CN110082321B - Fluorescent nano material for detecting various organic amines in water and application thereof - Google Patents
Fluorescent nano material for detecting various organic amines in water and application thereof Download PDFInfo
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- CN110082321B CN110082321B CN201811457367.0A CN201811457367A CN110082321B CN 110082321 B CN110082321 B CN 110082321B CN 201811457367 A CN201811457367 A CN 201811457367A CN 110082321 B CN110082321 B CN 110082321B
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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Abstract
The invention discloses a fluorescent nano material with a structure shown as a formula I and used for detecting various organic amines in a water body. The material has the advantages of simple preparation method, high yield, easy separation and high purity, can quickly and accurately detect the free organic amine molecules in the water phase according to the change of fluorescence intensity and color, and has very high sensitivity and selectivity. The material can be prepared into detection test paper by a relatively simple method, realizes simultaneous trace detection of various organic amines in an actual water sample, and makes important contributions to ecological environment protection, human health and agriculture, forestry and sideline development.
Wherein the content of the first and second substances,
the central Silica core is a nano Silica microsphere with the particle size of 200-300 nm.
Description
The technical field is as follows:
the invention relates to the technical field of chemical sensor materials, in particular to a fluorescent nano material for detecting various organic amines in water and application thereof.
Background art:
in recent years, the problem of environmental pollution has become more serious, and among them, most attention has been paid to organic amines which are highly harmful and have a wide range of harms. Amine components are produced in industrial production and animal and plant spoilage processes of many industries, such as chemical plants, pharmaceutical plants, leather plants, and garbage bins, sewers, etc., which are considered as sources of amine pollutants. The amines are generally volatile, and can be absorbed into human body through respiratory tract, digestive tract or skin to cause toxic damage, and have carcinogenic and mutagenic effects. Most countries list organic amine pollutants in main monitoring projects or preferentially monitor black lists of pollutants, and research on economic and efficient organic amine detection methods has become a hotspot and focus in the environmental field.
At present, the detection of organic amine pollutants in water at home and abroad mostly adopts conventional methods, such as azo spectrophotometry, gas chromatography-mass spectrometry, high performance liquid chromatography, electrochemical analysis and the like. The methods have the defects of complex pretreatment, poor detection sensitivity, expensive instrument, inconvenience in carrying, low detection speed and the like, and the emergency accident treatment with high instantaneity requirement is difficult to meet. Due to the fact that the types of pollutants in water are various, the traditional chemical reaction method is often insufficient in detection sensitivity and selectivity and difficult to distinguish different amine pollutants, and large-scale instrument detection is limited by factors such as expensive instruments and complex operation and cannot be popularized on a large scale. The fluorescence sensing technology has the characteristics of high sensitivity, quick response, easy integration, nondestructive detection and the like, and has wide application prospect in the fields of anti-terrorism, environmental protection, disease examination and the like. However, the fluorescence sensing technology has relatively few reports on the amine pollutants in water, and most of the literatures stay in the laboratory stage for detecting the organic amine in water, often need more complicated and fine detection means to realize the detection, and are not suitable for the rapid online detection of water samples in practical occasions. The synthesis of part of fluorescent sensing materials is complex, multiple steps of organic synthesis and separation operations are often needed, the preparation cost is high, and the popularization and the practical application are not facilitated. In order to solve the above problems, it is necessary to develop a novel fluorescent sensing material, which has relatively simple synthesis and separation steps and can be prepared into a small portable detection instrument, a device, test paper, etc. suitable for actual water sample detection by a simple method.
The invention content is as follows:
the invention aims to provide a fluorescent nano material for detecting micro-trace organic amine in a water body, the material is simple in preparation method, high in yield, easy to separate and high in purity, free organic amine molecules in a water phase can be rapidly and accurately detected according to changes of fluorescence intensity and color, and the material has high sensitivity and selectivity. The material can be prepared into detection test paper by a relatively simple method, realizes simultaneous trace detection of various organic amines in an actual water sample, and makes important contributions to ecological environment protection, human health and agriculture, forestry and sideline development.
The invention is realized by the following technical scheme:
one objective of the invention is to provide a fluorescent nanomaterial for detecting multiple types of organic amines in water, which has a structure shown in formula I:
wherein:
the central Silica core is a nano Silica microsphere with the particle size of 200-300nm, the periphery of the nano Silica microsphere is wrapped with a group containing double bonds, and aminocoumarin is introduced on the double bonds to serve as a sensing unit.
The synthetic route of the fluorescent nano material for detecting various organic amines in the water body is as follows:
the invention also aims to provide a preparation method of the fluorescent nano material for detecting various types of organic amines in the water body, which comprises the following steps:
(1) and (3) synthesis of nano silicon oxide microspheres: dissolving Tetraethoxysilane (TEOS) in ethanol, quickly adding the Tetraethoxysilane (TEOS) into a mixed solution of ammonia water, distilled water and ethanol, violently stirring for 5-10 minutes at the temperature of 35-40 ℃, dissolving Vinyl Triethoxysilane (VTEOS) in the ethanol, dropwise adding the mixture into the solution, continuously and violently stirring and heating for 20-30 minutes after the addition is finished, centrifuging the mixed solution at the speed of 3500 plus 4000rpm, washing with ethanol and water for multiple times, and drying to obtain white powdery nano silicon oxide microspheres; wherein the mass ratio of tetraethoxysilane to vinyltriethoxysilane is 1:2-2:1, and the mass ratio of tetraethoxysilane to ammonia contained in ammonia water is 1: 7-10;
(2) synthesis of 3-bromo-4-methyl-7-diethylaminocoumarin: taking 4-methyl-7-diethylaminocoumarin and N-bromosuccinimide in a mass ratio of 1:1, adding the 4-methyl-7-diethylaminocoumarin and the N-bromosuccinimide into N, N-dimethylformamide, adding azobisisobutyronitrile of which the mass is 3-5% of that of the 4-methyl-7-diethylaminocoumarin, heating and refluxing the mixture for 6-12 hours at 85-95 ℃, and separating the obtained reaction product by column chromatography to obtain 3-bromo-4-methyl-7-diethylaminocoumarin;
(3) and (3) synthesizing the aminocoumarin-substituted nano silicon oxide microspheres: under the inert gas atmosphere, adding nano silicon oxide microspheres and 3-bromo-4-methyl-7-diethylaminocoumarin into dried 1, 4-dioxane in a mass ratio of 2:1-1:1, then sequentially adding tri (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and dicyclohexylmethylamine, and carrying out reflux stirring at 90 ℃ for 48-72 hours under anhydrous and oxygen-free conditions, wherein the adding amount of the tri (dibenzylideneacetone) dipalladium is 6-10% of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, the adding amount of the tri-tert-butylphosphine is 6-10% of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, and the adding amount of the dicyclohexylmethylamine is 7-10 times of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin And after the reaction is finished, centrifuging, washing and drying the solution to obtain a light yellow powdery target product, namely the aminocoumarin substituted nano silicon oxide microsphere.
The preparation method provided by the invention is simple, high in yield, easy to separate and high in purity.
In the present invention, Tetraethoxysilane (TEOS) is dissolved in ethanol to prepare an ethanol solution of tetraethoxysilane, and a person skilled in the art can select the amount of the ethanol solution according to actual conditions, and Vinyltriethoxysilane (VTEOS) is dissolved in ethanol to prepare the ethanol solution of triethoxysilane by the same method.
When the fluorescent nano material for detecting organic amine in water body provided by the invention is excited by 365nm ultraviolet light, the material can emit cyan fluorescence, and the emission peak is positioned at 470 nm. When the material is contacted with aqueous solution containing various organic amines or saturated steam of the organic amines, the material and organic amine molecules perform specific reaction, the fluorescence intensity of the material can be enhanced and weakened to different degrees or gradually changed from cyan to blue, and the response time is within 5 minutes.
The invention also provides application of the fluorescent nano material for detecting various organic amines in the water body, wherein the fluorescent nano material is used for preparing a sensing thin-layer device or sensing test paper of a quartz plate substrate and detecting various organic amine molecules in the water phase according to the change of stimulated emission fluorescence.
Preferably, the preparation method of the sensing thin layer device comprises the following steps: dispersing nano silicon oxide microspheres substituted by aminocoumarin in ethanol, wherein the dispersion concentration is 2.5-3.5mg/mL, after ultrasonic oscillation, dropwise and slowly dropping the dispersion liquid into distilled water to form a nano microsphere thin layer on the surface of the solution, lifting the quartz plate substrate out of the liquid level from the ethanol-water dispersion liquid at a fixed angle to uniformly cover the nano microsphere thin layer on the surface of the quartz plate to form a sensing thin layer, and putting the quartz plate substrate into a vacuum drying oven to dry the residual liquid.
Preferably, the preparation method of the sensing test paper comprises the following steps: cutting common filter paper in a laboratory into strips, adjusting the size according to needs, dispersing the aminocoumarin substituted nano silicon oxide microspheres into ethanol, wherein the dispersion concentration is 2.5-3.5mg/mL, dropwise and slowly dropping the dispersion into distilled water after ultrasonic oscillation, forming a nano microsphere thin layer on the surface of the solution, pulling the strip-shaped filter paper out of the ethanol-water dispersion at a fixed angle, uniformly covering the nano microsphere thin layer on the surface of the filter paper, and naturally drying to prepare the sensing test paper.
The method for detecting various organic amine molecules by using the fluorescent nano material comprises the following steps: the fluorescent nano material for detecting organic amine in water, namely aminocoumarin substituted nano silicon oxide microspheres, is dispersed in ethanol, the dispersion concentration is 2.5-3.5mg/mL, then the dispersion liquid is slowly dripped into distilled water drop by drop, a nano microsphere thin layer is formed on the surface of the solution, the thin layer is uniformly coated on the surface of a quartz plate substrate or a filter paper strip through a solid phase transfer technology to form a sensing thin layer, when the sensing thin layer is contacted with a water sample containing various organic amines, the sensing thin layer and organic amine molecules generate specific chemical reaction, obvious fluorescence enhancement, attenuation or color change occurs within 5 minutes, and qualitative and semi-quantitative detection of various organic amines can be realized according to the change of the fluorescence color.
The invention has the beneficial effects that:
(1) the fluorescent nano material for detecting organic amine in water has no obvious response to other substances common in water, such as silt, inorganic salt, gasoline, edible oil, sulfur dioxide and the like, has very excellent selectivity, can be used for preparing a sensing thin-layer device or sensing test paper of a quartz substrate, and can detect various organic amine molecules in water phase according to the change of stimulated emission fluorescence.
(2) The material has the advantages of simple preparation method, high yield, easy separation and high purity, can quickly and accurately detect the free organic amine molecules in the water phase according to the change of fluorescence intensity and color, and has very high sensitivity and selectivity.
(3) The material can be prepared into detection test paper by a relatively simple method, realizes simultaneous trace detection of various organic amines in an actual water sample, and makes important contributions to ecological environment protection, human health and agriculture, forestry and sideline development.
Description of the drawings:
FIG. 1 is a graph of the infrared spectrum of the nano silica microspheres of example 1;
FIG. 2 is a graph of the IR spectrum of the target product 1 of example 1;
FIG. 3 is a graph showing the change of fluorescence spectrum of the sensor strip in example 4 after dropping an aqueous solution of n-propylamine thereon;
FIG. 4 is a graph showing the change of fluorescence spectrum of example 4 after adding an aqueous solution of diethylamine dropwise to the sensing strip;
FIG. 5 is a graph showing the change of fluorescence spectrum of the sensor strip in example 4 after aqueous solution of triethylamine was added dropwise thereto;
FIG. 6 is a graph showing the change of fluorescence spectrum of the sensor strip in example 4 after dropping an aqueous solution of aniline thereon.
FIG. 7 is an example of a visual observation of the sensor strip of example 5 after four aqueous solutions of organic amine were added dropwise.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
the preparation method of the fluorescent nano material for detecting various organic amines in the water body comprises the following steps:
(1) synthesis of nano silicon oxide microsphere
50mL of ethanol, 5.6g of 30% by mass aqueous ammonia and 4.5g of distilled water were placed in a 250mL flask and mixed uniformly, 2.5g (12mmol) of tetraethoxysilane was dissolved in 5mL of ethanol, the mixture was rapidly added to the solution, the mixture was vigorously stirred at 40 ℃ for 5 minutes, 2.4g (12mmol) of vinyltriethoxysilane was dissolved in 5mL of ethanol, and the solution was added dropwise to the solution. After the addition, the mixture solution is stirred vigorously and heated for 30 minutes, and then the mixed solution is centrifuged at 3500rpm, washed with ethanol and water for a plurality of times and dried to obtain 3.2g of white powdery nano silicon oxide microspheres.
(2) Synthesis of 3-bromo-4-methyl-7-diethylaminocoumarin
1.15g of 4-methyl-7-diethylaminocoumarin, 41mg of azobisisobutyronitrile and 20mL of N, N-dimethylformamide are placed in a 100mL flask, 0.98g N-bromosuccinimide is added in batches, the mixture is heated and refluxed for 6 hours at 90 ℃, and a reaction product is separated by silica gel column chromatography to obtain 1.03g of yellow-green powder, namely 3-bromo-4-methyl-7-diethylaminocoumarin.
(3) Synthesis of aminocoumarin substituted nano silicon oxide microsphere
400mg of nano silica microspheres, 200mg of 3-bromo-4-methyl-7-diethylaminocoumarin, 14mg of tris (dibenzylideneacetone) dipalladium and 14mg of tri-tert-butylphosphine were weighed and placed in a 100mL two-neck flask for degassing, and then a mixed solution of 1.6g of dicyclohexylmethylamine and 20mL of freshly distilled dioxane was added, and the mixture was stirred under reflux at 90 ℃ for 48 hours under anhydrous and oxygen-free conditions. After the reaction, the solution was centrifuged at 3500rpm, washed with tetrahydrofuran and ethanol several times, and dried to obtain 370mg of target product 1 as pale yellow powder.
And performing infrared spectrum characterization on the obtained nano silicon oxide microspheres and the target product 1, as shown in figures 1-2. By contrast, the obvious characteristic peaks of benzene rings of 1670-2000 nm and 600-900nm, the obvious characteristic peaks of ester groups of 1735nm and 1100nm and the like appear in FIG. 2, which proves that the aminocoumarin is successfully coupled to the nano silica microspheres.
And (3) carrying out fluorescence performance test on the target product 1, wherein when the fluorescent nano material is excited by 365nm ultraviolet light, the material can emit cyan fluorescence, and an emission peak is positioned at 470 nm.
Example 2:
the same as example 1, except that:
in the step (1), the mass ratio of TEOS to VTEOS is 1:2, namely 12mmol TEOS and 24mmol VTEOS, and the obtained nano silica microspheres and 3-bromo-4-methyl-7-diethylamino coumarin are reacted under the same reaction conditions to obtain a product 2.
Example 3:
the same as example 1, except that:
in the step (1), the mass ratio of TEOS to VTEOS is 2:1, namely 24mmol TEOS and 12mmol VTEOS, the rest reaction conditions are the same, and the obtained nano silicon oxide microspheres react with 3-bromo-4-methyl-7-diethylamino coumarin to obtain a product 3.
Example 4:
a thin sensing layer based on product 1 was prepared on filter paper by solid phase transfer technique. The preparation method comprises the following steps: cutting common filter paper in a laboratory into strips, adjusting the size according to needs, dispersing the aminocoumarin-substituted nano silicon oxide microspheres into ethanol, wherein the dispersion concentration is 3mg/mL, dropwise and slowly dropping the dispersion into distilled water after ultrasonic oscillation, forming a nano microsphere thin layer on the surface of the solution, pulling the strip-shaped filter paper out of the ethanol-water dispersion at a fixed angle, uniformly covering the nano microsphere thin layer on the surface of the filter paper, and naturally volatilizing to dry to form the sensing test paper.
The change of the fluorescence spectrum property of the sensing test paper can be tested by an ultraviolet-visible fluorescence spectrometer. Four representative types of aqueous organic amine solutions were prepared: n-propylamine, diethylamine, triethylamine and aniline at concentrations of 0.5mmol/L (about 50ppm) were used, and the results are shown in Table 1. When the sensing performance is tested, the prepared organic amine aqueous solution is sequentially dripped on sensing test paper, then the test paper is quickly put into a quartz cuvette, and the change of the fluorescence intensity and the color of the test paper is measured by using an ultraviolet-visible fluorescence spectrometer. As shown in FIGS. 3-6, the fluorescence emission peak at 465nm shows the phenomena of 73% enhancement, 29% enhancement, 20% attenuation, 24nm blue shift and 70% attenuation within 5 minutes, which fully shows that the material has good selectivity and rapid detection speed for various organic amines in water.
Comparative example 1:
a thin sensing layer based on the product 2 obtained in example 2 was prepared on a quartz plate substrate by a solid phase transfer technique similar to that of example 4, the dispersion concentration of the microspheres in ethanol was 3mg/mL, the microspheres were dropped into distilled water to obtain a thin layer of nanoparticles, the surface of the thin layer was covered by pulling up the quartz plate, and the thin layer was dried. When the sensing performance is tested, four types of organic amine aqueous solutions are taken: n-propylamine, diethylamine, triethylamine and aniline, the concentrations of which are all 0.5mmol/L (about 50ppm), are put into a quartz cuvette and then padded with absorbent cotton, the prepared organic amine aqueous solution is sequentially dripped on a sensing test paper, then the test paper is quickly put into the quartz cuvette, and the fluorescence intensity and the color change of the test paper are measured by using an ultraviolet-visible fluorescence spectrometer.
Comparative example 2:
a thin sensing layer based on the product 3 obtained in example 3 was prepared on a quartz plate substrate by a solid phase transfer technique similar to that of example 4, the dispersion concentration of the microspheres in ethanol was 3mg/mL, the microspheres were dropped into distilled water to obtain a thin layer of nanoparticles, the surface of the thin layer was covered by pulling up the quartz plate, and the thin layer was dried. When the sensing performance is tested, four types of organic amine aqueous solutions are taken: n-propylamine, diethylamine, triethylamine and aniline, the concentrations of which are all 0.5mmol/L (about 50ppm), are put into a quartz cuvette and then padded with absorbent cotton, the prepared organic amine aqueous solution is sequentially dripped on a sensing test paper, then the test paper is quickly put into the quartz cuvette, and the fluorescence intensity and the color change of the test paper are measured by using an ultraviolet-visible fluorescence spectrometer.
The results of comparing the three sets of experimental data of example 4, comparative example 1 and comparative example 2 are shown in table 1, and table 1 is a table for comparing the sensing performance of the three products of example 4, comparative example 1 and comparative example 2 to the four organic amine aqueous solutions. By comparison of data, the relationship between the ratio of TEOS to VTEOS and the sensing performance is substantially in a preferred distribution. The sensing performance is optimal when the ratio of the two is 1: 1.
TABLE 1
Example 5:
a thin sensing layer based on product 1 was prepared on filter paper by solid phase transfer technique. The preparation method comprises the following steps: cutting common filter paper in a laboratory into strips, adjusting the size according to needs, dispersing the aminocoumarin-substituted nano silicon oxide microspheres into ethanol, wherein the dispersion concentration is 3mg/mL, dropwise and slowly dropping the dispersion into distilled water after ultrasonic oscillation, forming a nano microsphere thin layer on the surface of the solution, pulling the strip-shaped filter paper out of the ethanol-water dispersion at a fixed angle, uniformly covering the nano microsphere thin layer on the surface of the filter paper, and naturally volatilizing to dry to form the sensing test paper.
The change in fluorescence intensity and color of the sensing strip can be observed by the naked eye. Four representative types of aqueous organic amine solutions were prepared: n-propylamine, diethylamine, triethylamine and aniline at a concentration of 0.5mmol/L (about 50 ppm). When the sensing performance is tested, the prepared organic amine aqueous solution is sequentially dripped on sensing test paper, then an ultraviolet light source with the wavelength of 365nm is used for irradiation, and the fluorescence intensity and the color change of the test paper are observed by naked eyes. As shown in FIG. 7, the sensing test paper can generate obvious fluorescence intensity change or fluorescence color change within 2 minutes, which fully shows that the material has good selectivity and rapid detection speed for various organic amines in water bodies, and is suitable for water quality field detection and rapid emergency detection of emergencies and other occasions of various water bodies.
Example 6:
the same as example 1, except that:
in the step (1), the quantity ratio of tetraethoxysilane to ammonia substances contained in ammonia water is 1:7, in the step (2), the mass of azobisisobutyronitrile is 5% of that of 4-methyl-7-diethylamino coumarin, and the heating reflux is carried out for 8 hours at the temperature of 85 ℃;
in the step (3), the mass ratio of the nano silicon oxide microspheres to the 3-bromo-4-methyl-7-diethylaminocoumarin is 1:1, the mixture is refluxed and stirred for 48 hours at 90 ℃ under anhydrous and oxygen-free conditions, the adding amount of tris (dibenzylideneacetone) dipalladium is 6% of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, the adding amount of tri-tert-butylphosphine is 6% of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, and the adding amount of dicyclohexylmethylamine is 7 times of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin.
Example 7:
in the step (1), the quantity ratio of tetraethoxysilane to ammonia substances contained in ammonia water is 1:10, in the step (2), the mass of azobisisobutyronitrile is 5% of that of 4-methyl-7-diethylamino coumarin, and the heating reflux is carried out for 12 hours at the temperature of 95 ℃;
in the step (3), the mass ratio of the nano silicon oxide microspheres to the 3-bromo-4-methyl-7-diethylaminocoumarin is 1:1, the mixture is refluxed and stirred for 72 hours at 90 ℃ under anhydrous and oxygen-free conditions, the adding amount of tris (dibenzylideneacetone) dipalladium is 10% of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, the adding amount of tri-tert-butylphosphine is 10% of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, and the adding amount of dicyclohexylmethylamine is 10 times of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be regarded as being equivalent to the replacement of the above embodiments, and are included in the scope of the present invention.
Claims (5)
1. A fluorescent nano-material for detecting various organic amines in water body, which has a structure shown as formula I:
wherein:
the central Silica core is a nano Silica microsphere with the particle size of 200-300 nm.
2. The method for preparing the fluorescent nano-material for detecting multiple types of organic amines in water bodies according to claim 1, which is characterized by comprising the following steps:
(1) adding an ethanol solution of tetraethoxysilane into a mixed solution of ammonia water, distilled water and ethanol, stirring for 5-10 minutes at 35-40 ℃, dropwise adding the ethanol solution of vinyl triethoxysilane into the solution, continuing stirring and heating for 20-30 minutes after the ethanol solution of vinyl triethoxysilane is dropwise added, centrifuging the stirred and heated mixed solution, washing, and drying to obtain white powdery nano silicon oxide microspheres; wherein the mass ratio of tetraethoxysilane to vinyltriethoxysilane is 1:2-2:1, and the mass ratio of tetraethoxysilane to ammonia contained in ammonia water is 1: 7-10;
(2) taking 4-methyl-7-diethylaminocoumarin and N-bromosuccinimide in a mass ratio of 1:1, adding the 4-methyl-7-diethylaminocoumarin and the N-bromosuccinimide into N, N-dimethylformamide, adding azobisisobutyronitrile of which the mass is 3-5% of that of the 4-methyl-7-diethylaminocoumarin, heating and refluxing the mixture at 85-95 ℃ for 6-12 hours, and separating the obtained reaction product by column chromatography to obtain 3-bromo-4-methyl-7-diethylaminocoumarin;
(3) under the inert gas atmosphere, adding nano silicon oxide microspheres and 3-bromo-4-methyl-7-diethylaminocoumarin into dried 1, 4-dioxane in a mass ratio of 2:1-1:1, then sequentially adding tri-tert-butylphosphine and dicyclohexylmethylamine into the dried 1, 4-dioxane, refluxing and stirring the mixture at 90 ℃ for 48 to 72 hours under anhydrous and oxygen-free conditions, wherein the adding amount of the tri-tert-butylphosphine is 7 percent of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, and the adding amount of the dicyclohexylmethylamine is 8 times of the mass of the 3-bromo-4-methyl-7-diethylaminocoumarin, and after the reaction is finished, centrifuging, washing and drying the solution to obtain a light yellow powdery target product, namely the aminocoumarin substituted nano silicon oxide microsphere.
3. The use of the fluorescent nanomaterial for detecting multiple classes of organic amines in a water body according to claim 1, wherein the fluorescent nanomaterial is used for preparing a sensing thin layer device or sensing test paper of a quartz plate substrate to detect various organic amine molecules in an aqueous phase according to the change of stimulated emission fluorescence.
4. The use of the fluorescent nanomaterial for detecting multiple classes of organic amines in a water body according to claim 3, wherein the preparation method of the sensing thin-layer device comprises the following steps: dispersing the fluorescent nano material in ethanol, wherein the dispersion concentration is 2.5-3.5mg/mL, slowly dropping the dispersion liquid into distilled water dropwise after ultrasonic oscillation, forming a nano microsphere thin layer on the surface of the solution, lifting the quartz plate substrate out of the liquid level from the ethanol-water dispersion liquid at a fixed angle, uniformly covering the nano microsphere thin layer on the surface of the quartz plate to form a sensing thin layer, and putting the sensing thin layer into a vacuum drying oven to dry the residual liquid.
5. The use of the fluorescent nanomaterial for detecting multiple classes of organic amines in a water body according to claim 3, wherein the preparation method of the sensing test paper comprises the following steps: cutting common filter paper in a laboratory into strips, dispersing fluorescent nano materials into ethanol, wherein the dispersion concentration is 2.5-3.5mg/mL, dropwise and slowly dropping the dispersion into distilled water after ultrasonic oscillation, forming a nano microsphere thin layer on the surface of the solution, pulling the strip-shaped filter paper out of the ethanol-water dispersion at a fixed angle, uniformly covering the nano microsphere thin layer on the surface of the filter paper, and naturally drying the filter paper to prepare the sensing test paper.
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