CN111253307B - Mustard gas fluorescent probe, kit, detection test paper and preparation method of detection test paper - Google Patents
Mustard gas fluorescent probe, kit, detection test paper and preparation method of detection test paper Download PDFInfo
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Abstract
The invention discloses a fluorescent probe compound 6-AQF or 7-AQF for rapidly detecting mustard gas, a kit thereof, test paper and a preparation method thereof, and is characterized in that quinoline is used as a fluorescent chromophore, thioamide is used as a reaction site, 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -ketone or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -ketone and Lawson reagent are subjected to oxygen-sulfur exchange reaction to obtain 6-AQF or 7-AQF, the 6-AQF, potassium hydroxide and absolute ethyl alcohol form the kit, the concentration of the mustard gas in a solution can be detected by a fluorescence titration standard curve method, the response speed is high, and the detection limit is low; the test paper for detecting the mustard gas is obtained by soaking filter paper in a solution prepared by dissolving 6-AQF or 7-AQF, potassium hydroxide and polyethylene oxide in acetonitrile and then airing, can visually monitor the mustard gas in a gas phase, and has the advantages of low cost, high sensitivity, good selectivity and good application prospect.
Description
Technical Field
The invention belongs to the technical field of mustard gas detection, and particularly relates to a fluorescent probe compound for detecting mustard gas based on quinoline dye, a kit formed by the fluorescent probe compound, potassium hydroxide and absolute ethyl alcohol, and a preparation method of a mustard gas detection test paper.
Background
Mustard gas, a common name for bis (2-chloroethyl) sulfide, is a colorless to amber oil-like liquid with a garlic-like odor. Since the first world war used, the most widely used chemical warfare agents in many military conflicts have accumulated to result in millions of casualties. Mustard gas is known as the "king of poison gas" and the "first choice chemical weapon in modern tactical wars". Exposure to mustard gas often results in dose-dependent skin damage, even necrosis, eye injury and even permanent blindness, respiratory failure and even death, and in addition, mustard gas may be carcinogenic and mutagenic to humans due to chromosomal damage. Compared with other chemical warfare agents, the mustard gas is easy to prepare, has more various toxic forms and is more likely to be used by terrorists, and the threat to national safety exists for a long time. Therefore, the development of the convenient, rapid and accurate fluorescence probe for the mustard gas and the detection system thereof have important significance.
Currently, there are fewer methods for detecting mustard gas than nerve agents, typically conventional instrumental methods, require expensive instrumentation and complex procedures, are non-specific, and often generate false positives. Compared with the prior art, the colorimetric fluorescent probe method has the advantages of low consumption, convenience, simplicity in operation and the like, and attracts people's extensive attention. However, in published literature on mustard gas detection, such as analytical chemistry (analytical. chem.,2018,90, 1417-. Therefore, the mustard gas fluorescent probe with simple synthesis steps, high detection sensitivity and quick response is developed, and has important application value.
Disclosure of Invention
The invention provides a fluorescent probe compound 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione (hereinafter referred to as 6-AQF or 7-AQF) for rapidly detecting mustard gas, a kit, detection test paper and a preparation method thereof, aiming at the problems in the existing technology for detecting the mustard gas. In this study, the present invention selected 2-chloroethyl ethyl sulfide as a mustard gas substitute having similar chemical properties to mustard gas, which in the test is referred to as 2-chloroethyl ethyl sulfide, but without the associated toxicological properties.
The fluorescent probe compound for rapidly detecting mustard gas is characterized by being a compound 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione (6-AQF or 7-AQF) which takes quinoline as a fluorescent chromophore and thioamide as a reaction site of the mustard gas, and having the structure shown in the following formula:
the invention discloses a synthesis method of a fluorescent probe compound 6-AQF or 7-AQF for rapidly detecting mustard gas, which is characterized by adopting a one-step oxygen-sulfur exchange reaction of 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -ketone or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -ketone compound (hereinafter referred to as a compound A) and a Lawson reagent, adding the compound A and the Lawson reagent into toluene according to a molar ratio of 1: 1-2, stirring at 80-120 ℃ under the protection of nitrogen, monitoring by thin layer chromatography until no compound A remains, and purifying a reaction crude product by column chromatography to obtain the probe compound 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione or 7- (diethylamino) -4- (trifluoromethyl) thione ) Quinoline-2 (1H) -thione (6-AQF or 7-AQF); the synthetic route can be represented as:
in the formula, R1The radical being diethylamino, R2The radical being hydrogen, or R1The radical being hydrogen, R2The radical is diethylamino.
On the basis of the synthesis of the probe compound 6-AQF or 7-AQF, a kit can be composed of the probe compound 6-AQF or 7-AQF of the present invention and absolute ethanol in a mass ratio of the probe compound KOH to 3:4.5 or 3:8.4, respectively.
Furthermore, the test paper for rapidly detecting mustard gas is characterized in that polyethylene oxide is used as a load material, 6-AQF or 7-AQF is dissolved in acetonitrile to prepare a solution according to the mass ratio of a probe compound KOH to polyethylene oxide of 3:4.5:1000 or 3:8.4:1000, and filter paper is soaked in the solution and then dried to obtain the test paper for rapidly detecting mustard gas.
The probe compound 6-AQF or 7-AQF adopts thioamide as a reaction site, has simple and convenient synthesis method, can be prepared by only one-step reaction, and has mild reaction condition, simple operation and high yield.
The probe compound 6-AQF or 7-AQF of the invention has the characteristics of rapid response and fluorescence detection of mustard gas within 1 minute at 60 ℃ and 24 minutes at room temperature.
The probe compound 6-AQF or 7-AQF, potassium hydroxide and absolute ethyl alcohol form a kit, and when the kit is used for testing, an ethanol solution of 6-AQF or 7-AQF and potassium hydroxide is prepared, and the solution does not have fluorescence under 365nm ultraviolet light; after the mustard gas is added into the solution, the fluorescent color under the ultraviolet light is green, and the detection limit of the mustard gas in the solution is as low as 0.28 mu M; the lowest detection limit of the existing mustard gas fluorescent probe is generally more than 1 mu M; by measuring the fluorescence standard curve diagram of the concentrations of the ethanol solution of the 6-AQF or the 7-AQF and the potassium hydroxide and the mustard gas, the quantitative detection of the mustard gas in the trace concentration range of less than 10 mu M in the solution can be realized; soaking filter paper in a solution prepared by dissolving 6-AQF or 7-AQF, potassium hydroxide and polyethylene oxide in acetonitrile, and drying to obtain a test paper for detecting mustard gas by fluorescence, wherein in the atmosphere of mustard gas, the fluorescence of the test paper changes from colorless to green under 365nm ultraviolet light, and the change is less than 1 minute; the response time of the existing mustard gas fluorescent probe is generally between 1 and 30 minutes; the probe 6-AQF or 7-AQF and the test paper thereof of the present invention have these responses only to mustard gas, but do not have the above responses to other similar analytes and gases, which indicates that the 6-AQF or 7-AQF and the test paper thereof of the present invention have very good selectivity to mustard gas. Particularly, the detection limit of the detection test paper to naked eyes of mustard gas is as low as 0.2 ppm.
In conclusion, the preparation method of the fluorescent probe compound 6-AQF or 7-AQF for rapidly detecting mustard gas adopts quinoline as a fluorescent chromophore and thioamide as a reaction site, and performs oxygen-sulfur exchange reaction on 6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one or 7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one and a Lawson reagent to obtain a kit of 6-AQF or 7-AQF, potassium hydroxide and absolute ethyl alcohol, wherein the concentration of the mustard gas in a solution can be detected by a fluorescence titration standard curve method, the response speed is high, and the detection limit is low; the test paper for detecting the mustard gas is obtained by soaking filter paper in a solution prepared by dissolving 6-AQF or 7-AQF, potassium hydroxide and polyethylene oxide in acetonitrile and then airing, can visually monitor the mustard gas in a gas phase, and has the advantages of low cost, high sensitivity, good selectivity and good application prospect.
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FIG. 1 is a graph of the UV/Vis absorption spectra of a solution of 7-AQF (20 μ M), potassium hydroxide (KOH, 300 μ M) in ethanol of the present invention after 30 minutes at room temperature with no addition of mustard gas and with the addition of mustard gas (2 mM).
FIG. 2 is a graph of the fluorescence spectra (excitation wavelength 400nm) of a solution of 7-AQF (20. mu.M), potassium hydroxide (KOH, 300. mu.M) in ethanol of the present invention after 30 minutes at room temperature with no addition of mustard gas and with addition of mustard gas (2 mM).
FIG. 3 is a photograph showing the color change of the test paper after exposure to mustard gas (0-125 ppm) with different concentrations under the irradiation of a fluorescent lamp (top view) and an ultraviolet lamp (365nm) (bottom view).
FIG. 4 is a graph of the fluorescence titration curve of a solution of 7-AQF (20 μ M) and potassium hydroxide (KOH, 300 μ M) in ethanol with added mustard gas (0-200 μ M) at a wavelength of 550nm, with the inset being a linear fit of the fluorescence intensity to the concentration of mustard gas (0-10 μ M) (excitation wavelength of 400 nm).
FIG. 5 is a graph showing the change of fluorescence emission peak intensity with time (excitation wavelength 400nm) at a wavelength of 550nm when mustard gas (2mM) is added to an ethanol solution of 7-AQF (20. mu.M), potassium hydroxide (KOH, 300. mu.M) of the present invention at room temperature.
FIG. 6 is a graph showing the change of fluorescence emission peak intensity with time (excitation wavelength 400nm) at a wavelength of 550nm when mustard gas (2mM) is added to an ethanol solution of 7-AQF (20. mu.M) and potassium hydroxide (KOH, 300. mu.M) of the present invention at 60 ℃.
FIG. 7 is a photograph showing the change in fluorescence color of the test paper after exposure to mustard gas (100ppm) for various periods of time under an ultraviolet lamp (365 nm).
FIG. 8 is a photograph showing the color change of test paper exposed to different gas environments under a fluorescent lamp (top view) and an ultraviolet lamp (365nm) (bottom view).
Detailed Description
The following examples further illustrate the fluorescent probe compound for rapidly detecting mustard gas, its synthesis method, detection kit, test paper, and its application in mustard gas detection.
Example 1: synthesis of Probe Compound 6-AQF
The reaction was carried out according to the following synthetic route:
6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one compound (compound 1) (100mg,0.35mmol) and Lawson's reagent (143mg,0.35mmol) were added to toluene (10mL), and after stirring at 80 ℃ under nitrogen protection and monitoring by thin layer chromatography until no 6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one (compound 1) remained, the solvent was removed under reduced pressure, and the crude reaction product was isolated by column chromatography as a red solid product (86mg) with a yield of 81%.
Its nuclear magnetic resonance hydrogen spectrum:1H NMR(DMSO-d6):δ14.03(s,1H),7.62(d,J＝9.3Hz,1H),7.45(s,1H),7.32(d,J＝9.3Hz,1H),6.68(s,1H),3.40(q,J＝6.9Hz,4H),1.12(t,J＝6.9Hz,6H)；
nuclear magnetic resonance carbon spectrum:13C NMR(DMSO-d6):δ175.0,145.0,132.8,129.8,129.5,124.8,119.7,118.8,118.6,101.8,44.6,12.6；
high-resolution mass spectrum: HRMS (ESI-TOF) m/z calcd for C14H16F3N2S+:301.0981[M+H+],found:301.0975.
The red solid product obtained in this example was confirmed to be the probe compound 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione (6-AQF) by its hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high resolution mass spectrum.
Example 2: synthesis of Probe Compound 6-AQF
6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one compound (compound 1) (100mg,0.35mmol) and Lawson's reagent (214mg,0.53mmol) were added to toluene (10mL), and after stirring at 100 ℃ under nitrogen protection and monitoring by thin layer chromatography until no 6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one (compound 1) remained, the solvent was removed under reduced pressure, and the crude reaction product was isolated by column chromatography as a red solid product (90mg) with a yield of 85%.
The red solid product prepared in this example was confirmed to be the probe compound 6-AQF by its hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high resolution mass spectrum.
Example 3: synthesis of Probe Compound 6-AQF
6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one compound (compound 1) (100mg,0.35mmol) and Lawson's reagent (285mg,0.70mmol) were added to toluene (10mL), and after stirring at 120 ℃ under nitrogen protection and monitoring by thin layer chromatography until no 6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one (compound 1) remained, the solvent was removed under reduced pressure, and the crude reaction product was isolated by column chromatography as a red solid product (89mg) with a yield of 84%.
The red solid product prepared in this example was confirmed to be probe 6-AQF by its hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high resolution mass spectrum.
Example 4: synthesis of Probe Compound 7-AQF
7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one compound (compound 2) (100mg,0.35mmol) and Lawson's reagent (143mg,0.35mmol) were added to toluene (10mL), and after stirring at 80 ℃ under nitrogen protection and monitoring by thin layer chromatography until no 7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one (compound 2) remained, the solvent was removed under reduced pressure, and the crude reaction product was isolated by column chromatography as an orange solid product (87mg) in 82% yield.
Its nuclear magnetic resonance hydrogen spectrum:1H NMR(DMSO-d6):δ13.50(s,1H),7.54(dd,J1＝1.6Hz,J2＝9.2Hz,1H),7.11(s,1H),6.96(dd,J1＝2.5Hz,J2＝9.4Hz,1H),6.89(d,J＝2.4Hz,1H),3.44(q,J＝7.0Hz,4H),1.16(t,J＝7.0Hz,6H)；
nuclear magnetic resonance carbon spectrum:13C NMR(CDCl3):δ178.3,150.0,142.6,125.8,124.2,123.1,121.5,112.5,109.1,95.0,45.0,12.4；
high-resolution mass spectrum: HRMS (ESI-TOF) m/z calcd for C14H15F3N2S+:300.0908[M+],found:300.0904.
The orange solid product prepared in this example was identified as probe compound 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione (7-AQF) by its hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high resolution mass spectrum.
Example 5: synthesis of Probe Compound 7-AQF
7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one compound (compound 2) (100mg,0.35mmol) and Lawson's reagent (214mg,0.53mmol) were added to toluene (10mL), stirred at 100 ℃ under nitrogen protection, and after monitoring by thin layer chromatography until no 7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one (compound 2) remained, the solvent was removed under reduced pressure, and the crude reaction product was isolated by column chromatography as an orange solid product (95mg) with a yield of 90%.
The orange solid product prepared in this example was identified as probe compound 7-AQF by its hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high resolution mass spectrum.
Example 6: synthesis of Probe Compound 7-AQF
7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one compound (compound 2) (100mg,0.35mmol) and Lawson's reagent (285mg,0.70mmol) were added to toluene (10mL), and after stirring at 120 ℃ under nitrogen protection and monitoring by thin layer chromatography until no 7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one (compound 2) remained, the solvent was removed under reduced pressure, and the crude reaction product was isolated by column chromatography as an orange solid product (90mg) in 85% yield.
The orange solid product prepared in this example was identified as probe compound 7-AQF by its hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and high resolution mass spectrum.
Example 7: detection experiment in Probe 6-AQF or 7-AQF solutions
3.0mg of the probe compound 6-AQF or 7-AQF, which was prepared by formulating a kit with 40mL of anhydrous ethanol and probe compounds with a mass ratio of KOH. RTM.3: 4.5 and 3:8.4, respectively, and separately containing the probe compound and potassium hydroxide in a 5mL volumetric flask with anhydrous ethanol, and separately taking 250. mu.L of the above-mentioned two solutions of the probe compound and potassium hydroxide, and formulating with anhydrous ethanol in the same 25mL volumetric flask, the concentration of the probe compound 6-AQF in the volumetric flask was 20. mu.M, the concentration of potassium hydroxide was 160. mu.M or the concentration of the probe compound 7-AQF was 20. mu.M, the concentration of potassium hydroxide was 300. mu.M, and then taking 2.4mL of the above-mentioned ethanol solution of the probe compound and potassium hydroxide, and then taking 100. mu.L of an ethanol solution containing 50mM mustard gas in the above-mentioned cuvette, at which the concentration of the probe compound 6-AQF or 7-AQF in the cuvette was 20. mu.M, the concentration of potassium hydroxide was 160. mu.M or 300. mu.M, the concentration of mustard gas was 2mM, the cuvette was shaken well and then left at room temperature for 30 minutes, and the UV/fluorescence spectrum changes of 6-AQF or 7-AQF before and after the reaction were recorded.
FIG. 1 is a graph of the UV/VIS absorption spectra of 7-AQF (20 μ M) and potassium hydroxide (300 μ M) in ethanol after 30 minutes without and with mustard gas (2 mM); FIG. 2 is a graph of the fluorescence spectra (excitation wavelength 400nm) of 7-AQF (20. mu.M) and potassium hydroxide (300. mu.M) in ethanol after 30 minutes without and with mustard gas (2 mM); FIG. 4 is a graph showing the fluorescence titration curve (excitation wavelength 400nm) at a wavelength of 550nm of a solution of 7-AQF (20. mu.M) and potassium hydroxide (300. mu.M) in ethanol of the present invention with addition of mustard gas (0-200. mu.M); FIG. 5 is a graph showing the change of fluorescence emission peak intensity at a wavelength of 550nm with time (excitation wavelength of 400nm) of an ethanol solution of 7-AQF (20. mu.M) and potassium hydroxide (300. mu.M) of the present invention added with mustard gas (2mM) at room temperature; FIG. 6 is a graph of the fluorescence emission peak intensity at wavelength 550nm as a function of time (excitation wavelength 400nm) for a solution of 7-AQF (20. mu.M) and potassium hydroxide (300. mu.M) in ethanol of the present invention at 60 ℃ after addition of mustard gas (2 mM). As can be seen from fig. 1: the addition of potassium hydroxide enables the absorption peak of 7-AQF to be blue-shifted from 458nm and 433nm to 408nm, the addition of mustard gas enables the absorption peak to be further blue-shifted from 408nm to 400nm, and the intensity of the absorption peak is continuously reduced; as can be seen from fig. 2: the addition of potassium hydroxide does not obviously influence the fluorescence emission peak intensity of 7-AQF at 550nm, and the addition of mustard gas obviously enhances the fluorescence emission peak intensity at 550 nm; as can be seen from fig. 4: when the mustard gas with a certain concentration range is added, the fluorescence emission peak intensity of the 7-AQF at 550nm and the concentration of the mustard gas form a linear relation; as can be seen from fig. 5 and 6: the addition of mustard gas rapidly enhanced the intensity of the fluorescence emission peak of 7-AQF at 550nm at room temperature and 60 ℃. The above phenomena illustrate that the 7-AQF is capable of responding to mustard gas in the liquid phase and rapidly detecting the response signal thereof quantitatively and qualitatively by UV/fluorescence spectroscopy.
Example 8: preparation of detection test paper for detecting mustard gas
Dissolving 1.0g of polyethylene oxide (molecular weight 100 ten thousand) in 20mL of acetonitrile, and stirring at room temperature until the solution is transparent and uniform; subsequently, 1mL of an ethanol solution containing 8.4mg of potassium hydroxide and 1mL of an acetonitrile solution containing 3mg of 6-AQF or 7-AQF were added thereto, and stirred at room temperature; immersing a piece of clean qualitative filter paper in the filter paper, taking out the filter paper after several seconds, and airing the filter paper; and finally, cutting the mustard gas into pieces with the size of 1.5cm multiplied by 0.8cm to obtain the detection test paper for detecting the mustard gas.
Example 9: detection of mustard gas in gas phase by detection test paper
The test paper in example 8 is fixed in a 5mL centrifuge tube, so as to facilitate subsequent use and operation; respectively transferring 10 mu L of mustard gas (0-317.93mg/L) solution with different concentrations to the bottoms of 6 sequentially numbered 5mL centrifuge tubes by using a microsyringe; covering the centrifugal tube, and slightly heating the bottom of the centrifugal tube to form gaseous mustard gas; after 4 minutes, removing the test paper, and recording the color change of the test paper; FIG. 3 is a photograph showing the color change of the test paper after exposure to mustard gas (0-125 ppm) with different concentrations under the irradiation of a fluorescent lamp (upper panel) and an ultraviolet lamp (365nm) (lower panel): under a fluorescent lamp, the color of the detection test paper becomes lighter; under the irradiation of an ultraviolet lamp (365nm), the detection test paper changes from non-fluorescence to green fluorescence.
The method specifically comprises the following steps:
no. 1 centrifuge tube: 10 μ L of dichloromethane solution as reference;
no. 2 centrifuge tube: 10 μ L of mustard gas in dichloromethane (0.51 mg/L);
no. 3 centrifuge tube: 10 μ L of mustard gas in dichloromethane (2.54 mg/L);
no. 4 centrifuge tube: 10 μ L of mustard gas in dichloromethane (12.72 mg/L);
no. 5 centrifuge tube: 10 μ L of mustard gas in dichloromethane (63.59 mg/L);
no. 6 centrifuge tube: 10 μ L of mustard gas in dichloromethane (317.93 mg/L);
assuming that the mustard gas is completely volatilized into the mustard gas, the concentration of the mustard gas in six 5mL centrifuge tubes can be respectively 0ppm,0.2ppm,1ppm,5ppm,25ppm and 125 ppm; by comparing the colors of the test paper in FIG. 3, it can be seen that the detection limit of the test paper in example 8 to mustard gas reaches 0.2ppm by "naked eye";
example 10: detecting response speed of test paper to mustard gas atmosphere
The test paper in example 8 is fixed in a 5mL centrifuge tube, so as to facilitate subsequent use and operation; preparing a dichloromethane solution of mustard gas, wherein the concentration of the dichloromethane solution is 254.35 mg/L; transferring 10 μ L of mustard gas solution to the bottoms of 45 mL centrifuge tubes numbered 1, 2, 3, and 4 in sequence by using a microsyringe, wherein the centrifuge tube numbered 0 does not contain detection gas and is used as a reference; covering the centrifugal tube, and slightly heating the bottom of the centrifugal tube to form gaseous mustard gas; removing the test paper from the No. 1, 2, 3 and 4 centrifuge tubes after 1, 2, 3 and 4 minutes respectively, and recording the change of the fluorescence color of the test paper; FIG. 7 is a photograph showing the change in fluorescence color of the test paper after exposure to mustard gas (100ppm) for various periods of time under UV light (365 nm); under the irradiation of an ultraviolet lamp (365nm), the detection test paper changes from non-fluorescence to green fluorescence, the change can be obvious within 1 minute, and the fluorescence intensity tends to be saturated within 4 minutes.
Example 11: selective identification experiment of detection test paper
The test paper in example 8 is fixed in a 5mL centrifuge tube, so as to facilitate subsequent use and operation; respectively preparing dichloromethane solutions of mustard gas, acetyl chloride, phosphorus oxychloride, iodoethane, 1-bromo-3-chloropropane, dichloroethyl ether, 2-ethoxychloroethane, diethyl chlorophosphate and diethyl cyanophosphate, wherein the concentration of the dichloromethane solutions is 2.55 mM; respectively transferring 10 mu L of the solution to the bottoms of 9 centrifuge tubes with the volume being 1, 2, 3, 9; no. 0 centrifugal tube contains no detection gas as reference; covering the centrifugal tube, and slightly heating the bottom of the centrifugal tube to form a gaseous detection object; after 4 minutes, removing the test paper, and recording the color change of the test paper; FIG. 8 is a photograph showing the color change of the test paper after exposure to different gas environments (i.e., the above-mentioned numbers 0 to 9 represent different gas environments: 1. air, 2. mustard gas, 3. acetyl chloride, 4. phosphorus oxychloride, 5. iodoethane, 6.1-bromo-3-chloropropane, 7. dichloroethyl ether, 8.2-ethoxychloroethane, 9. diethyl chlorophosphate, 10. diethyl cyanophosphate) under the irradiation of a fluorescent lamp (upper diagram) and an ultraviolet lamp (365nm) (lower diagram): as shown in FIG. 8, under a fluorescent lamp, only the yellow color of the test paper in the mustard gas atmosphere is obviously lighter, and under the irradiation of an ultraviolet lamp (365nm), the fluorescent color of the test paper is changed from colorless to green, which indicates that the test paper in example 8 can selectively detect the mustard gas in the gas phase.
In conclusion, compared with the existing technology for detecting mustard gas, the probe 6-AQF or 7-AQF provided by the invention is simple and convenient in synthesis method, can be prepared by only one-step reaction, and is mild in reaction condition, simple in operation and high in yield.
The probe compound 6-AQF or 7-AQF of the invention has the characteristics of rapid response and fluorescence detection of mustard gas within 1 minute at 60 ℃ and 24 minutes at room temperature. The probe compound 6-AQF or 7-AQF, potassium hydroxide and absolute ethyl alcohol form a kit, the prepared ethanol solution of 6-AQF or 7-AQF and potassium hydroxide has no fluorescence under 365nm ultraviolet light, the fluorescence color under the ultraviolet light is green after mustard gas is added into the solution, and the detection limit of the solution on the mustard gas is as low as 0.28 mu M; the fluorescence standard curve diagram of the concentrations of the ethanol solution of 6-AQF or 7-AQF and potassium hydroxide and the mustard gas is measured, so that the quantitative detection of the mustard gas in the trace concentration range of less than 10 mu M in the solution can be realized; dissolving 6-AQF or 7-AQF, potassium hydroxide and polyethylene oxide in acetonitrile to prepare a solution, soaking filter paper in the solution and drying to prepare a test paper for detecting mustard gas by fluorescence, wherein in the atmosphere of the mustard gas, the fluorescence of the test paper changes from colorless to green under 365nm ultraviolet light and changes for less than 1 minute; the probe 6-AQF or 7-AQF and the test paper thereof have the responses only to the mustard gas, but do not have the responses to other similar detectors and other gases, which indicates that the 6-AQF or 7-AQF and the test paper thereof have good selectivity to the mustard gas. Particularly, the detection limit of the detection test paper to naked eyes of mustard gas is as low as 0.2 ppm.
The probe 6-AQF or 7-AQF has the characteristic of fluorescent response to mustard gas, and has high response speed and low detection limit; the portable detection test paper prepared by 6-AQF or 7-AQF can visually monitor the mustard gas in the gas phase, and has the advantages of low cost, high sensitivity, good selectivity and good application prospect.
Claims (4)
1. A fluorescent probe compound 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione for rapidly detecting mustard gas is characterized in that the fluorescent probe compound is a compound 6-AQF or 7-AQF which takes quinoline as a fluorescent chromophore and takes thioamide as a reaction site of the mustard gas, and has the structure shown in the following formula:
2. the method for synthesizing the fluorescent probe compound 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione for rapidly detecting mustard gas as claimed in claim 1, wherein the compound A, i.e., 6- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one or 7- (diethylamino) -4- (trifluoromethyl) quinolin-2 (1H) -one compound and Lawson's reagent, is added into toluene at a molar ratio of 1: 1-2, stirred at 80-120 ℃ under nitrogen protection, and after monitoring by thin layer chromatography until no compound A remains, the solvent is removed under reduced pressure, purifying and separating the reaction crude product by column chromatography to obtain a probe compound 6-AQF or 7-AQF; the synthetic route is represented as:
in the formula, R1The radical being diethylamino, R2The radical being hydrogen, or R1The radical being hydrogen, R2The radical is diethylamino.
3. A fluorescent probe compound 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione kit for rapidly detecting mustard gas is characterized in that the fluorescent probe compound 6-AQF or 7-AQF, potassium hydroxide and absolute ethyl alcohol are used for forming, an ethanol solution of the 6-AQF or 7-AQF and the potassium hydroxide is prepared, and a fluorescence titration standard curve graph of the concentration of the mustard gas is determined by using the solution, so that the quantitative analysis of the mustard gas in a trace concentration range in the solution is realized.
4. A test paper for detecting mustard gas is characterized in that 6- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione (6-AQF) or 7- (diethylamino) -4- (trifluoromethyl) quinoline-2 (1H) -thione (7-AQF), potassium hydroxide and polyethylene oxide are dissolved in acetonitrile to prepare a solution, filter paper is soaked in the solution, and the test paper is obtained after drying.
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| CN113567430B (en) * | 2021-09-26 | 2021-12-10 | 北京市疾病预防控制中心 | Nano probe for detecting mustard gas and preparation method and application thereof |
| CN115304570B (en) * | 2022-08-04 | 2023-07-14 | 中国科学技术大学 | Pre-fluorescence probe and kit detection test strip for mustard gas and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999001737A2 (en) * | 1997-06-10 | 1999-01-14 | Calspan Corporation | Detection of chemical agent materials using a sorbent polymer and fluorescent probe |
| US7139072B1 (en) * | 2003-04-14 | 2006-11-21 | The United States Of America As Represented By The Secretary Of The Navy | Handheld thermo-electrically cooled surface-enhanced Raman spectroscopy (TEC-SERS) fiber optic probe |
-
2020
- 2020-03-02 CN CN202010136955.5A patent/CN111253307B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999001737A2 (en) * | 1997-06-10 | 1999-01-14 | Calspan Corporation | Detection of chemical agent materials using a sorbent polymer and fluorescent probe |
| US7139072B1 (en) * | 2003-04-14 | 2006-11-21 | The United States Of America As Represented By The Secretary Of The Navy | Handheld thermo-electrically cooled surface-enhanced Raman spectroscopy (TEC-SERS) fiber optic probe |
Non-Patent Citations (2)
| Title |
|---|
| Chemodosimeter for Selective and Sensitive Chromogenic and Fluorogenic Detection of Mustard Gas for Real Time Analysis;Vinod Kumar et al.;《Anal. Chem.》;20180104;第90卷;1417-1422 * |
| Development of a Series of Fluorescent Probes for the Early Diagnostic Imaging of Sulfur Mustard Poisoning;Wenqi Meng et al.;《ACS Sens.》;20190924;第4卷;2794-2801 * |
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