooled to 0 ℃ in an ice bath. The temperature of the suspension is kept below 20 ℃, potassium permanganate is slowly added into the mixture under the condition of intense stirring, and the reaction system is transferred to a water bath with the temperature of 35-40 ℃ for about half an hour, so that a thick paste substance is formed. Deionized water was added to the above, and the new solution formed was stirred for an additional 15min, followed by a slow addition of 30% hydrogen peroxide, at which time the color of the solution changed from brown to yellow. The metal ions in the solution were removed by filtration and washing with 10% aqueous HCl, and then the centrifugation was repeated to remove the excess acid. Finally, the obtained solid is redispersed in water, and the uniform aqueous solution of GO is obtained through ultrasonic treatment, centrifugation and dialysis purification. Wherein, graphite powder: sodium nitrate: weight ratio of potassium permanganate=1:0.5:3; the mass fraction of the graphite powder in the concentrated sulfuric acid is 5%; the volume of hydrogen peroxide accounts for 2.5 percent of the total volume of the solution.
Method for laboratory preparation of RGO: hydrazine hydrate (hydrazine hydrate: GO mass ratio is 0.008-0.01:1) is added dropwise into the GO uniform aqueous solution, after stirring for 1h, the solution is transferred into a 50mL reaction kettle, heated for 12h at 180 ℃, and then cooled to room temperature. The change in color from brown to black of RGO indicates that GO was reduced to RGO. And centrifuging the dispersion solution, washing the obtained precipitate with deionized water and ethanol in sequence, and finally drying the sample at 60 ℃ overnight to obtain RGO solid.
CDHB adopts the following synthesis steps:
accurately weighing 1.6202g of N, N' -Carbonyldiimidazole (CDI) and 1.5409g of 2, 4-dihydroxybenzoic acid, putting the materials into a 250mL round bottom flask, adding 20mL of anhydrous N, N-Dimethylformamide (DMF), dissolving the materials, magnetically stirring the materials for 1h in a water bath at 40 ℃, adding 2.2108g of cyclododecanol and 1.8214g of 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU) into the solution, continuously stirring the materials at 40 ℃ for 22h, adding 20mL of water and 20mL of dichloromethane into the solution after the reaction is finished, fully mixing the materials with the solution, standing the mixture for layering, taking a lower organic phase, sequentially and respectively repeating the steps of washing the organic phase for 3 times by 30mL of 10% (v/v) hydrochloric acid, water and saturated sodium bicarbonate solution, drying the anhydrous sodium sulfate overnight, centrifuging the upper oil phase product to be transferred into the 50mL round bottom flask, decompressing and steaming the solvent such as dichloromethane and the like under 40 ℃ to obtain a light yellow solid crude product.
In the prior art, silica gel column chromatography is adopted for purification, and the eluent is petroleum ether: ethyl acetate=32: 1 (v/v) slowly increases its polarity to petroleum ether: ethyl acetate = 16:1 (v/v), this method has the disadvantage of low yield (about 60%) and low purity (80% by HPLC).
The invention adopts high-efficiency countercurrent chromatography and preparation liquid phase method for purification, which can effectively solve the problems. The high-efficiency countercurrent chromatography adopts a solvent system of n-hexane, ethyl acetate, methanol and water for mixing and separation, wherein the upper phase is a HSCCC mobile phase, the lower phase is a stationary phase, and after experiments with different solvent ratios, n-hexane is selected: ethyl acetate: methanol: water = 1:0.2:1:0.2 The mobile phase speed is 2mL/min, the rotating speed is 800r/min, the loading quantity is 10mL, the loading mass concentration is 20mg/mL, the detection wavelength is 254nm, the yield is 70%, and the HPLC detection purity is 95%.
The volume ratio of the preparation liquid phase method is 40: the mixed solution of 60 water and acetonitrile is a mobile phase, the detection wavelength is 254nm, the flow rate is 16ml/min, the yield is 72%, and the purity is 97% by HPLC detection.
Graphene is formed by sp 2 The two-dimensional planar carbon material formed by hybridization connection has large specific surface area, mechanical strength and excellent electric conduction and heat conduction properties, so that graphene can be used as a carrier for preparing a molecular imprinting material. The molecularly imprinted polymer taking the graphene as the carrier has the advantages that the molecularly imprinted membrane is formed on the surface of a graphene sheet layer, the surface area is very large, the layer is relatively thin, the embedding phenomenon is reduced, and the imprinting process is performed on the surface of the graphene, so that the elution and the recognition of template molecules are facilitated; the graphene has good conductivity, and the molecularly imprinted electrochemical sensor taking the graphene as a carrier can realize high sensitivity and low detection limit; the stability and reproducibility of the molecularly imprinted membrane can be improved by the good thermal and mechanical properties of graphene.
The embodiment of the invention has the following advantages:
according to the zearalenone functionalized graphene surface molecularly imprinted material, 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, acetonitrile is used as a pore-forming agent, and static and selective adsorption experiments show that the 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 will be apparent to those of ordinary skill in the art that the drawings in the following description are exemplary only and that other implementations can be obtained from the extensions of the drawings provided without inventive effort.
FIG. 1 is a Scanning Electron Microscope (SEM) of a template-removed molecularly imprinted polymer (designated MIP) prepared in the second step of example 3;
FIG. 2 is a Scanning Electron Microscope (SEM) of a zearalenone functionalized graphene surface molecularly imprinted material (recorded as RGO-MIP) prepared in example 3;
FIG. 3 is X-ray photoelectron spectroscopy (XPS) of MIP and RGO-MIP, with the C/O ratio of RGO-MIP being higher than MIP, indicating the actual presence of functionalized graphene in RGO-MIP. The appearance of c=o and the increase of C-C, C-O (epoxy), C-OH compared to MIP for RGO-MIP suggests successful incorporation of functionalized graphene on MIP, whereas under reduction of hydrazine hydrate, O-c=o disappears, so that GO is reduced to RGO;
FIG. 4 is a comparison of the adsorption performance of three polymers at different adsorption times for ZEN;
fig. 5 is an adsorption kinetic model of a zearalenone functionalized graphene surface molecularly imprinted material provided by an embodiment of the invention.
Detailed Description
Other advantages and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, which, by way of illustration, is to be read in connection with certain specific embodiments, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material comprises the following steps:
dispersing 20.0mg of RGO into 20mL of DMF (dimethyl formamide) by ultrasonic, adding 4.0mg of N-vinylcarbazole, uniformly mixing for 2 hours by ultrasonic, adding 320.0mg of CDHB, 504.8mg of 1-ALPP and 10mL of acetonitrile, keeping the mixed solution for 15 minutes, adding 5.9264g of TRIM and 77.2mg of AIBN, uniformly mixing, introducing nitrogen into the system for 30 minutes, and irradiating a sealed reaction container under ultraviolet light (lambda=254 nm) for 24 hours to prepare the functionalized graphene surface molecularly imprinted polymer (in a gray black hard state);
grinding the obtained polymer in a mortar, sieving the ground polymer with a 200-mesh sieve, taking a mixed solution of methanol/acetic acid=96/4 (v/v) as an eluent, refluxing for a plurality of times to remove CDHB, and finally drying the mixture in an oven at 40 ℃ overnight to obtain the zearalenone functionalized graphene surface molecularly imprinted material.
Example 2
The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material comprises the following steps:
dispersing 20.0mg of RGO into 20mL of DMF (dimethyl formamide) by ultrasonic, adding 4.0mg of N-vinylcarbazole, uniformly mixing for 2 hours by ultrasonic, adding 320.0mg of CDHB, 757.2mg of 1-ALPP and 10mL of acetonitrile, keeping the mixed solution for 15 minutes, adding 5.9264g of TRIM and 77.2mg of AIBN, uniformly mixing, introducing nitrogen into the system for 30 minutes, placing a sealed reaction container in a water bath at 60 ℃ for constant temperature reaction for 24 hours, and obtaining the functionalized graphene surface molecularly imprinted polymer (in a gray black hard state);
grinding the obtained polymer in a mortar, sieving the ground polymer with a 200-mesh sieve, taking a mixed solution of methanol/acetic acid=96/4 (v/v) as an eluent, refluxing for a plurality of times to remove CDHB, and drying the mixture in an oven at 40 ℃ overnight to obtain the zearalenone functionalized graphene surface molecularly imprinted material.
Example 3
The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material comprises the following steps:
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 a sealed reaction vessel is placed under ultraviolet light (lambda=254 nm) and irradiated for 24h, so as to prepare the molecularly imprinted polymer (in a gray black hard state);
grinding the obtained polymer in a mortar and sieving with a 200-mesh sieve, taking a mixed solution of methanol/acetic acid=96/4 (v/v) as an eluent, refluxing for a plurality of times to remove CDHB, and finally drying overnight in an oven at 40 ℃ to obtain a molecularly imprinted polymer with a template removed;
adding 50mg of molecularly imprinted polymer with the template removed and 0.15mg of GO into 50mL of water, uniformly mixing by ultrasonic for 1h, 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, washing with water and ethanol for multiple times sequentially, and drying in an oven at 60 ℃ for 2h to obtain the zearalenone functionalized graphene surface molecularly imprinted material.
Example 4
The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material comprises the following steps:
320.0mg of CDHB, 1009.6mg 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 a sealed reaction vessel is placed in a water bath at 60 ℃ for constant temperature reaction for 24h, so as to prepare the molecularly imprinted polymer (in a gray black hard state);
grinding the obtained polymer in a mortar, sieving with a 200-mesh sieve, taking a mixed solution of methanol/acetic acid=96/4 (v/v) as eluent, refluxing for a plurality of times to remove CDHB, and finally drying in an oven at 40 ℃ overnight to obtain a molecularly imprinted polymer with a template removed;
adding 50mg of molecularly imprinted polymer with the template removed and 0.15mg of GO into 50mL of DMF, uniformly mixing by ultrasonic for 1h, adding 20 mu L of 1% hydrazine hydrate, heating by water bath at 95 ℃ for 6h, cooling to room temperature, filtering to obtain powder, washing by water and ethanol for multiple times sequentially, and drying by 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 in the embodiment is different from that in the embodiment 3 only in that: the addition amount of GO was 0.05mg.
Example 6
The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material in the embodiment is different from that in the embodiment 3 only in that: the addition amount of GO was 0.25mg.
Comparative example 1
The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material of the comparative example is different from that of the embodiment 3 only in that: 20 μL of 1% hydrazine hydrate was replaced with 6.25mg ascorbic acid.
Comparative example 2
The preparation method of the zearalenone functionalized graphene surface molecularly imprinted material in the embodiment is different from that in the embodiment 3 only in that: no reducing agent hydrazine hydrate is added.
Test example 1
And testing the adsorption capacity of the zearalenone functionalized graphene surface molecularly imprinted material prepared in examples 1-6 and comparative examples 1-2 on ZEN.
8 parts of 5mL of 0.5ppm ZEN acetonitrile solution are taken, the same amount of the materials are respectively added, ultrasonic stirring is carried out until adsorption is balanced, and then the influence of different modification modes on the adsorption capacity is observed.
The adsorption capacity was determined by the adsorption rate (Q), q= (C) 0 -C t )/C 0 *100, wherein C 0 And C t Represents the initial concentration of ZEN and the concentration of adsorption equilibrium (mg.L) -1 ). The results are shown in Table 1.
TABLE 1
Figure BDA0002571515250000091
The results show that: with the increase of RGO content, the adsorption capacity of RGO-MIP is improved, when the RGO content is 0.3%, the prepared RGO-MIP has the best adsorption effect, the ratio of RGO is continuously improved, and the adsorption capacity is reduced. Since the surface ductility of RGO increases the contact area between MIP and target molecule, the adsorption capacity is improved with the increase of RGO content, but when the RGO content is too large, the specific binding sites on the MIP surface are covered, and the specific binding with the target molecule is affected, so the optimal ratio of RGO is 0.3%.
The ascorbic acid used in comparative example 1 had a weak reduction effect, was unable to completely reduce GO, and had an influence on the adsorption effect, and the hydroxyl group thereof also inhibited adsorption of ZEN by the material, considering that there may be residual ascorbic acid on the surface of the material.
And like RGO, the surface ductility of GO increases the contact area of MIP and target molecules, so that the binding sites are more exposed, and functional groups such as carboxyl and hydroxyl on the GO surface can be combined with the target molecules through hydrogen bonding or electrostatic interaction force, so that in the single existence of target molecules (ZEN), comparative example 2 also shows good adsorption.
Test example 2
The specific adsorption capacity of the zearalenone functionalized graphene surface molecularly imprinted material prepared in the example 1, the example 3 and the comparative example 2 on ZEN is tested.
A mixed solution (each containing 0.5 ppm) of ZEN and DON was prepared, and the same amounts of GO-MIP and RGO-MIP were added, respectively, and 10mg was added. The adsorption capacity was determined by the adsorption rate (Q), q= (C) 0 -C t )/C 0 *100, wherein C 0 And C t Represents the initial concentration of ZEN and the concentration of adsorption equilibrium (mg.L) -1 ). The results are shown in Table 2.
TABLE 2
Figure BDA0002571515250000101
Figure BDA0002571515250000111
The results show that: the molecular imprinting material of comparative example 2 has weak specific adsorption capacity to ZEN, which indicates that the zearalenone functionalized graphene surface molecular imprinting material has strong specific adsorption capacity to ZEN.
The oxygen-containing functional groups are arranged on the surface of GO, and compounds with hydroxyl functional groups such as ZEN, DON and the like can be indiscriminately adsorbed, and the oxygen-containing functional groups can be reduced or disappear after being reduced to RGO, and the molecular imprinting material mainly plays an adsorption role, so that the specific adsorption capacity to ZEN is improved.
Test example 3
Preparing ZEN solution with a certain concentration, taking 10mg of zearalenone functionalized graphene surface molecularly imprinted material (recorded as RGO-MIP) prepared in example 3 (scanning electron microscope (see figure 2), template-removed molecularly imprinted polymer (recorded as MIP) prepared in the second step in example 3 (scanning electron microscope (see figure 1)) and NIP (namely blank control without CDHB added during synthesis), respectively adding into 100ml of ZEN solution (0.5 ppm), ultrasonically stirring and adsorbing for 5h, sampling every 1h, detecting with liquid phase, and calculating adsorption capacity (q) of the polymer to ZEN e )。q e Calculated according to the following formula:
q e ＝(C 0 -C t )V/m
wherein C is 0 And C t Represents the initial concentration of ZEN and the adsorption equilibrium concentration at a certain point (mg.L) -1 ) V represents the solution volume (L), and m represents the mass (g) of the adsorbent.
FIG. 4 is a comparison of the adsorption performance of three polymers at different adsorption times for ZEN.
In order to further study the adsorption mechanism of the zearalenone functionalized graphene surface molecularly imprinted material, fitting is performed by adopting a quasi-first-order model and a quasi-second-order model respectively, and as can be seen from fig. 5, adsorption dynamics are closer to the quasi-second-order dynamics model.
From the result, the adsorption performance of RGO-MIP and MIP is better than NIP, according to the formation principle of molecularly imprinted polymer, it can be deduced that CDHB is combined with functional monomer under the action of hydrogen bond after adding CDHB, then under the action of cross-linking agent and initiator, polymer is formed by means of ultraviolet light, when CDHB is eluted out of polymer in solution, the polymer surface forms hole site similar to ZEN structure, so that ZEN can be effectively combined with polymer surface hole; the adsorption performance of RGO-MIP is superior to MIP, which shows that the introduced graphene plays a role, when CDHB and graphene solution are mixed, the CDHB is introduced onto the graphene substrate, meanwhile, the hydrogen bond effect is combined with the functional monomer, and further, a polymer is formed on the surface of the graphene, so that the polymer is spread on the surface of the carrier more, more hole sites are exposed after the template is eluted, and more ZEN molecules can be adsorbed by RGO-MIP under the same condition.
While the invention has been described in detail in the foregoing general description and specific examples, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (6)

1. The 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;
the preparation method of the zearalenone functionalized graphene surface molecularly imprinted material comprises the following steps of:
sequentially adding RGO, N-vinylcarbazole, CDHB, 1-ALPP, TRIM, AIBN and acetonitrile into a solvent, uniformly mixing, filling nitrogen, deoxidizing, sealing, and carrying out constant-temperature reaction for 24 hours in a water bath at the temperature of 24 hours or 60 ℃ under ultraviolet irradiation to obtain a functionalized graphene surface molecularly imprinted polymer, wherein the solvent is DMF;
grinding the functionalized graphene surface molecularly imprinted polymer, sieving with a 100-200 mesh sieve, removing CDHB with eluent, and drying overnight at 40 ℃ to obtain the zearalenone functionalized graphene surface molecularly imprinted material, or,
the preparation method of the zearalenone functionalized graphene surface molecularly imprinted material comprises the following steps of:
sequentially adding CDHB, 1-ALPP, TRIM, AIBN and acetonitrile into a solvent, uniformly mixing, filling nitrogen, deoxidizing, sealing, and carrying out a water bath constant temperature reaction for 24 hours at the temperature of 24 hours or 60 ℃ under ultraviolet irradiation to prepare a molecular imprinting polymer, wherein the solvent is DMF;
grinding the molecularly imprinted polymer, sieving with a 100-200 mesh sieve, removing CDHB by using an eluent, and drying overnight at 40 ℃ to obtain the molecularly imprinted polymer with the template removed;
preparing a zearalenone functionalized graphene surface molecularly imprinted material by using GO and a molecularly imprinted polymer with a template removed through a water bath method;
dispersing the GO in water or DMF, adding the molecularly imprinted polymer with the template removed, adding hydrazine hydrate after ultrasonic mixing uniformly, heating the obtained mixed solution in a water bath at 90-95 ℃ for 4-6 hours, cooling to room temperature, filtering to obtain powder, washing with water and ethanol for multiple times sequentially, and drying at 60 ℃ for 1-2 hours to obtain the zearalenone functionalized graphene surface molecularly imprinted material.
2. The zearalenone functionalized graphene surface molecularly imprinted material of claim 1, wherein CDHB:1-ALPP: the molar ratio of TRIM is 1: 4-8: 20, the addition amount of AIBN is 10 to 20 percent of the weight of 1-ALPP, and the mol ratio of CDHB to acetonitrile is 1mol: 10-30 mL, and the mass concentration of RGO is 0.3-0.8 mg/mL.
3. The zearalenone functionalized graphene surface molecularly imprinted material according to claim 1, wherein the eluent is in a volume ratio of 96:4 with acetic acid.
4. The zearalenone functionalized graphene surface molecularly imprinted material according to claim 1, wherein the addition amount of GO is 0.1-0.5% of the weight of the molecularly imprinted polymer with the template removed, the concentration of hydrazine hydrate is 1-10%, and the ratio of the addition amount of hydrazine hydrate to the volume and the weight of GO is 1-2 μl:1mg.
5. The zearalenone functionalized graphene surface molecularly imprinted material according to claim 4, wherein the mass ratio of GO to template-removed molecularly imprinted polymer is 0.3%.
6. The zearalenone functionalized graphene surface molecularly imprinted material according to claim 1, wherein the preparation method of the CDHB comprises the following steps:
2, 4-dihydroxybenzoic acid and cyclododecanol are used as raw materials, CDI is used as an activator, DBU is used as a catalyst, DMF is used as a solvent, the reaction is carried out for 18-24 hours at 40-60 ℃, an organic phase is separated, and the crude product in a light yellow solid state is obtained after drying and reduced pressure evaporation of the solvent;
purifying the crude product by adopting a high-performance countercurrent chromatography or a preparation liquid phase method, wherein the high-performance countercurrent chromatography adopts the following steps of: 0.2:1:0.2 of mixed solution of n-hexane, ethyl acetate, methanol and water as a mobile phase, wherein the speed of the mobile phase is 2mL/min, the rotating speed is 800r/min, the sample loading amount is 10mL, the sample loading mass concentration is 20mg/mL, and the detection wavelength is 254nm; the volume ratio of the preparation liquid phase method is 40:60 with water and acetonitrile as a mobile phase, the detection wavelength was 254nm, and the flow rate was 16ml/min.
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