CN109748930B - Fluorescent probe molecule for detecting explosive RDX and preparation method and application thereof - Google Patents
Fluorescent probe molecule for detecting explosive RDX and preparation method and application thereof Download PDFInfo
- Publication number
- CN109748930B CN109748930B CN201711083499.7A CN201711083499A CN109748930B CN 109748930 B CN109748930 B CN 109748930B CN 201711083499 A CN201711083499 A CN 201711083499A CN 109748930 B CN109748930 B CN 109748930B
- Authority
- CN
- China
- Prior art keywords
- rdx
- probe molecule
- fluorescent probe
- solution
- explosive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention relates to a fluorescent probe molecule for detecting explosive RDX and a preparation method and application thereof. And then the RDX is indirectly detected through the response of the fluorescent probe to the photolysis product of the explosive RDX. The method has the advantages of mild reaction conditions, simple and convenient test conditions, high response sensitivity of probe molecules to the explosive RDX and good selectivity, and is a feasible attempt in the aspect of applying the fluorescent sensor to the detection of the explosive.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and particularly relates to a fluorescent probe molecule for detecting explosive RDX, and a preparation method and application thereof.
Background
In recent years, the detection of explosives has relied on large instrumentation such as gas/liquid chromatography, mass spectrometry, ion mobility spectrometry, etc. Although these large instruments can meet practical requirements in terms of sensitivity and detection limits, operating these large instruments often requires experienced technicians and many still have difficulty achieving real-time on-line detection in the field, and therefore developing a new method for rapid detection of explosives remains a very important research area.
Cyclotrimethylenetrinitramine (RDX) is an important explosive, and is difficult to directly detect due to the high lowest unoccupied orbital level and weak electron accepting capacity, but can be decomposed under proper conditions to generate common small-molecule substance formaldehyde. If the detection of formaldehyde which is a decomposition product of the explosive can be realized, the detection of the explosive RDX can be indirectly realized. This is a viable attempt at explosives detection, which will advance the research process for explosives detection.
In recent years, optical materials with great potential are widely concerned due to the characteristics of convenience, economy and portability, a fluorescent probe as a common optical material has the advantages of high sensitivity, good selectivity, quick response, wide synthesis route and the like, the fluorescent probe compound can make up for the defects of detection of large instruments when being used for detecting explosives, the targets of quick detection and instant response are realized, and fluorescent probe molecules have obvious advantages in the aspect of detecting explosives, so that the fluorescent probe compound has good research prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel fluorescent probe molecule and a preparation method thereof, and the invention also aims to provide the application of the fluorescent probe compound, namely the probe can be used for detecting explosive RDX.
The technical scheme of the invention is as follows: a fluorescent probe molecule for detecting explosive RDX has the following structural formula:
the invention provides a preparation method of a fluorescent probe molecule for detecting explosive RDX, which comprises the following steps:
(1) synthesis of chloroBODIPY derivatives: synthesis of chloroBODIPY derivatives: 0.5mL of the acid was dissolved in distilled water and placed in a 250mL flask. Pyrrole and p-tolualdehyde are added. After reacting for 1h at room temperature, quenching with ammonia water and filtering. The obtained solid is washed once by water and then twice by petroleum ether to obtain a milky white crude product. Adding tetrahydrofuran suspension containing NCS dropwise in 1h, reacting for 2h, adding 50mL water, extracting with dichloromethane, and extracting organic phase with anhydrous Na2SO4Drying to obtain the compound 2. The compound 2 was dissolved in methylene chloride, and a dispersion system of tetrachlorobenzoquinone in methylene chloride was added dropwise to the reaction system. Reacting at room temperature for 1h, and adding triethylThe amine was stirred for 1 h. Adding boron trifluoride-diethyl ether complex by syringe, reacting overnight in dark, washing with water, and adding anhydrous Na to organic phase2SO4Drying, suction filtering, adding a small amount of silica gel into the filtrate, and spin-drying the solvent under reduced pressure. The synthesis scheme of the chloroBODIPY derivative is shown in figure 1.
(2) Synthesis of fluorescent probe molecules: mixing the chloroBODIPY derivative and hydrazine hydrate in methanol, stirring and reacting for 8-12 hours at room temperature, performing rotary evaporation, and performing column chromatography separation to obtain an orange solid, namely the probe molecule with good fluorescence characteristic. A schematic of the synthesis of fluorescent probe molecules is shown in FIG. 2.
The acid in the step (1) is concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid;
the molar ratio of p-tolualdehyde to pyrrole in the step (1) is 1: (4-6);
the molar ratio of p-tolualdehyde to NCS in the step (1) is 1: (1-3);
the molar ratio of the compound 2 to chloranil in the step (1) is 1: (1-2);
the stirring speed in the step (2) is 500-2500 rpm;
the mol ratio of the chloroBODIPY derivative to hydrazine hydrate in the step (2) is 1: (10-20);
the invention also provides application of the fluorescent probe molecule for detecting the explosive RDX, and the probe can realize indirect detection of the explosive RDX through the change of fluorescence intensity in the acetonitrile-water mixed solution.
In the application, a reaction solution is prepared, explosives are photolyzed, and a fluorescence test process specifically comprises the following steps:
(1) preparation of fluorescent probe molecule solution: dissolving a product obtained by column chromatography in acetonitrile-water;
(2) preparation of RDX standard solution: taking the RDX solution, and diluting the RDX solution into standard solutions with different concentrations by using acetonitrile-water;
(3) reacting the fluorescent probe molecule with RDX: putting 10 mu L of the RDX standard solution with different concentrations in the step (2) into a 2mL centrifugal tube, irradiating under a portable ultraviolet lamp with the wavelength of 254nm to decompose the RDX standard solution, mixing 990 mu L of the probe molecule solution in the step (1) with 10 mu L of the RDX solution with different concentrations, and standing for a period of time;
(4) transferring the solution in the step (3) into a quartz cuvette with the thickness of 1 multiplied by 1cm, placing the quartz cuvette into a fluorescence spectrometer for fluorescence spectrum scanning, and exciting the wavelength lambdaex365nm, emission wavelength λem＝542nm；
(5) And recording the fluorescence intensity of the reaction product by using a fluorescence spectrometer, making a standard curve by using the fluorescence intensity and the concentration of the explosive RDX, and quantifying the RDX by using the standard curve.
The volume ratio of acetonitrile to water in the step (1) is 1: (0.25 to 1).
The concentration of the RDX solution in the step (2) is 5 x 10-6M～1×10-3M。
And (4) irradiating the portable ultraviolet lamp in the step (3) for 10-30 min.
The invention has the following advantages:
1. the fluorescent probe molecule has low preparation cost, simple synthetic route, mild reaction condition and convenient post-treatment;
2. the obtained fluorescent probe molecule has good fluorescence characteristic and light absorption characteristic in acetonitrile-water solution;
3. the prepared fluorescent probe molecule has good fluorescent response to a photolysis product of the explosive RDX, and the fluorescence intensity and the concentration of the RDX present a good linear relation, so that the fluorescent probe molecule can be used for indirectly quantifying the explosive RDX.
Drawings
FIG. 1 is a schematic diagram of the synthesis of chloroBODIPY derivatives;
FIG. 2 is a schematic diagram of the synthesis of a fluorescent probe molecule;
FIG. 3 of fluorescent Probe molecules1A HNMR profile;
FIG. 4 is an ESI-MS profile of a fluorescent probe molecule;
FIG. 5 is a graph of the fluorescence spectrum of a fluorescent probe molecule after reaction with a product of RDX photolysis;
FIG. 6 is a standard curve of fluorescence intensity of reaction products versus RDX concentration;
FIG. 7 is a fluorescence spectrum diagram of fluorescent probe molecules for selective detection of different explosives.
Detailed Description
The following examples further illustrate the invention but are not intended to limit it.
Example 1
The basic synthesis process of preparing fluorescent probe molecule is as follows:
(1) synthesis of chloroBODIPY derivatives: 0.5mL of concentrated HCl was dissolved in 100mL of distilled water and placed in a 250mL flask. 57.8mmol of pyrrole was added, and after stirring to clarify, 9.63mmol of p-tolualdehyde was added. After 1h reaction at room temperature, the reaction mixture was quenched with 2mL of aqueous ammonia and filtered. The obtained solid is washed with water for three times and then washed with petroleum ether for two times to obtain a milky white crude product. Adding 50mL of 9.63mmol NCS tetrahydrofuran suspension dropwise in 1h, continuing reaction for 2h, adding 50mL water, extracting with dichloromethane, and extracting organic phase with anhydrous Na2SO4Drying to obtain the compound 2. 2.4mmol of Compound 2 was dissolved in 25mL of dichloromethane, and a dispersion of 2.4mmol of chloranil in 10mL of dichloromethane was added dropwise to the reaction system. After reacting for 1h at room temperature, 18.7mmol of triethylamine is added and stirred for 1 h. Adding 37.4mmol boron trifluoride-diethyl ether complex by a syringe, reacting overnight in the dark, washing with water, and reacting the organic phase with anhydrous Na2SO4Drying, suction filtering, adding a small amount of silica gel into the filtrate, and spin-drying the solvent under reduced pressure.
(2) Synthesis of fluorescent probe molecules: mixing 90 mu mol of chloroBODIPY derivative and 0.9mmol of hydrazine hydrate in methanol, stirring and reacting for 8-12 hours at room temperature, performing rotary evaporation, and performing column chromatography separation to obtain an orange solid, namely the probe molecule with good fluorescence characteristic.
Of fluorescent probe molecules1The HNMR profile is shown in FIG. 3, and the ESI-MS profile is shown in FIG. 4.
Example 2
The basic synthesis process of preparing fluorescent probe molecule is as follows:
(1) synthesis of chloroBODIPY derivatives: 0.5mL of concentrated HCl was dissolved in 100mL of distilled water and placed in a 250mL flask. Adding 38.5mmol of pyrrole, stirring until the mixture is clear9.63mmol of p-tolualdehyde was added. After 1h reaction at room temperature, the reaction mixture was quenched with 2mL of aqueous ammonia and filtered. The obtained solid is washed with water for three times and then washed with petroleum ether for two times to obtain a milky white crude product. Adding 50mL of 28.9mmol NCS tetrahydrofuran suspension dropwise in 1h, continuing reaction for 2h, adding 50mL water, extracting with dichloromethane, and using anhydrous Na as organic phase2SO4Drying to obtain the compound 2. 2.4mmol of Compound 2 were dissolved in 25mL of dichloromethane, and a dispersion of 4.8mmol of chloranil in 10mL of dichloromethane was added dropwise to the reaction system. After reacting for 1h at room temperature, 18.7mmol of triethylamine is added and stirred for 1 h. Adding 37.4mmol boron trifluoride-diethyl ether complex by a syringe, reacting overnight in the dark, washing with water, and reacting the organic phase with anhydrous Na2SO4Drying, suction filtering, adding a small amount of silica gel into the filtrate, and spin-drying the solvent under reduced pressure.
(2) Synthesis of fluorescent probe molecules: mixing 90 mu mol of chloroBODIPY derivative and 1.8mmol of hydrazine hydrate in methanol, stirring and reacting for 8-12 hours at room temperature, performing rotary evaporation, and performing column chromatography separation to obtain an orange solid, namely the probe molecule with good fluorescence characteristic.
Example 3
Fluorescent probe molecules for detecting explosives RDX:
1000. mu.g/mL of RDX standard solution was diluted to 5X 10 with acetonitrile-water-6M,1×10-5M,2×10-5M,4×10-5M,6×10-5M,8×10-5M,1×10-4M,2×10-4M,4×10-4M，6×10-4M，8×10-4M，1×10-3M; putting the 10 mu L of RDX standard solution with different concentrations into a 2mL centrifuge tube, and irradiating for 10min under a portable ultraviolet lamp with the wavelength of 254nm to decompose the RDX standard solution; mixing 990 μ L of 145 μ M acetonitrile-water solution of fluorescent probe molecules of example 1 with the above 10 μ L of RDX solution of different concentrations, standing for 10min, transferring the above solution into 1 × 1cm quartz cuvette, placing into fluorescence spectrometer, performing fluorescence spectrum scanning, and exciting wavelength λex365nm, emission wavelength λem542 nm; the fluorescence spectrum of the fluorescent probe molecule after reaction with the RDX photolysis product is shown in FIG. 5; recording by fluorescence spectrometerThe fluorescence intensity of the reaction product is used for making a standard curve by using the fluorescence intensity and the concentration of explosive RDX, and the linear equation is as follows: y is 4.23x +63.8 as shown in fig. 6.
Example 4
Selectivity of fluorescent probe molecules for explosive RDX response:
taking a standard solution of 1000 mu g/mL of trinitrotoluene (TNT), Picric Acid (PA), 2, 4-Dinitrotoluene (DNT) trimethylene trinitroamine (RDX), and diluting the standard solution with acetonitrile-water to obtain a standard solution with the same concentration of 4 x 10-3M, respectively taking 10 mu L of the mixture in a 2mL centrifugal tube, and irradiating for 10min under a portable ultraviolet lamp with the wavelength of 254nm to decompose the mixture; mixing 990 μ L acetonitrile-water solution of fluorescent probe molecule in example 1 with concentration of 145 μ M with the above 10 μ L solution of different kinds of explosives, standing for 10min, transferring the above solution into 1 × 1cm quartz cuvette, placing into fluorescence spectrometer for fluorescence spectrum scanning, and exciting wavelength λex365nm, emission wavelength λemAs shown in fig. 7, the result shows that only RDX, an explosive, can increase the fluorescence intensity of the fluorescent probe molecule, TNT and DNT have no effect on the fluorescence of the probe molecule, and PA quenches the fluorescence of the probe molecule, which indicates that the probe molecule has a good recognition effect on the explosive RDX.
Claims (4)
1. The application of a fluorescent probe molecule for detecting explosive RDX is characterized in that the probe molecule can realize indirect detection of the explosive RDX through the change of fluorescence intensity in an acetonitrile-water mixed solution; the specific operation steps are as follows:
(1) preparation of fluorescent probe molecule solution: dissolving the probe molecule in acetonitrile-water;
(2) preparation of RDX standard solution: taking the RDX solution, and diluting the RDX solution into standard solutions with different concentrations by using acetonitrile-water;
(3) reacting the fluorescent probe molecule with RDX: putting 10 mu L of the RDX standard solution with different concentrations in the step (2) into a 2mL centrifugal tube, irradiating under a portable ultraviolet lamp with the wavelength of 254nm to decompose the RDX standard solution, mixing 990 mu L of the probe molecule solution in the step (1) with 10 mu L of the RDX solution with different concentrations, and standing for a period of time;
(4) mixing the solution in (3)Transferring into 1 × 1cm quartz cuvette, placing into fluorescence spectrometer for fluorescence spectrum scanning, and exciting wavelength λex365nm, emission wavelength λem＝542nm；
(5) Recording the fluorescence intensity of the reaction product by using a fluorescence spectrometer, making a standard curve by using the fluorescence intensity and the concentration of the explosive RDX, and quantifying the RDX by using the standard curve;
the structural formula of the fluorescent probe is as follows:
2. use of a fluorescent probe molecule for the detection of explosives RDX according to claim 1, characterized in that: the volume ratio of acetonitrile to water in the step (1) is 1: 0.25 to 1.
3. Use of a fluorescent probe molecule for the detection of explosives RDX according to claim 1, characterized in that: the concentration of the RDX solution in the step (2) is 5 x 10-6M～1×10-3M。
4. Use of a fluorescent probe molecule for the detection of explosives RDX according to claim 1, characterized in that: and (4) irradiating the portable ultraviolet lamp in the step (3) for 10-30 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711083499.7A CN109748930B (en) | 2017-11-07 | 2017-11-07 | Fluorescent probe molecule for detecting explosive RDX and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711083499.7A CN109748930B (en) | 2017-11-07 | 2017-11-07 | Fluorescent probe molecule for detecting explosive RDX and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109748930A CN109748930A (en) | 2019-05-14 |
| CN109748930B true CN109748930B (en) | 2021-06-01 |
Family
ID=66401313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711083499.7A Active CN109748930B (en) | 2017-11-07 | 2017-11-07 | Fluorescent probe molecule for detecting explosive RDX and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109748930B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111272684B (en) * | 2020-03-09 | 2023-03-10 | 欣旺达电动汽车电池有限公司 | Fe in electrolyte 2+ Method for measuring concentration |
| CN113008853B (en) * | 2021-02-25 | 2023-01-24 | 中国工程物理研究院化工材料研究所 | Method for in-situ marking and visual tracing of explosive based on fluorescent energetic molecules |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013493A (en) * | 2012-11-07 | 2013-04-03 | 中国科学院理化技术研究所 | Fluorescence chemical sensor capable of selectively detecting biological sulfhydryl compound, preparation method and application of fluorescence chemical sensor |
| CN103724255A (en) * | 2014-01-07 | 2014-04-16 | 大连理工大学 | Preparation method of compounds used for detecting explosive RDX (Research Department eXplosive) and based on acylamino dihydropyridine structure |
| CN106753339A (en) * | 2016-12-06 | 2017-05-31 | 北京师范大学 | It is a kind of can high selectivity recognize benzenethiol fluorescence probe, preparation method and application |
-
2017
- 2017-11-07 CN CN201711083499.7A patent/CN109748930B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103013493A (en) * | 2012-11-07 | 2013-04-03 | 中国科学院理化技术研究所 | Fluorescence chemical sensor capable of selectively detecting biological sulfhydryl compound, preparation method and application of fluorescence chemical sensor |
| CN103724255A (en) * | 2014-01-07 | 2014-04-16 | 大连理工大学 | Preparation method of compounds used for detecting explosive RDX (Research Department eXplosive) and based on acylamino dihydropyridine structure |
| CN106753339A (en) * | 2016-12-06 | 2017-05-31 | 北京师范大学 | It is a kind of can high selectivity recognize benzenethiol fluorescence probe, preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| "A BODIPY analogue from the tautomerization of sodium 3-oxide BODIPY";Peng-Zhong Chen等;《Chinese Chemical Letters》;20150418;第26卷;支持信息第S1-S2页 * |
| "A multi-stimuli-responsive fluorescence switch based on E–Z isomerization of hydrazone";Hai-Rong Zheng等;《RSC Adv.》;20160418;第6卷;支持信息第2页 * |
| "Photodegradation of RDX in Aqueous Solution:A Mechanistic Probe for Biodegradation with Rhodococcus sp.";J.HAWARI等;《Environ.Sci.Technol.》;20021102;第36卷(第23期);第5117-5123页 * |
| Hai-Rong Zheng等."A multi-stimuli-responsive fluorescence switch based on E–Z isomerization of hydrazone".《RSC Adv.》.2016,第6卷支持信息第2页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109748930A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Fabrication and characterization of a fluorescent sensor based on Rh 6G-functionlized silica nanoparticles for nitrite ion detection | |
| Wang et al. | A terbium metal–organic framework with stable luminescent emission in a wide pH range that acts as a quantitative detection material for nitroaromatics | |
| Jain et al. | Selective extraction, preconcentration and transport studies of thorium (IV) using octa-functionalized calix [4] resorcinarene-hydroxamic acid | |
| CN114591633B (en) | Xanthene-hemicyanine near-infrared fluorescent dye, and synthetic method and application thereof | |
| CN105842235A (en) | High-sensitivity fluorescent test paper capable of realizing naked-eye detection of volatile organic amine and preparation thereof | |
| CN109748930B (en) | Fluorescent probe molecule for detecting explosive RDX and preparation method and application thereof | |
| Zeng et al. | A new fluorescent probe for ultrasensitive detection of phosgene in solution and the gas phase | |
| CN111393461B (en) | Palladium ion fluorescent probe compound based on BODIPY and synthetic method thereof | |
| CN109879776A (en) | A kind of application of the sour cyanines derivative in water solubility side and its synthetic method and detection aldehyde compound | |
| Chen et al. | A novel turn-off fluorescent probe based on TICT for the detection of NO2 and nitramines with high sensitivity and selectivity | |
| Chen et al. | A novel bifunctional-group salamo-like multi-purpose dye probe based on ESIPT and RAHB effect: Distinction of cyanide and hydrazine through optical signal differential protocol | |
| Wu et al. | A novel “on-off-on” acylhydrazone-based fluorescent chemosensor for ultrasensitive detection of Pd2+ | |
| Chen et al. | A novel single-fluorophore-based ratiometric fluorescent probe for detection of formaldehyde in air | |
| Dey et al. | Triazole-based pyrene-sugar analogues for selective detection of picric acid in water medium and paper strips | |
| CN110627756B (en) | Colorimetric-fluorescent probe for detecting hypochlorite and preparation method and application thereof | |
| CN110423609B (en) | Fluorescent probe for identifying thiocyanate radical and preparation and identification method thereof | |
| CN109516979B (en) | Method for detecting dinitrate explosives by using fluorescence | |
| CN113880851B (en) | Trifluorene bridged hexaimidazole macrocyclic compound and preparation method and application thereof | |
| Li et al. | Rapid determination of illegally added Sudan I in cake by triphenylamine functionalized polyhedral oligomeric silsesquioxane fluorescence sensor | |
| CN113264893A (en) | Praseodymium ion fluorescent probe compound, and preparation method and application thereof | |
| CN106018358B (en) | It is a kind of to detect picric fluorescent optical sensor and preparation method thereof | |
| CN111208096B (en) | Method for detecting picric acid by using fluorescent sensor based on BODIPY derivative | |
| CN114751824B (en) | Preparation method and application of conjugated material containing ethyl benzoate structure | |
| CN112679432B (en) | Naphthalimide-diphenyl sulfone derivative fluorescent probe and preparation method and application thereof | |
| CN114181148B (en) | 'on-off' type fluorescent probe, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |