CN108680543B - Method for detecting nitroaromatic explosives - Google Patents

Method for detecting nitroaromatic explosives Download PDF

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CN108680543B
CN108680543B CN201810290469.1A CN201810290469A CN108680543B CN 108680543 B CN108680543 B CN 108680543B CN 201810290469 A CN201810290469 A CN 201810290469A CN 108680543 B CN108680543 B CN 108680543B
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modified polystyrene
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pyrene
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CN108680543A (en
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崔月芝
张汉君
陶芙蓉
李天铎
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Qilu University of Technology
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Abstract

The invention discloses a method for detecting nitroaromatic explosives, which comprises the steps of placing a fluorescence sensor based on amino modified polystyrene at a position to be detected, detecting the fluorescence intensity of the fluorescence sensor based on the amino modified polystyrene at intervals, and obtaining the quenching efficiency of the fluorescence sensor based on the amino modified polystyrene, wherein the fluorescence sensor based on the amino modified polystyrene comprises an aminated glass sheet and a sensing layer, the sensing layer is placed on the surface of the aminated glass sheet, the sensing layer is an electrostatic spinning film prepared by blending the amino modified polystyrene and pyrene, and the structural formula of the amino modified polystyrene is as follows
Figure DDA0001617354100000011
Wherein m: n is 8 to 12:1, and the amino-modified polystyrene has a weight average molecular weight of 4 to 5 x 104g/mol, and the relative mass distribution index is 1.3-1.4. The detection method disclosed by the invention has higher sensitivity on the detection of NACs.

Description

Method for detecting nitroaromatic explosives
Technical Field
The invention relates to a method for detecting nitroaromatic explosives.
Background
The explosive articles heard in daily life are various. A large number of explosive materials can be grouped into six broad categories by their structure: nitroalkanes (e.g. 2, 3-dimethyl-2, 3-dinitrobutane DMNB, nitroanthrene NM), nitroarenes (e.g. 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene NT, 2, 4-dinitrotoluene DNT, 2,4, 6-trinitrotoluene TNT, 2,4, 6-trinitrophenol PA, nitrobenzene DNB), nitramines (e.g. cyclotrimethylenetrinitrilamine RDX, 1,3,5, 7-tetranitro-1, 3,5, 7-tetraazacyclooctane HMX, 2,4, 6-trinitrobenzene nitrosamine Tetryl), nitrates (e.g. nitroglycerine NG, pentaerythritol tetranitrate PETN), peroxides (e.g. hydrogen peroxide HP, tripropylene peroxide TATP, hexamethylene triperoxydiamine HMTD).
Most explosives contain nitroaromatic compounds (NACs), and Detection of the compounds mainly comprises Bulk Detection technology (Bulk Detection) and Trace Detection technology (Trace Detection). The body detection technology mainly comprises imaging detection and nuclear detection, and the technology mainly aims at carrying out macroscopic detection on explosives with larger volume and higher content. Whereas trace detection techniques are directed to detecting explosive particles or gases that are difficult to detect with the naked eye. Explosives generally have a certain volatility and may adhere to the surroundings of their storage location or to the surface of persons or objects in contact with the explosives. The method for detecting the micro-trace mainly comprises a chemiluminescence method, a redox method, an ion mobility spectrometry method, a chemical reagent method, a surface acoustic wave method, a gas-mass spectrometry combined method, a chemical sensor and a canine analysis method. Among the most sensitive detection methods for explosives is the gas-mass spectrometry (10)-4g/cm-1). In addition, the sensitivity of the ion mobility spectrometry to the detection of the explosives can also reach 10-3g/cm-1However, the apparatus is expensive, large in size and needs to be operated by professional personnel, so that the method is limited in wide application.
Because the common detection method has limitation and is difficult to be widely applied, it is more urgent to find a simple, convenient, rapid, low-cost and high-sensitivity detection method to meet the actual requirements.
Disclosure of Invention
In order to solve the defects of the prior art, one of the purposes of the invention is to provide an application of a fluorescence sensor of amino modified polystyrene in detecting nitroaromatic explosives, wherein the fluorescence sensor adopted by the invention can effectively enrich nitroaromatic compounds and has higher sensitivity in detecting NACs.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the fluorescence sensor of the amino modified polystyrene comprises a glass sheet with aminated surface and a sensing layer, wherein the sensing layer is arranged on the surface of the glass sheet with aminated surface, the sensing layer is an electrostatic spinning film spun by the amino modified polystyrene and pyrene, and the structural formula of the amino modified polystyrene is shown in the specification
Figure BDA0001617354080000021
Wherein m: n is 8 to 12:1, and the amino-modified polystyrene has a weight average molecular weight of 4 to 5 x 104g/mol, and the relative mass distribution index is 1.3-1.4.
The invention also provides a method for detecting nitroaromatic compounds in explosives, which comprises the steps of placing a fluorescence sensor of amino modified polystyrene at a position to be detected, detecting the fluorescence intensity of the fluorescence sensor of the amino modified polystyrene at intervals, and obtaining the quenching time of the fluorescence sensor of the amino modified polystyrene, wherein the fluorescence sensor of the amino modified polystyrene comprises a glass sheet with aminated surface and a sensing layer, the sensing layer is placed on the surface of the glass sheet with aminated surface, the sensing layer is an electrostatic spinning film spun by the amino modified polystyrene and pyrene, and the structural formula of the amino modified polystyrene is shown in the specification
Figure BDA0001617354080000022
Wherein m: n is 8 to 12:1, and the amino-modified polystyrene has a weight average molecular weight of 4 to 5 x 104g/mol, and the relative mass distribution index is 1.3-1.4.
The invention has the beneficial effects that:
1. the sensor of the invention is prepared by an electrostatic spinning method. The sensing layer has the advantages of large specific surface area, high porosity, good gas permeability, controllable morphology and the like. These advantages all contribute to the rapid contact between the analyte and the sensing substance; meanwhile, the sensing layer prepared by the method is amino modified polystyrene, the surface amination is carried out on the adopted glass sheet carrier, and a large amount of amino can act with the nitroaromatic compound through hydrogen bonds, so that the nitroaromatic compound can be effectively enriched on the surface of the sensor. The enrichment effect greatly improves the response sensitivity of the sensor to the micro-trace amount of the nitroaromatic compound.
2. The sensors of the present invention have better selectivity for DNT, TNT and PA with quenching efficiencies of 91%, 82% and 36% for DNT, TNT and PA, respectively, while the sensors of the present invention have little response to other organic or inorganic interferents such as 3, 5-dinitroaniline, commercial fragrances, urea, ammonium nitrate and sodium nitrite, etc.
3. The sensor of the invention has good reusability.
4. The invention can detect the trace amount of nitroaromatic compounds in the air, and when the nitroaromatic compounds are placed in TNT steam of 10ppb for 150s, the quenching rate can reach 65.4%.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a schematic illustration of the steps for the functionalization of a glass sheet carrier;
FIG. 2 is a scheme showing the synthesis of amino-functionalized polystyrene;
fig. 3 contact angle of secondary water after different treatments of the aminated glass slide carrier, G: blank glass sheet, G-OH: hydroxylated glass flakes, G-NH2: the aminated glass sheet has a contact angle of secondary water;
FIG. 4 is XPS photoelectron spectroscopy of aminated glass slide supports after various treatments, G: blank glass sheet, G-NH2: a surface aminated glass sheet;
FIG. 5 is an infrared spectrum of (a) 4-vinylbenzylamine and styrene; (b) PS-NH2And PS;
FIG. 6 shows NMR spectra of (a) 4-vinylbenzylphthalic acid diamide (b), 4-vinylbenzylamine and (c) PS-NH2；
FIG. 7 shows PS and PS-NH2Thermal stability analysis of (a) TGA, (b) DTG
FIG. 8 shows PS-NH2An electrostatic spinning nanofiber membrane electron microscope picture, (a) SEM, (b) TEM;
FIG. 9 shows (PS-NH) at different receiving times2/pyrene) quenching efficiency of sensor prepared by electrospinning membrane for TNT gasex＝333nm)；
FIG. 10 shows (PS-NH)2/pyrene)/G-NH2Fluorescence stability (lambda) of sensor in airex＝333nm)；
FIG. 11a is (PS-NH)2/pyrene)/G-NH2Sensor to TNT fluorescence quenching spectrum (lambda)ex333nm), fig. 11b is (PS-NH)2/pyrene)/G-NH2Fluorescence image of the sensor before quenching TNT, FIG. 11c is (PS-NH)2/pyrene)/G-NH2Fluorescence image of sensor after quenching TNT, FIG. 11d is (PS/pyrene)/G, (PS/pyrene)/G-NH2、(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2Sensor versus TNT quenching efficiency comparison plots;
FIG. 12 is a fluorescent image of different sensors placed in a saturated TNT vapor for 150s before and after quenching, where a is a (PS/pyrene)/G sensor and b is a (PS/pyrene)/G-NH sensor2Sensor, c is (PS-NH)2a/pyrene/G sensor, d is (PS-NH)2/pyrene)/G-NH2The sensor is (1) before quenching and (2) after quenching;
FIG. 13 shows PS-NH2Quenching performance photo of/pyrene electrospun nanofiber film, wherein a is quenching characterization of sensor to DNT, b is quenching characterization of sensor to TNT, c is quenching characterization of sensor to PA, and 1 and 3 are ultraviolet light (lambda)ex254nm), 2 and 4 are fluorescent lamps;
FIG. 14 shows (PS-NH)2/pyrene)/G-NH2The sensor is used for carrying out fluorescence quenching histogram on different objects to be detected;
FIG. 15 shows (PS-NH)2/pyrene)/G-NH2Reuse of saturated TNT detection by the sensor is compared.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background of the invention, the prior art has the defect that the prior sensor is difficult to carry out micro-trace gas phase detection on NACs, and in order to solve the technical problems, the application provides a method for detecting nitroaromatic explosives.
The application provides an application of a fluorescence sensor of amino modified polystyrene in detecting nitroaromatic explosives, the fluorescence sensor of amino modified polystyrene comprises a surface aminated glass sheet and a sensing layer, the surface of the surface aminated glass sheet is arranged in the sensing layer, the sensing layer is an electrostatic spinning film spun by amino modified polystyrene and pyrene, and the structural formula of the amino modified polystyrene is
Figure BDA0001617354080000041
Wherein m: n is 8 to 12:1, and the amino-modified polystyrene has a weight average molecular weight of 4 to 5 x 104g/mol, and the relative mass distribution index is 1.3-1.4.
In another embodiment of the present application, a method for detecting nitroaromatic explosives is provided, in which a fluorescence sensor of amino-modified polystyrene is placed at a position to be detected, and the fluorescence intensity of the fluorescence sensor of amino-modified polystyrene is detected at intervals to obtain amino groupsThe quenching time of the fluorescence sensor of the modified polystyrene is characterized in that the fluorescence sensor of the amino modified polystyrene comprises a glass sheet with aminated surface and a sensing layer, the sensing layer is arranged on the surface of the glass sheet with aminated surface, the sensing layer is an electrostatic spinning film spun by the amino modified polystyrene and pyrene, and the structural formula of the amino modified polystyrene is shown in the specification
Figure BDA0001617354080000042
Wherein m: n is 8 to 12:1, and the amino-modified polystyrene has a weight average molecular weight of 4 to 5 x 104g/mol, and the relative mass distribution index is 1.3-1.4.
Preferably, the thickness of the sensing layer is 0.5-1.5 μm. Further preferably, the thickness of the sensing layer is 1.0 μm.
Preferably, the mass ratio of the amino modified polystyrene to the pyrene is 2-10: 1.
Preferably, the preparation method of the fluorescence sensor of amino modified polystyrene comprises the steps of uniformly mixing the amino modified polystyrene and pyrene to prepare a spinning solution, and spinning the spinning solution into an electrostatic spinning film on the surface of a glass sheet with aminated surface by adopting electrostatic spinning, so as to obtain the sensor.
Further preferably, the amino modified polystyrene and the pyrene are added into the mixed solution of the N, N-dimethylformamide and the tetrahydrofuran, and the mixed solution is stirred for 12 +/-1 h at room temperature to obtain the movable spinning solution.
Further preferably, the electrostatic spinning conditions are that the spinning voltage is 20kV, the injection speed of the injector is 0.04mm/min, the receiving distance is 18-22 cm, and the receiving time is 1-8 min. Even more preferably, the reception time is 5 min.
Further preferably, the preparation method of the amino modified polystyrene comprises the following steps: dissolving styrene, 4-vinylbenzylamine and Azobisisobutyronitrile (AIBN) in a solvent, and heating to 70 +/-5 ℃ to perform polymerization reaction for 20 +/-5 hours. More preferably, the amino-modified polystyrene is purified by dissolving the product of the polymerization reaction in methylene chloride and then precipitating the product by adding ice methanol. The glacial methanol is prepared by placing methanol in an environment with the temperature lower than 0 ℃ for 5-24 h.
The 4-vinylbenzylamine used in the present application can be purchased directly or synthesized by itself.
The application preferably discloses a synthesis method of 4-vinylbenzylamine, which comprises the steps of reacting potassium phthalimide with 4-chloromethylstyrene to obtain 4-vinylbenzylphthalic diamide, and reacting 4-vinylbenzylphthalic diamide with hydrazine hydrate to obtain the 4-vinylbenzylamine. The reaction process is as follows:
Figure BDA0001617354080000051
more preferably, the 4-vinylbenzylphthalic acid amide is prepared by heating to 55 +/-1 ℃ in a nitrogen atmosphere and reacting for 15-16 h.
More preferably, the reaction condition of the 4-vinylbenzylphthalic diamide and the hydrazine hydrate is reflux for 5 +/-0.5 h under the nitrogen atmosphere.
The surface-aminated glass sheet used in the present application can be produced by a known method from a general glass sheet.
The preparation method of the surface aminated glass sheet preferably comprises the steps of putting the glass sheet into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, treating for a period of time at 95-100 ℃ to obtain the surface hydroxylated glass sheet, and adding the surface hydroxylated glass sheet into a solution of 3-aminopropyltriethoxysilane, heating and refluxing for a period of time to obtain the surface aminated glass sheet.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
Reagent:
3-aminopropyltriethoxysilane (98%) supplied by Aladdin reagent Inc.;
p-chloromethyl styrene (98%) was supplied by Jiuding chemical (Shanghai) science and technology, Inc.;
phthalimide potassium salt (98%), available from sahn chemical technology (shanghai) ltd;
hydrazine hydrate (80%), dichloromethane (AR), methanol (AR), sodium hydroxide, toluene (AR), hydrochloric acid (AR, 37%), azobisisobutyronitrile (AIBN, recrystallized from methanol), chloroform (AR), Acetone (AR), ethanol (AR), supplied by fujin, fuyu fine chemicals ltd.
Example 1
Amino functionalized glass flakes (G-NH)2) Preparation of
G-NH2The preparation steps are schematically shown in FIG. 1. The cover glass was cut into 10X 20mm and calcined at a high temperature of 500 ℃ in a muffle furnace in order to remove organic impurities on the surface to obtain a blank glass sheet (G). And then putting the calcined glass sheet into a flask filled with a mixed solution of concentrated sulfuric acid and hydrogen peroxide (7:3), stirring and reacting for 1h at 98 ℃, stopping the reaction, cooling to about 25 ℃, taking out, putting into deionized water, ultrasonically washing for 10min, and repeating for 3 times to ensure that the sulfuric acid and the hydrogen peroxide are cleaned. And (3) placing the cleaned glass sheet in a vacuum drying oven at 40 ℃ for removing water to obtain a hydroxylated glass sheet (G-OH).
Dripping 1mL of 3-aminopropyltriethoxysilane into a three-neck flask containing 10mL of toluene, uniformly mixing, putting the hydroxylated glass sheet into the mixed solution, heating and refluxing for reaction for 12h, stopping the reaction, cooling to about 25 ℃, taking out the glass sheet, and sequentially ultrasonically cleaning the glass sheet by chloroform, acetone and absolute ethyl alcohol for 10min respectively. Ensuring to remove unreacted siloxane attached on the glass sheet, and finally placing the cleaned glass sheet in a drying oven for drying for later use to obtain aminated glass sheet (G-NH)2)。
Example 2
Amino-modified polystyrene (PS-NH)2) Preparation of
(PS-NH2) The synthetic route of (2) is shown in FIG. 2. Potassium phthalimide (5.075g, 27.4mmol) and 4-chloromethylstyrene (4.06g, 26.6mmol) were dissolved in 30mL of anhydrous DMF. In N2Stirring and reacting at 55 deg.C for 15 hr under protection, removing solvent from reaction solution, and collecting the restThe material was dissolved in chloroform. The solution was washed with 0.2M aqueous sodium hydroxide solution, then with water several times, and then with anhydrous MgSO4Drying, filtering and evaporating to obtain a crude product. Recrystallizing in methanol solution for several times, and purifying the crude product to obtain the 4-vinyl benzyl phthalic diamide. The product was white crystals (yield: 5.46g, 78%).1H NMR(CDCl3,ppm):7.9-7.7(m,4H),7.4-7.2(m,4H),6.7(dd,1H),5.8-5.2(d,2H),4.8(s,2H)。
4-Vinylbenzylphthalimide (5.1g, 19.3mmol) and 80% hydrazine hydrate (1.6g, 32mmol) were dissolved in 50mL of ethanol. And the reaction was stirred under reflux for 5 hours under nitrogen. The solvent was then removed under reduced pressure, and the solid residue was extracted with 50mL of chloroform and treated with 20% aqueous NaOH (50 mL). The aqueous phase was then separated, extracted with chloroform, the combined extracts were dried over anhydrous MgSO4Drying, filtering and evaporating. The obtained crude oil was purified by column chromatography (silica gel, methanol: ethyl acetate ═ 1:3) to obtain a transparent oil (yield: 1.78g, 69%).1H NMR(CDCl3,ppm):7.4-7.2(m,4H),6.7(dd,1H),5.8-5.2(d,2H),3.8(s,2H)。
Styrene (3.95g, 38mmol), 4-vinylbenzylamine (0.51g, 3.8mmol) and AIBN (0.045g, 0.27mmol) were dissolved in DMF under nitrogen protection and the reaction stirred in a constant temperature oil bath at 70 ℃ for 20 hours. The reaction mixture was then cooled to room temperature, and the crude polymerization product was dissolved in dichloromethane and purified by precipitation in cold methanol. Vacuum drying the product at 40 ℃ for 24 hours to obtain PS-NH2(yield: 2.9g, 65%).1H NMR(CDCl3,ppm):6.3-7.2(C6H4and C6H5)；4.4(C6H4CH2NH2) (ii) a 1.1-2.2(polymer backbone). The weight average molecular weight of the amino-modified polystyrene was 4.580X 10-4g/mol, relative mass distribution index 1.38.
Example 3
(PS-NH2/pyrene)/G-NH2Preparation of electrostatic spinning film sensor
0.4g of pyrene and 1.6g of amino-modified polyphenyleneEthylene (PS-NH)2) Dissolved in 10mL of a mixed solution of N, N-dimethylformamide and tetrahydrofuran (DMF: TNF ═ 3: 1) stirring for 12h at 25 ℃ to obtain pyrene-doped PS-NH2Electrospinning the solution. The spinning solution is placed in an injector, bubbles in the spinning solution are discharged, a needle head is connected with a positive high-voltage wire, a glass sheet is adhered to a receiving roller, the receiving distance is 20cm under the spinning voltage of 20KV, the injector receives the spinning solution for a certain time at the injection speed of 0.04mm/min and the temperature of 25 ℃, and the electrostatic spinning film is prepared. The prepared electrostatic spinning film sensor is placed in a vacuum drying oven and dried for 12 hours at the temperature of 60 ℃ to remove residual organic solvent.
Example 4
Detection of gas phase TNT by sensor
Firstly, 100g of nitro-aromatic compound to be detected is placed at the bottom of a cuvette, and a piece of filter paper with proper size is covered on an object to be detected so as to prevent a sensor from directly touching the object to be detected. Then, the cuvette was sealed and placed at room temperature for 12h to ensure that the nitroarene in the cuvette reached saturated vapor pressure. The cuvette was then placed in a fluorescence spectrophotometer model F-4600 and the prepared sensor was placed in the cuvette rapidly against the excitation light source for testing, collecting data every 30 s.
Example 5
With PS-NH2The/pyrene mixed solution is a spinning solution, the nanofiber film is prepared by adopting an electrostatic spinning technology, the spinning time is 10 hours, and the spinning film is uncovered for standby. Three identical petri dishes were then taken and filled with sandy soil. DNT, TNT and PA0.5g were taken and buried in soil to a depth of 1 cm. And standing at 40 ℃ for 24 hours, so that the gas diffusion of the nitro-aromatic explosive simulates a real environment. Then PS-NH2The fluorescent nanofiber membrane was covered on the soil surface of three petri dishes and left at room temperature for 5 hours. Then placing the culture dish under an ultraviolet lamp for observing PS-NH2And detecting the nitro-aromatic explosive by the/pyrene electrostatic spinning membrane.
The characterization results for examples 1-5 are as follows:
1. amino-grafted glass sheets (G-NH)2) Characterization of
As can be seen from fig. 3, the contact angle of the glass sheet to water shows a corresponding regular change after different treatments. The blank glass sheet (G) from which the organic impurities on the surface were removed after the high-temperature calcination had a water contact angle of 34.9. + -. 0.2 ℃. And when the G is hydroxylated by the treatment of the mixed liquid of concentrated sulfuric acid and hydrogen peroxide, the water contact angle is 27.06 +/-0.2 degrees. The contact angle becomes smaller probably because the number of hydroxyl groups on the surface of the glass sheet increases, resulting in an increase in hydrophilicity thereof. Amino-grafted glass sheets (G-NH)2) The water contact angle of (2) is 77.51 + -0.2 deg. The contact angle is significantly larger than that of the first two glass sheets, and the main reason is probably that the hydroxylated glass sheet (G-OH) is grafted with aminopropyltriethoxysilane in a toluene solution to remove alcoholic hydroxyl groups, so that silane chains on the glass surface are obviously increased, and the glass sheet (G-NH) is reduced2) The hydrophobicity of the surface is greatly enhanced, and the contact angle is obviously increased. The change in regularity of the contact angle test indicates that the corresponding chemical reaction did occur at the surface of the glass sheet.
As can be seen from FIG. 4, the amino-modified glass sheet exhibited a distinct nitrogen peak (N1s) at 401eV as compared to the blank glass sheet. This further confirms the occurrence of grafting reactions on the surface of the glass sheet. The successful grafting of the amino groups onto the glass sheet surface is illustrated by a combination of FIGS. 3 and 4.
PS-NH2Synthesis and use thereof1H NMR, FT-IR and thermal stability analysis
FIG. 5(a) shows PS-NH2And the infrared spectrum of PS. PS-NH compared with the IR spectrum of PS2At 2854-2918cm-1The stretching vibration absorption peaks of saturated hydrocarbon of 4-vinylbenzylamine were observed in the vicinity of the peak, and at 3372 and 3285cm-1The N-H stretching vibration absorption peak in 4-vinylbenzylamine appears at 1241cm-1C-N stretching vibration absorption peaks appear, which are evidence of the structure of 4-vinylbenzylamine. FIG. 5(b) is PS-NH2And infrared contrast plots of PS. PS-NH in contrast to PS23435cm in center-1The strong absorption peak occurs mainly due to the stretching vibration of N-H. At 1253cm-1The C-N stretching vibration absorption peak of (A) proves that (PS-NH)2And (4) synthesizing.
FIG. 6 shows PS-NH2Of products obtained at each step of the preparation process1HNMR spectrogram. The chemical shifts of the hydrogenation of the aromatic ring C-H and the double bond C-H in 4-vinylbenzylphthalic acid amide and 4-vinylbenzylamine are in the range of 7.4-7.2ppm and 6.8-5.2ppm, respectively. With 4-vinylbenzylphthalic acid diamides1Compared with the HNMR spectrum, in the 4-vinylbenzylamine spectrum, no signal of aromatic H in phthalimide is observed at 7.7 and 7.9ppm, but chemical shift of methylene hydrogen at the ortho-position of benzene ring is observed at 3.8 ppm. In PS-NH2Is/are as follows1The HNMR spectrum observed a chemical shift of 4.4ppm of methylene hydride. These results strongly demonstrate the structure of the product of each step.
FIG. 7 shows PS and PS-NH2TGA versus DTG graph of (a). In FIG. 7(a), the decomposition temperature (Ti) at which PS is lost 5% is 315 ℃. And PS-NH2The decomposition temperature at 5% weight loss was increased to-369 ℃. PS-NH2The reason for the higher thermal decomposition temperature is-NH in its molecule2Structural stability can be enhanced by hydrogen bonding interactions. Further, as shown in FIG. 7(b), PS-NH2The fastest decomposition temperature of the catalyst is higher than that of PS, and better thermal stability is presented.
Morphology analysis of electrospun nanofibers
FIG. 8 shows PS-NH2The micro-morphology of the electrospun nanofiber film. As seen in FIG. 8(a), PS-NH2The electrostatic fibers are in a uniform and smooth form. Fig. 8(b) is a projection image taken under an optical microscope, and it can be seen from fig. 8(b) that the whole prepared electrospun membrane has good porosity, which is beneficial for the diffusion of the detected object in the nanofiber membrane.
(PS-NH2/pyrene)/G-NH2Sensor to TNT sensing performance characterization
The influence of the film thickness on the sensor detection results was detected depending on the reception time of the electrospun nanofibers, as shown in fig. 9. Eight nanofiber membrane sensors (1-8 min) with different receiving times were prepared and were separately subjected to quenching studies on saturated TNT vapor. As can be seen from fig. 9, the thicker the thin film is, the better the detection effect is, but the quenching rate of the saturated TNT increases and then decreases with the increase of the thickness, and the thin film sensor has the highest quenching efficiency of the saturated TNT when the receiving time is 5 min. The acceptance time of the tested nanofiber films was therefore chosen to be 5min (thickness 1 μm).
As shown in FIG. 10, (PS-NH)2/pyrene)/G-NH2The intensity of fluorescence of the sensor placed in air for 1200s was slightly reduced, indicating (PS-NH)2/pyrene)/G-NH2The nanofiber membrane sensor has good fluorescence stability in air, and eliminates the possibility of self-quenching in the research on quenching of nitroarene explosives.
The fluorescence quenching spectrum of the sensor for saturated 2,4, 6-trinitrotoluene vapor is shown in FIG. 11 a. In TNT saturated vapor, the sensor has better responsiveness to TNT. Fig. 11b and fig. 11c are comparative images of the nanofiber sensor under a fluorescence microscope before and after quenching of TNT, and the significant decrease in the fluorescence intensity of the nanofibers in the sensor after quenching can be clearly seen with the naked eye. In this partial characterization, four sensors were prepared, respectively (PS/pyrene)/G, (PS/pyrene)/G-NH2，(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2. And (3) respectively carrying out fluorescence sensing detection on the saturated TNT steam by using the four sensors. FIG. 11d is (PS/pyrene)/G, (PS/pyrene)/G-NH2，(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2Fluorescence quenching efficiency of four thin film sensors is compared. As can be seen in FIG. 11d, (PS/pyrene)/G, (PS/pyrene)/G-NH at 150s2，(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2The fluorescence quenching efficiencies of (a) were 18.8%, 51.1%, 40.8% and 65.4%, respectively. By comparison, (PS-NH)2/pyrene)/G-NH2The quenching effect of the sensor is the best, because the fluorescence sensor contains a large amount of amino groups, and the nitro aromatic hydrocarbon can be enriched by hydrogen bonds, so that the quenching rate is improved. Two types of strong interactions between the electron-deficient aromatic ring and the electron-rich amino group of TNT may occur: (i) charge transfer from the amino group to the aromatic ring results in the formation of a Meisenheimer complex between the TNT and the primary amine groupA compound (I) is provided. (ii) As a generally accepted mechanism, the TNT molecule is
Figure BDA0001617354080000091
Lowry acids, which can be deprotonated at the methyl group by basic amines. The negative charge on the TNT anion is distributed throughout the molecule by resonance stabilization of the three electron-withdrawing nitro groups, thus leading to the formation of acid-base pairing interactions. Therefore, the fluorescence sensor containing a large amount of amino has an enrichment effect on nitroarene, and is beneficial to detecting trace NACs.
In order to more intuitively observe the detection rate of the prepared four film sensors on the saturated TNT gas, a fluorescence microscope is utilized to respectively observe (PS/pyrene)/G, (PS/pyrene)/G-NH2、(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2Fluorescence images of the sensor before and after quenching of saturated TNT vapor. The four prepared thin-film sensors were first placed in a fluorescence microscope, and fluorescence images of the four sensors when they were not quenched were observed, then the four sensors were each placed in saturated TNT vapor for 150 seconds, and then the four sensors after quenching were each placed in a fluorescence microscope, and fluorescence images after each quenching were observed, as shown in fig. 12. FIG. 12a (1), FIG. 12b (1), FIG. 12c (1) and FIG. 12d (1) represent (PS/pyrene)/G, (PS/pyrene)/G-NH, respectively2、(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2The fluorescence images before quenching of the four sensors are shown in FIG. 12a (2), FIG. 12b (2), FIG. 12c (2) and FIG. 12d (2) as (PS/pyrene)/G, (PS/pyrene)/G-NH, respectively2、(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2Fluorescence images after quenching for the four sensors. It can be seen that all four sensors emit strong bright blue fluorescence before quenching. After being placed in saturated TNT steam for 150s, the quenching effect is different, and the best quenching effect is shown in figure 12d (2) namely (PS-NH) as shown by comparison2/pyrene)/G-NH2A sensor. The possible reasons are that the sensor carrier and the nano-fiber both contain a large number of amino groups, so that the enrichment effect on nitro compounds is strong, and the quenching efficiency of the sensor is greatly improved. As can be seen from the fluorescence images of FIG. 12b (2) and FIG. 12c (2), (PS/pyrene)/G-NH2Quenching effect ratio (PS-NH) of sensor2The good/pyrene/G sensor may be due to the amino modified glass sheet having a large number of amino groups on both sides, whereas the amino content in the nanofibers is less than on the glass sheet, thus (PS-NH)2The quenching effect of the/pyrene/G sensor is relatively poor. Compared with the quenching effect of the (PS/pyrene)/G sensor, the fluorescence quenching effect of the sensor modified by the amino group is better than that of the sensor without the amino group. Therefore, the introduction of the electron-rich group amino can greatly improve the detection effect of the sensor on NACs.
Simulating PS-NH in real environment2The method for detecting the nitro aromatic compounds by the aid of the/pyrene electrospun nanofiber membrane comprises the steps of firstly preparing three identical culture dishes and filling the culture dishes with sandy soil, and then burying DNT, TNT and PA0.5g of DNT, TNT and PA0.5g of. Then, the three dishes were placed at 40 ℃ for 24 hours, and then PS-NH doped with pyrene was added2The fluorescent nanofiber membranes are respectively covered on the soil surfaces of the three culture dishes and placed for 5 hours at room temperature for nitryl arene detection. In fig. 13, columns a, b, and c are detection DNT, TNT, and PA, respectively, and fig. 13a (1), 13b (1), 13c (1), 13a (3), 13b (3), and 13c (3) are detection DNT, TNT, and PA, respectively, under ultraviolet irradiation (λ:)ex＝254nm)PS-NH2A comparison of the/pyrene fluorescent nanofiber membrane before and after quenching shows a bright blue color when initially unquenched. After 5 hours, PS-NH2Quenching of the/pyrene fluorescent nanofiber membrane, wherein the quenching points in the figure indicate the positions of the nitro-aromatic compounds buried under the soil in the culture dish, and comparing the positions of the nitro-aromatic compounds with the positions of PS-NH in FIGS. 13a (3), 13b (3) and 13c (3) shows2The quenching effect of the/pyrene nano-fiber film on the three nitroaromatic compounds is as follows: DNT > TNT > PA, the best quenching effect on DNT is shown, because DNT has higher saturated vapor pressure (1.1X 10)- 4Torr) is TNT saturated autoclaved (5.8X 10)-6Torr) 18 times higher. And PA has a lower saturated vapor pressure (5.8X 10)- 9Torr) resulting in non-ideal detection thereof. Comparing FIGS. 13a (2), 13b (2), 13c (2) and 13a (4),As can be seen in FIGS. 13b (4) and 13c (4), PS-NH is applied to a fluorescent lamp2The/pyrene nano fiber film is white, and the three films have no obvious difference under a fluorescent lamp.
Fluorescence quenching characterization of sensors for different analytes
(PS-NH2/pyrene)/G-NH2A comparative fluorescence quenching plot for the sensor against some chemicals (e.g., TNT, DNT, PA, 3, 5-dinitroaniline, commercial fragrances, urea, ammonium nitrate, and sodium nitrite) is shown in fig. 14. As can be seen from FIG. 14, (PS-NH)2/pyrene)/G-NH2The sensor showed fluorescent responses for DNT, TNT and PA with corresponding quenching efficiencies of 91%, 82% and 36%, respectively. However, other organic or inorganic interfering substances such as 3, 5-dinitroaniline, commercial perfumes, urea, ammonium nitrate and sodium nitrite etc. (PS-NH)2/pyrene)/G-NH2The sensor has little response.
The sensors show different quenching efficiencies for different NACs, mainly due to the different saturated vapor pressures of the explosives. The vapor pressures of DNT, TNT and PA were 280ppb, 10ppb and 0.0077ppb, respectively, at room temperature. The vapor pressure of DNT is much higher than that of TNT, so the quenching efficiency for DNT (91%) is much higher than for TNT (82%). Although TNT has three strong electron-withdrawing nitro groups on the phenyl ring, the saturated vapor pressure of the test substance plays a major role in this process. The PA shows a relatively low quenching efficiency (36%) due to its vapor pressure, which is too low. In addition, since 3, 5-dinitroaniline and commercial perfumes are electron-rich aromatic compounds, no significant quenching of fluorescence results. Commonly used nitrogen fertilizers, such as ammonium nitrate, urea, sodium nitrite, etc., cause only negligible quenching. Further demonstration of the combination of all the above results (PS-NH)2/pyrene)/G-NH2The sensor has higher sensitivity and better selectivity to NACs in gas phase.
(PS-NH2/pyrene)/G-NH2Sensor reusability characterization
For (PS-NH)2/pyrene)/G-NH2The research process for testing the reusability of the sensor is as follows: first of all, the first step is to,100g of nitro-aromatic compound TNT to be detected is placed at the bottom of a cuvette, and a piece of filter paper with a proper size is covered on the TNT to prevent a sensor from directly touching an object to be detected. And then, sealing the cuvette and then placing the cuvette for 12h at room temperature for later use to ensure that the gas phase in the cuvette reaches the saturated vapor pressure of the substance to be detected. Will additionally prepare (PS-NH)2/pyrene)/G-NH2The sensor is placed in a clean space ratio cuvette and placed in a fluorescence detection instrument, so that the sensor film is opposite to an excitation light source, and the original fluorescence intensity of the sensor before quenching is measured. The fluorescence intensity of the sensor at this time was measured after the sensor was subsequently placed in a previously prepared cuvette containing saturated TNT vapor for 0.5 hours. Then taking out (PS-NH)2/pyrene)/G-NH2The sensor was treated with a stream of nitrogen for 0.5 hours to remove TNT from the sensor. The treated sensor was placed in a clean air-to-air cuvette to re-detect the fluorescence intensity. The procedure was repeated 5 times, and the results are shown in FIG. 15. (PS-NH) after the first cycle of fluorescence quenching and recovery2/pyrene)/G-NH2The fluorescence intensity of the sensor decreased by approximately 10%. During the 4 cycles thereafter, the signal strength of the sensor did not decrease significantly, which indicates that the sensor has good recyclability.
Summary of the invention
(PS/pyrene)/G, (PS/pyrene)/G-NH were studied by fluorescence microscope and fluorescence spectrometer, respectively2、(PS-NH2/pyrene)/G and (PS-NH)2/pyrene)/G-NH2The appearance of the sensing film and the quenching performance of the sensing film on saturated TNT steam discover (PS-NH)2/pyrene)/G-NH2The sensor has the best quenching effect. In the fluorescence sensing system, a large number of electron-rich amino groups are introduced, and the amino groups can interact with electron-deficient Nitroarenes (NACs) through hydrogen bonds, so that the NACs can be effectively enriched. At 150s (PS-NH)2/pyrene)/G-NH2The quenching rate of the fluorescent sensor to TNT steam (10 ppb) reaches 65.4 percent.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (6)

1. A method for detecting nitro-aromatic explosives is characterized in that a fluorescence sensor based on amino-modified polystyrene is placed at a position to be detected, the fluorescence intensity of the fluorescence sensor based on amino-modified polystyrene is detected at intervals, and the quenching efficiency of the fluorescence sensor based on amino-modified polystyrene is obtained; the fluorescence sensor based on the amino modified polystyrene comprises a glass sheet with an aminated surface and a sensing layer, wherein the sensing layer is arranged on the surface of the aminated glass sheet, the sensing layer is an electrostatic spinning film prepared by blending the amino modified polystyrene and pyrene, and the structural formula of the amino modified polystyrene is shown in the specification
Figure FDA0002616979190000011
Wherein m: n is 8 to 12:1, and the amino-modified polystyrene has a weight average molecular weight of 4 to 5 x 104 g/mol, the relative mass distribution index is 1.3-1.4; the thickness of the sensing layer is 1.0 mu m; the mass ratio of the amino modified polystyrene to the pyrene is 2-10: 1; the electrostatic spinning conditions are that the spinning voltage is 20kV, the injection speed of the injector is 0.04mm/min, the receiving distance is 18-22 cm, and the receiving time is 5 min.
2. The method of claim 1, wherein the fluorescence sensor based on amino-modified polystyrene is prepared by uniformly mixing amino-modified polystyrene and pyrene to prepare a spinning solution, and spinning the spinning solution into an electrospun film on the surface of the aminated glass sheet by an electrospinning method, thereby obtaining the sensor.
3. The method for detecting nitroaromatic explosives in accordance with claim 2, wherein the spinning solution is obtained by adding amino-modified polystyrene and pyrene to a mixed solution of N, N-dimethylformamide and tetrahydrofuran, and stirring at room temperature for 12 ± 1 h.
4. The method for detecting nitroaromatic explosives in accordance with claim 2, wherein the preparation method of the amino-modified polystyrene comprises the following steps: dissolving styrene, 4-vinylbenzylamine and azobisisobutyronitrile in a solvent, and heating to 70 +/-5 ℃ to perform polymerization reaction for 20 +/-5 hours.
5. The method for detecting nitroaromatic explosives in accordance with claim 2, wherein the synthesis method of 4-vinylbenzylamine comprises the following steps: the method comprises the following steps of reacting potassium phthalimide with 4-chloromethyl styrene to obtain 4-vinyl benzyl phthalic diamide, and reacting the 4-vinyl benzyl phthalic diamide with hydrazine hydrate to obtain 4-vinyl benzyl amine.
6. The method for detecting nitroaromatic explosives in accordance with claim 2, wherein the surface aminated glass sheet is prepared by: and (2) putting the glass sheet into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, treating for a period of time at 95-100 ℃ to obtain a surface hydroxylated glass sheet, adding the surface hydroxylated glass sheet into a solution of 3-aminopropyltriethoxysilane, and heating and refluxing for a period of time to obtain the surface aminated glass sheet.
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