CN109666110B - Preparation method and application of tetracycline magnetic molecularly imprinted nanoparticles - Google Patents
Preparation method and application of tetracycline magnetic molecularly imprinted nanoparticles Download PDFInfo
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- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 85
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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Abstract
The invention relates to the field of preparation of functional materials for food analysis and detection, and discloses a preparation method and application of tetracycline magnetic molecularly imprinted nanoparticles3O4Nanoparticles (Fe)3O4@ CA NPs); performing prepolymerization by using tetracycline as a template molecule, methacrylic acid as a functional monomer, water and ethanol as solvents, and then performing surface carboxylation on Fe3O4The nano particles are used as a carrier, ethylene glycol dimethacrylate is used as a cross-linking agent, and azodiisobutyronitrile is used as an initiator to prepare the magnetic molecularly imprinted nano particles (MMIPs NPs) with specific adsorption to tetracycline. The tetracycline magnetic molecularly imprinted nanoparticles (MMIPs NPs) prepared by the method have good superparamagnetism and tetracycline selectivity, are more suitable for magnetic enrichment and separation of tetracycline in a complex food matrix, and are also beneficial to subsequent use with an analysis and detection instrument.
Description
Technical Field
The invention relates to the field of preparation of functional materials for food analysis and detection, and in particular relates to a preparation method and application of tetracycline magnetic molecularly imprinted nanoparticles.
Background
Tetracycline antibiotics are broad-spectrum antibacterial drugs taking polycyclic tetracarboxyamide as a mother nucleus, and because the drugs have the advantages of low price, wide antibacterial spectrum and the like, the drugs are widely used in the fields of livestock raising, aquaculture and the like, such as prevention and treatment of mastitis and metritis, intestinal infection and promotion of animal growth. The action mechanism of the inhibitor is that the normal operation of the whole process is influenced by inhibiting the growth of certain related peptide chains in the synthesis process of bacterial protein, and the inhibitor has good inhibition effect on bacteria, mycoplasma and the like. However, due to human factors such as non-compliance with drug withdrawal periods, excessive use of antibiotics, etc., tetracycline antibiotics remain in soil, water environment, meat, dairy products, eggs, etc. Tetracycline antibiotics have certain toxicity, and have certain damage to liver and kidney functions even have carcinogenic, teratogenic and mutagenic effects after long-term consumption of foods containing antibiotics, so that in-vivo drug-resistant bacteria are increased easily to cause the failure of antibacterial drugs, and the residue of the tetracycline antibiotics in soil and water environments also causes wide attention of environmental ecology, so that the establishment of an effective treatment means for selectively enriching and separating the residual tetracycline antibiotics in the environments or the foods is extremely urgent.
The molecularly imprinted polymer is a high-selectivity polymer particle prepared aiming at different substrates, and a three-dimensional hole which is completely matched with an imprinted molecule (template molecule) in space and has a specific binding function with the template molecule is left in a network structure, namely, the molecularly imprinted polymer has a specific recognition effect on the template molecule. The molecular imprinting polymer has binding sites and holes matched with template molecules, simultaneously has a novel high-molecular bionic material with strong recognition capability, has the characteristics of specificity, high selectivity, high strength and the like of an antibody, and is simple to prepare, low in cost and reusable. Molecularly imprinted polymers have been widely applied to the fields of solid-phase extraction, separation, enzyme catalysis, sensors and the like, and in recent years, more and more researchers are dedicated to the application of the molecularly imprinted technology in the field of food safety analysis and detection. Currently, ferroferric oxide nanoparticles (Fe)3O4NPs) due to simple preparation methodThe molecular imprinting polymer has the advantages of low cost, easy obtainment, low toxicity, controllable motion under an external magnetic field and the like, and is widely used as a magnetic carrier for preparing the molecular imprinting polymer. Magnetic Molecular Imprinted Polymers (MMIPs) are Polymers having specific molecular recognition sites, which are carried by Magnetic materials. Under the action of an external magnetic field, the polymer can be directly and selectively enriched and separated to analyze an object to be detected, so that the problems of long time consumption, difficult separation and the like in the pretreatment of food samples can be effectively solved. However, the application of the magnetic molecularly imprinted polymer to the detection or separation of tetracycline antibiotics is only reported, and the existing tetracycline magnetic molecularly imprinted polymer has large size, and the preparation method is mostly organic phase reaction, so that the preparation process is complex and the cost is high.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a tetracycline magnetic molecularly imprinted nanoparticle, which effectively improves the superparamagnetism and the selectivity of the tetracycline magnetic molecularly imprinted nanoparticle, has simple preparation method and low cost and is beneficial to industrialized popularization.
In order to achieve the above object, one aspect of the present invention provides a method for preparing tetracycline magnetic molecularly imprinted nanoparticles, comprising:
(1) dissolving ferric chloride hexahydrate in water, introducing nitrogen to remove oxygen, stirring, adding ferrous chloride tetrahydrate, a sodium hydroxide solution and citric acid, and reacting for 1-2 hours at the temperature of 75-95 ℃ and the rotating speed of 500-;
(2) cooling the solution prepared in the step (1) to room temperature, separating by using a magnet, collecting a product A, washing the product A by using water until the pH value is 6-7, and drying in vacuum to prepare surface carboxylated Fe3O4Nanoparticles (Fe)3O4@CA NPs)；
(3) Adding tetracycline and methacrylic acid into an ethanol-water solution, and stirring for 20-40min to obtain a pre-assembled solution; the surface carboxylation Fe prepared in the step (2)3O4Nanoparticles (Fe)3O4@ CA NPs) and ethylene glycol dimethacrylate into the preassembly solution, ultrasonic treatment 2Obtaining a prepolymerization solution within 0-40 min; adding the prepolymerization solution into a polyvinylpyrrolidone-ethanol solution, adding azobisisobutyronitrile, introducing nitrogen for protection, and reacting for 20-30h at the temperature of 50-70 ℃ and the rotation speed of 250-350 r/min; and (3) enriching, separating and collecting a product B by using a magnet, washing the product B by using a methanol-acetic acid solution, washing by using water, and drying in vacuum to obtain the tetracycline magnetic molecularly imprinted nanoparticles (MMIPs NPs).
Preferably, the mass ratio of ferric chloride hexahydrate, ferrous chloride tetrahydrate, sodium hydroxide and citric acid in the step (1) is (4.5-5.5): (1.5-2.5): (3-3.5): 1.
preferably, in the step (1), the mass of the ferric chloride hexahydrate is 4.5 to 5.5g relative to 100mL of the water.
Preferably, the washing in step (2) and/or step (3) is ultrasonic washing.
Preferably, the volume ratio of water to ethanol in the ethanol-water solution in the step (3) is (7-10): 1, the volume ratio of methanol to acetic acid in the methanol-acetic acid solution is (4-9): 1.
preferably, tetracycline, methacrylic acid, surface carboxylated Fe in said step (3)3O4Nanoparticles (Fe)3O4@ CA NPs), ethylene glycol dimethacrylate, polyvinylpyrrolidone and azobisisobutyronitrile in a mass ratio of (4-5): (2-9): (2.5-10): (37-42): (3.5-4.5): 1.
preferably, the magnet is a neodymium iron boron strong magnet.
In a second aspect, the invention provides a tetracycline magnetic molecularly imprinted nanoparticle prepared by the method.
The third aspect of the invention provides application of the tetracycline magnetic molecularly imprinted nanoparticle in enrichment and separation of tetracycline and/or detection of tetracycline.
Through the technical scheme, the preparation method provided by the invention has the advantages that the most common reagent is mixed with ferric salt for reaction, tetracycline is taken as a template molecule, and through optimization treatment, the size of the prepared tetracycline magnetic molecularly imprinted nano particle is only 13nm, and the prepared tetracycline magnetic molecularly imprinted nano particle has good superparamagnetism and tetracycline resistanceThe method has the advantages of selectivity, suitability for magnetic enrichment and separation of tetracycline in a complex food matrix, improvement of tetracycline enrichment and separation efficiency, contribution to subsequent use with an analysis and detection instrument, and effects of shortening analysis time and improving analysis efficiency. Surface carboxylated Fe3O4The synthesis of the nano particles adopts a coprecipitation method and a water phase reaction system, does not need to use an organic solvent, has mild reaction conditions, and synthesizes the surface carboxylated Fe3O4The nano particles are pure and have certain size controllability, and the agglomeration among the particles is reduced through the electrostatic repulsion between the particles, so that the dispersity is improved. The method is simple, short in time, low in cost and convenient for industrial popularization.
Drawings
FIG. 1 is Fe in example 2 of the present invention3O4 NPs(a)、Fe3O4Transmission electron micrographs of @ CA NPs (b), MMIPsNPs (c);
FIG. 2 is Fe in example 2 of the present invention3O4 NPs(a)、Fe3O4Fourier infrared spectrograms of @ CA NPs (b), MMIPsNPs (c);
FIG. 3 is Fe in example 2 of the present invention3O4 NPs(a)、Fe3O4Vibration sample magnetometer patterns of @ CA NPs (b), MMIPsNPs (c);
FIG. 4 is a graph showing the static adsorption curves of MMIPs NPs and MNIPs NPs to tetracycline in example 2 of the present invention;
FIG. 5 is a graph showing the adsorption kinetics of MMIPs NPs and MNIPs NPs to tetracycline in example 2 of the present invention;
FIG. 6 shows the specificity of adsorption of MMIPs NPs and MNIPs NPs to tetracycline, aureomycin, sulfadiazine and norfloxacin in example 2 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the invention provides a preparation method of a tetracycline magnetic molecularly imprinted nanoparticle, which comprises the following steps:
(1) dissolving ferric chloride hexahydrate in water, introducing nitrogen to remove oxygen, stirring, adding ferrous chloride tetrahydrate, a sodium hydroxide solution and citric acid, and reacting for 1-2 hours at the temperature of 75-95 ℃ and the rotating speed of 500-;
(2) cooling the solution prepared in the step (1) to room temperature, separating by using a magnet, collecting a product A, washing the product A by using water until the pH value is 6-7, and drying in vacuum to prepare surface carboxylated Fe3O4Nanoparticles (Fe)3O4@CA NPs)；
(3) Adding tetracycline and methacrylic acid into an ethanol-water solution, and stirring for 20-40min to obtain a pre-assembled solution; the surface carboxylation Fe prepared in the step (2)3O4Nanoparticles (Fe)3O4@ CA NPs) and ethylene glycol dimethacrylate are added into the preassembly solution, and the ultrasonic treatment is carried out for 20-40min to obtain a prepolymerization solution; adding the prepolymerization solution into a polyvinylpyrrolidone-ethanol solution, adding azobisisobutyronitrile, introducing nitrogen for protection, and reacting for 20-30h at the temperature of 50-70 ℃ and the rotation speed of 250-350 r/min; and (3) enriching, separating and collecting a product B by using a magnet, washing the product B by using a methanol-acetic acid solution, washing by using water, and drying in vacuum to obtain the tetracycline magnetic molecularly imprinted nanoparticles (MMIPs NPs).
In the present invention, the water may be ultrapure water, distilled water or deionized water.
Preferably, the mass ratio of ferric chloride hexahydrate, ferrous chloride tetrahydrate, sodium hydroxide and citric acid in the step (1) is (4.5-5.5): (1.5-2.5): (3-3.5): 1.
preferably, in the step (1), the mass of the ferric chloride hexahydrate is 4.5 to 5.5g relative to 100mL of the water.
Preferably, the washing in step (2) or/and step (3) is ultrasonic washing.
Preferably, the volume ratio of water to ethanol in the ethanol-water solution in the step (3) is (7-10): 1, the volume ratio of methanol to acetic acid in the methanol-acetic acid solution is (4-9): 1.
preferably, tetracycline, methacrylic acid, surface carboxylated Fe in said step (3)3O4Nanoparticles (Fe)3O4@ CA MNPs), ethylene glycol dimethacrylate, polyvinylpyrrolidone and azobisisobutyronitrile in a mass ratio of (4-5): (2-9): (2.5-10): (37-42): (3.5-4.5): 1.
preferably, the magnet is a neodymium iron boron strong magnet.
Adopting the same preparation method, but not adding tetracycline as a template molecule in the process, and synthesizing magnetic non-molecularly imprinted nanoparticles (MNIPs NPs); fe3O4Nanoparticles (Fe)3O4NPs) was prepared by the following procedure: dissolving ferric chloride hexahydrate in water, introducing nitrogen to remove oxygen, stirring, adding ferrous chloride tetrahydrate and sodium hydroxide solution, and reacting for 1-2h at the temperature of 75-95 ℃ and the rotation speed of 500-.
In a second aspect, the present invention provides a tetracycline magnetic molecularly imprinted nanoparticle prepared by the above method.
In a third aspect, the invention provides an application of the tetracycline magnetic molecularly imprinted nanoparticle in enrichment and separation of tetracycline and/or detection of tetracycline.
The method for enriching and separating the tetracycline by using the magnetic molecularly imprinted nanoparticles comprises the following steps: and adding MMIPs NPs into a sample solution containing tetracycline, carrying out vortex oscillation for 30-50min, standing for 5-10min, and carrying out magnet enrichment and separation to obtain the tetracycline MMIPs NPs.
The present invention will be described in detail below by way of examples.
In the following examples, the transmission electron microscope is FEI, Inc. of U.S. with model Tecnai G20; the Fourier infrared spectrometer is made by Shimadzu corporation of Japan and has the model of IRaffinity-1; the vibration sample magnetometer is manufactured by Quantum Design company in the United states and has the model of MPMS-XL-7; the UV-visible spectrophotometer is available from Shimadzu corporation, Japan, and is UV-2450. Tetracycline is available from Yongsheng Biotech, Inc., Shanghai Rui; methacrylic acid was purchased from Shanghai Michelin Biotechnology, Inc.; ethylene glycol dimethacrylate was purchased from Shanghai Aladdin Biotechnology Ltd; polyvinylpyrrolidone is available from national pharmaceutical group chemical agents, ltd; azobisisobutyronitrile was purchased from Shanghai Shanpu chemical Co., Ltd; other reagents were all commercially available.
In a specific embodiment of the present invention, the adsorption performance is evaluated by the following method: this was done using static adsorption experiments. Adding 2mL of tetracycline solutions with different concentrations (0.01-0.1mg/mL) into a centrifuge tube, respectively adding 4mg of MMIPS NPs or 4mg of MNIPs NPs into the centrifuge tube, standing in a constant-temperature water bath, performing magnetic separation and collection after adsorption is saturated to obtain a supernatant, measuring the concentration of the non-adsorbed tetracycline molecules in a test solution by using an ultraviolet visible spectrophotometer, and calculating to obtain the adsorption capacity Q.
Q＝(Co-Cs)V/m
In the formula, CoIs the initial concentration of tetracycline (mg/mL), CsIs the concentration of tetracycline in the supernatant (mg/mL), V is the volume of solution (mL), and m is the mass (g) of MMIPS NPs or MNIPs NPs.
Example 1
(1) Dissolving 4.5g of ferric chloride hexahydrate in 100mL of ultrapure water, introducing nitrogen, removing oxygen, and stirring; adding 1.5g of ferrous chloride tetrahydrate, 37.5mL of 2mol/L sodium hydroxide solution and 1g of citric acid, and reacting for 1h at the temperature of 75 ℃ and the rotating speed of 500 r/min;
(2) cooling the solution prepared in the step (1) to room temperature, separating by using a magnet, collecting a product A, repeatedly washing the product A by using ultrapure water until the pH value is 6, carrying out ultrasonic treatment for 3 times, and carrying out vacuum drying to obtain the surface carboxylated Fe3O4Nanoparticles (Fe)3O4@CA NPs)；
(3) 0.4g of tetracycline and 0.35g of methacrylic acid were added to 10mL of an ethanol-water solution (V)Water (W)：VEthanol7:1) and stirring for 20min to obtain a preassembly solution; 0.25g of surface carboxylated Fe prepared in the step (2) is taken3O4Nanoparticles and 3.7g ethylene glycol dimethacrylate were added to the pre-groupLoading into the solution, and performing ultrasonic treatment for 20min to obtain a prepolymerization solution; adding the prepolymerization solution into 100mL ethanol solution containing 0.35g of polyvinylpyrrolidone, adding 0.1g of azobisisobutyronitrile, introducing nitrogen for protection, and reacting for 20h at the temperature of 50 ℃ and the rotating speed of 250 r/min; collecting product B by enrichment and separation with magnet, and treating with methanol-acetic acid solution (V)Methanol：VAcetic acid7:1), washing for 6 times, then washing for 2 times by using ultrapure water, and drying in vacuum to obtain the tetracycline magnetic molecularly imprinted nanoparticles (MMIPs NPs).
Example 2
(1) Dissolving 5g of ferric chloride hexahydrate in 100mL of ultrapure water, introducing nitrogen to remove oxygen, and stirring; adding 2g of ferrous chloride tetrahydrate, 40mL of sodium hydroxide solution with the concentration of 2mol/L and 1g of citric acid, and reacting for 1.5h under the conditions that the temperature is 85 ℃ and the rotating speed is 550 r/min;
(2) cooling the solution prepared in the step (1) to room temperature, separating by using a magnet, collecting a product A, repeatedly washing the product A by using ultrapure water until the pH value is 6.5, and drying in vacuum to prepare the surface carboxylated Fe3O4Nanoparticles (Fe)3O4@CA NPs)；
(3) 0.45g of tetracycline and 0.65g of methacrylic acid were added to 10mL of an ethanol-water solution (V)Water (W)：VEthanol9:1) and stirring for 30min to obtain a preassembly solution; 0.5g of the surface carboxylated Fe prepared in the step (2) is taken3O4Adding nanoparticles and 3.9g of ethylene glycol dimethacrylate into the pre-assembly solution, and carrying out ultrasonic treatment for 30min to obtain a pre-polymerization solution; adding the prepolymerization solution into 100mL ethanol solution containing 0.4g polyvinylpyrrolidone, adding 0.1g azobisisobutyronitrile, introducing nitrogen for protection, and reacting for 24h at 60 ℃ and 300 r/min; collecting product B by enrichment and separation with magnet, and treating with methanol-acetic acid solution (V)Methanol：VAcetic acidWashing 7 times with ultrapure water, washing 3 times with ultrapure water, and vacuum drying to obtain tetracycline magnetic molecularly imprinted nanoparticles (MMIPs NPs).
The same preparation method was adopted, but no template molecule (tetracycline) was added in the process, resulting in magnetic non-molecularly imprinted nanoparticles (MNIPs NPs).
Fe3O4Nanoparticles (Fe)3O4NPs) was prepared by the following procedure: dissolving 5g of ferric chloride hexahydrate in 100mL of ultrapure water, introducing nitrogen to remove oxygen, and stirring; adding 2g of ferrous chloride tetrahydrate and 40mL of sodium hydroxide solution with the concentration of 2mol/L, and reacting for 1.5h under the conditions that the temperature is 85 ℃ and the rotating speed is 550 r/min.
For the prepared Fe3O4 NPs(a)、Fe3O4@ CANPs (b), MMIPs NPs (c) are subjected to transmission electron microscopy analysis, Fourier infrared spectroscopy analysis and vibration sample magnetometer analysis, and the analysis results are shown in FIGS. 1-3. As can be seen from FIG. 1, Fe3O4NPs (a) are mostly irregular cuboids, with a size of about 11.49 nm; fe3O4The @ CA NPs (b) show monodispersity and have good spherical structure with the size of about 9.79nm, which indicates that the application of citric acid in Fe is successful3O4NPs are surface-modified with carboxyl; MMIPsNPs (c) had a rough surface and a significantly increased average particle size of about 12.73nm, which is shown in Fe3O4The surface of the @ CA NPs forms a tetracycline molecular imprinted membrane.
As can be seen from FIG. 2, Fe3O4@ CA NPs (b) at about 575cm-1A characteristic absorption peak of Fe-O appears, which is similar to Fe3O4NPs (a) at 1730cm-1The absorption peak at (A) is the stretching vibration peak of C ═ O in COOH; at 1429cm-1Of the occurrence of-CH2Stretching vibration peak from-CH enriched in citric acid modified on the surface of nanoparticles2This indicates Fe3O4NPs have been successfully surface carboxylated with citric acid. MMIPs NPs (C) show C-O at 1093cm-1And 1259cm-1The peak of stretching vibration, C ═ O at 1730cm-1A stretching vibration peak of, and-CH2and-CH3At 2945cm-1the-CH stretching vibration peak shows that the functional monomer methacrylic acid and the cross-linking agent ethylene glycol dimethacrylate have been successfully fixed on Fe3O4@ CA NPs surface.
As can be seen from FIG. 3, Fe3O4 NPs(a)、Fe3O4The @ CA NPs (b) and the MMIPPs NPs (c) have no hysteresis, and the remanence and the coercive force are zero, which indicates that the sample has superparamagnetism. Fe3O4NPs(a)、Fe3O4The saturation magnetizations of the @ CA NPs (b) and MMIPPs NPs (c) were gradually decreased to 43.99emu/g, 40.67emu/g, and 24.55emu/g, respectively, and the decrease in magnetization indicates Fe3O4The addition of the surface modification layer and the imprinting layer reduces the magnetic susceptibility of magnetite, as shown in fig. 3, although the magnetic properties of MMIPs NPs are reduced, they can still be rapidly enriched and separated from the solution in the presence of an external magnetic field.
Example 3
(1) Dissolving 5.5g of ferric chloride hexahydrate in 100mL of distilled water, introducing nitrogen to remove oxygen, and stirring; adding 2.5g of ferrous chloride tetrahydrate, 44mL of sodium hydroxide solution with the concentration of 2mol/L and 1g of citric acid, and reacting for 2 hours at the temperature of 95 ℃ and the rotating speed of 600 r/min;
(2) cooling the solution prepared in the step (1) to room temperature, separating by using a magnet, collecting a product A, repeatedly washing the product A by using distilled water until the pH value is 7, and drying in vacuum to prepare surface carboxylated Fe3O4Nanoparticles (Fe)3O4@CA NPs)；
(3) 0.5g of tetracycline, 0.85g of methacrylic acid were added to 10mL of an ethanol-water solution (V)Water (W)：VEthanol10:1) and stirring for 40min to obtain a preassembly solution; 0.75g of surface carboxylated Fe prepared in the step (2) is taken3O4Adding nanoparticles and 4.2g of ethylene glycol dimethacrylate into the pre-assembly solution, and carrying out ultrasonic treatment for 40min to obtain a pre-polymerization solution; adding the prepolymerization solution into 100mL of ethanol solution containing 0.45g of polyvinylpyrrolidone, adding 0.1g of azobisisobutyronitrile, introducing nitrogen for protection, and reacting for 30h at the temperature of 70 ℃ and the rotating speed of 350 r/min; collecting product B by enrichment and separation with magnet, and treating with methanol-acetic acid solution (V)Methanol：VAcetic acid9:1) washing for 8 times, washing with distilled water for 2 times, and vacuum drying to obtain tetracycline magnetic molecularly imprinted nanoparticles (MMIPs NPs).
Experimental example 1
2mL of tetracycline solutions with initial concentrations of 0.01mg/mL, 0.02mg/mL, 0.03mg/mL, 0.04mg/mL, 0.05mg/mL, 0.06mg/mL, 0.07mg/mL, 0.08mg/mL, 0.09mg/mL and 0.1mg/mL are respectively added into a centrifuge tube, 4mg of NPs of MMIPs prepared in example 2 or 4mg of NPs of MNIPs prepared in example 2 are respectively added, the sample solutions are shaken at 300r/min for 12h under the constant temperature condition of 25 ℃, supernatant is collected by magnetic enrichment separation, the concentration of the unadsorbed tetracycline is measured by an ultraviolet-visible spectrophotometer, and the adsorption capacity is calculated according to the results. As shown in the result of FIG. 4, the adsorption capacity is gradually increased with the increase of the concentration of tetracycline, and finally the adsorption equilibrium is reached, and under different concentrations, the adsorption curves of the MMIPPs NPs and the MNIPs NPs for tetracycline are consistent, but the adsorption capacity of the MMIPs NPs is always larger than that of the MNIPs NPs, and when the adsorption equilibrium is reached, the adsorption capacity of the MMIPPs NPs is 2.76 times of that of the MNIPs NPs, which indicates that the MMIPs NPs have specific adsorption on the tetracycline.
Experimental example 2
Adding 2mL of tetracycline solution with the concentration of 0.08mg/mL into a centrifuge tube, respectively adding 4mg of MMIPs NPs prepared in the embodiment 2 or 4mg of MNIPs NPs prepared in the embodiment 2, respectively shaking the sample solution at the constant temperature of 25 ℃ at the rotating speed of 300r/min for 10min, 20min, 30min, 40min, 60min, 90min, 120min and 150min, magnetically enriching, separating and collecting supernatant, measuring the concentration of non-adsorbed tetracycline molecules by using an ultraviolet-visible spectrophotometer, and calculating the adsorption capacity according to the result. As shown in the results of FIG. 5, the MMIPs NPs and MNIPs NPs can rapidly adsorb tetracycline in the first 40min of the adsorption process, and then the adsorption rate gradually slows down, and finally the adsorption equilibrium is reached at 60 min. The adsorption capacity of the MMIPS NPs to the tetracycline is 34.89mg/g, which is 2.74 times of the adsorption capacity (12.74mg/g) of the MNIPs NPs to the tetracycline, and the fact that the MMIPS NPs have specific adsorption to the tetracycline is shown.
Experimental example 3
Adding 2mL of solution with tetracycline, aureomycin, sulfadiazine and norfloxacin concentration of 0.08mg/mL into a centrifuge tube, respectively adding 4mg of MMIPs NPs prepared in example 2 or 4mg of MNIPs NPs prepared in example 2, respectively oscillating the sample solution at the constant temperature of 25 ℃ at the rotating speed of 300r/min for 12h, carrying out magnetic separation to collect supernatant, measuring the concentration of unadsorbed tetracycline molecules by using an ultraviolet-visible spectrophotometer, and calculating the adsorption capacity according to the result. The results show that, as shown in FIG. 6, the adsorption capacity of MMPs NPs to tetracycline is 34.88mg/g, which is 3.18 times of that of MMPs NPs to sulfadiazine and 2.56 times of that of MMPs NPs to norfloxacin, indicating that the adsorption of MMPs NPs to sulfadiazine and norfloxacin is non-specific. The adsorption capacity of MMIPsNPs to tetracycline is only 1.19 times of that of MMIPPs NPs to aureomycin, because the structures of tetracycline and aureomycin are very similar, the adsorption capacity of MMIPs NPs to aureomycin is relatively high. Meanwhile, the adsorption capacity of MNIPs NPs to tetracycline is smaller than 1/2 of the adsorption capacity of MMIPs NPs to tetracycline, which indicates that the adsorption of MNIPs NPs to tetracycline is mainly caused by non-specific adsorption, and further indicates that MMIPs NPs have specific adsorption to tetracycline.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (8)
1. A preparation method of tetracycline magnetic molecularly imprinted nanoparticles is characterized by comprising the following steps:
(1) dissolving ferric chloride hexahydrate in water, introducing nitrogen to remove oxygen, stirring, adding ferrous chloride tetrahydrate, a sodium hydroxide solution and citric acid, and reacting for 1-2 hours at the temperature of 75-95 ℃ and the rotating speed of 500-;
(2) cooling the solution prepared in the step (1) to room temperature, separating by using a magnet, collecting a product A, washing the product A by using water until the pH value is 6-7, and drying in vacuum to prepare surface carboxylated Fe3O4Nanoparticles;
(3) adding tetracycline and methacrylic acid into an ethanol-water solution, and stirring for 20-40min to obtain a pre-assembled solution; the surface carboxylation Fe prepared in the step (2)3O4Adding the nano particles and ethylene glycol dimethacrylate into the pre-assembly solution, and carrying out ultrasonic treatment for 20-40min to obtain a pre-polymerization solution; adding the prepolymerization solution into a polyvinylpyrrolidone-ethanol solution, adding azobisisobutyronitrile, introducing nitrogen for protection, and reacting for 20-30h at the temperature of 50-70 ℃ and the rotation speed of 250-350 r/min; collecting a product B by utilizing enrichment separation of a magnet, washing the product B by using a methanol-acetic acid solution, then washing by using water, and drying in vacuum to obtain magnetic molecularly imprinted nanoparticles with specific adsorption on tetracycline;
tetracycline, methacrylic acid and surface carboxylation Fe in the step (3)3O4The mass ratio of the nano particles to the ethylene glycol dimethacrylate to the polyvinylpyrrolidone to the azobisisobutyronitrile is (4-5): (2-9): (2.5-10): (37-42): (3.5-4.5): 1.
2. the preparation method of the tetracycline magnetic molecularly imprinted nanoparticle according to claim 1, wherein the mass ratio of ferric chloride hexahydrate, ferrous chloride tetrahydrate, sodium hydroxide and citric acid in step (1) is (4.5-5.5): (1.5-2.5): (3-3.5): 1.
3. the method for preparing the tetracycline magnetic molecularly imprinted nanoparticle according to claim 1, wherein in step (1), the mass of the ferric chloride hexahydrate is 4.5-5.5g relative to 100mL of the water.
4. The preparation method of the tetracycline magnetic molecularly imprinted nanoparticle according to claim 1, wherein the washing in step (2) or/and step (3) is ultrasonic washing.
5. The method for preparing magnetic molecularly imprinted nanoparticles according to claim 1, wherein the volume ratio of water to ethanol in the ethanol-water solution in step (3) is (7-10): 1, the volume ratio of methanol to acetic acid in the methanol-acetic acid solution is (4-9): 1.
6. the method for preparing the tetracycline magnetic molecularly imprinted nanoparticle of claim 1, wherein the magnet is a neodymium iron boron strong magnet.
7. A tetracycline magnetic molecularly imprinted nanoparticle prepared by the method of any one of claims 1-6.
8. The tetracycline magnetic molecularly imprinted nanoparticle of claim 7, for use in enrichment separation and/or detection of tetracycline.
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