CN115181465A - Preparation method of molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles - Google Patents
Preparation method of molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles Download PDFInfo
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Abstract
The invention discloses a preparation method of a molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles, which comprises the following steps: under the constant temperature condition of 10-40 ℃, immersing a polished copper bar subjected to ultrasonic cleaning pretreatment into a silver trifluoroacetate aqueous solution for reaction for 2-8 min, and taking out the copper bar to obtain a silver nanoparticle layer on the surface of the copper bar; sequentially adding a functional monomer, a cross-linking agent and template molecules into a reaction container, introducing inert gas to remove oxygen, immediately placing the obtained copper rod wetting initiator attached with the silver nanoparticle layer into the reaction container for sealing, carrying out polymerization reaction for 0.5-1 h at 70-85 ℃ under the protection of the inert gas, then removing the template molecules through elution, and drying to obtain the molecularly imprinted polymer coating; the method does not need special instruments and equipment, has simple preparation steps and low production cost, and can prepare the molecularly imprinted polymer which can specifically identify and adsorb enrofloxacin from a complex matrix and can be recycled.
Description
Technical Field
The invention relates to the technical field of preparation of nano materials and molecular imprinting, in particular to a preparation method of a molecular imprinting polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles.
Background
As a functional material with various excellent performances, the nano material has various potential application values which are widely known by people and are the most active and most approximate important components in the field of new materials at present. The silver nano material has simple preparation method and excellent catalytic performance, and is one of important materials for basic field research. More importantly, due to the unique size and structure of the silver nano material, the silver nano material has a quantum size effect, a small size effect, a surface effect and a macroscopic quantum tunneling effect, presents a series of physicochemical properties which are not possessed by conventional materials and even macroscopic materials, and is widely applied to the fields of electronic circuits, environmental detection, industrial catalysis, biosensing, surface enhanced Raman scattering and the like.
Molecularly Imprinted Polymers (MIPs) are prepared by polymerizing functional monomers, template molecules, an initiator, a cross-linking agent and the like to form a three-dimensional cross-linked structure around the template molecules, and removing the template molecules to obtain an imprinted cavity which can be matched with the size, shape and functional groups of the template molecules. The polymer can selectively recombine with the template in a substance with a similar structure in a complex environment to specifically recognize and extract a target analyte, and has the advantages of simple preparation, low cost and long service life.
Disclosure of Invention
The invention aims to provide a preparation method of a molecularly imprinted polymer coating which is simple in process, low in cost and high in selectivity and can specifically identify enrofloxacin based on silver nanoparticles.
The technical scheme of the invention is as follows:
a preparation method of a molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles comprises the following steps:
(1) Under the constant temperature condition of 10-40 ℃, immersing a polished copper bar subjected to ultrasonic cleaning pretreatment into a silver trifluoroacetate aqueous solution for reaction for 2-8 min, and taking out the copper bar to obtain a silver nanoparticle layer on the surface of the copper bar;
specifically, the copper bar pretreatment method comprises the following steps: polishing a copper bar, then ultrasonically cleaning for 2-5 min by using distilled water, ethanol, acetone and tetrahydrofuran in sequence, and removing impurities and oxides on the surface for later use;
the concentration of the silver trifluoroacetate aqueous solution is 5-10 mg/mL;
(2) Sequentially adding a functional monomer, a cross-linking agent and template molecules into a reaction container, introducing inert gas to remove oxygen (6 min), soaking the copper rod attached with the silver nanoparticle layer obtained in the step (1) with an initiator, immediately placing the copper rod into the reaction container for sealing, carrying out polymerization reaction for 0.5-1 h at 70-85 ℃ under the protection of the inert gas, then removing the template molecules through elution, and drying to obtain the molecularly imprinted polymer coating;
the functional monomer is methyl methacrylate;
the cross-linking agent is 1, 4-butanediol dimethacrylate;
the template molecule is enrofloxacin;
the initiator is phenyl silane;
the mass ratio of the template molecule to the functional monomer to the cross-linking agent to the initiator is 1:280 to 290:15 to 25:10 to 20, preferably 1:283:20:14.
the invention has the following advantages:
firstly, special instruments and equipment are not needed, the preparation steps are simple, and the production cost is low;
second, a molecularly imprinted polymer that specifically recognizes, adsorbs enrofloxacin from a complex matrix and can be recycled can be prepared.
Drawings
FIG. 1 is a schematic diagram of the preparation of the molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles.
Fig. 2 is a scanning electron microscope image of silver nanoparticles prepared in example 1 of the present invention.
FIG. 3 is a scanning electron microscope image of a molecularly imprinted polymer coating prepared based on silver nanoparticles and capable of specifically recognizing enrofloxacin in example 1 of the invention.
Fig. 4 is a scanning electron microscope image of silver nanoparticles prepared in example 2 of the present invention.
Fig. 5 is a scanning electron microscope image of a molecularly imprinted polymer coating prepared based on silver nanoparticles and capable of specifically recognizing enrofloxacin in example 2 of the present invention.
Fig. 6 is a scanning electron microscope image of silver nanoparticles prepared in example 3 of the present invention.
FIG. 7 is a scanning electron microscope image of a molecularly imprinted polymer coating prepared based on silver nanoparticles and capable of specifically recognizing enrofloxacin in example 3 of the invention.
Fig. 8 is a scanning electron microscope image of a cross section of silver nanoparticles prepared in example 4 of the present invention.
FIG. 9 is a scanning electron microscope image of the cross section of a molecularly imprinted polymer coating prepared based on silver nanoparticles and capable of specifically recognizing enrofloxacin in example 4 of the invention.
Fig. 10 is an EDX spectrum image of a molecularly imprinted polymer coating prepared based on silver nanoparticles for specifically recognizing enrofloxacin in example 4 of the present invention.
Fig. 11 is a comparison of raman spectrograms of the silver nanoparticle layer, the molecularly imprinted polymer MIP coating and the NIP coating prepared without adding a template molecule, which are provided in example 5 of the present invention, after respectively adsorbing enrofloxacin.
Fig. 12 is a raman spectrum of the enrofloxacin and its analog solutions adsorbed by the molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles provided in example 6 of the present invention.
Fig. 13 is a raman spectrum of enrofloxacin and similar mixed solutions adsorbed by the molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles provided in example 7 of the present invention.
Detailed Description
Objects, advantages and implementation details of the present invention are further explained and illustrated by the following specific examples, which are intended to provide a better understanding of the technical content described by the public, and the specific substances and amounts thereof recited in the examples as well as other detailed conditions should not be construed to limit the present invention. Numerous other modifications and embodiments can be devised by those skilled in the art in light of this disclosure and will fall within the scope of the appended claims.
Product testing and characterization methods: and (4) characterizing by using a scanning electron microscope, an energy dispersive X ray and a surface enhanced Raman spectrum to obtain an SEM picture, an EDX electron energy spectrum and an SERS spectrum.
Example 1:
cutting a 5cm copper bar (diameter is 1 mm), polishing the copper bar with 600-mesh abrasive paper smoothly, sequentially carrying out ultrasonic cleaning on distilled water, ethanol, acetone and tetrahydrofuran for 5min to remove impurities and oxides on the surface, preparing 2.0mL silver trifluoroacetate aqueous solution with the concentration of 5mg/mL, adding the silver trifluoroacetate aqueous solution into a 5mL centrifugal tube, placing the centrifugal tube on a digital display constant temperature heating plate with the constant temperature of 10 ℃, heating the copper bar for 15min to the constant temperature, immersing the copper bar into the silver trifluoroacetate aqueous solution for reaction for 2min, taking out the copper bar, respectively washing off the residual silver trifluoroacetate solution on the surface with distilled water and ethanol, observing that a silver gray attachment layer exists on the surface of the copper bar, stopping the reaction, obtaining a silver nanoparticle film on the surface of the copper bar, wherein the average particle size of the silver nanoparticles obtained under the condition is 15.64nm. Adding MMA monomer 1.5mL into 5mL reaction tube, sequentially adding 1, 4-butanediol dimethacrylate crosslinking agent 100 μ L and enrofloxacin 5.0mg, ultrasonic treating for 1min to dissolve, and introducing high purity nitrogen (N) 2 ) And (4) deoxidizing for 6min. Will be adhered with silver filmSoaking a layer of phenyl silane on the copper rod, immediately placing the copper rod into a reaction tube for sealing, carrying out polymerization reaction at a constant temperature of 75 ℃, stopping the polymerization reaction after 1h, and taking out the copper rod with the MIP film. And (3) putting the dried MIP membrane into a 5mL centrifuge tube, adding 10% acetic acid methanol solution as an elution solvent, putting the centrifuge tube into a digital display circumferential oscillation table concentrator (300 r/min) for elution for 3h, and replacing the elution solvent every 20min in the elution process. And after the elution is finished and the natural airing is carried out, the molecularly imprinted polymer is obtained.
Example 2:
cutting a 5cm copper bar (diameter is 1 mm), polishing the copper bar smoothly by using 600-mesh abrasive paper, sequentially carrying out ultrasonic cleaning on distilled water, ethanol, acetone and tetrahydrofuran for 5min to remove impurities and oxides on the surface, preparing 2.0mL silver trifluoroacetate aqueous solution with the concentration of 10mg/mL, adding the silver trifluoroacetate aqueous solution into a 5mL centrifuge tube, placing the centrifuge tube on a digital display constant temperature heating plate with the constant temperature of 20 ℃, soaking the copper bar into the silver trifluoroacetate aqueous solution after heating to the constant temperature for reaction for 3min, taking out the copper bar, washing off residual silver trifluoroacetate solution on the surface by using distilled water and ethanol respectively, stopping the reaction, observing that a layer of silver black attachment exists on the surface of the copper bar, obtaining a layer of silver nanoparticle film on the surface of the copper bar, wherein the average particle size of silver nanoparticles obtained under the condition is 78.80nm. Adding MMA monomer 1.5mL into 5mL reaction tube, sequentially adding 1, 4-butanediol dimethacrylate crosslinking agent 100 μ L and enrofloxacin 5.0mg, ultrasonic treating for 1min to dissolve, and introducing high purity nitrogen (N) 2 ) And (5) deoxidizing for 6min. And soaking a layer of phenyl silane on the copper rod attached with the silver film, immediately placing the copper rod into a reaction tube for sealing, carrying out polymerization reaction at a constant temperature of 75 ℃, stopping the polymerization reaction after 1h, and taking out the copper rod with the MIP film. And (3) putting the dried MIP membrane into a 5mL centrifuge tube, adding 10% acetic acid methanol solution as an elution solvent, putting the centrifuge tube into a digital display circumferential oscillation table concentrator (300 r/min) for elution for 3h, and replacing the elution solvent every 20min in the elution process. And after the elution is finished and the natural airing is carried out, obtaining the molecularly imprinted polymer.
Example 3:
cutting 5cm copper bar (diameter 1 mm), polishing with 600 mesh sand paper, sequentially ultrasonic cleaning with distilled water, ethanol, acetone, and tetrahydrofuran for 5min, removingRemoving impurities and oxides on the surface, preparing 2.0mL of silver trifluoroacetate aqueous solution with the concentration of 10mg/mL, adding the aqueous solution into a 5mL centrifugal tube, placing the centrifugal tube on a digital display constant-temperature heating plate with the constant temperature of 20 ℃, immersing a copper rod into the silver trifluoroacetate aqueous solution after heating to the constant temperature for reaction for 4min, taking out the silver trifluoroacetate aqueous solution, washing away the residual silver trifluoroacetate solution on the surface by using distilled water and ethanol respectively, stopping the reaction, observing that a layer of silver black attachment exists on the surface of the copper rod, and obtaining a layer of silver nanoparticle film on the surface of the copper rod, wherein the average particle size of silver nanoparticles obtained under the condition is 80.46nm. Adding MMA monomer 1.5mL into 5mL reaction tube, sequentially adding 1, 4-butanediol dimethacrylate crosslinking agent 100 μ L and enrofloxacin 5.0mg, ultrasonic treating for 1min to dissolve, and introducing high purity nitrogen (N) 2 ) And (4) deoxidizing for 6min. And soaking a layer of phenyl silane on the copper bar with the silver film, immediately putting the copper bar into a reaction tube for sealing, carrying out polymerization reaction at a constant temperature of 75 ℃, stopping the polymerization reaction after 1h, and taking out the copper bar with the MIP film. And (3) putting the dried MIP membrane into a 5mL centrifuge tube, adding a 10% acetic acid methanol solution as an elution solvent, putting the centrifuge tube into a digital display circumferential oscillation table concentrator (300 r/min) for elution for 3 hours, and replacing the elution solvent once every 20min in the elution process. And after the elution is finished and the natural airing is carried out, the molecularly imprinted polymer is obtained.
Example 4:
cutting a 5cm copper bar (diameter is 1 mm), polishing the copper bar with 600-mesh abrasive paper smoothly, sequentially carrying out ultrasonic cleaning on distilled water, ethanol, acetone and tetrahydrofuran for 5min to remove impurities and oxides on the surface, preparing 2.0mL silver trifluoroacetate aqueous solution with the concentration of 10mg/mL, adding the silver trifluoroacetate aqueous solution into a 5mL centrifugal tube, placing the centrifugal tube on a digital display constant temperature heating plate with the constant temperature of 30 ℃, soaking the copper bar into the silver trifluoroacetate aqueous solution after heating to the constant temperature for reaction for 4min, taking out the copper bar, respectively washing off residual silver trifluoroacetate solution on the surface with distilled water and ethanol, stopping the reaction, observing that a layer of black silver attachment exists on the surface of the copper bar, and obtaining a layer of silver nanoparticle film on the surface of the copper bar, wherein the average particle size of the silver nanoparticles obtained under the condition is 83.76nm. Adding 1.5mL MMA monomer into 5mL reaction tube, sequentially adding 100 μ L1, 4-butanediol dimethacrylate crosslinker and 5.0mg enrofloxacin, and subjecting to ultrasonic treatment for 1minIt was sufficiently dissolved, and then high-purity nitrogen gas (N) was introduced into the tube 2 ) And (4) deoxidizing for 6min. And soaking a layer of phenyl silane on the copper rod attached with the silver film, immediately placing the copper rod into a reaction tube for sealing, carrying out polymerization reaction at a constant temperature of 75 ℃, stopping the polymerization reaction after 1h, and taking out the copper rod with the MIP film. And (3) putting the dried MIP membrane into a 5mL centrifuge tube, adding 10% acetic acid methanol solution as an elution solvent, putting the centrifuge tube into a digital display circumferential oscillation table concentrator (300 r/min) for elution for 3h, and replacing the elution solvent every 20min in the elution process. And after the elution is finished and the natural airing is carried out, obtaining the molecularly imprinted polymer.
Example 5:
three 5cm copper rods (diameter of 1 mm) are cut out and polished smoothly by 600-mesh abrasive paper, ultrasonic cleaning is sequentially carried out on distilled water, ethanol, acetone and tetrahydrofuran for 5min to remove impurities and oxides on the surface, 2.0mL silver trifluoroacetate aqueous solution with concentration of 10mg/mL is prepared and added into a 5mL centrifugal tube, the centrifugal tube is placed on a digital display constant temperature heating plate with constant temperature of 30 ℃, the copper rods are immersed into the silver trifluoroacetate aqueous solution after being heated to the constant temperature for reaction for 4min and then taken out, distilled water and ethanol are respectively used for washing out residual silver trifluoroacetate solution on the surface, the reaction is stopped, and a layer of silver nanoparticle film is obtained on the surface of the copper rods.
Taking a copper rod with a silver nanoparticle layer plated on the surface to synthesize a MIP (molecular imprinting polymer) with template molecules, sequentially adding 1mL of methyl methacrylate monomer, 100 mu L of 1, 4-butanediol dimethacrylate cross-linking agent and 0.5mg of enrofloxacin template molecules into a centrifuge tube, introducing inert gas to remove oxygen for 6min, putting the copper rod with the silver nanoparticle layer into the centrifuge tube with a phenylsilane initiator for 20s, immediately putting the silver nanoparticle layer surface soaked with a layer of initiator into a reaction tube for sealing, carrying out polymerization reaction for 1h at 75 ℃, then eluting the template molecules for 120min by 10% acetic acid methanol solution, and drying to obtain the MIP with template molecules.
Taking another copper rod with a silver nanoparticle layer plated on the surface to synthesize an NIP film without template molecules, sequentially adding 1mL of methyl methacrylate monomer and 100 mu L of 1, 4-butanediol dimethacrylate cross-linking agent into a centrifugal tube, adding no enrofloxacin template molecules, introducing inert gas to remove oxygen for 6min, putting the copper rod attached with the silver nanoparticle layer into the centrifugal tube with a phenylsilane initiator for 20s, immediately putting the silver nanoparticle layer surface into a reaction tube after being soaked with a layer of initiator, sealing, carrying out polymerization reaction at 75 ℃ for 1h, and drying to obtain the NIP molecularly imprinted polymer without template molecules.
Respectively placing a copper rod with a first surface plated with a silver nanoparticle layer, a second MIP (MIP) membrane with template molecules and an NIP (NIP) membrane without template molecules in 2mL enrofloxacin solution with the concentration of 1mg/mL for soaking for 10min, taking out, washing off enrofloxacin on the surface by using 10% acetic acid methanol solution, naturally airing, selecting 10 different positions of a polymer, and detecting by using a Raman analyzer for 1629cm -1 The peak intensity is set to be High, the integration time is set to be 20 s/time, and the average value is obtained by repeating the steps for three times. Comparing spectrograms of respectively adsorbing enrofloxacin by using the MIP film and the NIP film, and observing an obvious enrofloxacin characteristic peak on the spectrogram for detecting enrofloxacin by using the MIP film as an SERS substrate; in contrast, the spectrum of the NIP film combined SERS detection enrofloxacin has no characteristic peak of enrofloxacin. Therefore, the prepared MIP membrane contains imprinting holes matched with the enrofloxacin molecular structure, enrofloxacin molecules can be selectively adsorbed, and the combination of the NIP membrane and the enrofloxacin molecules mainly passes through the physical adsorption effect and cannot selectively adsorb the enrofloxacin molecules.
Example 6:
soaking four molecularly imprinted polymers prepared in example 4 in 2mL of solutions of enrofloxacin, ciprofloxacin, moxifloxacin and norfloxacin with the concentration of 1mg/mL for 10min respectively to enable the MIP membrane to adsorb the enrofloxacin, ciprofloxacin, moxifloxacin and norfloxacin, washing off compounds on the surface by using 10% acetic acid methanol solution, selecting 10 different positions of the polymers after natural airing, and detecting 1629cm by using a Raman instrument -1 The peak intensity is set to be High, the integration time is set to be 20 s/time, the average value is obtained by repeating the three times, the obtained Raman peak shape is compared with the peak shape of the enrofloxacin solution adsorbed by the MIP film, the MIP film is detected by SERS after being adsorbed in the enrofloxacin solution for a period of time, and the spectrum shows brightObvious enrofloxacin characteristic peak signals; and the SERS spectrogram of the MIP film adsorbing the ciprofloxacin, moxifloxacin and norfloxacin solution does not have characteristic peak signals of corresponding substances, so that the specific adsorption of the molecularly imprinted polymer on the enrofloxacin is judged.
Example 7:
two of the molecularly imprinted polymers prepared in example 4 were placed in 2mL of a mixed solution of enrofloxacin, ciprofloxacin, moxifloxacin and norfloxacin (volume ratio 1 -1 The peak intensity is set to be High, the integration time is 20 s/time, the average value is obtained by repeating the three times, the obtained Raman peak shape is compared with a spectrogram for adsorbing the enrofloxacin solution by using the MIP membrane, after the MIP membrane adsorbs the mixed solution of the four substances, an obvious enrofloxacin characteristic peak signal appears in the SERS spectrogram, and therefore the MIP membrane is judged to have the capability of specifically identifying and adsorbing enrofloxacin molecules in a complex environment.
Claims (5)
1. A preparation method of a molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles is characterized by comprising the following steps:
(1) Under the constant temperature condition of 10-40 ℃, immersing a polished copper bar subjected to ultrasonic cleaning pretreatment into a silver trifluoroacetate aqueous solution for reaction for 2-8 min, and taking out the copper bar to obtain a silver nanoparticle layer on the surface of the copper bar;
(2) Sequentially adding a functional monomer, a cross-linking agent and template molecules into a reaction container, introducing inert gas to remove oxygen, soaking the copper rod attached with the silver nanoparticle layer obtained in the step (1) with an initiator, immediately placing the copper rod into the reaction container for sealing, carrying out polymerization reaction for 0.5-1 h at 70-85 ℃ under the protection of the inert gas, then removing the template molecules through elution, and drying to obtain the molecularly imprinted polymer coating;
the functional monomer is methyl methacrylate;
the cross-linking agent is 1, 4-butanediol dimethacrylate;
the template molecule is enrofloxacin;
the initiator is phenyl silane.
2. The method for preparing the molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles according to claim 1, wherein in the step (1), the copper rod is pretreated by the following steps: polishing the copper bar, then ultrasonically cleaning for 2-5 min by using distilled water, ethanol, acetone and tetrahydrofuran in sequence, and removing impurities and oxides on the surface for later use.
3. The method for preparing the molecularly imprinted polymer coating layer capable of specifically recognizing enrofloxacin based on silver nanoparticles as claimed in claim 1, wherein in the step (1), the concentration of the silver trifluoroacetate aqueous solution is 5-10 mg/mL.
4. The method for preparing the molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles as claimed in claim 1, wherein in the step (2), the mass ratio of the template molecule, the functional monomer, the cross-linking agent and the initiator is 1: 280-290: 15 to 25:10 to 20.
5. The preparation method of the molecularly imprinted polymer coating capable of specifically recognizing enrofloxacin based on silver nanoparticles as claimed in claim 4, wherein in the step (2), the mass ratio of the template molecule, the functional monomer, the cross-linking agent and the initiator is 1:283:20:14.
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| CN112540069A (en) * | 2019-09-20 | 2021-03-23 | 吉林师范大学 | SERS (surface enhanced Raman Scattering) imprinted sensor based on cuprous oxide-silver and used for selectively detecting 2, 6-dichlorophenol |
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| US20150299366A1 (en) * | 2012-11-20 | 2015-10-22 | Nankai University | Molecularly imprinted polymer nanoparticles compatible with biological samples and preparation method thereof |
| CN103063649A (en) * | 2013-01-16 | 2013-04-24 | 哈尔滨工业大学 | Method for surface-enhanced Raman scattering spectrum detection by using silver-surface molecularly imprinted polymer |
| CN108409894A (en) * | 2017-02-09 | 2018-08-17 | 浙江工业大学 | The method that transition metal nanoparticles are catalyzed polymerization of vinyl monomer reaction |
| CN107860759A (en) * | 2017-10-31 | 2018-03-30 | 江苏大学 | A kind of preparation method of molecular engram sensor with SERS activity and application |
| CN108579696A (en) * | 2018-03-12 | 2018-09-28 | 中国人民解放军第二军医大学 | A kind of theophylline molecular engram material and its preparation method and application of silver nano-grain doping |
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