CN112110913A - Preparation and application of novel fluorescent probe and test paper for hydrazine hydrate detection - Google Patents
Preparation and application of novel fluorescent probe and test paper for hydrazine hydrate detection Download PDFInfo
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Abstract
The invention relates to a novel fluorescent probe for hydrazine hydrate detection and preparation and application of test paper, and belongs to the technical field of analytical chemistry. The fluorescence probe takes benzothiazole mother nucleus as a parent body and acetyl as a recognition site, and the chemical structure of the fluorescence probe is shown as a formula (I). When the fluorescent probe acts with hydrazine hydrate, acetyl of the fluorescent probe is hydrolyzed into hydroxyl in PBS-CH3CN (10 mM,3:7, v/v, pH = 7.4) buffer solution generates fluorescent substance with high fluorescence emission capability, the fluorescence changes from blue to green, and the ratiometric detection of hydrazine hydrate is realized. In addition, the fluorescent probe only responds to hydrazine hydrate, does not respond to small molecules such as methylamine, ethylamine, ethylenediamine, butylamine, dodecylamine, n-hexylamine, octadecylamine, aniline, Cys, GSH and the like, and can realize specific recognition of hydrazine hydrate. In addition, the fluorescent probe can be used for quickly detecting hydrazine hydrate in the environment, and has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of analytical chemistry, relates to preparation and application of a novel fluorescent probe and test paper for hydrazine hydrate detection, and particularly relates to application of the fluorescent molecular probe in hydrazine hydrate detection in systems such as environment.
Background
Hydrazine hydrate (N)2H4•H2O), also called hydrazine hydrate, is a colorless, transparent, moisture-absorbing, alkaline, oily liquid. Hydrazine hydrate has strong reducibility and is widely applied in the fields of pesticides, medicines and fine chemicals. In addition, it can also be used as a chemical blowing agent in heating systemsAnd a slow release agent used as a high energy fuel and explosive material in rocket propulsion systems. Meanwhile, hydrazine hydrate is extremely toxic, and has non-negligible harm to the environment and human body. If it has good water solubility, it is easy to be absorbed by human body, and after it enters human body through respiration, diet or skin contact, it can produce serious damage to lung, kidney, liver and nervous system, even can result in gene mutation and cancer. The U.S. Environmental Protection Agency (EPA) currently has a maximum allowable value of 10 ppb. Therefore, it is urgently required to develop a hydrazine hydrate detection method with high sensitivity, high selectivity and high safety so as to realize specific detection of hydrazine hydrate under the environment closely related to human beings, which is very important and meaningful.
Heretofore, various methods have been available for the detection of hydrazine hydrate, including chromatography-mass spectrometry, electrochemical analysis, spectrophotometry, and the like. However, the traditional analysis methods have many disadvantages, such as tedious sample processing and operation process, need of expensive instruments, difficulty in online real-time detection and the like, difficulty in achieving low cost, simple operation and rapid detection, and difficulty in meeting the market demand for rapid detection of hydrazine hydrate. Fluorescent molecular probes have become a research hotspot due to the characteristics of high sensitivity, high selectivity, low cost, simple operation and the like, and have been used for detecting hydrazine hydrate in different contents. However, these reported fluorescent probes have several limitations, including: 1. the probe types are few, the turn-on type is taken as the main type, the influence of the detection environment is large, and the detection accuracy is low; 2. the response speed is slow, and most probes need tens of minutes or even several hours to complete the corresponding reaction after the hydrazine hydrate is added, so that the rapid detection market demand cannot be met. Therefore, there is an urgent need to develop a hydrazine hydrate probe which can be rapidly and sensitively used and can be widely applied to environmental detection.
Disclosure of Invention
Aiming at the defects of the existing fluorescent probe for detecting hydrazine hydrate, the invention aims to provide a fluorescent molecular probe capable of realizing the rapid detection of hydrazine hydrate.
The second purpose of the invention is to provide a method for preparing the fluorescent molecular probe, which is simple to operate and has easily available raw materials.
The third purpose of the invention is to provide a fluorescent test paper for rapidly detecting hydrazine hydrate and application thereof.
The fourth purpose of the invention is to provide a method for preparing the fluorescent test paper for rapidly detecting hydrazine hydrate, which is simple to operate and mild in conditions.
In order to achieve the technical purpose, the invention provides a fluorescent probe, which has a structure shown in formula I:
formula I
1. The preparation method of the fluorescent probe is preferably as follows:
using 2, 4-dihydroxy benzaldehyde as raw material, and reacting with diethyl malonate at 90%oAnd C, refluxing the ethanol solution, cooling to room temperature after the reaction is finished, dropwise adding the mixture into ice water, filtering the precipitate, washing the precipitate with absolute ethyl alcohol, and drying to obtain a yellow solid. Dissolving the solid in trifluoroacetic acid, adding hexamethyl-hydroxylamine, stirring, heating to 90 deg.CoC, refluxing. After the reaction is finished, cooling to room temperature, dropwise adding into ice water, adjusting the pH value of the system to be neutral, filtering and washing the precipitate, and separating and purifying by silica gel column chromatography. Dissolving the purified product in absolute ethyl alcohol, adding 2-aminothiophenol, stirring at room temperature until the reaction is complete, pouring into ice water, filtering and washing the precipitate, and separating and purifying by silica gel column chromatography. The purified product was dissolved in dichloromethane at 0 oSlowly adding dichloromethane solution containing acetyl chloride under C to change the color of the system solution from yellow to colorless, and respectively adding water and saturated NaHCO after the reaction is completed3Extracting the solution and saturated saline solution, combining organic layers, drying by anhydrous magnesium sulfate, concentrating, and finally drying to obtain a yellow solid product.
The synthesis of the invention is as follows:
the invention provides application of the fluorescent probe, which can be applied to detection of hydrazine hydrate. The detection principle of the probe is as follows: by utilizing an excited-state intramolecular proton transfer (ESIPT) mechanism and utilizing ester groups to hinder ESIPT action of the probe, the probe only generates enol-type emission, and after hydrazine hydrate is added, the ESIPT action of the probe is recovered, so that the probe recovers keto-type emission, and finally the ratiometric detection of the hydrazine hydrate is realized. The detection mechanism is shown as the following formula:
the invention provides a method for determining hydrazine hydrate by using the fluorescent probe. The determination method comprises the following steps: under the condition of room temperature, the fluorescent probe is dissolved in a solution prepared by acetonitrile, dichloromethane or dimethyl sulfoxide and water according to a certain proportion, and the concentration of the fluorescent probe is configured to be 10 mu M-40 mu M. Adding hydrazine hydrate aqueous solutions with different concentrations into a probe system, measuring the fluorescence intensity of the solution, and realizing the quantitative detection of the hydrazine hydrate through the linear relation between the fluorescence intensity and the hydrazine hydrate concentration.
In the above detection method, the solvent system is preferably PBS-CH3CN= 3:7 (v/v)。
Preferably, the pH of the detection method is 7.4.
In the above detection method, the concentration of the fluorescent probe is preferably 10. mu.M.
The invention also provides fluorescent test paper capable of realizing rapid detection of hydrazine hydrate, which is characterized in that: the fluorescent test paper is a rectangular white filter paper sheet, the length, the width and the thickness are 100-70 mm, 5-15 mm, 0.5-1 mm, and the content of a fluorescent probe loaded on each piece of fluorescent test paper is not less than 0.01 mg.
The preferable size of the fluorescent test paper for realizing the rapid detection of hydrazine hydrate is 80 mm multiplied by 15 mm multiplied by 0.5 mm.
The preparation method of the fluorescent test paper capable of realizing the rapid detection of hydrazine hydrate, provided by the invention, preferably comprises the following steps:
(1) with PBS-CH3CN (10 mM,3:7, v/v, pH = 7.4) buffer solution is used as a solvent to prepare a fluorescent probe solution with the solubility of 1 mM;
(2) soaking the cut white square filter paper with the length, width and thickness of 70-100 mm, 5-15 mm, 0.5-1 mm in the solution prepared in the step (1), taking out after 10 minutes, and airing at room temperature;
(3) the fluorescent test paper which is white under sunlight and shows blue fluorescence under an ultraviolet lamp can be obtained.
The fluorescent test paper capable of realizing the rapid detection of hydrazine hydrate, disclosed by the invention, has the specific application in detecting the hydrazine hydrate in water as follows: and dripping the hydrazine hydrate solution on the surface of the fluorescent test paper, then placing the fluorescent test paper under a 365 nm ultraviolet lamp to observe whether the fluorescence changes from blue to green, and judging whether the fluorescent test paper can realize qualitative detection on the hydrazine hydrate solution according to the change of the fluorescence.
The fluorescent test paper capable of realizing the rapid detection of hydrazine hydrate, disclosed by the invention, has the specific application in detecting hydrazine hydrate in air as follows: and placing the fluorescent test paper in an ampoule bottle, vacuumizing, injecting hydrazine hydrate by using an injector, then placing the ampoule bottle under a 365 nm ultraviolet lamp to observe whether the fluorescence changes from blue to green, and judging whether the fluorescent test paper can realize qualitative detection of the hydrazine hydrate according to the change of the fluorescence.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
(1) the fluorescent probe has the advantage of good selectivity, and methylamine, ethylamine, ethylenediamine, butylamine, dodecylamine, n-hexylamine, octadecylamine, aniline, Cys, GSH and the like do not interfere with detection of hydrazine hydrate.
(2) The fluorescent probe has the advantage of high sensitivity, the fluorescence intensity of the probe solution and the concentration of hydrazine hydrate have a good linear relationship in the range of 0-25 mu M, the quantitative detection characteristic is shown, the detection limit is as low as 0.29 mu M, and the detection requirement of the content of hydrazine hydrate in the environment can be completely met.
(3) The preparation method of the fluorescent probe and the detection test paper provided by the invention is simple, low in cost, quick in response (150 s), free of complex instruments, and beneficial to large-scale production, so that the fluorescent probe and the detection test paper are suitable for popularization and application.
Drawings
FIG. 1 shows fluorescent probes prepared in the practice of the present invention1H NMR spectrum;
FIG. 2 is a graph showing the change of fluorescence emission spectrum between the fluorescence intensity of the fluorescent probe and the concentration of hydrazine hydrate in the practice of the present invention, wherein the abscissa is the concentration of hydrazine hydrate and the ordinate is the fluorescence intensity;
FIG. 3 is a graph showing a linear relationship between the fluorescence intensity of the fluorescent probe and the concentration of hydrazine hydrate in the practice of the present invention, wherein the abscissa is the concentration of hydrazine hydrate and the ordinate is the fluorescence intensity;
FIG. 4 is a time response graph of a fluorescent probe to hydrazine hydrate in the practice of the present invention;
FIG. 5 is a graph showing the selectivity of fluorescent probes for hydrazine hydrate in the practice of the present invention;
FIG. 6 is a photograph showing real-time monitoring of liquid hydrazine hydrate with different concentrations by using fluorescent test paper in the practice of the present invention;
FIG. 7 is a photograph showing real-time monitoring of gaseous hydrazine hydrate with different concentrations by using fluorescent test paper in the practice of the present invention;
Detailed Description
The following embodiments are intended to further illustrate the present invention and are not intended to limit the present invention.
Example 1
Synthesis and structural characterization of compound 2 (ethyl 7-hydroxy-2-oxo-2H-chromene-3-carboxylate)
2, 4-dihydroxybenzaldehyde (2.76 g, 20 mmol) was dissolved in 10 mL of anhydrous ethanol at room temperature, diethyl malonate (6.40 g, 40 mmol) and 20 mmol of piperidine were added, and the temperature was raised to 90%oReflux was heated under C and the reaction was monitored by TLC until complete. After the reaction was cooled down, the absolute ethanol was removed by rotary evaporation, and the remaining liquid was dropped into water dropwise, whereby a large amount of yellow solid was precipitated. The filter cake was filtered and washed and dried to give 3.76 g of a yellow solid product in 80.5% yield.1H NMR (400 MHz, DMSO-d6): （ppm）= 11.08 (s, 1H), 8.87 (s, 1H), 7.75 (d, J = 8.8 Hz, 1H), 6.84 (dd, J 1 = 8.8 Hz, J 2 = 2.4 Hz, 1H), 6.72 (d, J = 2.4 Hz, 1H), 4.26 (q, J= 7.2 Hz, 2H), 1.30 (t, J = 7.2 Hz, 3H)。
Synthesis and structural characterization of Compound 3 (ethyl 8-formyl-7-hydroxy-2-oxo-2H-chromene-3-carboxylate)
Compound 2 (3.51 g, 15 mmol) was dissolved in 10 mL of trifluoroacetic acid at room temperature, and hexamethyl-triamine (8.40 g, 60 mmol), 90oReflux was heated under C and monitored by TLC until the reaction. The reaction was taken down and left to cool, dropwise added into 500 mL of ice water, the pH was adjusted to near neutrality with 1N NaOH solution, a precipitate was found to precipitate out, the filter cake was filtered and washed, dried and separated and purified by silica gel column chromatography to obtain 585 mg of a yellow product with a yield of 15.2%.1H NMR (400 MHz, CDCl3): （ppm）12.51 (s, 1H), 10.61 (d, J = 0.4 Hz, 1H), 8.53 (s, 1H), 7.73 (d, J = 8.8 Hz, 1H), 6.96 (dd, J 1 = 8.8 Hz, J 2 = 0.4 Hz, 1H), 4.43 (q, J = 7.2 Hz, 2H), 1.43 (t, J = 7.2 Hz, 3H). 13C NMR (100 MHz, CDCl3): （ppm）193.0, 167.8, 162.9, 158.5, 155.3, 148.8, 137.6, 115.7, 114.7, 110.2, 108.5, 62.2, 14.4. HRMS (ESI): m/z [M+H]+ calcd. for C13H11O6: 263.0550; found: 263.0548.
Synthesis and structural characterization of compound 4 (ethyl 8- (benzol-2-yl) -7-hydroxy-2-oxo-2H-chromene-3-carboxylate)
Compound 3 (544 mg, 2 mmol) was dissolved in 10 mL of anhydrous ethanol at room temperature, followed by addition of 2-aminothiophenol (300 mg, 2.4 mmol), 37% HCl (1 mmol) and 30% H2O2(1.2 mmol), and stirred at room temperature. The reaction was monitored by TLC until completion, the reaction system was poured into 200 mL of water, collected by suction filtration and washed to obtain a filter cake, which was vacuum-dried and then subjected to silica gel column chromatography (petroleum ether: ethyl acetate =1: 1) to obtain 556 mg of a yellow product with a yield of 81.3%.1H NMR (400 MHz, CDCl3): （ppm）8.57 (s, 1H), 8.08-7.98 (m, 2H), 7.58 (t, J = 8.8 Hz, 2H), 7.49 (t, J = 7.5 Hz, 1H), 7.10 (d, J = 8.7 Hz, 1H), 4.43 (q, J = 7.1 Hz, 2H), 1.43 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, CDCl3): （ppm）165.6, 163.4, 162.9, 155.7, 154.8, 149.6, 148.8, 133.8, 132.8, 127.1, 126.1, 121.9, 121.8, 116.1, 113.0, 110.1, 105.7, 62.0, 14.4. HRMS (ESI): m/z [M+H]+ calcd. for C19H14NO5S: 368.0587; found: 368.0588.
Synthesis and structural characterization of compound 5 (ethyl 7-acetoxy-8- (benzod) thiazole-2-yl) -2-oxo-2H-chromene-3-carboxylate)
Adding compound 4 (347 mg, 1 mmol) into 25 mL round-bottom flask, dissolving in 10 mL dichloromethane to obtain system A, adding acetyl chloride (90 mg, 1 mmol) into 10 mL dichloromethane to obtain system B, 0 oAnd C, adding 1 mmol of triethylamine into the system A, and slowly adding the system B. 0 oStirring at C, changing the color of the solution of the system from yellow to colorless, and monitoring the reaction by TLC until the reaction is complete. Respectively using water and saturated NaHCO3The solution and saturated saline were extracted, and the organic layers were combined, dried over anhydrous magnesium sulfate, and rotary evaporated to remove the solvent, whereby 225 mg of the target fluorescent probe was obtained with a yield of 55.5%.1H NMR (500 MHz, DMSO-d6): （ppm） 8.04 (d, 1H), 7.96 (d, 1H), 7.91 (s, 1H), 7.72 (s, 1H), 7.56 (m, 1H), 7.46(t, 1H), 7.28 (s, 1H), 4.25 (q, 2H), 2.57 (s, 3H), 1.29 (t, 3H). HRMS (ESI): m/z [M+H]+ calcd. for C21H16NO6S: 410.0699; found: 410.0721.
Example 2
Preparation of fluorescent probe mother liquor
The product isolated above and having a purity of 99% was accurately weighed at 4.10 mg and carefully transferred into a 50 mL volumetric flask, to which CH was added at room temperature3CN, fully shaking up to completely dissolve the probe, and finally fixing the volume to a scale mark to obtain 1 mM probe mother liquor. During the test, each time using a microThe sample measuring device measures 20 μ L of the above solution, dissolves it in the test system, and ensures that the total volume of each test is 2 mL, at which time the concentration of the fluorescent probe in the test system is 10 μ M.
Example 3
Preparation of hydrazine hydrate mother liquor
Hydrazine hydrate was prepared in 5 mL stock solutions in different concentration gradients (0.1 mM, 0.2 mM, 0.4 mM, 0.7 mM, 1 mM, 1.5 mM, 2.0 mM, 2.5 mM, 3.0 mM, 3.5 mM, 4.0 mM) in PBS buffer. The rest of the tests required the use of small molecules and inorganic salts were separately prepared in PBS buffer solution to a 3 mM concentration of stock solution.
Example 4
Change of fluorescence intensity of fluorescent probe and concentration of hydrazine hydrate
50. mu.L of a 1 mM concentration probe stock solution was dissolved in a mixed solution of 1450. mu.L and 3450. mu.L each of a PBS buffer solution and an acetonitrile solution, and then 50. mu.L of different concentrations of hydrazine hydrate stock solutions were transferred to the system so that the concentration of the probe in the entire detection system was 10. mu.M and the concentrations of hydrazine hydrate were 1. mu.M, 2. mu.M, 4. mu.M, 7. mu.M, 10. mu.M, 15. mu.M, 20. mu.M, 25. mu.M, 30. mu.M, 35. mu.M, and 40. mu.M, respectively. After incubation for 20 min at room temperature with sufficient response, the fluorescence spectra of the different systems were tested in 10 mm cuvettes. The fluorescence emission spectrum change is shown in figure 2. The result shows that the fluorescence emission intensity of the system at 448 nm gradually decreases with the increase of the concentration of hydrazine hydrate, a new fluorescence emission peak is generated at 516 nm, and the fluorescence intensity gradually increases with the increase of the concentration of hydrazine hydrate.
Example 5
Linear relationship between fluorescence intensity of fluorescent probe and concentration of hydrazine hydrate
The fluorescence intensity in each system in example 4 was calculated to establish a standard curve of fluorescence intensity versus hydrazine hydrate concentration, which is shown in FIG. 3, and the results show that when the hydrazine hydrate concentration is in the range of 0-25. mu.M, I is measured516 nm/I448 nmHas good linear relation with the concentration of hydrazine hydrate, and the regression linear equation is y =0.2022x +0.2018, and the linear correlation coefficient R2= 0.9983. By means of a formula meterAccording to calculation, the detection limit of the response of the probe to the hydrazine hydrate is 0.29 mu M, which shows that the response of the fluorescent probe to the hydrazine hydrate has good sensitivity.
Example 6
Kinetic study of fluorescent probes on response to hydrazine hydrate at different concentrations
Hydrazine hydrate was added to the detection system containing 10. mu.M of the probe at a low concentration (4. mu.M) and at a high concentration (25. mu.M), respectively, and the change with time of the fluorescence intensity at 516 nm of the system was measured, and the results are shown in FIG. 4. The result shows that the fluorescent probe can complete the response to the hydrazine hydrate with high concentration within 150 seconds.
Example 7
Selectivity of fluorescent probes for different substances
Dissolving 50 μ L of 1 mM fluorescence probe mother liquor in 1450 μ L and 3450 μ L mixed solution of PBS buffer solution and acetonitrile solution, respectively, and transferring 50 μ L of 3 mM methylamine, ethylamine, ethylenediamine, butylamine, dodecylamine, n-hexylamine, octadecylamine, aniline, Cys, GSH, and CuCl2、ZnCl2Respectively adding NaCl mother liquor and KBr mother liquor into a detection system, incubating for 20 min at room temperature for full response, testing fluorescence spectra of different systems, recording fluorescence intensity at 516 nm and 448 nm, and calculating I516 nm/I448 nmThe value of (c). The result is shown in figure 5, and the fluorescent probe is found to have obvious fluorescence enhancement on hydrazine hydrate and only have weak fluorescence change on other tested small molecules. Indicating that the fluorescent probe has good selectivity to hydrazine hydrate.
Example 8
Preparation of fluorescent test paper for quick detection of hydrazine hydrate
(1) With PBS-CH3CN (10 mM,3:7, v/v, pH = 7.4) buffer solution is used as a solvent to prepare a fluorescent probe solution with the solubility of 1 mM;
(2) soaking the cut white square filter paper with the length, width and thickness of 70-100 mm, 5-15 mm, 0.5-1 mm in the solution prepared in the step (1), taking out after 10 minutes, and airing at room temperature;
(3) the fluorescent test paper which is white under sunlight and shows blue fluorescence under an ultraviolet lamp can be obtained.
Example 9
Detection of liquid hydrazine hydrate by fluorescent test paper
For detection, probe solutions were prepared at a final concentration of 20. mu.M, and hydrazine hydrate solutions at final concentrations of 15. mu.M, 30. mu.M, 60. mu.M, and 80. mu.M, respectively. The test paper is immersed in the probe solution for a few seconds to enable the test paper to be uniformly adsorbed, and then the test paper is placed at 40oAnd C, drying the mixture in an environment. Then the probe test paper is respectively immersed in hydrazine hydrate solutions with different concentrations, and the dried probe test paper is placed under a 365 nm ultraviolet lamp, and the result is shown in figure 6. The test paper can be seen to have obvious blue-green fluorescence, and the fluorescence intensity generated by the test paper is obviously increased along with the increase of the concentration of hydrazine hydrate. The test paper can realize the rapid qualitative detection of the liquid hydrazine hydrate.
Example 10
Detection of gaseous hydrazine hydrate by fluorescent test paper
In the detection, the test paper loaded with 20 μ M probe is placed in an ampoule bottle, after vacuum pumping, gaseous hydrazine hydrate with different concentrations is injected by an injector, the final concentrations of the hydrazine hydrate are respectively 10 μ M, 45 μ M, 60 μ M and 70 μ M, and the ampoule bottle is placed under a 365 nm ultraviolet lamp, and the result is shown in figure 7. The test paper can be seen to have obvious blue-green fluorescence, and the fluorescence intensity generated by the test paper is obviously increased along with the increase of the concentration of the gaseous hydrazine hydrate. The test paper can realize the rapid qualitative detection of the gaseous hydrazine hydrate.
Although the present invention has been described with reference to the specific embodiments shown in the drawings, it is not intended to limit the scope of the present invention, and various modifications or variations can be made by those skilled in the art from the disclosure of the present invention without inventive efforts.
Claims (9)
1. A novel fluorescent probe for detecting hydrazine hydrate, which is characterized by having a structure shown in formula (I):
formula I.
2. The method for preparing a novel fluorescent probe for detecting gaseous hydrazine hydrate according to claim 1, wherein the method comprises the following steps: using 2, 4-dihydroxy benzaldehyde as raw material, and reacting with diethyl malonate at 90%oC, refluxing the ethanol solution, cooling to room temperature after the reaction is finished, dropwise adding the mixture into ice water, filtering the precipitate, washing the precipitate with absolute ethyl alcohol, and drying to obtain a yellow solid;
dissolving the yellow solid in trifluoroacetic acid, adding hexamethyl-hydroxylamine, stirring, and heating to 90 deg.CoC, refluxing, cooling to room temperature after the reaction is finished, dropwise adding into ice water, adjusting the pH value of the system to be neutral, filtering and washing the precipitate, and separating and purifying by silica gel column chromatography;
dissolving the purified product in absolute ethyl alcohol, adding 2-aminothiophenol, stirring at room temperature until the reaction is complete, pouring into ice water, filtering and washing the precipitate, and separating and purifying by silica gel column chromatography;
the purified product was dissolved in dichloromethane at 0 oCThen slowly adding dichloromethane solution containing acetyl chloride, changing the color of the solution of the system from yellow to colorless, after the reaction is completed, respectively using water and saturated NaHCO3Extracting the solution and saturated saline solution, combining organic layers, drying by anhydrous magnesium sulfate, concentrating, and finally drying to obtain a yellow solid product.
3. Use of the fluorescent probe according to claims 1 and 2 for the detection of hydrazine hydrate and for the quantitative fluorescent analysis.
4. Use of a fluorescent probe according to any of claims 1 to 3, characterized in that the hydrazine hydrate is detected under the following conditions: excitation wavelength is 380 nm, fluorescence emission spectrum detection is carried out within the range of 400-700 nm, the pH of the detection system is 6.0-8.6, and the solvent of the detection system is PBS: CH3CN=3:7（v/v）。
5. The use according to claim 4, wherein the sample to be tested is added to a detection solution of a fluorescent probe, and the fluorescence intensity of the solution is determined as an evaluation index of the hydrazine hydrate and the hydrazine hydrate concentration.
6. A fluorescent test paper capable of rapidly detecting hydrazine hydrate, which is loaded by the fluorescent probe of claim 1 onto a test paper or a filter paper without the addition of a fluorescent whitening agent, and is characterized by comprising: the fluorescent test paper is rectangular, the length, the width and the thickness are 70-100 mm, 5-15 mm, 0.5-1 mm, and the content of the fluorescent probe loaded on each piece of fluorescent test paper is not less than 0.01 mg.
7. The method for preparing the fluorescent test paper for rapidly detecting hydrazine hydrate as claimed in claim 6, which comprises the following steps:
with PBS-CH3CN (10 mM,3:7, v/v, pH = 7.4) buffer solution is used as a solvent to prepare a fluorescent probe solution with the solubility of 1 mM;
soaking the cut white square filter paper with the length, width and thickness of 70-100 mm, 5-15 mm, 0.5-1 mm in the solution prepared in the step (1), taking out after 10 minutes, and airing at room temperature;
the obtained fluorescent test paper for quickly detecting hydrazine hydrate is characterized by being white under sunlight and showing blue fluorescence under an ultraviolet lamp.
8. The use of the fluorescent test paper for the rapid detection of hydrazine hydrate according to claims 3-7, wherein: the method is used for analyzing and detecting hydrazine hydrate in systems such as environment.
9. The method for applying the fluorescent test paper for rapidly detecting hydrazine hydrate as claimed in claims 3 to 8, wherein the solution containing hydrazine hydrate or gaseous hydrazine hydrate is added to the surface of the fluorescent test paper for rapidly detecting hydrazine hydrate as claimed in claims 3 to 7, and the mixture is observed under an ultraviolet lamp of 365 nm after 1 to 3 minutes.
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| CN113861076A (en) * | 2021-10-27 | 2021-12-31 | 南京师范大学 | AIE type triphenylamine derivative fluorescent probe, preparation method thereof and application thereof in hydrazine hydrate detection |
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| CN113861076B (en) * | 2021-10-27 | 2023-08-08 | 南京师范大学 | AIE triphenylamine derivative fluorescent probe, preparation method thereof and application thereof in hydrazine hydrate detection |
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