CN113030025A - Preparation method and application of molecularly imprinted photonic crystal for detecting sulphaguanidine - Google Patents

Preparation method and application of molecularly imprinted photonic crystal for detecting sulphaguanidine Download PDF

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CN113030025A
CN113030025A CN202110288851.0A CN202110288851A CN113030025A CN 113030025 A CN113030025 A CN 113030025A CN 202110288851 A CN202110288851 A CN 202110288851A CN 113030025 A CN113030025 A CN 113030025A
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photonic crystal
molecularly imprinted
sulfaguanidine
eluent
detecting
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余莉萍
南境
王滨
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Tianjin University
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/47Scattering, i.e. diffuse reflection
    • G01N21/4788Diffraction
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour

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Abstract

The invention discloses a preparation method and application of a molecular imprinting photonic crystal for detecting sulphaguanidine, wherein a vertical deposition method is firstly utilized to uniformly deposit polystyrene microspheres with a certain size on the surface of a glass slide to form a photonic crystal template, then a capillary force action is utilized to fill a precursor solution containing imprinting molecules, a functional monomer, a cross-linking agent and an initiator into gaps of the polystyrene microspheres of the photonic crystal template, and after thermal initiation polymerization reaction, the polystyrene microspheres and the imprinting molecules are removed by utilizing an eluent in sequence to obtain the molecular imprinting photonic crystal with an inverse opal structure. The molecularly imprinted photonic crystal obtained by the invention is placed in sulfaguanidine solutions with different concentrations to present different structural colors, the concentration range of the sulfaguanidine solution can be judged by visual observation, and the Bragg diffraction peak displacement of the molecularly imprinted photonic crystal is further measured by using a fiber optic spectrometer, so that the quantitative measurement of trace sulfaguanidine can be realized.

Description

Preparation method and application of molecularly imprinted photonic crystal for detecting sulphaguanidine
Technical Field
The invention relates to the technical field of antibiotic detection, in particular to a preparation method and application of a molecularly imprinted photonic crystal for detecting sulphaguanidine.
Background
Sulfanilamide antibiotics are artificially synthesized antibacterial drugs taking sulfanilamide as a structural main body, have high stability, broad-spectrum antibacterial property and lower price, and are widely applied to modern agriculture. However, a large amount of antibiotics enter natural water along with agricultural wastewater, so that the evolution and the propagation of drug-resistant bacteria are accelerated, the ecological balance is destroyed, and the serious threat to the human health is caused. The sulfaguanidine is one of sulfonamide antibiotics with larger dosage, is not easy to degrade, and has the problem of sulfaguanidine pollution in various natural water bodies at present. Therefore, the establishment of an analysis and detection method for sulfaguanidine in the water body has important significance for controlling antibiotic pollution. The molecularly imprinted photonic crystal is a novel chemical sensor, has a three-dimensional ordered structure of the photonic crystal, can respond to external stimulation, is displayed through the change of color and Bragg diffraction peak, has specific identification capability aiming at specific target molecules due to the introduction of a molecularly imprinted technology, and improves the detection selectivity. Therefore, the method has a wide development prospect in constructing a visual and specific detection system for the sulfaguanidine in the water body by utilizing the molecular imprinting photonic crystal technology.
Disclosure of Invention
The invention aims to provide a preparation method and application of a molecularly imprinted photonic crystal for detecting sulfaguanidine.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a molecularly imprinted photonic crystal for detecting sulphaguanidine comprises the following steps:
s1: dissolving the imprinted molecules, the functional monomers, the cross-linking agent and the initiator in water to prepare a precursor solution with a certain concentration, and introducing nitrogen to remove dissolved oxygen;
s2: uniformly depositing polystyrene microspheres with a certain size on the surface of a glass slide by using a vertical deposition method, fully drying, covering and fixing another glass slide on the surface of the glass slide to obtain a photonic crystal template;
s3: dripping the precursor liquid on the upper edge of a photonic crystal film carrier glass slide, filling the precursor liquid in the microsphere gap on the template by utilizing the capillary action, carrying out constant-temperature polymerization reaction for a period of time, and stripping the glass slide to obtain the molecularly imprinted photonic crystal film;
s4: and soaking the molecularly imprinted photonic crystal film with a first eluent and a second eluent in sequence, and airing to obtain the molecularly imprinted photonic crystal.
In the step S1, the imprinted molecule in the precursor solution is sulfaguanidine, and the addition amount of the sulfaguanidine accounts for 0.15-0.30% of the mass of the precursor solution.
In the step S1, the addition amount of the functional monomer accounts for 30-45% of the mass of the precursor solution, the functional monomer is a combination of three substances of acrylamide, methacrylic acid and 4-vinylpyridine, and the mass percentages of the functional monomer are (25-35)%, and (35-45)%, preferably 30%, 28%, and 42%.
In the step S1, the cross-linking agent is N, N' -methylene bisacrylamide, and the addition amount of the cross-linking agent accounts for 0.05-0.15% of the mass of the precursor liquid.
In the step S1, the initiator is 2, 2' -azabicyclo (2-imidazoline) dihydrochloride, and the addition amount thereof accounts for 0.10-0.25% of the mass of the precursor solution.
In the step S2, the polystyrene microsphere has a solid content of 1.0-2.5% and a particle size of 500-650 nm, preferably 625 nm.
In the step S3, the reaction time is 5-10 hours at constant temperature, the reaction temperature is 40-55 ℃, and the preferred temperature is 45 ℃.
In step S4, the first eluent is a mixed solvent of dichloromethane and tetrahydrofuran, and the volume ratio of the two solvents is (5: 5) - (8: 2), preferably 7: 3.
in the step S4, the second eluent is a mixed solution of methanol, acetic acid and sodium dodecyl sulfate, and the mass percentage of methanol, acetic acid and sodium dodecyl sulfate is (5-15)%: (83-93)%: (1-2)%, preferably 10%: 89%: 1 percent.
The molecularly imprinted photonic crystal for detecting sulfaguanidine, prepared by the preparation method, is applied to water body detection.
The invention has the beneficial effects that:
the prepared molecularly imprinted gel photonic crystal has an inverse opal structure, is large in specific surface area, has many acting sites with sulphaguanidine, is strong in specific recognition effect, can show obvious color change after acting, can be used for primarily judging the sulphaguanidine concentration range through naked eye observation, and can realize quantitative determination of sulphaguanidine by utilizing an optical fiber spectrometer to determine the Bragg diffraction peak change of the molecularly imprinted gel photonic crystal.
Drawings
FIG. 1 is a diagram showing the Bragg diffraction peak change of the molecularly imprinted photonic crystal prepared by the method after swelling in sulfadiazine aqueous solutions with different concentrations.
FIG. 2 is an optical photograph of the molecularly imprinted photonic crystal prepared by the method in sulfaguanidine aqueous solutions with different concentrations.
Detailed description of the invention
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the embodiment of the invention, the preparation method of the molecularly imprinted photonic crystal for detecting sulfaguanidine comprises the following steps:
step S1: and (3) dissolving the imprinted molecules, the functional monomer, the cross-linking agent and the initiator in water, introducing nitrogen and maintaining for 10 minutes to obtain the precursor solution.
In the embodiment of the invention, the mass percentages of the imprinted molecules, the functional monomers, the cross-linking agent and the initiator in the precursor solution are (0.15-0.30)%: (30.00-45.00)%: (0.05-0.15)%: (0.10-0.25)%, and the balance of water.
In an embodiment of the invention, the imprinted molecule is sulfadiazine.
In the embodiment of the invention, the functional monomer is a combination of acrylamide, methacrylic acid and 4-vinylpyridine, and the mass percentage of the functional monomer is (25-35)%: (25-35)%: (35-45)%.
In an embodiment of the invention, the cross-linking agent is N, N' -methylenebisacrylamide.
In the present examples, the initiator is 2, 2' -azabicyclo (2-imidazoline) dihydrochloride.
Step S2: and uniformly depositing the polystyrene microspheres on the surface of the glass slide by using a vertical deposition method, fully drying, and covering the surface of the glass slide with another glass slide to obtain the photonic crystal template.
In the embodiment of the invention, the solid content of the polystyrene microsphere is 1.0-2.5%, and the particle size is 500-650 nm.
In the embodiment of the invention, the temperature in the drying temperature process is 70-85 ℃.
Step S3: and (3) dripping the precursor liquid on the upper edge of a glass slide of the photonic crystal film, horizontally placing the photonic crystal film in a thermostat for polymerization reaction for a period of time after the template gap is filled with the precursor liquid, and stripping the molecularly imprinted photonic crystal film from the glass slide.
It should be noted that, during the process of filling the photonic crystal template with the precursor liquid, the photonic crystal template needs to be kept inclined at a certain angle, and the whole device is kept in a static state.
In the embodiment of the invention, the polymerization reaction temperature is 40-55 ℃, and the reaction time is 5-10 hours.
Step S4: and soaking the molecularly imprinted photonic crystal film with a first eluent and a second eluent in sequence, and airing to obtain the molecularly imprinted photonic crystal.
In the embodiment of the invention, the first eluent is a mixed solvent of dichloromethane and tetrahydrofuran, the volume ratio of the dichloromethane to the tetrahydrofuran is (5: 5) - (8: 2), and the soaking time is 12-24 hours.
In the embodiment of the present invention, the second eluent is a mixed solution of methanol, acetic acid and sodium dodecyl sulfate, and the mass percentages of the three solutions are (5-15)%: (83-93)%: (1-2)%.
The step of treating the molecularly imprinted photonic crystal film with the second eluent needs to be repeated for multiple times, and the eluent is detected by using an ultraviolet-visible spectrometer until the characteristic absorption peak of the sulfaguanidine cannot be detected in the spectrum.
The molecularly imprinted photonic crystal for detecting sulfaguanidine, prepared by the preparation method, is applied to water body detection.
Examples of certain embodiments of the invention are given below, which are not intended to limit the scope of the invention.
Example 1
0.02g of sulfaguanidine, 1.20g of acrylamide, 1.2g of methacrylic acid, 1.60g of 4-vinylpyridine, 0.01g of N, N '-methylenebisacrylamide, 0.015g of 2, 2' -azabicyclo (2-imidazoline) dihydrochloride and 6g of water are respectively added into a 50mL centrifuge tube, and after uniform stirring and dissolution, nitrogen is introduced for 20 minutes to prepare a precursor solution.
Vertically fixing a clean glass slide in a 150mL beaker, slowly pouring 50mL of polystyrene microspheres with solid content of 1.5% and particle size of 625nm into the beaker, transferring the beaker to a 45 ℃ constant-temperature water bath, preserving heat for 48 hours, transferring the beaker to a 75 ℃ oven, baking for 1 hour, covering the other glass slide on the surface of the photonic crystal, and fixing the two glass slides by using an adhesive tape to obtain the photonic crystal template.
Dropping 2.0mL of precursor liquid on the upper edge of a photonic crystal template glass slide, slightly inclining the glass slide, standing to enable the precursor liquid to fill the gap of the photonic crystal template, transferring the photonic crystal template into a 45 ℃ oven, carrying out constant-temperature polymerization reaction for 5 hours, cooling to room temperature, and stripping the polymer from the glass slide to obtain the molecularly imprinted photonic crystal film.
Putting the molecularly imprinted photonic crystal film in a first eluent, wherein the first eluent is a mixed solvent of dichloromethane and tetrahydrofuran, and the volume ratio of the two is 6: 4, soaking for 12 hours, taking out, washing for 3 times by using methanol, then placing the film in a second eluent, and placing the film in a constant temperature shaking table at 25 ℃, wherein the second eluent is a mixed solvent of methanol, acetic acid and sodium dodecyl sulfate, and the mass ratio of the three is 10: 89: and 1, replacing the second eluent every 2 hours, monitoring the concentration of the sulfaguanidine in the eluent by using an ultraviolet-visible spectrometer until the characteristic absorption peak of the sulfaguanidine cannot be monitored, taking out the film, washing the film for 3 times by using methanol, and airing to obtain the molecularly imprinted photonic crystal.
Example 2
0.017g of sulfaguanidine, 1.05g of acrylamide, 1.15g of methacrylic acid, 1.50g of 4-vinylpyridine, 0.015g of N, N '-methylenebisacrylamide, 0.015g of 2, 2' -azabicyclo (2-imidazoline) dihydrochloride and 6.3g of water are respectively added into a 50mL centrifuge tube, and after uniform stirring and dissolution, nitrogen is introduced for 20 minutes to prepare a precursor solution.
Vertically fixing a clean glass slide in a 150mL beaker, slowly pouring 50mL of polystyrene microspheres with the solid content of 2.0% and the particle size of 525nm into the flask, transferring the beaker to a 45 ℃ constant-temperature water bath, preserving heat for 48 hours, transferring the beaker to a 75 ℃ oven, drying for 1 hour, finally covering the other glass slide on the surface of the photonic crystal, and fixing the two glass slides by using an adhesive tape to obtain the photonic crystal template.
Dropping 2.0mL of precursor liquid on the upper edge of a photonic crystal template glass slide, slightly inclining the glass slide, standing to enable the precursor liquid to fill the gap of the photonic crystal template, transferring the photonic crystal template into a 45 ℃ oven, carrying out constant-temperature polymerization reaction for 10 hours, cooling to room temperature, and stripping the polymer from the glass slide to obtain the molecularly imprinted photonic crystal film.
Putting the molecularly imprinted photonic crystal film in a first eluent, wherein the first eluent is a mixed solvent of dichloromethane and tetrahydrofuran, and the volume ratio of the two is 8: 2, soaking for 16 hours, taking out and repeatedly washing with methanol; and then placing the film in a second eluent, and placing the film in a constant temperature shaking table at 25 ℃, wherein the second eluent is a mixed solvent of methanol, acetic acid and sodium dodecyl sulfate, and the mass ratio of the methanol to the acetic acid to the sodium dodecyl sulfate is 9: 90: and 1, replacing the second eluent every 2 hours, monitoring the concentration of the sulfaguanidine in the eluent by using an ultraviolet-visible spectrometer until the characteristic absorption peak of the sulfaguanidine cannot be monitored, taking out the film, washing the film by using methanol, and airing to obtain the molecularly imprinted photonic crystal.
Example 3
0.025g of sulphaguanidine, 1.35g of acrylamide, 1.15g of methacrylic acid, 1.80g of 4-vinylpyridine, 0.01g of N, N '-methylenebisacrylamide, 0.015g of 2, 2' -azabicyclo (2-imidazoline) dihydrochloride and 5.7g of water are respectively added into a 50mL centrifuge tube, and after uniform stirring and dissolution, nitrogen is introduced for 20 minutes to prepare a precursor solution.
Vertically fixing a clean glass slide in a 150mL beaker, slowly pouring 50mL of polystyrene microspheres with the solid content of 2.5% and the particle size of 575nm into the flask, transferring the beaker to a 45 ℃ constant-temperature water bath, preserving heat for 48 hours, transferring the beaker to a 75 ℃ oven, drying for 1 hour, finally covering the other glass slide on the surface of the photonic crystal, and fixing the two glass slides by using an adhesive tape to obtain the photonic crystal template.
Dropping 2.0mL of precursor liquid on the upper edge of a photonic crystal template glass slide, slightly inclining the glass slide, standing to enable the precursor liquid to fill the gap of the photonic crystal template, transferring the photonic crystal template into a 45 ℃ oven, carrying out constant-temperature polymerization reaction for 7 hours, cooling to room temperature, and stripping the polymer from the glass slide to obtain the molecularly imprinted photonic crystal film.
Putting the molecularly imprinted photonic crystal film in a first eluent, wherein the first eluent is a mixed solvent of dichloromethane and tetrahydrofuran, and the volume ratio of the two is 7: 3, soaking for 24 hours, taking out, repeatedly washing with methanol, then placing the film in a second eluent, and placing the film in a constant temperature shaking table at 25 ℃, wherein the second eluent is a mixed solvent of methanol, acetic acid and sodium dodecyl sulfate, and the mass ratio of the three is 5: 44: and 1, replacing the second eluent every 2 hours, monitoring the concentration of the sulfaguanidine in the eluent by using an ultraviolet-visible spectrometer until the characteristic absorption peak of the sulfaguanidine cannot be monitored, taking out the film, washing the film by using methanol, and airing to obtain the molecularly imprinted photonic crystal.
Application example 1
In the application example, acetic acid-sodium acetate buffer solutions with pH value of 5.0 are prepared respectively, and then sulfaguanidine with different amounts is added into the buffer solutions to prepare sulfaguanidine standard solutions with concentration of 0.0 μ M, 2.0 μ M, 4.0 μ M, 6.0 μ M, 8.0 μ M, 10.0 μ M, 12.0 μ M, 14.0 μ M, 16.0 μ M, 18.0 μ M and 20.0 μ M respectively.
The molecularly imprinted photonic crystal in example 1 was immersed in sulfadiazine solutions of different concentrations 10After the minute, the Bragg diffraction peak spectrum of the molecular imprinted photonic crystal is measured by a fiber optic spectrometer, as shown in figure 1, and then a camera is used for taking an optical photo of the molecular imprinted photonic crystal, as shown in figure 2. As can be seen from FIG. 1, as the concentration of sulfaguanidine increases, the Bragg diffraction peak of the molecularly imprinted photonic crystal is red-shifted from 578nm to 645nm, sulfaguanidine has a good linear relation with the red-shifted wavelength Delta lambda of the Bragg diffraction peak in the concentration range of 3-14 mu M, the linear fitting equation is that Delta lambda is 5.26c +1.27, and the correlation coefficient R is20.998, detection limit LOD 1.55 μ M (3 σ/b, N20). As can be seen from FIG. 2, the molecularly imprinted photonic crystal gradually changes from green to red with the increase of the sulfadiazine concentration in the solution.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. A preparation method of a molecularly imprinted photonic crystal for detecting sulphaguanidine is characterized by comprising the following steps:
s1: dissolving sulfaguanidine, a functional monomer, a cross-linking agent and an initiator which are used as imprinted molecules in water to prepare a precursor solution with a certain concentration, and introducing nitrogen to remove dissolved oxygen, wherein the mass percentages of the imprinted molecules, the functional monomer, the cross-linking agent and the initiator are (0.15-0.30)%, (30.00-45.00)%, (0.05-0.15)%, (0.10-0.25)%, and the balance is water;
s2: uniformly depositing polystyrene microspheres with a certain size on the surface of a glass slide by using a vertical deposition method, fully drying, covering and fixing another glass slide on the surface of the glass slide to obtain a photonic crystal template;
s3: dripping the precursor liquid on the upper edge of a photonic crystal film carrier glass slide, filling the precursor liquid in the microsphere gap on the template by utilizing the capillary action, carrying out constant-temperature polymerization reaction for a period of time, and stripping the glass slide to obtain a molecularly imprinted photonic crystal film;
s4: and soaking the molecularly imprinted photonic crystal film by using the first eluent and the second eluent in sequence, and airing to obtain the molecularly imprinted photonic crystal.
2. The preparation method of the molecularly imprinted photonic crystal for detecting sulfaguanidine according to claim 1, wherein the functional monomer is a combination of three substances of (25-35)% of acrylamide, (25-35)% of methacrylic acid and (35-45)% of 4-vinylpyridine, and the percentages are mass percent.
3. The preparation method of the molecularly imprinted photonic crystal for detecting sulfaguanidine according to claim 1, characterized in that the cross-linking agent is N, N' -methylenebisacrylamide.
4. The preparation method of the molecularly imprinted photonic crystal for detecting sulfaguanidine according to claim 1, wherein the initiator is 2, 2' -azabicyclo (2-imidazoline) dihydrochloride.
5. The method for preparing molecularly imprinted photonic crystals for detecting sulfaguanidine according to claim 1, wherein in step S2, the polystyrene microspheres have a solid content of 1.0-2.5% and a particle size of 500-650 nm.
6. The method for preparing the molecularly imprinted photonic crystal for detecting sulfaguanidine according to claim 1, wherein in step S3, the reaction time is 5-10 hours at constant temperature, and the reaction temperature is 40-55 ℃.
7. The method for preparing molecularly imprinted photonic crystal for detecting sulfaguanidine according to claim 1, wherein in step S4, the first eluent is a mixed solvent of dichloromethane and tetrahydrofuran, and the volume ratio of the dichloromethane to the tetrahydrofuran is (5: 5) - (8: 2).
8. The method for preparing a molecularly imprinted photonic crystal for detecting sulfaguanidine according to claim 1, wherein in step S4, the second eluent is a mixed solution of methanol, acetic acid and sodium dodecyl sulfate, and the mass percentages of methanol, acetic acid and sodium dodecyl sulfate are (5-15)%, (83-93)%, and (1-2)%.
9. The method for preparing a molecularly imprinted photonic crystal for detecting sulfaguanidine according to claim 1, wherein in step S4, the molecularly imprinted photonic crystal film is first soaked in the first eluent for 12-24 hours and then soaked in the second eluent, the content of imprinted molecules in the eluent is detected by ultraviolet spectrum, and the second eluent is replaced every 2 hours until no imprinted molecules are detected in the eluent.
10. The application of the molecularly imprinted photonic crystal for detecting sulfadiazine prepared by the preparation method of claim 1 in water body detection.
CN202110288851.0A 2021-03-18 2021-03-18 Preparation method and application of molecularly imprinted photonic crystal for detecting sulphaguanidine Pending CN113030025A (en)

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