CN114106218B - Fluorescent probe based on aggregation-induced emission mechanism, preparation method thereof and application thereof in detecting methamphetamine in sewage - Google Patents
Fluorescent probe based on aggregation-induced emission mechanism, preparation method thereof and application thereof in detecting methamphetamine in sewage Download PDFInfo
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Abstract
The invention relates to the technical field of fluorescent probe compounds, in particular to a fluorescent probe based on an aggregation-induced emission mechanism, a preparation method thereof and application thereof in detecting methamphetamine in sewage. The fluorescent probe TPE-2 COOH@gamma-CD is obtained by compounding AIE molecule TPE-2COOH with gamma-CD through esterification reaction. The gamma-CD captures methamphetamine in the solution through the size matching effect, and because the main guest action capability of the methamphetamine and the cyclodextrin is better than the acting force between the cyclodextrin and the TPE-2COOH, when the methamphetamine enters the gamma-CD cavity, the TPE-2COOH is replaced, fluorescence quenching is caused, and detection of the methamphetamine is realized. The blue fluorescent probe can be used for rapidly detecting the methamphetamine in the urban sewage.
Description
Technical Field
The invention relates to the technical field of fluorescent probe compounds, in particular to a fluorescent probe based on an aggregation-induced emission mechanism, a preparation method thereof and application thereof in detecting methamphetamine in sewage.
Background
In the chemical field, the fluorescence method is always the most focused technical means of scientists in all circles, and has the advantages of high sensitivity, simplicity in operation, low cost efficiency and the like, thereby attracting the attention of the students in all circles. Materials with AIE properties have attracted increasing attention due to their unique properties as an effective method to overcome the aggregation-induced quenching (ACQ) problem in conventional fluorescent dyes. AIE materials emit intense fluorescence in poor solvents due to the limiting mechanism of intramolecular rotation to form aggregates. Currently, the construction of AIE aggregates and their use in various fields is an important topic of AIE research development. While tetraphenyl ethylene (TPE) is a good AIE-active fluorescence sensor, exhibiting weak emission in both solution states and high fluorescence emission in the aggregated state. The molecule with AIE characteristic as fluorescent probe has the incomparable advantage of the traditional fluorescent probe molecule in the field of biological detection. On the one hand, more AIE probe molecules can be combined to the substances to be detected to obtain fluorescence with high brightness, and fluorescence quenching caused by aggregation does not need to be worried about as in the traditional fluorescent molecules, so that convenience is brought to fluorescence detection. On the other hand, the characteristic that fluorescence generated after aggregation suddenly becomes bright can be used as a quantitative basis for fluorescence amplification detection.
Disclosure of Invention
The invention relates to preparation of a fluorescent probe based on an aggregation-induced emission (AIE) mechanism and application of the fluorescent probe molecule TPE-2COOH for rapidly detecting methamphetamine in urban sewage, and the fluorescent probe TPE-2 COOH@gamma-CD is prepared by compounding esterification reaction and gamma-CD, so that the composite material has the main and guest identification function and the aggregation-induced emission characteristic. The fluorescent probe prepared by the fluorescent probe has the advantages of larger Stokes displacement, good fluorescence stability, pH stability, quick response time and the like.
The invention is realized by the following technical scheme: a fluorescent probe based on aggregation-induced emission mechanism is obtained by compounding AIE molecule TPE-2COOH with gamma-CD through esterification reaction.
The preparation method of the fluorescent probe based on the aggregation-induced emission mechanism comprises the following steps:
1) 3, 5-dicarboxyphenyl boric acid, absolute ethyl alcohol and concentrated sulfuric acid are put into a three-neck flask, heated for reflux reaction, concentrated solution is evaporated, water is added for filtration, and 1, 3-diethyl isophthalic acid diethyl ester-5-boric acid white solid is obtained;
2) Diethyl 1, 3-diethyl isophthalate-5-boric acid, bromotriphenylethylene, anhydrous potassium carbonate, tetramethyl ammonium bromide and tetrakis (triphenylphosphine) palladium are put into a round-bottomed flask, tetrahydrofuran and water are added, the obtained mixture is heated and stirred under nitrogen atmosphere, after cooling to room temperature, the mixture is extracted and evaporated by methylene chloride, and the ethyl 3,5- (1, 2-triphenylvinyl) isophthalate white solid TPE-2COOEt is obtained by purifying by column chromatography;
3) Dissolving TPE-2COOEt and sodium hydroxide in a mixture of tetrahydrofuran, methanol and water, heating and stirring the mixture solution, cooling to room temperature, rotationally evaporating an organic solvent, adjusting the pH value, and drying under reduced pressure to obtain carboxyl-derivatized TPE-2COOH, namely 3,5- (1, 2-triphenylvinyl) isophthalic acid white solid;
4) Under nitrogen atmosphere, putting TPE-2COOH, gamma-CD, N, N-dimethylformamide into a round bottom flask, stirring and dissolving, dissolving N, N' -dicyclohexylcarbodiimide into DMF, dripping the solution into the solution, heating to room temperature, stirring under nitrogen, filtering by a glass funnel after the reaction is stopped, heating filtrate, dripping the filtrate into a large amount of diethyl ether, vigorously stirring, filtering, and drying in vacuum overnight to obtain the fluorescent probe TPE-2 COOH@gamma-CD.
In the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism, in the step 1), 3, 5-dicarboxyphenyl boric acid is prepared according to the mass ratio: concentrated sulfuric acid: absolute ethanol = 1:11: (140-160).
In the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism, in the step 1), the heating temperature is 60-80 ℃ and the time is 10-12 hours.
In the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism, in the step 2), the following molar ratio is adopted: diethyl 1, 3-diethyl isophthalic acid-5-boric acid: anhydrous potassium carbonate = 1:1: (2-3).
In the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism, in the step 2), the heating temperature is 60-80 ℃ and the time is 20-24 hours.
In the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism, in the step 3), TPE-2COOEt is prepared by the following molar ratio: naoh=1: (1-3).
In the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism, in the step 3), the heating temperature is 60-80 ℃ and the time is 8-12 hours.
In the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism, in the step 4), TPE-2COOH is prepared according to the molar ratio: gamma-CD: dmf=1: (1-3): (1-3).
The fluorescent probe based on the aggregation-induced emission mechanism is applied to rapidly detecting methamphetamine in urban sewage.
The beneficial effects of the invention are as follows:
1) The fluorescent probe of the invention is a novel fluorescent probe for detecting methamphetamine. The supramolecular compound cyclodextrin is used as an identification unit, and AIE molecule TPE-2COOH is used as a fluorescent group for quantitatively detecting methamphetamine. The fluorescent probe shows good fluorescent response effect within the concentration of methamphetamine of 0.10-0.26mg/mL, and the minimum detection limit is 0.0035mg/mL. The fluorescent probe has the advantages of good sensitivity, fluorescence stability, pH stability and the like. The pretreatment and enrichment are carried out on urban sewage in Dalian city, and the standard adding detection is carried out on methamphetamine in the sewage, the enrichment multiple of the fluorescent probe is 80 times, the standard adding recovery rate is between 96% and 114%, and the relative standard deviation is 7% to 18%.
2) The fluorescent probe of the invention basically does not emit fluorescence in a dispersion state under the action of 314nm excitation light, and emits obvious blue fluorescence at about 472nm when the fluorescent probe is in an aggregation state or rotation is blocked. The fluorescent probe provided by the invention recognizes methamphetamine to obtain high-brightness fluorescence, and the fluorescent probe cannot be influenced by fluorescence quenching caused by aggregation like the traditional fluorescent molecules. In addition, the characteristic that fluorescence which occurs after aggregation or internal rotation is blocked suddenly lightens can be used as a quantitative basis for fluorescence amplification detection, and the mode can greatly reduce the influence of high concentration and improve the detection precision and accuracy.
3) The gamma-CD captures methamphetamine in the solution through the size matching effect, and because the main guest action capability of the methamphetamine and the cyclodextrin is better than the acting force between the cyclodextrin and the TPE-2COOH, when the methamphetamine enters the gamma-CD cavity, the TPE-2COOH is replaced, fluorescence quenching is caused, and detection of the methamphetamine is realized. The blue fluorescent probe can be used for rapidly detecting the methamphetamine in the urban sewage.
Drawings
FIG. 1 is a synthetic route pattern of the fluorescent probe TPE-2 COOH@gamma-CD of example 1.
FIG. 2 is an absorption spectrum and a fluorescence spectrum of the fluorescent probe TPE-2 COOH@gamma-CD of example 2.
FIG. 3 is a fluorescent probe TPE-2 COOH@gamma-CD in example 2 at H 2 Fluorescence spectrum in O-THF mixture.
FIG. 4 is a graph of the critical aggregation concentration of the fluorescent probe TPE-2 COOH@gamma-CD of example 3.
FIG. 5 is a graph showing fluorescence spectra of the fluorescent probe TPE-2 COOH@gamma-CD of example 4 in buffer solutions of different pH.
FIG. 6 is a diagram of an experimental apparatus for enrichment of municipal sewage in example 5.
FIG. 7 is a graph showing fluorescence spectra of the fluorescent probe TPE-2 COOH@gamma-CD of example 6 in solutions of different concentrations of Methamphetamine (METH).
FIG. 8 is a standard graph of the detection of methamphetamine by the fluorescent probe TPE-2 COOH@gamma-CD of example 6.
Detailed Description
Example 1 fluorescent probe TPE-2COOH @ gamma-CD
The synthetic route pattern of the fluorescent probe TPE-2 COOH@gamma-CD is shown in FIG. 1.
The preparation process flow of the fluorescent probe TPE-2 COOH@gamma-CD is as follows:
1) 3, 5-dicarboxyphenyl boronic acid (0.50 g), absolute ethanol (100 mL), 98% concentrated sulfuric acid (3 mL) were placed in a three-necked flask and refluxed at 80℃for 12 hours. The resulting solution was concentrated to 50mL by evaporation, water (100 mL) was added and filtered to give 1, 3-diethyl-5-diethyl-isophthalate as a white solid in 89.4% yield.
2) Bromotriphenylethylene (1.34 g,4 mmol), diethyl 1, 3-diethylisophthalic acid-5-boric acid (1.06 g,4 mmol), anhydrous potassium carbonate (1.38 g,10.0 mmol), tetramethylammonium bromide (TBAB) (0.01 g,0.03 mmol) and tetrakis (triphenylphosphine) palladium (115.6 mg,0.1 mmol) were placed in a 150mL round bottom flask, tetrahydrofuran (40 mL) and water (5 mL) were added and the resulting mixture stirred under nitrogen at 80℃for 24 hours. After cooling to room temperature, the mixture was extracted with dichloromethane and evaporated. Purification by column chromatography gave TPE-2COOEt as a white solid (1.32 g,2.82 mmol) in 70.5% yield.
3) TPE-2COOEt (0.4760 g,1.0 mmol) and NaOH (0.800 g,20 mmol) were dissolved in a mixture of tetrahydrofuran (40 mL), methanol (40 mL) and water (40 mL), and the mixture solution was stirred at 60℃for 10 hours. After cooling to room temperature, the organic solvent was rotary evaporated. The pH of the mixture was adjusted to 6 by using a 2mol/L hydrochloric acid solution and dried under reduced pressure to give TPE-2COOH as a white solid (0.39 g,0.925 mmol) in 92.5% yield.
4) TPE-2COOH (0.0940 g,0.25 mmol), gamma-CD (0.6485 g,0.5 mmol) was dissolved in 10mL anhydrous DMF under nitrogen at 0deg.C in a 50mL round bottom flask with stirring. 0.1030g (0.5 mmol) of N, N' -dicyclohexylcarbodiimide was dissolved in 5mL of anhydrous DMF, this solution was added dropwise to the above solution, and the temperature was raised to room temperature and stirred under nitrogen for 3 days. After the reaction was stopped, it was filtered through a glass funnel, the filtrate was heated to 90℃and added dropwise to a large amount of diethyl ether, stirred vigorously, filtered, and dried under vacuum overnight at 40℃to give TPE-2 COOH@gamma-CD as a white solid.
Example 2 aggregation-induced emission Properties of fluorescent Probe TPE-2COOH @ gamma-CD
As shown in FIG. 2, the absorption spectrum and the fluorescence emission spectrum of the fluorescent probe are not overlapped, and the fluorescent probe has larger Stokes shift (158 nm), so that the interference of a background fluorescence signal generated by overlapping the excitation spectrum and the emission spectrum can be avoided, and the detection accuracy is improved. As shown in fig. 3, first, the aggregation-induced emission characteristics of the fluorescent probe TPE-2cooh@γ -CD were tested by fluorescence spectrometry, and the fluorescent probe TPE-2cooh@γ -CD had a fluorescence intensity of almost 0 in a pure THF solvent because TPE-2cooh@γ -CD was in a dispersed state, and the benzene ring on tetraphenyl ethylene was rotated around a carbon-carbon double bond, so that the excited state energy was attenuated in a non-radiative form; when the water content in the mixed system reaches 90%, the fluorescence intensity of the fluorescent probe TPE-2 COOH@gamma-CD is obviously increased, because the TPE-2 COOH@gamma-CD is aggregated in a poor solvent, the free movement in the molecule is limited, the excited state energy is attenuated in a radiation transition mode, and the fluorescent spectrum test result shows that the fluorescent probe TPE-2 COOH@gamma-CD has AIE characteristics.
Example 3 determination of the Critical aggregation concentration of the fluorescent Probe TPE-2COOH @ gamma-CD
As shown in FIG. 4, when the concentration is small, TPE-2 COOH@gamma-CD can freely rotate in the solution, and as the concentration of the solution increases, TPE-2 COOH@gamma-CD can aggregate. Thus, the Critical Aggregation Concentration (CAC) of TPE-2 COOH@gamma-CD was determined by fluorescence spectroscopy in this experiment. Adding fluorescent probes with different masses into distilled water, performing ultrasonic dispersion to prepare a dispersion liquid with the concentration of 0.001 mg/mL-1 mg/mL, and determining the Critical Aggregation Concentration (CAC) of the fluorescent probes in the aqueous solution by using a fluorescence spectrometry method. As shown in FIG. 4, the aqueous solution of TPE-2 COOH@gamma-CD emitted weakly at low concentrations, and when the concentration exceeded 0.25mg/mL, the fluorescence intensity increased rapidly, so the critical aggregation concentration of TPE-2 COOH@gamma-CD was determined to be 0.25mg/mL.
Example 4 measurement of fluorescence stability of fluorescent probe TPE-2 COOH@gamma-CD
As shown in FIG. 5, since the application environment of the fluorescent probe is generally relatively complex, the pH value is not fixed, for example, the pH of domestic sewage is mostly acidic, and the change of the pH value can affect the fluorescence intensity of the fluorescent probe, so that the sensitivity of fluorescent detection is greatly reduced, and the fluorescent property of the fluorescent probe TPE-2 COOH@gamma-CD in different pH solutions is tested. The fluorescent probe TPE-2 COOH@gamma-CD is added into a solution with different pH values, the fluorescence intensity of the material is strongest at the pH value of 7, and the fluorescence intensity of the fluorescent probe TPE-2 COOH@gamma-CD is still strong at the pH value of 1, which indicates that the fluorescent probe TPE-2 COOH@gamma-CD still has good stability under the acidic condition.
Example 5 urban Sewage enrichment experiment
As shown in the device of FIG. 6, suspended impurities are removed by filtering 200mL of sewage from sewage treatment plants in various areas of the large area. 100mg of TPE-2 COOH@gamma-CD was weighed into a micro glass column (30 mm long and 3mm wide), the middle space of the column was filled with quartz sand and cotton, the column was rinsed with 0.5mol/L hydrochloric acid solution and distilled water, the wastewater was concentrated by flowing through the glass column at a rate of 5mL/min, and then eluted with 0.5mol/L hydrochloric acid solution.
Example 6 detection of methamphetamine by fluorescent probe TPE-2COOH @ gamma-CD fluorescent probe
As shown in fig. 7 and 8, the excitation wavelength of methamphetamine is 245nm, the emission wavelength is 310nm, the selected emission wavelength is 472nm, the excitation wavelength and the emission wavelength of the methamphetamine and TPE-2 cooh@gamma-CD are not coincident, and the detection accuracy is improved. As the concentration of methamphetamine increases, fluorescence quenching occurs. When the concentration of methamphetamine is 0.1-0.26mg/mL, the fluorescence intensity of the fluorescent probe TPE-2 COOH@gamma-CD at 472nm has a linear relation with the concentration of methamphetamine, and a regression equation can be obtained as follows: i 0 /I-1＝7.758[METH]－0.593(R 2 =0.97). To evaluate the detection sensitivity of the fluorescent probe TPE-2COOH @ γ -CD para-methamphetamine, the detection limit of TPE-2COOH @ γ -CD para-methamphetamine was calculated according to the formula LOD = 3 σ/S, where LOD is the detection limit of TPE-2COOH @ γ -CD para-methamphetamine, σ is the standard deviation (0.90%) obtained by 10 measurements, and S represents the slope (7.758) of the regression equation. The detection limit was calculated to be 0.0035mg/mL.
Claims (8)
1. The application of the fluorescent probe based on the aggregation-induced emission mechanism in the rapid detection of methamphetamine in urban sewage is characterized in that the fluorescent probe TPE-2 COOH@gamma-CD is obtained by compositing AIE molecule TPE-2COOH with gamma-CD through esterification reaction;
the preparation method of the fluorescent probe based on the aggregation-induced emission mechanism comprises the following steps:
1) 3, 5-dicarboxyphenyl boric acid, absolute ethyl alcohol and concentrated sulfuric acid are put into a three-neck flask, heated for reflux reaction, concentrated solution is evaporated, water is added for filtration, and 1, 3-diethyl isophthalic acid diethyl ester-5-boric acid white solid is obtained;
2) Diethyl 1, 3-diethyl isophthalate-5-boric acid, bromotriphenylethylene, anhydrous potassium carbonate, tetramethyl ammonium bromide and tetrakis (triphenylphosphine) palladium are put into a round-bottomed flask, tetrahydrofuran and water are added, the obtained mixture is heated and stirred under nitrogen atmosphere, after cooling to room temperature, the mixture is extracted and evaporated by methylene chloride, and the ethyl 3,5- (1, 2-triphenylvinyl) isophthalate white solid TPE-2COOEt is obtained by purifying by column chromatography;
3) Dissolving TPE-2COOEt and sodium hydroxide in a mixture of tetrahydrofuran, methanol and water, heating and stirring the mixture solution, cooling to room temperature, rotationally evaporating an organic solvent, adjusting the pH value, and drying under reduced pressure to obtain carboxyl-derivatized TPE-2COOH, namely 3,5- (1, 2-triphenylvinyl) isophthalic acid white solid;
4) Under nitrogen atmosphere, putting TPE-2COOH, gamma-CD, N, N-dimethylformamide into a round bottom flask, stirring and dissolving, dissolving N, N' -dicyclohexylcarbodiimide into DMF, dripping the solution into the solution, heating to room temperature, stirring under nitrogen, filtering by a glass funnel after the reaction is stopped, heating filtrate, dripping the filtrate into a large amount of diethyl ether, vigorously stirring, filtering, and drying in vacuum overnight to obtain the fluorescent probe TPE-2 COOH@gamma-CD.
2. The use of a fluorescent probe based on an aggregation-induced emission mechanism for rapid detection of methamphetamine in municipal wastewater according to claim 1, wherein in step 1), 3, 5-dicarboxyphenyl boric acid is prepared by: concentrated sulfuric acid: absolute ethanol = 1:11: (140-160).
3. The use of a fluorescent probe based on an aggregation-induced emission mechanism for rapid detection of methamphetamine in municipal wastewater according to claim 2, wherein in step 1), the heating temperature is 60-80 ℃ for 10-12 hours.
4. The use of a fluorescent probe based on an aggregation-induced emission mechanism for rapid detection of methamphetamine in municipal wastewater according to claim 3, wherein in step 2), the molar ratio of bromotriphenylethylene: diethyl 1, 3-diethyl isophthalic acid-5-boric acid: anhydrous potassium carbonate = 1:1: (2-3).
5. The use of a fluorescent probe based on an aggregation-induced emission mechanism for rapid detection of methamphetamine in municipal wastewater according to claim 4, wherein in step 2), the heating temperature is 60-80 ℃ for 20-24 hours.
6. The use of a fluorescent probe based on an aggregation-induced emission mechanism for rapid detection of methamphetamine in municipal wastewater according to claim 5, wherein in step 3), TPE-2COOEt: naoh=1: (1-3).
7. The use of a fluorescent probe based on an aggregation-induced emission mechanism for rapid detection of methamphetamine in municipal wastewater according to claim 6, wherein in step 3), the heating temperature is 60-80 ℃ for 8-12 hours.
8. The use of a fluorescent probe based on an aggregation-induced emission mechanism for rapid detection of methamphetamine in municipal wastewater according to claim 7, wherein in step 4), TPE-2COOH is used in a molar ratio of: gamma-CD: dmf=1: (1-3): (1-3).
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