CN112300335B - Preparation method and application of molecular imprinting sensor based on F-PDA (Fabry-Perot digital Assistant) - Google Patents
Preparation method and application of molecular imprinting sensor based on F-PDA (Fabry-Perot digital Assistant) Download PDFInfo
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Abstract
The invention belongs to the technical field of novel nano material preparation, and discloses a preparation method and application of a molecular imprinting fluorescence sensor based on F-PDA. The invention provides a preparation method of a molecular imprinting fluorescence sensor based on F-PDA, which is used for preparing the molecular imprinting fluorescence sensor based on F-PDA by a precipitation polymerization method. In addition, the prepared fluorescent polydopamine has the remarkable advantages of no toxicity, stable luminous performance, simple preparation, good biocompatibility and the like. The F-PDA-based molecularly imprinted fluorescent sensor has good stability and optical performance, and has high sensitivity and high selective recognition capability on p-nitrophenol in an aqueous solution.
Description
Technical Field
The invention particularly relates to a preparation method and application of a molecular imprinting sensor based on F-PDA (Fabry-Perot-PDA), belonging to the field of preparation of novel nano materials.
Background
P-Nitrophenol (P-Nitrophenol, abbreviated as P-NP) is an important raw material in chemical industry, and is also an important intermediate in the production of chemical products, and is widely applied to the fields of manufacture of pesticides, dyes, explosives, drugs, and the like. However, as one of the main pollutants in industrial wastewater, p-nitrophenol has high toxicity, high pathogenicity and weak biodegradability, and can cause harm to human health such as headache, fever, blood vessel, musculoskeletal, liver and kidney injury and the like when being taken in low concentration. Therefore, the content determination of p-nitrophenol is very urgent for both human health and environmental protection. In recent years, research on a method for detecting nitrophenol has received much attention. Common detection methods for p-nitrophenol include ultraviolet-visible spectrophotometry, fluorescence, electrochemistry, capillary electrophoresis, High Performance Liquid Chromatography (HPLC), and the like.
In recent years, fluorescent polydopamine (F-PDA) has attracted extensive attention of researchers in various countries as a new organic fluorescent nano material. Compared with quantum dots, F-PDA has a series of significant advantages of no toxicity, stable luminescence property, simple preparation, good biocompatibility and the like, and has been widely researched in the fields of energy, environment, biosensing and the like. In addition, the surface of the F-PDA contains active functional groups such as amino and hydroxyl which are beneficial to imprinting polymerization. Therefore, the F-PDA can be used as a fluorescent monomer and a blotting functional monomer at the same time, so that the F-PDA can be uniformly distributed in the synthesized fluorescent blotting material, and the defect that the fluorescence performance of the traditional fluorescent monomer is reduced due to embedding can be avoided. However, the actual size of the F-PDA is nano-scale, a large amount of cross-linking agents are used in the traditional imprinting process, the free radical polymerization process is not controllable, and the F-PDA is bound to be embedded. Therefore, the method for controlling the size of the fluorescent imprinting material by controllable polymerization while introducing the F-PDA as a fluorescent monomer and a functional monomer is still of great significance for determining the fluorescent property of the fluorescent imprinting material.
Molecular Imprinting Technology (MIT) is a synthesis technology of Molecular Imprinted Polymers (MIPs) for obtaining a Molecular imprinted polymer that can be matched with a target analyte in terms of spatial shape, size and functional group and can recognize the target analyte with high selectivity in a complex environment.
The related technology for detecting the p-nitrophenol by combining the fluorescent polydopamine with the molecular imprinting technology is not reported.
Disclosure of Invention
The invention aims to overcome the technical defects in the prior art, such as: the process for detecting the p-nitrophenol is complex and time-consuming in operation, long in pretreatment time, poor in method stability, expensive and precise in instrument and the like. The invention uses F-PDA as a fluorescent substrate, utilizes a molecular imprinting technology to prepare a fluorescent polydopamine molecular imprinting fluorescent sensor, provides the polydopamine molecular imprinting fluorescent sensor (F-PDA @ MIPs) for identifying and detecting p-nitrophenol with high sensitivity and high selectivity, has the characteristics of simple preparation method, low cost, good stability and optical performance and the like, can be used for identifying and detecting the specificity of the p-nitrophenol in an aqueous solution, and realizes the qualitative and quantitative detection of the p-nitrophenol by optimizing the sensor.
Specifically, the invention is carried out according to the following technical scheme:
a preparation method of a molecular imprinting sensor based on F-PDA comprises the following steps:
(1) preparing high-fluorescence polydopamine quantum dot F-PDA:
dissolving a certain amount of dopamine DA hydrochloride and polyethyleneimine PEI in deionized water, ultrasonically dispersing uniformly, and standing for a period of time; finally, adjusting the pH value with dilute hydrochloric acid, filtering, freeze-drying, and adding a proper amount of deionized water for dissolving to obtain an F-PDA solution for later use;
(2) preparing an F-PDA molecular imprinting sensor F-PDA @ MIPs:
adding ethylene glycol dimethacrylate EGDMA, methacrylic acid MAA, ethanol and p-nitrophenol in sequence according to a proportion, ultrasonically dispersing uniformly, and standing; obtaining a mixed solution A;
taking the F-PDA solution obtained in the step (1), dissolving with deionized water, and adding acetonitrile to obtain a mixed solution B;
and adding the mixed solution A into the mixed solution B, adding azobisisobutyronitrile AIBN, uniformly mixing, introducing nitrogen for a period of time, carrying out water bath reaction, centrifuging, washing and drying after the reaction is finished, and finally obtaining the F-PDA molecularly imprinted polymer.
In the step (1), the dosage ratio of DA, PEI and deionized water is 100 mg: 0.1 mL: 20mL, the standing time is 3.0h, the concentration of dilute hydrochloric acid is 1.0M, and the pH value is 7.0.
In the step (1), the dosage ratio of the F-PDA to the deionized water in the F-PDA solution is 20 mg: 3 mL.
In the step (2), the dosage ratio of the EGDMA, the MAA, the ethanol and the p-nitrophenol in the mixed solution A is 264 mu L: 129 mu L of: 20mL of: 13.9mg, standing for 2.0 h.
In the step (2), in the mixed solution B, the dosage ratio of the F-PDA solution to the deionized water to the acetonitrile is 1.0-1.5 mL: 2.0-5.0 mL: 35-48 mL.
In the step (2), the dosage ratio of the mixed solution A, the mixed solution B and the AIBN is 20 mL: 40-55 mL: 7.5-10 mg.
In the step (2), the introduction of N2The time of (2) is 15-20 min.
In the step (2), the water bath reaction time and temperature are respectively 50 ℃ for 6.0h, and the reaction time and temperature are 16-24 h after the temperature is raised to 60 ℃.
The F-PDA molecular imprinting sensor prepared by the invention has the advantages of uniform dispersion of F-PDA quantum dots, no agglomeration phenomenon and high fluorescence efficiency.
The F-PDA molecular imprinting sensor prepared by the invention is used for detecting p-nitrophenol in water.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fluorescent polydopamine quantum dots prepared by the method are uniformly dispersed, have no agglomeration and have excellent fluorescent effect, and meanwhile, the fluorescent polydopamine prepared by the method can be used for preparing a molecular imprinting fluorescent sensor based on F-PDA. Compared with a complex preparation method, the preparation method is simpler, more convenient and safer, has low raw material cost, reduces the waste of other resources, and can be used for quickly identifying the p-nitrophenol.
(2) In the case of nitro compounds, the electron-withdrawing property is so large that electrons that have been transferred to an excited state can be pulled to a group, so that the probability of electron transfer from the excited state to the ground state is reduced, and the appearance is shown as a weak fluorescence emission. The addition of p-nitrophenol leads to fluorescence quenching of the F-PDA based molecularly imprinted fluorescent sensor. And fitting a linear relation through different fluorescence quenching degrees of p-nitrophenol with different concentrations on the F-PDA-based molecularly imprinted fluorescent sensor, thereby realizing the quantitative detection of p-nitrophenol. Meanwhile, the recognition effect of the imprinted fluorescent sensor on p-nitrophenol analogues is explored, and the best quenching effect of p-nitrophenol on the molecularly imprinted fluorescent sensor is found, so that the F-PDA-based molecularly imprinted fluorescent sensor prepared by the method can be used for carrying out quantitative detection and analysis on p-nitrophenol in a sample with high sensitivity and high selectivity.
Drawings
FIG. 1 is a laser confocal microscope (LSCM) of the F-PDA based molecularly imprinted fluorescent sensor prepared according to the present invention;
FIG. 2 is a graph showing the fluorescence intensity of the F-PDA based molecularly imprinted fluorescent sensor of the present invention after being reacted with p-nitrophenol at different concentrations;
FIG. 3 is a linear relationship diagram of relative fluorescence intensity of the F-PDA based molecularly imprinted fluorescent sensor after the sensor is reacted with p-nitrophenol solution with different concentrations;
FIG. 4 is a graph showing the selectivity of the F-PDA based molecularly imprinted fluorescent sensor of the present invention to p-nitrophenol and its analogues at the same concentration.
Detailed Description
The invention will be further illustrated by the following examples
Dopamine hydrochloride, polyethyleneimine, EGDMA, MAA and p-nitrophenol used in the present invention were all purchased from shanghai alatin reagent limited, and deionized water from Jiangsu university laboratories.
Example 1:
(1) preparation of F-PDA
Dissolving 100mg of dopamine hydrochloride and 0.1mL of polyethyleneimine in 20mL of deionized water, ultrasonically dispersing uniformly, and standing at room temperature for 3.0 h; and finally, adjusting the pH value to 7.0 by using 1.0M dilute hydrochloric acid, filtering, freeze-drying, and adding 3.0mL of deionized water for dissolving to obtain an F-PDA solution for later use.
(2) Preparation of F-PDA molecular imprinting fluorescence sensor
264 mu L of EGDMA, 129 mu L of MAA, 20mL of ethanol and 13.9mg of p-nitrophenol are sequentially added into a beaker, uniformly dispersed by ultrasonic waves and kept stand for 2.0h at room temperature.
And adding 1.0mL of F-PDA solution into another 100mL flask, dissolving with 5.0mL of deionized water, adding 35mL of acetonitrile, adding the above 20mL of ethanol mixed solution, adding 7.5mg of AIBN, uniformly mixing, introducing nitrogen for 15min, carrying out water bath reaction, reacting at 50 ℃ for 6.0h, heating to 60 ℃ and reacting for 24 h. And after the reaction is finished, centrifugally washing the mixture for three times by using deionized water, washing out the template molecules, and finally drying the mixture at the temperature of 60 ℃ for later use.
FIG. 1 is a confocal laser microscope of the F-PDA based molecularly imprinted fluorescence sensor of the present invention, from which it can be seen that F-PDA @ MIPs has good polymerization effect and high fluorescence efficiency.
Example 2:
(1) preparation of F-PDA
Dissolving 100mg of dopamine hydrochloride and 0.1mL of polyethyleneimine in 20mL of deionized water, ultrasonically dispersing uniformly, and standing at room temperature for 3.0 h; and finally, adjusting the pH value to 7.0 by using 1.0M dilute hydrochloric acid, filtering, freeze-drying, and adding 3.0mL of deionized water for dissolving to obtain an F-PDA solution for later use.
(2) Preparation of F-PDA molecular imprinting fluorescence sensor
264 mu L of EGDMA, 129 mu L of MAA, 20mL of ethanol and 13.9mg of p-nitrophenol are sequentially added into a beaker, uniformly dispersed by ultrasonic waves and kept stand for 2.0h at room temperature.
And adding 1.0mL of F-PDA solution into another 100mL flask, dissolving with 2.0mL of deionized water, adding 48mL of acetonitrile, adding the above 20mL of ethanol mixed solution, adding 7.5mg of AIBN, uniformly mixing, introducing nitrogen for 20min, carrying out water bath reaction, reacting at 50 ℃ for 6.0h, heating to 60 ℃ and reacting for 16 h. And after the reaction is finished, centrifugally washing the mixture for three times by using deionized water, washing out the template molecules, and finally drying the mixture at the temperature of 60 ℃ for later use.
Example 3:
(1) preparation of F-PDA
Dissolving 100mg of dopamine hydrochloride and 0.1mL of polyethyleneimine in 20mL of deionized water, ultrasonically dispersing uniformly, and standing at room temperature for 3.0 h; and finally, adjusting the pH value to 7.0 by using 1.0M dilute hydrochloric acid, filtering, freeze-drying, and adding 3.0mL of deionized water for dissolving to obtain an F-PDA solution for later use.
(2) Preparation of F-PDA molecular imprinting fluorescence sensor
264 mu L of EGDMA, 129 mu L of MAA, 20mL of ethanol and 13.9mg of p-nitrophenol are sequentially added into a beaker, uniformly dispersed by ultrasonic waves and kept stand for 2.0h at room temperature.
And adding 1.2mL of F-PDA solution into another 100mL flask, dissolving with 2.0mL of deionized water, adding 48mL of acetonitrile, adding the above 20mL of ethanol mixed solution, adding 10mg of AIBN, uniformly mixing, introducing nitrogen for 20min, carrying out water bath reaction, reacting at 50 ℃ for 6.0h, heating to 60 ℃ and reacting for 24 h. And after the reaction is finished, centrifugally washing the mixture for three times by using deionized water, washing out the template molecules, and finally drying the mixture at the temperature of 60 ℃ for later use.
F-PDA based molecularly imprinted fluorescent sensor for detecting p-nitrophenol:
test example 1:
preparing p-nitrophenol aqueous solutions with different concentrations (0 nM, 100nM, 200nM, 300nM, 400nM, 500nM, 600nM, 700nM, 800nM, 900nM, 1000nM and 1100nM respectively), weighing 1.39mg of p-nitrophenol, adding 100mL of deionized water to prepare a p-nitrophenol aqueous solution, adding 50 μ L of the molecularly imprinted polymer dispersion and 10 μ L of the p-nitrophenol solution into a 10mL colorimetric tube, adding deionized water to a constant volume of 10mL, oscillating at room temperature, and standing for 3.0 min. Under the conditions that the excitation wavelength of 360nm, the slit width of the excitation wavelength and the slit width of the emission wavelength are both 10nm, the voltage of a photomultiplier is 800V, and the scanning wavelength range is 450-750nm, a fluorescence spectrophotometer is used for researching the influence of p-nitrophenol with different concentrations on the fluorescence intensity of the molecularly imprinted polymer with the same concentration.
FIG. 2 is a graph showing the effect of the molecularly imprinted fluorescent sensor of the present invention on p-nitrophenol at different concentrations, wherein each line represents the fluorescence intensity of the molecularly imprinted fluorescent sensor after the effect of the p-nitrophenol solution at the concentration of 0nM, 100nM, 200nM, 300nM, 400nM, 500nM, 600nM, 700nM, 800nM, 900nM, 1000nM, and 1100nM, respectively, from top to bottom. It can be visually seen from the figure that the fluorescence intensity of the molecularly imprinted fluorescent sensor is gradually reduced along with the increase of the concentration of the p-nitrophenol solution, which indicates that the molecularly imprinted fluorescent sensor can qualitatively detect the p-nitrophenol.
FIG. 3 is a linear graph of relative fluorescence intensity of the F-PDA based molecularly imprinted fluorescent sensor of the present invention after mixing with p-nitrophenol solutions of different concentrations; as can be seen from FIG. 3, the concentration of p-nitrophenol [ c ]]As the abscissa, F0the/F is a fluorescence response curve drawn by a vertical coordinate, and a corresponding equation is obtained: F/F0＝0.00199CP-NP+0.92566(R20.99304) in the linear range of 0-1100 nM. The result shows that the F-PDA-based molecularly imprinted fluorescent sensor has simple detection method for p-nitrophenol, does not need complex sample pretreatment, has high sensitivity and has good optical detection capability.
Test example 2:
target (P-nitrophenol, P-NP) and its analogues (catechol, O-NP, cellulose acetate, CA, 2, 6-dichlorophenol, 2,6-DP) were prepared into 0.1mM aqueous solutions, and mixed by sonication. Adding 50 mu L of imprinted polymer F-PDA @ MIPs dispersion liquid into a 10mL colorimetric tube, adding 10 mu L of aqueous solution of p-nitrophenol or the like, fixing the volume to 10mL by using deionized water, respectively oscillating the mixed solution at room temperature, standing for 3.0min, and respectively recording the fluorescence intensity of the mixed solution before and after the p-nitrophenol and the like are added by using a fluorescence spectrophotometer.
FIG. 4 is a graph of the relative fluorescence intensity of the imprinted polymer F-PDA @ MIPs of the present invention versus p-nitrophenol and its analogs at the same concentration; as can be seen from the graph, the relative fluorescence intensity value (F) based on the F-PDA molecular imprinting fluorescence sensor (blue line) before and after the addition of p-nitrophenol0The linear amplitude of the fluorescence intensity signal is larger than that of the fluorescence intensity signal, and the relative fluorescence intensity values (F) before and after the addition of O-NP (green line), CA (red line) and 2,6-DP (yellow line) are larger than that of the fluorescence intensity signal0/F) the linear amplitude variation range is small. The detection result shows that the quenching amount of the p-nitrophenol on the F-PDA @ MIPs based molecularly imprinted fluorescent sensor is the largest and is obviously higher than that of a p-nitrophenol analog, and the F-PDA @ MIPs based molecularly imprinted fluorescent sensor has obvious specific recognition effect on the p-nitrophenol.
Claims (10)
1. A preparation method of a molecular imprinting sensor based on F-PDA is characterized by comprising the following steps:
(1) preparing high-fluorescence polydopamine quantum dot F-PDA:
dissolving a certain amount of dopamine DA hydrochloride and polyethyleneimine PEI in deionized water, ultrasonically dispersing uniformly, and standing for a period of time; finally, adjusting the pH value with dilute hydrochloric acid, filtering, freeze-drying, and adding a proper amount of deionized water for dissolving to obtain an F-PDA solution for later use;
(2) preparing an F-PDA molecular imprinting sensor F-PDA @ MIPs:
adding ethylene glycol dimethacrylate EGDMA, methacrylic acid MAA, ethanol and p-nitrophenol in sequence according to a proportion, ultrasonically dispersing uniformly, and standing; obtaining a mixed solution A;
taking the F-PDA solution obtained in the step (1), dissolving with deionized water, and adding acetonitrile to obtain a mixed solution B;
and adding the mixed solution A into the mixed solution B, adding azobisisobutyronitrile AIBN, uniformly mixing, introducing nitrogen for a period of time, carrying out water bath reaction, centrifuging, washing and drying after the reaction is finished, and finally obtaining the F-PDA molecularly imprinted polymer.
2. The method for preparing a F-PDA based molecularly imprinted sensor according to claim 1, wherein in the step (1), the dosage ratio of DA, PEI and deionized water is 100 mg: 0.1 mL: 20mL, the standing time is 3.0h, the concentration of dilute hydrochloric acid is 1.0M, and the pH value is 7.0.
3. The method for preparing a F-PDA based molecularly imprinted sensor according to claim 1, wherein in the step (1), the ratio of the dosage of the F-PDA to the dosage of the deionized water in the F-PDA solution is 20 mg: 3 mL.
4. The preparation method of the F-PDA-based molecularly imprinted sensor according to claim 1, wherein in the step (2), the dosage ratio of EGDMA, MAA, ethanol and p-nitrophenol in the mixed solution A is 264 μ L: 129 muL: 20mL of: 13.9mg, standing for 2.0 h.
5. The preparation method of the F-PDA-based molecularly imprinted sensor according to claim 1, wherein in the step (2), the dosage ratio of the F-PDA solution, deionized water and acetonitrile in the mixed solution B is 1.0-1.5 mL: 2.0-5.0 mL: 35-48 mL.
6. The method for preparing a F-PDA molecular imprinting-based sensor, according to claim 1, wherein in the step (2), the dosage ratio of the mixed solution A, the mixed solution B and the AIBN is 20 mL: 40-55 mL: 7.5-10 mg.
7. The method for preparing a F-PDA based molecular imprinting sensor according to claim 1, wherein the nitrogen gas is introduced for 15-20min in step (2).
8. The preparation method of the F-PDA-based molecularly imprinted sensor as claimed in claim 1, wherein in the step (2), the water bath reaction time and temperature are respectively 50 ℃ for 6.0h, and the reaction time and temperature are 16-24 h after the temperature is raised to 60 ℃.
9. The F-PDA molecularly imprinted sensor prepared by the method of any one of claims 1 to 8, wherein the F-PDA quantum dots are free of agglomeration.
10. Use of the F-PDA molecularly imprinted sensor of claim 9 for detecting p-nitrophenol in a body of water.
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| CN110487882A (en) * | 2019-09-22 | 2019-11-22 | 东北石油大学 | The molecular imprinting electrochemical sensor of Selective recognition p-nitrophenol and its application |
| CN111534299A (en) * | 2020-04-29 | 2020-08-14 | 上海应用技术大学 | GOQDs @ PDA-ir-MIP molecularly imprinted fluorescence sensor and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110487882A (en) * | 2019-09-22 | 2019-11-22 | 东北石油大学 | The molecular imprinting electrochemical sensor of Selective recognition p-nitrophenol and its application |
| CN111534299A (en) * | 2020-04-29 | 2020-08-14 | 上海应用技术大学 | GOQDs @ PDA-ir-MIP molecularly imprinted fluorescence sensor and preparation method and application thereof |
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| Preparation and characterization of hydrophilic polydopamine-coated Fe3O4/oxide graphene imprinted nanocomposites for removal of bisphenol A in waters;Suyu Ren 等;《Korean J. Chem. Eng.》;20180720;1836-1843 * |
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