CN114527153A - Surface molecularly imprinted gel photonic crystal sensor and preparation method and application thereof - Google Patents
Surface molecularly imprinted gel photonic crystal sensor and preparation method and application thereof Download PDFInfo
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- CN114527153A CN114527153A CN202210141586.8A CN202210141586A CN114527153A CN 114527153 A CN114527153 A CN 114527153A CN 202210141586 A CN202210141586 A CN 202210141586A CN 114527153 A CN114527153 A CN 114527153A
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- 239000004038 photonic crystal Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 47
- 239000004098 Tetracycline Substances 0.000 claims abstract description 37
- 229960002180 tetracycline Drugs 0.000 claims abstract description 37
- 229930101283 tetracycline Natural products 0.000 claims abstract description 37
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 37
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 24
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 15
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 15
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004005 microsphere Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000010556 emulsion polymerization method Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 11
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 108010031480 Artificial Receptors Proteins 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003380 quartz crystal microbalance Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
- G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
Abstract
The invention relates to a surface molecular imprinting gel photonic crystal sensor and a preparation method and application thereof. The surface molecularly imprinted gel photonic crystal sensor is prepared by polymerizing a colloidal crystal formed by simultaneously self-assembling tetracycline and polystyrene-acrylic acid (PSA) colloidal particles as a template and acrylamide and itaconic acid as bifunctional monomers in gaps of the colloidal crystal. The resulting sensor responds faster (<60 s) to the target molecule, the Bragg diffraction wavelength is red-shifted with increasing concentration of the target compound in solution, and a visible color change can be observed. The amount of bathochromic shift (Δ λ) is linear with the negative logarithm of the target molecule concentration (-logC), making the sensor useful for quantitative detection. The invention improves the sensitivity and the detection speed of the molecular imprinting gel photonic crystal sensor.
Description
Technical Field
The invention belongs to the technical field of analysis and detection, and particularly relates to a surface molecular imprinting gel photonic crystal sensor and a preparation method and application thereof.
Background
Molecularly imprinted polymers with specific molecular recognition sites have become one of the most competitive artificial receptors due to their ease of synthesis, low cost, high stability and extremely high specific binding capacity. Therefore, molecularly imprinted polymer-based sensors, such as electrochemical sensors, quartz crystal microbalance sensors and gel photonic crystal sensors, exhibit high selectivity, excellent stability and long service life. Unlike other sensors, due to the unique photonic band gap, the molecularly imprinted gel photonic crystal sensor can directly convert molecular recognition behavior into visually perceivable color changes, thereby rapidly detecting target molecules without any instrument, and thus is of great interest.
At present, the preparation of the molecular imprinting gel photonic crystal sensor is mainly realized through the processes of obtaining colloidal crystals through colloidal particle assembly, polymerizing precursor liquid in gaps of the colloidal crystals, eluting and removing colloidal particles and template molecules. However, in the obtained molecularly imprinted gel photonic crystal sensor, the specific molecule recognition sites are mostly positioned in the gel matrix, which hinders the transportation of target molecules to the recognition sites to a certain extent and limits the full utilization of the recognition sites, resulting in poor sensitivity and slow response kinetics. The molecularly imprinted polymer with recognition sites distributed on the surface can be prepared by means of a surface molecularly imprinted technology. However, the colloidal particles used in the preparation of the molecularly imprinted gel photonic crystal sensor lack functional groups, and target molecules are difficult to fix on the colloidal particles, so that the preparation of the surface molecularly imprinted gel photonic crystal sensor still has challenges.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention discloses a surface molecularly imprinted gel photonic crystal sensor and a preparation method and application thereof.
A preparation method of a surface molecularly imprinted gel photonic crystal sensor comprises the following steps:
preparing PSA colloidal crystals with tetracycline uniformly distributed on the surfaces of the polystyrene-acrylic acid PSA colloidal particles;
covering a layer of glass sheet on the surface of the PSA colloidal crystal, and fixing by using a clamp to obtain a PSA colloidal crystal template;
dripping the precursor liquid on the upper edge of the PSA colloidal crystal template until the PSA colloidal crystal template is changed from opaque to transparent;
polymerizing the transparent PSA colloidal crystal template to obtain gel;
soaking the gel in deionized water for plate removal treatment, performing post-treatment on the gel separated from the glass sheet, and removing PSA colloidal crystals in the gel;
and placing the gel after post-treatment in a sodium dodecyl sulfate/acetic acid mixed solution to prepare the surface molecularly imprinted gel photonic crystal sensor.
Further, the preparation method of the PSA colloidal crystal comprises the following steps:
preparing PSA polystyrene-acrylic acid microsphere emulsion by a soap-free emulsion polymerization method, wherein the monodispersion coefficient of the emulsion is less than 0.005;
diluting the prepared PSA microsphere emulsion to obtain emulsion A;
adding tetracycline into the emulsion A to obtain emulsion B;
and (3) vertically putting the hydrophilic glass sheet into the emulsion B, and putting the emulsion B into a constant temperature and humidity box to prepare the PSA colloidal crystal.
Furthermore, the prepared PSA microsphere emulsion has the particle size of 200 nm and the monodispersion coefficient of less than 0.005.
Further, the temperature of the constant-temperature moisture preservation box is 60 ℃, the humidity is 40%, and the heat preservation time is 24 hours.
Further, the preparation method of the precursor liquid comprises the following steps: dissolving a functional monomer, a cross-linking agent and distilled water twice, uniformly mixing, and adding an initiator to prepare a precursor solution;
the functional monomers comprise acrylamide and itaconic acid;
and/or the cross-linking agent is N, N-methylene bisacrylamide;
and/or ammonium persulfate is adopted as the initiator.
Further, the molar ratio of the acrylamide to the itaconic acid to the N, N-methylene bisacrylamide to the water to the ammonium persulfate is 1142-4000: 857-1000: 40-200: 80: 1.
further, the composition of the precursor liquid is that the molar ratio of the acrylamide, the itaconic acid, the N, N-methylene bisacrylamide, the water and the ammonium persulfate is 2000:1000:120:80: 1.
Further, the polymerization treatment comprises that the PSA colloidal crystal template in a transparent state is placed at 60 ℃ to be polymerized for 3 h;
and/or, the method of post-treatment comprises drying the gel off the glass sheet and then placing the dried gel in xylene for 48 h.
The second purpose of the invention is to provide a surface molecularly imprinted gel photonic crystal sensor, which is prepared by the method.
The third purpose of the invention is to provide an application of the surface molecularly imprinted gel photonic crystal sensor in tetracycline determination.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts polystyrene-acrylic acid (PSA) colloidal particles with carboxyl on the surface, so that tetracycline molecules can be adsorbed on the surface of the polystyrene-acrylic acid (PSA) colloidal particles through hydrogen bond action, and the tetracycline and the polystyrene-acrylic acid (PSA) colloidal particles can be simultaneously self-assembled to form colloidal crystals, and the surface molecular imprinting gel photonic crystal sensor with molecular imprinting identification sites distributed on the surface of a substrate is prepared by taking the colloidal crystals formed by simultaneously self-assembling the tetracycline and the polystyrene-acrylic acid (PSA) colloidal particles as a template through the polymerization of functional monomers;
(2) according to the invention, the gel containing PSA colloidal particles and tetracycline, which is adhered to the glass sheet, is soaked in deionized water, so that the preparation of the surface molecular imprinting gel photonic crystal sensor without depending on the glass sheet as a carrier is realized;
(3) the surface molecularly imprinted gel photonic crystal sensor prepared by the invention has a three-dimensional ordered macroporous structure, shows macroscopic color change in tetracycline solutions with different concentrations, and has different Bragg diffraction wavelengths in the tetracycline solutions with different concentrations. The red shift is generated along with the increase of the concentration of the tetracycline in the solution, and the red shift amount (delta lambda) and the negative logarithm (-logC) of the concentration of the target molecule form a linear relation, so that the sensor can be used for quantitative detection, and the rapid naked eye detection of the tetracycline is realized.
Drawings
FIG. 1 is SEM and digital photographs of colloidal crystals prepared in examples 1-6;
FIG. 2 is an SEM photograph of a surface molecularly imprinted gel photonic crystal sensor prepared in example 2;
FIG. 3 is a reflection spectrum of the surface molecularly imprinted gel photonic crystal sensor in example 7 in tetracycline solutions of different concentrations;
FIG. 4 is a line graph of the amount of red shift (Δ λ) of the reflectance spectrum of FIG. 3 versus the negative logarithm of the concentration of target molecules (-logC);
FIG. 5 shows the surface-imprinted gel photonic crystal sensors of example 7 placed at different concentrations (0 mol/L, 10)-9 mol/L，10-8 mol/L，10-7 mol/L，10-6 mol/L，10-5 mol/L，10-4mol/L) optical photograph in tetracycline solution.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
Firstly, preparing polystyrene-acrylic acid colloidal crystal (hereinafter referred to as PSA colloidal crystal)
Preparing PSA microsphere emulsion: the PSA colloidal particle emulsion is prepared by a soap-free emulsion polymerization method, the mass fraction of the PSA colloidal particle emulsion is 7.3%, the particle size is 200 nm, and the monodispersion coefficient is less than 0.005.
Preparation of PSA colloidal crystals: diluting the prepared PSA microsphere emulsion to 1% to obtain emulsion A. Dissolving 0.1 mg of tetracycline in the emulsion A to prepare emulsion B; and then vertically placing the hydrophilic glass sheet into the emulsion B, and placing the emulsion B in a constant temperature and humidity box with the temperature of 60 ℃ and the humidity of 40% for 24 hours to prepare the PSA colloidal crystals with the tetracycline uniformly distributed on the surfaces of the colloidal particles on the glass sheet.
Secondly, preparing the surface molecular imprinting gel photonic crystal sensor
Dissolving the functional monomer, the cross-linking agent and the secondary distilled water of 5 mL and mixingUniformly mixing, adding an initiator, and uniformly mixing to obtain a precursor solution, wherein the functional monomer adopts acrylamide (hereinafter abbreviated as AM) and itaconic acid (hereinafter abbreviated as IA), the cross-linking agent adopts N, N-methylene bisacrylamide (hereinafter abbreviated as BIS), the initiator adopts ammonium persulfate (hereinafter abbreviated as APS), and the molar ratio of the acrylamide to the itaconic acid to the N, N-methylene bisacrylamide to the water to the ammonium persulfate is 1142-4000: 857-1000: 40-200: 80: 1. in this example, 4 mmol of acrylamide (hereinafter abbreviated as AM) and 3 mmol of itaconic acid (hereinafter abbreviated as IA) were used as the functional monomers, 0.14 mmol of N, N-methylenebisacrylamide (hereinafter abbreviated as BIS) was used as the crosslinking agent, 0.0035 mmol of ammonium persulfate (hereinafter abbreviated as APS) was used as the initiator, and redistilled water (H) was used as the initiator2O) was added in an amount of 5 mL.
Covering a layer of glass sheet on the surface of the PSA colloidal crystal, fixing the glass sheet by a clamp, placing the glass sheet at an angle of 15 degrees with the horizontal plane, and dropwise adding the precursor liquid on the upper edge of the PSA colloidal crystal until the PSA colloidal crystal is changed from opaque to transparent.
And polymerizing the transparent PSA colloidal crystal at 60 ℃ for 3h to obtain the gel containing the PSA colloidal particles and tetracycline.
Soaking the gel in deionized water, wherein the gel can automatically fall off from the glass sheet; the exfoliated gel was dried and then placed in xylene for 48h to remove the PSA colloidal crystals.
And finally, placing the gel with the PSA colloidal crystals removed in a sodium dodecyl sulfate/acetic acid mixed solution for 3 hours, and removing tetracycline to obtain the surface molecularly imprinted gel photonic crystal sensor.
Example 2
Unlike example 1, when preparing the PSA colloidal crystals, tetracycline was added in an amount of 0.5 mg by mass; when the precursor solution is prepared, 7 mmol of acrylamide (hereinafter abbreviated as AM) and 3.5 mmol of itaconic acid (hereinafter abbreviated as IA) are adopted as the functional monomers, 0.42 mmol of N, N-methylene bisacrylamide (hereinafter abbreviated as BIS) is adopted as the crosslinking agent, and 0.0035 mmol of ammonium persulfate (hereinafter abbreviated as APS) is adopted as the initiator. Finally, the surface molecularly imprinted gel photonic crystal sensor is prepared.
Example 3
Unlike example 1, when preparing the PSA colloidal crystals, tetracycline was added in an amount of 1 mg by mass; when the precursor solution is prepared, 14 mmol of acrylamide (hereinafter abbreviated as AM) and 3.5 mmol of itaconic acid (hereinafter abbreviated as IA) are adopted as the functional monomers, 0.7 mmol of N, N-methylene bisacrylamide (hereinafter abbreviated as BIS) is adopted as the crosslinking agent, and 0.0035 mmol of ammonium persulfate (hereinafter abbreviated as APS) is adopted as the initiator. Finally, the surface molecularly imprinted gel photonic crystal sensor is prepared.
Example 4
Unlike example 1, when preparing the PSA colloidal crystals, tetracycline was added in an amount of 2.5 mg by mass; when the precursor solution is prepared, 7 mmol of acrylamide (hereinafter abbreviated as AM) and 3.5 mmol of itaconic acid (hereinafter abbreviated as IA) are adopted as the functional monomers, 0.42 mmol of N, N-methylene bisacrylamide (hereinafter abbreviated as BIS) is adopted as the crosslinking agent, and 0.0035 mmol of ammonium persulfate (hereinafter abbreviated as APS) is adopted as the initiator. Finally, the surface molecularly imprinted gel photonic crystal sensor is prepared.
Example 5
Unlike example 1, when preparing the PSA colloidal crystals, tetracycline was added in an amount of 10 mg by mass; when the precursor solution is prepared, 7 mmol of acrylamide (hereinafter abbreviated as AM) and 3.5 mmol of itaconic acid (hereinafter abbreviated as IA) are adopted as the functional monomers, 0.42 mmol of N, N-methylene bisacrylamide (hereinafter abbreviated as BIS) is adopted as the crosslinking agent, and 0.0035 mmol of ammonium persulfate (hereinafter abbreviated as APS) is adopted as the initiator. Finally, the surface molecularly imprinted gel photonic crystal sensor is prepared.
Example 6
Unlike example 1, when preparing the PSA colloidal crystals, tetracycline was added in an amount of 20 mg by mass; when the precursor solution is prepared, 7 mmol of acrylamide (hereinafter abbreviated as AM) and 3.5 mmol of itaconic acid (hereinafter abbreviated as IA) are adopted as the functional monomers, 0.42 mmol of N, N-methylene bisacrylamide (hereinafter abbreviated as BIS) is adopted as the crosslinking agent, and 0.0035 mmol of ammonium persulfate (hereinafter abbreviated as APS) is adopted as the initiator. Finally, the surface molecularly imprinted gel photonic crystal sensor is prepared.
Example 7
This example provides surface molecularly imprinted gel photonic crystal sensing prepared in example 2The method for measuring tetracycline by the instrument. The preparation concentration is 0 mol/L, 10-9 mol/L，10-8 mol/L，10-7 mol/L，10-6 mol/L，10-5 mol/L，10-4And (3) putting the obtained surface molecularly imprinted gel photonic crystal sensors into the solution in sequence by using a mol/L tetracycline aqueous solution, and taking out the sensors after the swelling reaches the balance.
When the PSA colloidal crystals are photographed and the SEM pictures and digital pictures are shown in FIG. 1, it can be seen that the order of the colloidal crystals is affected to a certain extent by the increase of the tetracycline dosage, so that the dosage of template molecules needs to be strictly controlled.
The surface molecularly imprinted gel photonic crystal sensor is photographed, the SEM picture of the surface molecularly imprinted gel photonic crystal sensor is shown in figure 2, and the surface molecularly imprinted gel photonic crystal sensor has a three-dimensional ordered macroporous structure as can be seen from the SEM picture.
For the surface molecularly imprinted gel photonic crystal sensor taken out in example 6, the reflection spectrum thereof was measured by a fiber optic spectrometer, as shown in fig. 3 and 4, and the reflection spectrum in fig. 3 is 0 mol/L and 10 mol/L from left to right according to the highest peak in sequence-9 mol/L、10-8mol/L、10-7 mol/L、10-6 mol/L、10-5mol/L and 10-4According to the reflection wavelength curve of mol/L, the reflection wavelength is red-shifted along with the increase of the concentration of the solution, and the red shift amount is 126 nm. Furthermore, it can be seen from FIG. 4 that the amount of red shift (Δ λ) is linear with the negative logarithm of the concentration of the target molecule (-logC), making the sensor useful for quantitative detection. Meanwhile, a digital camera is used for taking corresponding optical photos of the taken surface molecularly imprinted gel photonic crystal sensor, as shown in fig. 5.
The invention adopts polystyrene-acrylic acid (PSA) colloidal particles with carboxyl on the surface, so that tetracycline molecules can be adsorbed on the surface of the polystyrene-acrylic acid (PSA) colloidal particles through hydrogen bond action, and the tetracycline and the polystyrene-acrylic acid (PSA) colloidal particles can be simultaneously self-assembled to form colloidal crystals, and the surface molecular imprinting gel photonic crystal sensor with molecular imprinting identification sites distributed on the surface of a substrate is prepared by taking the colloidal crystals formed by simultaneously self-assembling the tetracycline and the polystyrene-acrylic acid (PSA) colloidal particles as a template through the polymerization of functional monomers; meanwhile, the gel containing PSA colloidal particles and tetracycline and adhered to the glass sheet is soaked in deionized water, so that the preparation of the surface molecular imprinting gel photonic crystal sensor without depending on the glass sheet as a carrier is realized. The prepared surface molecularly imprinted gel photonic crystal sensor has a three-dimensional ordered macroporous structure, shows macroscopic color change in tetracycline solutions with different concentrations, and has different Bragg diffraction wavelengths in the tetracycline solutions with different concentrations. The red shift is generated along with the increase of the concentration of the tetracycline in the solution, and the red shift amount (delta lambda) and the negative logarithm (-logC) of the concentration of the target molecule form a linear relation, so that the sensor can be used for quantitative detection, and the rapid naked eye detection of the tetracycline is realized.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a surface molecularly imprinted gel photonic crystal sensor is characterized by comprising the following steps:
preparing PSA colloidal crystals with tetracycline uniformly distributed on the surfaces of the polystyrene-acrylic acid PSA colloidal particles;
covering a layer of glass sheet on the surface of the PSA colloidal crystal, and fixing by using a clamp to obtain a PSA colloidal crystal template;
dripping the precursor liquid on the upper edge of the PSA colloidal crystal template until the PSA colloidal crystal template is changed from opaque to transparent;
polymerizing the transparent PSA colloidal crystal template to obtain gel;
soaking the gel in deionized water for plate removal treatment, performing post-treatment on the gel separated from the glass sheet, and removing PSA colloidal crystals in the gel;
and placing the gel after post-treatment in a sodium dodecyl sulfate/acetic acid mixed solution to prepare the surface molecularly imprinted gel photonic crystal sensor.
2. The method for preparing the surface molecularly imprinted gel photonic crystal sensor according to claim 1, wherein the PSA colloidal crystal is prepared by:
preparing PSA polystyrene-acrylic acid microsphere emulsion by adopting a soap-free emulsion polymerization method;
diluting the prepared PSA microsphere emulsion to obtain emulsion A;
adding tetracycline into the emulsion A to obtain emulsion B;
and (3) vertically putting the hydrophilic glass sheet into the emulsion B, and putting the emulsion B into a constant temperature and humidity box to prepare the PSA colloidal crystal.
3. The preparation method of the surface molecularly imprinted gel photonic crystal sensor according to claim 2, wherein the prepared PSA microsphere emulsion has a particle size of 200 nm and a monodispersion coefficient of less than 0.005.
4. The preparation method of the surface molecularly imprinted gel photonic crystal sensor according to claim 2, wherein the temperature of the constant temperature and moisture preservation box is 60 ℃, the humidity is 40%, and the temperature preservation time is 24 h.
5. The method for preparing the surface molecularly imprinted gel photonic crystal sensor according to claim 1, wherein the method for preparing the precursor solution comprises: dissolving a functional monomer, a cross-linking agent and distilled water twice, uniformly mixing, and adding an initiator to prepare a precursor solution;
the functional monomers comprise acrylamide and itaconic acid;
and/or the cross-linking agent is N, N-methylene bisacrylamide;
and/or ammonium persulfate is adopted as the initiator.
6. The method for preparing the surface molecular imprinting gel photonic crystal sensor according to claim 5, wherein the molar ratio of the acrylamide, the itaconic acid, the N, N-methylene bisacrylamide, the water and the ammonium persulfate is 1142-4000: 857-1000: 40-200: 80: 1.
7. the method for preparing the surface molecularly imprinted gel photonic crystal sensor according to claim 6, wherein the composition of the precursor solution is as follows: the molar ratio of acrylamide, itaconic acid, N-methylene bisacrylamide, water and ammonium persulfate is 2000:1000:120:80: 1.
8. The preparation method of the surface molecularly imprinted gel photonic crystal sensor according to claim 1, wherein the polymerization treatment comprises polymerizing the transparent PSA colloidal crystal template at 60 ℃ for 3 h; and/or, the method of post-treatment comprises drying the gel off the glass sheet and then placing the dried gel in xylene for 48 h.
9. A surface molecularly imprinted gel photonic crystal sensor, characterized in that the crystal sensor is prepared according to the method of claims 1-8.
10. Use of the surface molecularly imprinted gel photonic crystal sensor of claim 9 in the determination of tetracycline.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210141586.8A CN114527153A (en) | 2022-02-16 | 2022-02-16 | Surface molecularly imprinted gel photonic crystal sensor and preparation method and application thereof |
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| CN202210141586.8A CN114527153A (en) | 2022-02-16 | 2022-02-16 | Surface molecularly imprinted gel photonic crystal sensor and preparation method and application thereof |
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- 2022-02-16 CN CN202210141586.8A patent/CN114527153A/en not_active Withdrawn
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