CN111808130A - Synthesis and application of fluorescent probe for detecting diethyl chlorophosphate - Google Patents
Synthesis and application of fluorescent probe for detecting diethyl chlorophosphate Download PDFInfo
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- CN111808130A CN111808130A CN202010601221.XA CN202010601221A CN111808130A CN 111808130 A CN111808130 A CN 111808130A CN 202010601221 A CN202010601221 A CN 202010601221A CN 111808130 A CN111808130 A CN 111808130A
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- diethyl chlorophosphate
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- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 98
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 29
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 29
- 239000000523 sample Substances 0.000 claims abstract description 53
- 239000013307 optical fiber Substances 0.000 claims abstract description 49
- 238000001514 detection method Methods 0.000 claims abstract description 42
- 230000005284 excitation Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000002381 microspectrum Methods 0.000 claims abstract description 15
- 230000008054 signal transmission Effects 0.000 claims abstract description 12
- 238000004020 luminiscence type Methods 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 7
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 35
- -1 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol Chemical compound 0.000 claims description 23
- 238000012360 testing method Methods 0.000 claims description 17
- 230000008859 change Effects 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- UTCSSFWDNNEEBH-UHFFFAOYSA-N imidazo[1,2-a]pyridine Chemical compound C1=CC=CC2=NC=CN21 UTCSSFWDNNEEBH-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- CZQYPRJUZNAMEG-UHFFFAOYSA-N 3-hydroxy-4-(2-hydroxynaphthalen-1-yl)naphthalene-2-carbaldehyde Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C(C=O)=CC2=C1 CZQYPRJUZNAMEG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
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- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 claims description 5
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 claims description 5
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 5
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 5
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
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- DVWQNBIUTWDZMW-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalen-2-ol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=CC=CC2=C1 DVWQNBIUTWDZMW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011895 specific detection Methods 0.000 abstract description 4
- 230000000007 visual effect Effects 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 108700012359 toxins Proteins 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
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- 238000001228 spectrum Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IGMWDYQIKLLYQH-UHFFFAOYSA-N cyanomethyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCC#N IGMWDYQIKLLYQH-UHFFFAOYSA-N 0.000 description 6
- ZWWWLCMDTZFSOO-UHFFFAOYSA-N diethoxyphosphorylformonitrile Chemical compound CCOP(=O)(C#N)OCC ZWWWLCMDTZFSOO-UHFFFAOYSA-N 0.000 description 6
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- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 5
- 238000011897 real-time detection Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- QCCNSXFQVAAQDA-UHFFFAOYSA-M P(=O)(OCC)(OCC)[O-].[Cl+] Chemical compound P(=O)(OCC)(OCC)[O-].[Cl+] QCCNSXFQVAAQDA-UHFFFAOYSA-M 0.000 description 3
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- 150000003384 small molecules Chemical class 0.000 description 3
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- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
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- 102000004190 Enzymes Human genes 0.000 description 2
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GRXKLBBBQUKJJZ-UHFFFAOYSA-N Soman Chemical compound CC(C)(C)C(C)OP(C)(F)=O GRXKLBBBQUKJJZ-UHFFFAOYSA-N 0.000 description 2
- PJVJTCIRVMBVIA-JTQLQIEISA-N [dimethylamino(ethoxy)phosphoryl]formonitrile Chemical compound CCO[P@@](=O)(C#N)N(C)C PJVJTCIRVMBVIA-JTQLQIEISA-N 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 208000010476 Respiratory Paralysis Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- SNTRKUOVAPUGAY-UHFFFAOYSA-N cyclosarin Chemical compound CP(F)(=O)OC1CCCCC1 SNTRKUOVAPUGAY-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a fluorescent probe for detecting diethyl chlorophosphate and its synthesis and application, synthesizing a silicon compound fluorescent probe based on 1,1' -binaphthol structure, which can realize the specific detection of war toxin simulant diethyl chlorophosphate, and has the advantages of fast response speed, low detection limit, longer luminescence wavelength, high commercialization degree, greatly reducing the cost required by probe synthesis, and also discloses an application method of the fluorescent probe for detecting diethyl chlorophosphate based on normalized processing data, which comprises a micro spectrum analyzer, an excitation light source and a computer, wherein the three carry out signal transmission through signal transmission optical fibers, and has unique electromagnetic interference resistance advantage, the optical fiber probe has the advantage of corrosion resistance, and the sensor is different from the conventional visual observation due to the accuracy of optical signals, the method has the characteristic of high detection accuracy on the diethyl chlorophosphate steam.
Description
Technical Field
The invention relates to synthesis and application of a fluorescent probe for detecting diethyl chlorophosphate, belonging to the technical field of synthesis and application of fluorescent probes for war nerve agent mimics.
Background
Organic phosphorus compounds (OPS) have been widely used in agriculture as pesticides and herbicides due to their high toxicity, and have been used in warfare as Chemical Warfare Agents (CWA). Among these, G-type nerve agents occur during world war ii and include Tabun (Tabun), Sarin (Sarin), Soman (Soman) and cyclicin (Cyclosarin). They may cause irreversible damage to acetylcholinesterase in the human nervous system and affect neurotransmission, and death from respiratory paralysis occurs within minutes of the person exposed to nerve agents. Although such CWA is strictly restricted in international society, there are still events with which terrorists take people away from life, such as terrorist attacks on the tokyo subway. Therefore, rapid detection of these nerve agents in a convenient manner is of paramount importance to public safety systems. Since CWA is a national regulated chemical, we generally tested using a simulant, diethyl chlorophosphate, as a substitute, that is similar in activity to CWA, but relatively less toxic. Since CWA has similar activity to its mimetics, if a probe responds to a mimetic, it must also respond similarly to CWA. Thus, it is generally accepted in the industry to replace chemical warfare agents with simulants for toxic gas research.
The current research shows that electrochemical methods, mass spectrometry methods, enzymatic chemical methods and the like are common in the detection method of war toxin mimics. Electrochemical analysis is the science of characterizing and measuring using the electrical and electrochemical properties of a substance, which is an important component of the disciplines of electrochemical and analytical chemistry; mass spectrometry is a method in which moving ions are separated according to their mass-to-charge ratios by an electric field and a magnetic field and then detected; the enzyme analysis method is a biological and pharmaceutical analysis method, and realizes the detection of a substance to be detected by using the specificity and high catalysis of the enzyme. These several common approaches all enable accurate detection of war agent simulants.
In recent years, some nanofibers and small organic molecules have been developed as fluorescent probes to detect mimics of nerve agents due to their ease of preparation, high sensitivity and rapid response. Compared with other analytes, scientists have found a plurality of methods for detecting nerve gas, including gas chromatography, mass spectrometry, ion mobility spectrometry, enzyme sensors, capillary electrophoresis, colorimetry and the like, but the fluorescence probes reported to be used for detecting nerve agents are still deficient, and according to the current research, although the common detection mode for war toxin mimics can realize accurate detection of the war toxins, the common detection mode also has the defects of complex detection mode, high detection cost and the like. The fluorescence method has the advantages of convenient detection mode, low detection cost and the like. In addition, although some fluorescent probes are currently used to detect war agent mimics, most of the applications for such fluorescent probe molecules are in solution or on test strips. For example, research works of s.huang, y.wu, f.zeng, l.sun, s.wu, etc. are mostly based on detection test paper for detecting the vapors of diethyl chlorophosphate, and such applications have problems that the detection cannot be represented by accurate datamation and can only be identified by visual observation.
The optical fiber sensing technology is widely concerned by students and researchers in the early stage of birth, originally developed in the FOSS project of the research institute of the navy of the united states, and is still one of the most important branches of the application of the photoelectric technology and the most rapid development of the technology so far. Compared with the traditional detection mode, the optical fiber sensing technology has the advantages of electromagnetic interference resistance, chemical corrosion resistance, high sensitivity, wide application environment range and the like, so that the test precision and the application range of the optical fiber sensor are more excellent than those of the traditional test method, and as most of organic small molecules have excellent solubility in common organic solvents, the film forming effect of the organic small molecule fluorescent probe on the optical fiber is better than that of common inorganic substances. If the organic small-molecule fluorescent probe can be combined with the optical fiber sensing technology, compared with other fluorescent probes which can be used for detecting war toxin mimics, the optical fiber sensor which can be used for detecting the diethyl chlorophosphate steam can be prepared theoretically. Theoretically, the real-time detection of the object to be detected can be realized, and the device has good stability and higher real-time precision.
Therefore, it is important to design and synthesize a fluorescent probe with high commercial cost, prepare a warfare agent gas detection fluorescent probe with high electromagnetic interference resistance, high corrosion resistance and high detection precision, and obtain an application method combined with an optical fiber probe.
Disclosure of Invention
The invention mainly overcomes the defects in the prior art and provides synthesis and application of a fluorescent probe for detecting diethyl chlorophosphate. The invention discloses a synthesis and application of a fluorescent probe for detecting diethyl chlorophosphate, which synthesizes a silicon compound fluorescent probe based on 1,1' -binaphthol structure, can realize the specific detection of the war toxin simulant diethyl chlorophosphate, has the advantages of high response speed, low detection limit, longer luminescence wavelength and the like, has high commercialization degree, greatly reduces the cost required by probe synthesis, and also discloses an application method of the fluorescent probe for detecting the diethyl chlorophosphate based on normalized processing data, which comprises a micro spectrum analyzer, an excitation light source and a computer, wherein the three parts carry out signal transmission through a signal transmission optical fiber, and have unique electromagnetic interference resistance advantage, the optical fiber probe has the advantage of corrosion resistance, and the sensor is different from the conventional naked eye observation due to the accuracy of optical signals, the method has the characteristic of high detection accuracy on the diethyl chlorophosphate steam.
The technical scheme provided by the invention for solving the technical problems is as follows: the synthesis and application of the fluorescent probe for detecting the diethyl chlorophosphate are characterized in that the synthesis of the fluorescent probe for detecting the diethyl chlorophosphate comprises the following steps:
(1) under the protection of inert gas atmosphere, putting 2, 2 '-dihydroxy- [1, 1' -binaphthyl ] -3-formaldehyde into a round-bottom flask, and adding a certain amount of ultra-dry ethanol to fully dissolve the mixture;
(2) adding 2, 3-diaminonaphthalene at room temperature, and then adding sodium metabisulfite;
(3) heating and refluxing for a certain time under a proper temperature condition, cooling to room temperature, performing rotary evaporation to remove the solvent, performing multiple extraction with ethyl acetate, washing an organic phase, drying with anhydrous sodium sulfate, performing rotary evaporation to obtain a brown solid crude product, performing column chromatography purification, and performing vacuum drying to obtain 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol;
(4) under the protection of inert gas atmosphere, 3- (1H-naphtho [2, 3-d ] imidazole-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol is placed in a round-bottom flask, and a certain amount of redistilled tetrahydrofuran is added to be fully dissolved;
(5) adding redistilled triethylamine dropwise at room temperature, wherein the reaction system is changed from yellow to brown;
(6) after a certain time, the Ph is added dropwise2SiCl2The color of the reaction system becomes lighter;
(7) after a certain time, TLC detection is carried out, when the raw materials are basically completely reacted, ethyl acetate is used for multiple times of extraction, an organic phase is washed, anhydrous sodium sulfate is used for drying, a yellow solid crude product is obtained through rotary evaporation, column chromatography purification and vacuum drying are carried out, and the fluorescent probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasililin-8-onium is obtained.
Preferably, when the inert gas in the step (1) and the step (4) is argon, the molar mass of 2, 2 '-dihydroxy- [1, 1' -binaphthyl ] -3-formaldehyde in the step (1) is 1mmol, the using amount of the ultra-dry ethanol is 30mL, the suitable temperature in the step (3) is 85 ℃, the certain time is 3h, the extraction time of the ethyl acetate is 2 times, the organic phase washing process sequentially comprises distilled water and saturated saline solution washing, and the volume ratio of the elution phases of the column chromatography purification is petroleum ether: ethyl acetate 3: 1.
Preferably, in the step (1) and the step (2), the ratio of 2, 2 '-dihydroxy- [1, 1' -binaphthyl ] -3-carbaldehyde: 2, 3-diaminonaphthalene: the molar mass ratio of the sodium metabisulfite is 1 mmol: 1.2 mmol: 1.2 mmol.
Preferably, when the molar mass of the 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol in the step (4) is 0.5mmol, the amount of the redistilled tetrahydrofuran is 30 mL; in the step (7), the extraction frequency of ethyl acetate is 2 times, the washing process of the organic phase sequentially comprises washing with distilled water and saturated saline solution, and the volume ratio of the elution phase of column chromatography purification is petroleum ether: ethyl acetate 3: 1.
Preferably, the 3- (1H-naphtho [2, 3-d ] in the steps (4) to (6)]Imidazol-2-yl) - [1, 1' -binaphthyl]-2, 2' -diol: redistilled triethylamine: ph2SiCl2The molar mass ratio of (a) to (b) is 0.5 mmol: 1.5 mmol: 1.3 mmol.
Preferably, the certain time in the step (6) is 5min, and the certain time in the step (7) is 30 min.
Further, synthesis and application of a fluorescent probe for detecting diethyl chlorophosphate are characterized in that the fluorescent probe comprises the following application steps:
(1) dissolving 10.0 mu mol of fluorescent probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasilin-8-onium in 10.0mL of acetone, after the full dissolution, uniformly coating the solution on an optical fiber probe part of a micro spectrometer, and then forming a fluorescent probe film after the solution naturally volatilizes;
(2) using exciting light with certain wavelength as exciting light source, performing fluorescence excitation via fiber probe part of micro spectrum analyzer, and recording original luminescence intensity I via computer0；
(3) Mixing the diethyl chlorophosphate steam and nitrogen by using a gas collection bag, and mixing the diethyl chlorophosphate steam with different concentrations to be detected;
(4) inserting the optical fiber probe part of the micro spectrum analyzer into gas collection bags of diethyl chlorophosphate steam with different concentrations for testing, recording the optimal emission fluorescence intensity I, and carrying out normalization processing on the change degree of the optimal emission fluorescence intensity data;
(5) performing linear fitting through software to obtain a fitting function between the concentration of the diethyl chlorophosphate vapor and the normalized data of the change degree of the optimal emitted fluorescence intensity data;
(6) when detecting the diethyl chlorophosphate steam with unknown concentration, calculating to obtain the normalized data of the change degree of the optimal emission fluorescence intensity data under the concentration after detecting the diethyl chlorophosphate steam with unknown concentration, and substituting the normalized data into the fitting function obtained in the step (5) to obtain the concentration of the diethyl chlorophosphate steam;
(7) and (3) when the theoretical value of the fluorescent probe to the low detection limit of diethyl chlorophosphate is detected, substituting the signal-to-noise ratio of the micro spectrum analyzer into the fitting function obtained in the step (5) to obtain the theoretical value of the fluorescent probe to the low detection limit of diethyl chlorophosphate.
Preferably, the wavelength of the excitation light with a certain wavelength in the step (2) is 380nm, and the fitting software in the step (5) is origin software.
Preferably, the micro spectrum analyzer, the excitation light source and the computer transmit signals through signal transmission optical fibers, wherein the signals are luminous intensity and fluorescence intensity, and the optical fiber probe in the step (1) comprises an incident light optical fiber and a fluorescence absorption optical fiber.
Preferably, the method for normalizing the variation degree of the optimal fluorescence intensity data in the step (4) is to subtract the original luminescence intensity I of the fluorescent probe film from the real-time optimal fluorescence intensity I of the diethyl chlorophosphate steam with different concentrations obtained by the test0Then divided by the original luminous intensity I of the fluorescent probe film0The intensity of the fluorescence which represents the optimal emission can be obtainedData normalized to the degree of change in the data.
Compared with the prior art, the invention has the following advantages:
the invention discloses a synthesis and application of a fluorescent probe for detecting diethyl chlorophosphate, which synthesizes a silicon compound fluorescent probe based on 1,1' -binaphthol structure, can realize the specific detection of the war toxin simulant diethyl chlorophosphate, has the advantages of high response speed, low detection limit, longer luminescence wavelength and the like, has high commercialization degree, greatly reduces the cost required by probe synthesis, and also discloses an application method of the fluorescent probe for detecting the diethyl chlorophosphate based on normalized processing data, which comprises a micro spectrum analyzer, an excitation light source and a computer, wherein the three parts carry out signal transmission through a signal transmission optical fiber, and have unique electromagnetic interference resistance advantage, the optical fiber probe has the advantage of corrosion resistance, and the sensor is different from the conventional naked eye observation due to the accuracy of optical signals, the method has the characteristic of high detection accuracy on the diethyl chlorophosphate steam.
Drawings
FIG. 1 is 3- (1H-naphtho [2, 3-d ]]Imidazol-2-yl) - [1, 1' -binaphthyl]-2, 2' -diol hydrogen spectrum (400MHz, DMSO-d)6)；
FIG. 2 is 3- (1H-naphtho [2, 3-d ]]Imidazol-2-yl) - [1, 1' -binaphthyl]Carbon spectrum of (100MHz, DMSO-d) 2, 2' -diol6)；
FIG. 3 is a mass spectrum of 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol;
FIG. 4 is 5- (2-hydroxynaphthalen-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ]]Naphtho [2 ', 3': 4, 5]]Imidazo [1, 2-c ]][1，3，2]Oxasilin-8-ium hydrogen spectrum (400MHz, DMSO-d)6)；
FIG. 5 is 5- (2-hydroxynaphthalen-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ]]Naphtho [2 ', 3': 4, 5]]Imidazo [1, 2-c ]][1，3，2]Oxasilin-8-ium carbon spectrum (100MHz, DMSO-d)6)；
FIG. 6 is a 5- (2-hydroxynaphthalen-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasilin-8-ium mass spectrum;
FIG. 7 shows fluorescence emission spectra of fluorescent probes in different solvents (E)Xslit＝5.0nm，Emslit＝5.0nm)；
FIG. 8 shows the fluorescence response of probe (10.0. mu.M) to DMMP, DCNP, DCMP and DCP (all 50. mu.M) under optimal excitation (λ ex ═ 334nm) (curves from top to bottom for individual probes, probe + DMMP, probe + DCNP, probe + DCMP, probe + DCP);
FIG. 9 is a competition response experiment for probes (10.0 μ M) with different war toxin mimics (20.0 μ M);
FIG. 10 is a graph of fluorescence titration spectra of probe and DCP of different concentrations;
FIG. 11 is a schematic view of an apparatus for detecting the use of a fluorescent probe for diethyl chlorophosphate;
FIG. 12 is a schematic view of the microstructure of the fiber optic probe;
wherein, 1 is an absorption optical fiber for absorbing the fluorescent signal of the sensitive film, 2 is an optical fiber for providing an excitation light source, and 3 is an optical fiber probe.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example (b):
(1) synthesis of a fluorescent probe for detecting diethyl chlorophosphate:
a fluorescent probe synthesis for detecting diethyl chlorophosphate comprises the following steps:
(1) placing 2, 2 '-dihydroxy- [1, 1' -binaphthyl ] -3-formaldehyde (314.0mg, 1mmol) in a 100mL round-bottom flask under the protection of argon, and adding 30mL of ultra-dry ethanol to fully dissolve the mixture;
(2) 2, 3-diaminonaphthalene (196.0mg, 1.2mmol) was added at room temperature, followed by sodium metabisulfite (228.0mg, 1.2 mmol);
(3) heating and refluxing for 3 hours at 85 ℃, cooling to room temperature, performing rotary evaporation to remove the solvent, extracting for 2 times by using ethyl acetate 30mL, washing an organic phase by using distilled water and saturated saline water, drying by using anhydrous sodium sulfate, performing rotary evaporation to obtain a brown solid crude product, performing column chromatography purification by using petroleum ether and ethyl acetate with the volume ratio of 3:1 as an elution phase, and performing vacuum drying to obtain 241.0mg of ligand 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol with the yield of 56.2%;
(4) placing 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol (226.0mg, 0.5mmol) in a 100mL round-bottom flask under argon protection, and adding 30mL of redistilled tetrahydrofuran to fully dissolve the diol;
(5) redistilled triethylamine (1.5mmol, 0.25mL) is added dropwise at room temperature, and the reaction system turns brown from yellow;
(6) after 5min, further dropwise adding Ph2SiCl2(1.3mmol, 0.25mL), the color of the reaction system became lighter;
(7) after 30min, TLC detection is carried out, when the raw materials are basically completely reacted, the raw materials are extracted for 2 times by using 30mL of ethyl acetate, organic phases are washed by distilled water and saturated saline solution in turn, dried by anhydrous sodium sulfate and rotated and evaporated to obtain a yellow solid crude product, the crude product is taken as an elution phase with the volume ratio of petroleum ether to ethyl acetate being 3:1, column chromatography purification and vacuum drying are carried out to obtain 16.0mg of the fluorescent probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasilin-8-onium, and the yield is 6.2%.
(2) Characterization of a fluorescent probe for detection of diethyl chlorophosphate:
(a) laboratory apparatus
1H and13CNMR Japanese Electron (JEOL) JNM-ECS 400 and Varian INOVA 600M Hz NMR spectrometer with CDCl as deuterated reagent3And d6DMSO, TMS as internal standard.
ESI-MS: bruker Daltonics instrument 6000 specrometer and Bruker Daltonics APEXII 47e FT-ICR specrometer were used.
A fluorescence spectrometer: hitachi F-7000fluorescence spectrophotometer.
(b) Test conditions
Preparing a 10.0mM N, N-dimethylformamide (spectrum level) stock solution by using a probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasilin-8-onium; diethyl chlorophosphate was prepared as a 10.0mM DMF stock solution; all solvents in the selection of test solvents were spectroscopic grade N, N-Dimethylformamide (DMF), spectroscopic grade dimethyl sulfoxide (DMSO), chromatographically pure Acetone (ACT), and chromatographically pure Dichloromethane (DCM). The remaining fluorescence measurements were performed in spectroscopic grade N, N-Dimethylformamide (DMF).
The fluorescence excitation wavelength of the probe is lambdaex334 nm; the test slit was 5.0 nm.
(c) Structural characterization of 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol
As shown in the figures 1-3 of the drawings,1H NMR(400MHz,DMSO–d6):＝13.65(s,1H),13.34(s,1H), 9.35(s,1H),8.95(s,1H),8.21(s,2H),8.07(s,2H),8.03(d,J＝8.0Hz,1H),7.92(d, J＝8.8Hz,1H),7.90(d,J＝8.0Hz,1H),7.44–7.32(m,5H),7.27(td,J＝6.8,0.8Hz, 1H),7.20(td,J＝8.4,1.2Hz,1H),7.04(d,J＝8.4Hz,2H)ppm；13C NMR(100 MHz,DMSO–d6):＝155.8,154.0,153.1,152.8,152.5,135.2,133.8,128.8,128.6, 128.1,127.8,127.7,127.2,127.0,125.8,124.4,124.1,123.3,122.2,118.5,117.5, 114.9,114.4ppm；ESI–MS:m/z＝453.4[M+H]+shows 3- (1H-naphtho [2, 3-d ]]Imidazol-2-yl) - [1, 1' -binaphthyl]The synthesis of the (2, 2' -diol) was indeed successful.
(d) Structural characterization of fluorescent probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasilin-8-ium
As shown in the figures 3-6 of the drawings,1H NMR(DMSO-d6,400MHz):＝14.15(s,1H),13.46(s,1H), 9.05(s,1H),8.96(d,J＝8.8Hz,1H),8.72(d,J＝7.6Hz,1H),8.41-8.39(m,1H),8.09 (d,J＝8.4Hz,1H),7.89-7.85(m,1H),7.79-7.75(m,2H),7.66-7.63(m,3H), 7.41-7.37(m,1H),7.30-7.26(m,4H),7.15-7.10(m,4H),6.98-6.92(m,4H)ppm.13C NMR(DMSO-d6,100MHz):＝154.8,151.3,137.1,136.7,136.6,135.9,134.7, 134.6(2C),134.5(4C),134.2,131.5,130.5,130.4,130.2,130.1,129.8,129.7,128.8, 128.7,128.1(2C),128.0(4C),127.9(2C),126.8,126.0,125.3,124.9,124.4,123.0, 119.4,119.3,113.6,113.1,113.0,111.4ppm.HRMS(ESI):m/z calcd for C43H29N2O2Si+[M+H2O]+:651.2098,found:651.2100.
(e) fluorescent probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasilin-8-ium spectral property
1) Fluorescent response of probes in different solvents
The fluorescent probes show different fluorescent colors in different solvents, and in order to better study the luminescence property of the fluorescent probes, four common organic solvents (ACT, DCM, DMSO and DMF) are selected and respectively subjected to fluorescence tests under optimal excitation. FIG. 7 shows fluorescence emission spectra of fluorescent probes in different solvents, from which it can be seen that the probes have longer emission wavelengths in DMF and DMSO and higher probe emission intensities, while in DCM and ACT the fluorescence intensity is overall lower and the emission wavelength is shorter. In consideration of later practical application, the DMF solvent with longer emission wavelength and higher fluorescence intensity is finally selected as the test environment of the probe molecules.
2) Fluorescent response studies of probes to different warfare agent simulants
After selecting DMF as the test environment, we tested four common warfare agent mimics with fluorescent probes under optimal excitation: dimethyl phosphate (DMMP), Diethyl Cyanophosphate (DCNP), Diethyl Cyanomethylphosphate (DCMP) and Diethyl Chlorophosphate (DCP). As shown in fig. 8, the test results found that the fluorescent probe molecule exhibited a fluorescence quenching response only to diethylchlorophosphate, while exhibiting little change in fluorescence to the other three common warfare agent mimics. The probe is a fluorescence quenching type probe, when the probe reacts with diethyl chlorophosphate, a fluorescence quenching effect is shown at 565nm, and the color of the solution is changed from green to light green under the irradiation of an ultraviolet lamp with an excitation wavelength of 365 nm. These results indicate that the fluorescent probe has excellent selectivity for diethyl chlorophosphate and a macroscopic color change can be observed under ultraviolet lamp irradiation. And the fluorescent probes have larger Stokes shift.
3) Competition and interference experiments with probes
In order to research the specific recognition of the fluorescent probe to the diethyl chlorophosphate in the presence of different war toxin mimics, four common war toxin mimics DMMP, DCNP, DCMP and DCP are selected to carry out interference experiments on the fluorescent probe. As shown in FIG. 9, the red bars represent the fluorescence intensity of the fluorescent probe after addition of diethylchlorophosphate, and the black bars represent the fluorescence intensity of the fluorescent probe after addition of other war toxin mimics (1-3 are DMMP, DCNP and DCMP, respectively). In the presence of the other warfare agent mimics described above, no quenching effect was seen at 565nm for the fluorescent probe, whereas significant fluorescence quenching occurred after the addition of diethylchlorophosphate. This phenomenon indicates that the fluorescent probe can still achieve effective identification of the diethylchlorophosphate even in the presence of other war toxin mimics.
4) Probe fluorescence titration study
To further investigate the relationship between the concentration of diethylchlorophosphate and fluorescence of the fluorescent probe, a fluorescence titration experiment of diethylchlorophosphate molecules was performed. As shown in FIG. 10, the fluorescence spectra of the fluorescent probes reacted with different concentrations of diethylchlorophosphate (0.0,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0,12.0and 13.0. mu.M). As a result of the test, it was found that when the concentration of diethyl chlorophosphate reached 10.0. mu.M (1.0eq), the fluorescence intensity of the fluorescent probe at 565nm was minimized, which was one fifth of that before the reaction with diethyl chlorophosphate. The fluorescence intensity value of the fluorescent probe at 565nm is plotted against different concentrations of the diethyl chlorophosphate (0.0,1.0,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0,11.0,12.0and 13.0 μ M), the fluorescent probe and the concentration of the added diethyl chlorophosphate (0.0-10.0 μ M) show good linear relation, and the R value of the reaction of the fluorescent probe and the diethyl chlorophosphate in the added concentration range of the diethyl chlorophosphate is 0.9989 by linear fitting. Therefore, the concentration of the diethyl chlorophosphate is within 0.0-10.0 mu M, and the fluorescent probe and the diethyl chlorophosphate show good linear relation.
In conclusion, the fluorescent probe based on the binaphthol structure silicon compound is successfully synthesized, can realize the specific identification of the warfare agent simulant diethyl chlorophosphate, has the advantages of high sensitivity and short reaction time, and has a good detection effect on the diethyl chlorophosphate.
(3) An application method of a fluorescent probe for detecting diethyl chlorophosphate comprises the following steps:
in recent years, many subject groups have designed and synthesized fluorescent probes that can be used to detect war agent mimics. However, many probes have some limitations in application, such as preparing test paper or silica gel plate for detecting the chlorine diethyl phosphate vapor. These probes lack to some extent the ability for accurate real-time detection with some degree of utility and accuracy. The current methods for gas detection and analysis are, for example: the problems of poor field real-time detection maneuverability exist in gas chromatography, infrared absorption, thermal conductivity analysis and the like. Therefore, it is important to find a gas sensor that is cost effective, sensitive, and portable.
Since the probe itself has good fluorescence properties and the portability of the sensor is considered, an F-4600FL Spectrophotometer micro spectrometer of Ocean Optics company is finally selected as a component of the optical fiber sensor, and a fluorescence quenching type gas optical fiber sensor is manufactured. A schematic diagram of the optical fiber sensing device is shown in fig. 11. The structure of the optical fiber gas sensor mainly comprises four parts: an excitation light source (380 nm relatively close to a silicon compound fluorescent probe is selected as the excitation light wavelength because the wavelength of the portable light source is only a part of fixed wavelength of each waveband, and cannot be selected arbitrarily), an optical fiber probe for optical signal transmission and reception, a micro spectrum analyzer and a computer for data processing.
The core part of the optical fiber gas sensor is a gas-sensitive film which is excited to generate fluorescence, and the relative intensity and the change degree of the fluorescence emitted by the sensitive film are important indexes for judging the performance of the optical fiber gas sensor. Because the manufactured probe belongs to organic micromolecules and has very good compatibility with organic solvents, the fluorescent probe with the particle size of 10.0 mu M is dissolved in 10.0mL of acetone, and is uniformly coated on the optical fiber probe part after being fully dissolved, and then the organic sensitive films can be respectively formed after being naturally volatilized. The microstructure of the optical fiber probe is shown in fig. 12, the optical fiber 2 in the center of the probe is an optical fiber for providing an excitation light source, the 6 surrounding optical fibers 1 are absorption type optical fibers for absorbing a fluorescent signal of a sensitive film, the whole element has the capability of providing excitation light and absorbing an emitted optical signal at the same time, and the detection of the chlorine diethyl phosphate vapor can be directly made by coating a fluorescent probe on the surface of the optical fiber probe to be a sensitive element.
An application method of a fluorescent probe for detecting diethyl chlorophosphate comprises the following steps:
(1) dissolving 10.0 mu mol of fluorescent probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasilin-8-ium in 10.0mL of acetone, after the acetone is fully dissolved, uniformly coating the acetone on an optical fiber probe part of an F-4600FL Spectrophotometer micro spectrometer of Ocean Optics company, and forming a fluorescent probe film after the acetone is naturally volatilized;
(2) fluorescence excitation was performed by the fiber probe portion of the micro spectrometer using excitation light of 380nm as excitation light source, and the original luminescence intensity I was recorded by a computer0Is 102 a.u;
(3) proportioning diethyl chlorophosphate steam and nitrogen by using a gas collection bag, wherein the proportioning of diethyl chlorophosphate steam to be measured with different concentrations is 0.0125ppm, 0.025ppm, 0.05ppm, 0.1ppm, 0.2ppm, 0.4ppm, 0.8ppm, 1.6ppm, 3.2ppm, 6.5ppm, 12.9ppm, 25.7ppm, 51.4 ppm and 103ppm respectively;
(4) the method comprises the steps of inserting the optical fiber probe part of a micro spectrum analyzer into gas collecting bags of the diethyl chlorophosphate steam with different concentrations for testing, recording the optimal emission fluorescence intensity I, normalizing the change degree of the optimal emission fluorescence intensity data, and normalizing the change degree of the optimal emission fluorescence intensity data by subtracting the original luminous intensity I of a fluorescent probe film from the real-time optimal emission fluorescence intensity I of the diethyl chlorophosphate steam with different concentrations obtained by testing0Then divided by the original luminous intensity I of the fluorescent probe film0Obtaining normalized data representing the variation degree of the optimal emitted fluorescence intensity data;
(5) performing linear fitting through origin software to obtain a fitting function between the vapor concentration of the diethyl chlorophosphate and the normalized data of the change degree of the optimal emitted fluorescence intensity data, and obtaining a fitting function Y which is 0.3983X +0.00175, wherein X is the vapor concentration (unit: ppm) of the diethyl chlorophosphate, and Y is the normalized data of the change degree of the optimal emitted fluorescence intensity data;
(6) when detecting the diethyl chlorophosphate steam with unknown concentration, calculating to obtain the normalized data of the change degree of the optimal emission fluorescence intensity data under the concentration after detecting the diethyl chlorophosphate steam with unknown concentration, and substituting the normalized data into the fitting function obtained in the step (5) to obtain the concentration of the diethyl chlorophosphate steam;
(7) and (3) when the theoretical value of the fluorescent probe to the low detection limit of diethyl chlorophosphate is detected, substituting the signal-to-noise ratio of the micro spectrum analyzer into the fitting function obtained in the step (5) to obtain the theoretical value of the fluorescent probe to the low detection limit of diethyl chlorophosphate. For example, the signal-to-noise ratio Y of the spectrum analyzer is 1: and 300, substituting the obtained fitting function to obtain a theoretical value X of 6.5ppb of the lower detection limit of the fluorescent probe to the diethyl chlorophosphate.
In conclusion, experiments prove that the prepared optical fiber sensor can realize the real-time detection of the low concentration of the diethyl chlorophosphate steam, and the detection limit can be as low as 6.5ppb theoretically and is lower than the concentration 7.0ppb which causes direct danger to the life health. An optical fiber gas sensor for detecting the chlorine diethyl phosphate vapor is also designed and synthesized, and the sensor has the advantages of electromagnetic interference resistance, high detection precision, wider use environment, chemical corrosion resistance and the like. Experiments show that the sensor can realize real-time detection of an object to be detected, and the lowest detection limit of diethyl chlorophosphate steam reaches 6.5ppb, which is far lower than the IDLH (life and health hazard) concentration of 7.0ppb of Sarin. The optical fiber sensing technology is combined with the fluorescent probe for the first time, and the low-concentration detection of the diethyl chlorophosphate steam is realized.
The invention discloses a synthesis and application of a fluorescent probe for detecting diethyl chlorophosphate, which synthesizes a silicon compound fluorescent probe based on 1,1' -binaphthol structure, can realize the specific detection of the war toxin simulant diethyl chlorophosphate, has the advantages of high response speed, low detection limit, longer luminescence wavelength and the like, has high commercialization degree, greatly reduces the cost required by probe synthesis, and also discloses an application method of the fluorescent probe for detecting the diethyl chlorophosphate based on normalized processing data, which comprises a micro spectrum analyzer, an excitation light source and a computer, wherein the three parts carry out signal transmission through a signal transmission optical fiber, and have unique electromagnetic interference resistance advantage, the optical fiber probe has the advantage of corrosion resistance, and the sensor is different from the conventional naked eye observation due to the accuracy of optical signals, the method has the characteristic of high detection accuracy on the diethyl chlorophosphate steam.
Although the present invention has been described with reference to the above embodiments, it should be understood that the present invention is not limited to the above embodiments, and those skilled in the art can make various changes and modifications without departing from the scope of the present invention.
Claims (10)
1. The synthesis and application of the fluorescent probe for detecting the diethyl chlorophosphate are characterized in that the synthesis of the fluorescent probe for detecting the diethyl chlorophosphate comprises the following steps:
(1) under the protection of inert gas atmosphere, putting 2, 2 '-dihydroxy- [1, 1' -binaphthyl ] -3-formaldehyde into a round-bottom flask, and adding a certain amount of ultra-dry ethanol to fully dissolve the mixture;
(2) adding 2, 3-diaminonaphthalene at room temperature, and then adding sodium metabisulfite;
(3) heating and refluxing for a certain time under a proper temperature condition, cooling to room temperature, performing rotary evaporation to remove the solvent, performing multiple extraction with ethyl acetate, washing an organic phase, drying with anhydrous sodium sulfate, performing rotary evaporation to obtain a brown solid crude product, performing column chromatography purification, and performing vacuum drying to obtain 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol;
(4) under the protection of inert gas atmosphere, 3- (1H-naphtho [2, 3-d ] imidazole-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol is placed in a round-bottom flask, and a certain amount of redistilled tetrahydrofuran is added to be fully dissolved;
(5) adding redistilled triethylamine dropwise at room temperature, wherein the reaction system is changed from yellow to brown;
(6) after a certain time, the Ph is added dropwise2SiCl2The color of the reaction system becomes lighter;
(7) after a certain time, TLC detection is carried out, when the raw materials are basically completely reacted, ethyl acetate is used for multiple times of extraction, an organic phase is washed, anhydrous sodium sulfate is used for drying, a yellow solid crude product is obtained through rotary evaporation, column chromatography purification and vacuum drying are carried out, and the fluorescent probe 5- (2-hydroxynaphthalene-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e ] naphtho [2 ', 3': 4, 5] imidazo [1, 2-c ] [1, 3, 2] oxasililin-8-onium is obtained.
2. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate according to claim 1, wherein the inert gas in step (1) and step (4) is argon, when the molar mass of 2, 2 '-dihydroxy- [1, 1' -binaphthyl ] -3-formaldehyde in step (1) is 1mmol, the amount of the ultra-dry ethanol is 30mL, the suitable temperature in step (3) is 85 ℃, the certain time is 3h, the number of extraction times of ethyl acetate is 2, the organic phase washing process sequentially comprises washing with distilled water and saturated saline, and the volume ratio of the elution phases of the column chromatography purification is petroleum ether: ethyl acetate 3: 1.
3. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate according to claim 1, wherein in the step (1) and the step (2), the ratio of 2, 2 '-dihydroxy- [1, 1' -binaphthyl ] -3-formaldehyde: 2, 3-diaminonaphthalene: the molar mass ratio of the sodium metabisulfite is 1 mmol: 1.2 mmol: 1.2 mmol.
4. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate of claim 1, wherein in the step (4), when the molar mass of 3- (1H-naphtho [2, 3-d ] imidazol-2-yl) - [1, 1 '-binaphthyl ] -2, 2' -diol is 0.5mmol, the amount of redistilled tetrahydrofuran is 30 mL; in the step (7), the extraction frequency of ethyl acetate is 2 times, the washing process of the organic phase sequentially comprises washing with distilled water and saturated saline solution, and the volume ratio of the elution phase of column chromatography purification is petroleum ether: ethyl acetate 3: 1.
5. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate of claim 1, wherein 3- (1H-naphtho [2, 3-d ] in the steps (4) to (6)]Imidazol-2-yl) - [1, 1' -binaphthyl]-2, 2' -diol: redistilled triethylamine: ph2SiCl2The molar mass ratio of (a) to (b) is 0.5 mmol: 1.5 mmol: 1.3 mmol.
6. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate of claim 1, wherein the fixed time in step (6) is 5min, and the fixed time in step (7) is 30 min.
7. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate of claims 1-6, wherein the fluorescent probe is applied by the steps of:
(1) 10.0. mu. mol of fluorescent probeNeedle5- (2-hydroxynaphthalen-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2, 3-e]Naphtho [2 ', 3': 4, 5]]Imidazo [1, 2-c ]][1，3，2]Dissolving oxasilin-8-onium in 10.0mL of acetone, uniformly coating the acetone on an optical fiber probe part of a micro spectrum analyzer after the acetone is fully dissolved, and then forming a fluorescent probe film after the acetone is naturally volatilized;
(2) using exciting light with certain wavelength as exciting light source, performing fluorescence excitation via fiber probe part of micro spectrum analyzer, and recording original luminescence intensity I via computer0；
(3) Mixing the diethyl chlorophosphate steam and nitrogen by using a gas collection bag, and mixing the diethyl chlorophosphate steam with different concentrations to be detected;
(4) inserting the optical fiber probe part of the micro spectrum analyzer into gas collection bags of diethyl chlorophosphate steam with different concentrations for testing, recording the optimal emission fluorescence intensity I, and carrying out normalization processing on the change degree of the optimal emission fluorescence intensity data;
(5) performing linear fitting through software to obtain a fitting function between the concentration of the diethyl chlorophosphate vapor and the normalized data of the change degree of the optimal emitted fluorescence intensity data;
(6) when detecting the diethyl chlorophosphate steam with unknown concentration, calculating to obtain the normalized data of the change degree of the optimal emission fluorescence intensity data under the concentration after detecting the diethyl chlorophosphate steam with unknown concentration, and substituting the normalized data into the fitting function obtained in the step (5) to obtain the concentration of the diethyl chlorophosphate steam;
(7) and (3) when the theoretical value of the fluorescent probe to the low detection limit of diethyl chlorophosphate is detected, substituting the signal-to-noise ratio of the micro spectrum analyzer into the fitting function obtained in the step (5) to obtain the theoretical value of the fluorescent probe to the low detection limit of diethyl chlorophosphate.
8. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate according to claim 7, wherein the wavelength of the excitation light with a certain wavelength in the step (2) is 380nm, and the fitting software in the step (5) is origin software.
9. The synthesis and application of the fluorescent probe for detecting diethyl chlorophosphate according to claim 7, wherein the micro-spectrometer, the excitation light source and the computer perform signal transmission through the signal transmission optical fiber, the signal is luminous intensity and fluorescence intensity, and the optical fiber probe in the step (1) comprises an incident light optical fiber and a fluorescence absorption optical fiber.
10. The method for synthesizing fluorescent probe for detecting diethyl chlorophosphate according to claim 7, wherein the normalization of the variation degree of the optimal fluorescence intensity data in step (4) is performed by subtracting the original fluorescence intensity I of the fluorescent probe film from the real-time optimal fluorescence intensity I of the tested diethyl chlorophosphate vapor with different concentrations0Then divided by the original luminous intensity I of the fluorescent probe film0Normalized data representing the degree of change in the data for the optimal emitted fluorescence intensity can be obtained.
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