CN111808130B - Fluorescent probe synthesis and application for detecting diethyl chlorophosphate - Google Patents
Fluorescent probe synthesis and application for detecting diethyl chlorophosphate Download PDFInfo
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- CN111808130B CN111808130B CN202010601221.XA CN202010601221A CN111808130B CN 111808130 B CN111808130 B CN 111808130B CN 202010601221 A CN202010601221 A CN 202010601221A CN 111808130 B CN111808130 B CN 111808130B
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- diethyl chlorophosphate
- fluorescent probe
- optical fiber
- binaphthyl
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- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000007850 fluorescent dye Substances 0.000 title claims abstract description 95
- 230000015572 biosynthetic process Effects 0.000 title abstract description 17
- 238000003786 synthesis reaction Methods 0.000 title abstract description 17
- 239000000523 sample Substances 0.000 claims abstract description 50
- 238000001514 detection method Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000013307 optical fiber Substances 0.000 claims description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 230000005284 excitation Effects 0.000 claims description 30
- -1 3- (1H-naphtho [2,3-d ] imidazol-2-yl) - [1,1 '-binaphthyl ] -2,2' -diol Chemical compound 0.000 claims description 24
- 238000012360 testing method Methods 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000002381 microspectrum Methods 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 230000008054 signal transmission Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000012074 organic phase Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001228 spectrum Methods 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
- 238000000605 extraction Methods 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000005406 washing Methods 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
- 239000012043 crude product Substances 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 claims description 5
- 239000011261 inert gas Substances 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
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 claims description 4
- 238000010606 normalization Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
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- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 26
- 230000008901 benefit Effects 0.000 abstract description 13
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- 150000003377 silicon compounds Chemical class 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 5
- 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 239000002575 chemical warfare agent Substances 0.000 description 8
- KWMBADTWRIGGGG-UHFFFAOYSA-N 2-diethoxyphosphorylacetonitrile Chemical compound CCOP(=O)(CC#N)OCC KWMBADTWRIGGGG-UHFFFAOYSA-N 0.000 description 6
- ZWWWLCMDTZFSOO-UHFFFAOYSA-N diethoxyphosphorylformonitrile Chemical compound CCOP(=O)(C#N)OCC ZWWWLCMDTZFSOO-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- VONWDASPFIQPDY-UHFFFAOYSA-N dimethyl methylphosphonate Chemical compound COP(C)(=O)OC VONWDASPFIQPDY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011897 real-time detection Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
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- 238000002474 experimental method Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- DYAHQFWOVKZOOW-UHFFFAOYSA-N Sarin Chemical compound CC(C)OP(C)(F)=O DYAHQFWOVKZOOW-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 210000005036 nerve Anatomy 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 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
- 238000004458 analytical method Methods 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 229940088598 enzyme Drugs 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 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 1
- 102000012440 Acetylcholinesterase Human genes 0.000 description 1
- 108010022752 Acetylcholinesterase Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PMATZTZNYRCHOR-CGLBZJNRSA-N Cyclosporin A Chemical compound CC[C@@H]1NC(=O)[C@H]([C@H](O)[C@H](C)C\C=C\C)N(C)C(=O)[C@H](C(C)C)N(C)C(=O)[C@H](CC(C)C)N(C)C(=O)[C@H](CC(C)C)N(C)C(=O)[C@@H](C)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)N(C)C(=O)[C@H](C(C)C)NC(=O)[C@H](CC(C)C)N(C)C(=O)CN(C)C1=O PMATZTZNYRCHOR-CGLBZJNRSA-N 0.000 description 1
- 229930105110 Cyclosporin A Natural products 0.000 description 1
- 108010036949 Cyclosporine Proteins 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 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
- 229940022698 acetylcholinesterase Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960001265 ciclosporin Drugs 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 229930182912 cyclosporin Natural products 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000001952 enzyme assay Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 238000001871 ion mobility spectroscopy Methods 0.000 description 1
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- 230000003278 mimic effect Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000003958 nerve gas Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 231100000421 neurotoxicant Toxicity 0.000 description 1
- 239000012244 neurotoxicant Substances 0.000 description 1
- 230000001682 neurotoxicant effect Effects 0.000 description 1
- 239000002581 neurotoxin Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6402—Atomic fluorescence; Laser induced fluorescence
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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Abstract
The invention discloses a fluorescent probe synthesis and application for detecting diethyl chlorophosphate, which synthesizes a silicon compound fluorescent probe based on a 1,1' -binaphthol structure, the silicon compound fluorescent probe can realize specific detection of a warfare agent simulative diethyl chlorophosphate, has the advantages of high response speed, low detection limit, longer luminous 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 diethyl chlorophosphate based on normalized processing data.
Description
Technical Field
The invention relates to synthesis and application of a fluorescent probe for detecting diethyl chlorophosphate, and belongs to the technical field of synthesis and application of a warfare agent simulator fluorescent probe.
Background
Organophosphorus compounds (OPS) have been widely used in agriculture as pesticides and herbicides due to their high toxicity, and have also been used in war as Chemical Warfare Agents (CWA). Among them, type G neurotoxicants appear during world war ii, including Taban (Taban), sarin (Sarin), soman (Soman) and cyclosporin (cycloparain). They may cause irreversible damage to the acetylcholinesterase of the human nervous system and affect neurotransmission, and the number of people in contact with neurotoxic agents dies from respiratory paralysis within minutes. Although such CWA is severely limited in international society, there are events by which terrorists take their lives, such as terrorist attacks on tokyo subways. Thus, rapid detection of these nerve agents in a convenient manner is critical to public safety systems. Since CWA is a nationally regulated chemical, we generally used a mimic diethyl chlorophosphate as a surrogate that was similar in activity to CWA, but relatively less toxic. Since CWA has similar activity to its mimetic, if the probe exhibits a response to the mimetic, it must also exhibit similar response to CWA. Thus, it is generally accepted in the industry to replace chemical warfare agents with simulators.
Current research shows that electrochemical methods, mass spectrometry, enzymatic chemistry, and the like are common to the detection methods of warfare agent mimics. Electrochemical analysis is the science of using the electrical and electrochemical properties of a substance for characterization and measurement, which is an important component of the electrochemical and analytical chemistry disciplines; mass spectrometry is a method for detecting moving ions after separating the ions according to the mass-to-charge ratio by using an electric field and a magnetic field; the enzyme assay is an assay that is biased towards biology and pharmacy and enables the detection of a substance to be detected by using the specificity and high catalytic properties of enzymes. These several common approaches all enable accurate detection of a warfare agent mimetic.
In recent years, due to the ease of preparation, high sensitivity and rapid response of fluorescent probes, some nanofibers and small organic molecules have been developed as mimics of fluorescent probes for detecting nerve agents. Although scientists have found various methods of detecting nerve gas as compared to other analytes, including gas chromatography, mass spectrometry, ion mobility spectrometry, enzyme sensors, capillary electrophoresis, colorimetry, etc., fluorescent probes reported to be useful for detection of nerve agents are still lacking, and according to current research, the common detection methods for warfare agent simulants have the disadvantages of complicated detection methods and expensive detection costs, although they can achieve accurate detection of warfare agents. The fluorescence rule has the advantages of convenient detection mode, low detection cost and the like. In addition, while some fluorescent probes are currently used to effect detection of warfare agent mimics, most applications for such fluorescent probe molecules are those that reside in solution or on test paper. For example, research work of S.Huang, Y.Wu, F.Zeng, L.Sun, S.Wu et al is mostly based on detection test paper, and the detection of diethyl chlorophosphate steam is mostly based on the detection test paper, so that the problem that the diethyl chlorophosphate steam cannot be identified by accurate data representation and only can be identified by naked eye observation exists, and research work of S.K.Sheet, B.Sen, S.Khatua et al shows that the current fluorescence detection test paper is qualitatively described and identified by naked eye observation, and the concentration of diethyl chlorophosphate steam is judged by the response condition of different concentrations of diethyl chlorophosphate steam to fluorescence, and the concentration of diethyl chlorophosphate steam cannot be accurately detected due to the fact that the solution has more interference, the detection accuracy is poor, the difference is obvious, and the detection of the concentration of diethyl chlorophosphate steam cannot be accurately performed.
The optical fiber sensing technology is widely focused by scholars and researchers in the early stage of the birth, and is originally born in the FOSS project of the naval institute in the united states, so far, the technology is one of the most practical important branches of the most rapid technical development in the application of photoelectric technology. Compared with the traditional detection mode, the optical fiber sensing technology has the advantages of electromagnetic interference resistance, chemical corrosion resistance, high sensitivity, wider application environment range and the like, so that the optical fiber sensor has more excellent test precision and application range compared with the traditional test method, and because 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 matters. If the organic small molecular fluorescent probe can be combined with the optical fiber sensing technology, compared with other fluorescent probes which can be used for detecting the warfare agent simulants, the optical fiber sensor which can be used for detecting the diethyl chlorophosphate vapor can be theoretically prepared. The real-time detection of the object to be detected can be realized in theory, and the object to be detected can have good stability and higher real-time precision.
Therefore, the design and synthesis of the fluorescent probe with higher commercialization cost, the preparation of the warfare agent gas detection fluorescent probe with high electromagnetic interference resistance, high corrosion resistance and higher detection precision, and the application method combined with the optical fiber probe are particularly important.
Disclosure of Invention
The invention mainly overcomes the defects in the prior art, and provides a fluorescent probe for detecting diethyl chlorophosphate and synthesis and application thereof. The invention discloses a fluorescent probe for detecting diethyl chlorophosphate and application thereof, which synthesizes a silicon compound fluorescent probe based on a 1,1' -binaphthol structure, the silicon compound fluorescent probe can realize the specific detection of the diethyl chlorophosphate as a warfare agent simulant, has the advantages of high response speed, low detection limit, longer luminous 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 diethyl chlorophosphate based on normalized processing data, which comprises a micro spectrum analyzer, an excitation light source and a computer, wherein the micro spectrum analyzer, the excitation light source and the computer perform signal transmission through a signal transmission optical fiber, and the optical fiber probe has the unique electromagnetic interference resistance advantage, and has the characteristic of higher detection accuracy of diethyl chlorophosphate vapor because of the accuracy of optical signals, which is different from the conventional naked eye observation.
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, placing 2,2 '-dihydroxyl- [1,1' -binaphthyl ] -3-formaldehyde into a round bottom flask, and adding a certain amount of ultra-dry ethanol to fully dissolve the 2,2 '-dihydroxyl- [1,1' -binaphthyl ] -3-formaldehyde;
(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, removing a solvent by rotary evaporation, extracting with ethyl acetate for multiple times, washing an organic phase, drying with anhydrous sodium sulfate, rotary evaporating to obtain a brown solid crude product, purifying by column chromatography, and 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 then a certain amount of redistilled tetrahydrofuran is added to fully dissolve the 3- (1H-naphtho [2,3-d ] imidazole-2-yl) - [1,1 '-binaphthyl ] -2,2' -diol;
(5) Dropwise adding redistilled triethylamine at room temperature, and changing the reaction system from yellow to brown;
(6) After a certain period of time, ph is added dropwise 2 SiCl 2 The color of the reaction system becomes light;
(7) After a certain time, TLC detection is carried out, after the raw materials are basically completely reacted, ethyl acetate is used for multiple extraction, an organic phase is washed, anhydrous sodium sulfate is dried, rotary evaporation is carried out to obtain a yellow solid crude product, column chromatography purification is carried out, and vacuum drying is carried out to obtain 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] oxasilalin-8-onium.
Preferably, the inert gas in the step (1) and the step (4) is argon, when the molar mass of the 2,2 '-dihydroxyl- [1,1' -binaphthyl ] -3-formaldehyde in the step (1) is 1mmol, the dosage of the ultra-dry ethanol is 30mL, the proper temperature in the step (3) is 85 ℃, the certain time is 3h, the extraction times of the ethyl acetate are 2 times, the washing process of the organic phase is distilled water and saturated saline water in sequence, and the volume ratio of the elution phase of the column chromatography purification is petroleum ether: ethyl acetate=3:1.
Preferably, in the step (1) and the step (2), 2 '-dihydroxy- [1,1' -binaphthyl ] -3-formaldehyde: 2, 3-diaminonaphthalene: sodium metabisulfite has a molar mass ratio of 1mmol:1.2mmol:1.2mmol.
Preferably, in the step (4), when the molar mass of the 3- (1H-naphtho [2,3-d ] imidazol-2-yl) - [1,1 '-binaphthyl ] -2,2' -diol is 0.5mmol, the amount of the redistilled tetrahydrofuran is 30mL; in the step (7), the extraction times of ethyl acetate are 2, the washing process of the organic phase is sequentially distilled water and saturated saline water, and the volume ratio of the elution phase of column chromatography purification is petroleum ether: ethyl acetate=3:1.
Preferably3- (1H-naphtho [2, 3-d) in said step (4) -step (6)]Imidazol-2-yl) - [1,1' -binaphthyl]-2,2' -diol: re-steaming triethylamine: ph (Ph) 2 SiCl 2 The molar mass ratio of (2) is 0.5mmol:1.5mmol:1.3mmol.
Preferably, the certain time in the step (6) is 5min, and the certain time in the step (7) is 30min.
Further, the synthesis and application of the 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-hydroxynaphthalen-1-yl) -7, 7-diphenyl-7, 15-dihydronaphtho [2,3-e ] naphtho [2',3':4,5] imidazo [1,2-c ] [1,3,2] oxasila-8-onium in 10.0mL of acetone, uniformly coating the solution on an optical fiber probe part of a miniature spectrum analyzer after the solution is fully dissolved, and forming a fluorescent probe film after the solution is naturally volatilized;
(2) Using excitation light with a certain wavelength as an excitation light source, performing fluorescence excitation through an optical fiber probe part of a micro spectrum analyzer, and recording the original luminous intensity I through a computer 0 ；
(3) Proportioning diethyl chlorophosphate steam and nitrogen by using a gas collecting bag, and proportioning diethyl chlorophosphate steam to be detected with different concentrations;
(4) Inserting an optical fiber probe part of a micro spectrum analyzer into gas collecting bags of diethyl chlorophosphate steam with different concentrations for testing, recording the optimal emitted fluorescence intensity I, and carrying out normalization treatment on the variation degree of the optimal emitted fluorescence intensity data;
(5) Performing linear fitting by software to obtain a fitting function between the concentration of diethyl chlorophosphate vapor and the normalized data of the variation degree of the optimal emitted fluorescence intensity data;
(6) When diethyl chlorophosphate steam with unknown concentration is detected, after diethyl chlorophosphate steam with unknown concentration is detected, calculating normalized data of the change degree of the best emission fluorescence intensity data under the concentration, and carrying the normalized data into the fitting function obtained in the step (5), so that the concentration of the diethyl chlorophosphate steam can be obtained;
(7) When the theoretical value of the low detection limit of the fluorescent probe for the diethyl chlorophosphate is detected, the signal-to-noise value of the micro spectrum analyzer is brought into the fitting function obtained in the step (5), so that the theoretical value of the low detection limit of the fluorescent probe for the diethyl chlorophosphate is obtained.
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 perform signal transmission through a signal transmission optical fiber, 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 type optical fiber.
Preferably, the method for normalizing the variation degree of the best emitted fluorescence intensity data in the step (4) is to test the obtained real-time best emitted fluorescence intensity I of the diethyl chlorophosphate vapor with different concentrations minus the original luminescence intensity I of the fluorescent probe film 0 Dividing by the original luminous intensity I of the fluorescent probe film 0 Normalized data representing the degree of variation of the best emitted fluorescence intensity data can be obtained.
Compared with the prior art, the invention has the following advantages:
the invention discloses a fluorescent probe for detecting diethyl chlorophosphate and application thereof, which synthesizes a silicon compound fluorescent probe based on a 1,1' -binaphthol structure, the silicon compound fluorescent probe can realize the specific detection of the diethyl chlorophosphate as a warfare agent simulant, has the advantages of high response speed, low detection limit, longer luminous 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 diethyl chlorophosphate based on normalized processing data, which comprises a micro spectrum analyzer, an excitation light source and a computer, wherein the micro spectrum analyzer, the excitation light source and the computer perform signal transmission through a signal transmission optical fiber, and the optical fiber probe has the unique electromagnetic interference resistance advantage, and has the characteristic of higher detection accuracy of diethyl chlorophosphate vapor because of the accuracy of optical signals, which is different from the conventional naked eye observation.
Drawings
FIG. 1 is a schematic diagram of 3- (1H-naphtho [2, 3-d)]Imidazol-2-yl) - [1,1' -binaphthyl]-2,2' -diol hydrogen Spectrum (400 MHz, DMSO-d 6 )；
FIG. 2 is a schematic diagram of 3- (1H-naphtho [2, 3-d)]Imidazol-2-yl) - [1,1' -binaphthyl]-2,2' -diol carbon spectrum (100 MHz, DMSO-d) 6 )；
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]Oxasilalin-8-onium hydrogen Spectrum (400 MHz, 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]Oxasilalin-8-onium carbon Spectrum (100 MHz, DMSO-d) 6 )；
FIG. 6 is a mass spectrum of 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] oxasiladin-8-ium;
FIG. 7 is a graph showing fluorescence emission spectra of fluorescent probes in different solvents (E Xslit ＝5.0nm，E mslit ＝5.0nm)；
FIG. 8 shows fluorescence response of probes (10.0. Mu.M) to DMMP, DCNP, DCMP and DCP (50. Mu.M each) at optimal excitation (λex=334 nm) (curves for probe+DMMP, probe+DCNP, probe+DCMP, probe+DCP, respectively, from top to bottom);
FIG. 9 is a plot of the competition response of the probe (10.0. Mu.M) with a different warfare agent mimetic (20.0. Mu.M);
FIG. 10 is a graph of fluorescence titration of probe with DCP at different concentrations;
FIG. 11 is a schematic diagram of a fluorescent probe application apparatus for detecting diethyl chlorophosphate;
FIG. 12 is a schematic diagram of the microstructure of a fiber optic probe;
wherein 1 is an absorption type optical fiber for absorbing fluorescent signals of a sensitive film, 2 is an optical fiber for providing an excitation light source, and 3 is an optical fiber probe.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Examples:
(1) Fluorescent probe synthesis for detecting diethyl chlorophosphate:
a fluorescent probe synthesis for detecting diethyl chlorophosphate, comprising the steps of:
(1) 2,2 '-dihydroxy- [1,1' -binaphthyl ] -3-carbaldehyde (314.0 mg,1 mmol) was placed in a 100mL round bottom flask under argon protection, and then 30mL of ultra-dry ethanol was added to make it fully dissolved;
(2) 2, 3-diaminonaphthalene (196.0 mg,1.2 mmol) was added at room temperature, followed by sodium metabisulfite (228.0 mg,1.2 mmol);
(3) Heating and refluxing for 3 hours at 85 ℃, cooling to room temperature, removing the solvent by rotary evaporation, extracting with 30mL of ethyl acetate for 2 times, washing the organic phase by distilled water and saturated saline water sequentially, drying by anhydrous sodium sulfate, obtaining a brown solid crude product by rotary evaporation, purifying by column chromatography by adopting petroleum ether and ethyl acetate with the volume ratio of 3:1 as eluting phases, and 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) 3- (1H-naphtho [2,3-d ] imidazol-2-yl) - [1,1 '-binaphthyl ] -2,2' -diol (226.0 mg,0.5 mmol) was placed in a 100mL round bottom flask under the protection of argon, and then 30mL of redistilled tetrahydrofuran was added to make it fully dissolved;
(5) Re-evaporated triethylamine (1.5 mmol,0.25 ml) was added dropwise at room temperature and the reaction turned from yellow to brown;
(6) After 5min, ph is added dropwise 2 SiCl 2 (1.3 mmol,0.25 mL) and the reaction system became lighter in color;
(7) After 30min, TLC detection is carried out, after the raw materials are basically reacted, ethyl acetate 30mL is used for extraction for 2 times, the organic phase is sequentially washed by distilled water and saturated saline water, dried by anhydrous sodium sulfate, rotary evaporation is carried out to obtain a yellow solid crude product, petroleum ether and ethyl acetate with the volume ratio of 3:1 are adopted as eluting phases, column chromatography purification is carried out, and vacuum drying is carried out to obtain fluorescent probe 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] oxasilalin-8-onium with the yield of 16.0mg and 6.2 percent.
(2) Fluorescent probe characterization for detection of diethyl chlorophosphate:
(a) Experimental instrument
1 H and 13 CNMR Japanese Electron (JEOL) JNM-ECS 400 and Varian INOVA 600 MHz nuclear magnetic resonance spectrometer, deuterated reagent CDCl 3 And d 6 DMSO, TMS as internal standard.
ESI-MS: bruker Daltonics esquire 6000 and Bruker Daltonics APEXII e FT-ICR scanner were used.
Fluorescence spectrometer: hitachi F-7000fluorescence spectrophotometer.
(b) Test conditions
Probe 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] oxasilan-8-ium to prepare 10.0mM N, N-dimethylformamide (spectral grade) stock solution; diethyl chlorophosphate was prepared as a stock solution of 10.0mM DMF; all solvents used in the selection of the test solvents were spectral grade N, N-Dimethylformamide (DMF), spectral grade dimethyl sulfoxide (DMSO), chromatographic pure Acetone (ACT) and chromatographic pure Dichloromethane (DCM). The rest of the fluorescence tests were performed in spectral grade N, N-Dimethylformamide (DMF).
The fluorescence excitation wavelength of the probe is lambda ex =334 nm; the test slit was 5.0nm.
(c) Structural characterization of 3- (1H-naphtho [2,3-d ] imidazol-2-yl) - [1,1 '-binaphthyl ] -2,2' -diol
As shown in figures 1-3 of the drawings, 1 H NMR(400MHz,DMSO–d 6 ):δ＝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； 13 C NMR(100MHz,DMSO–d 6 ):δ＝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] + indicating 3- (1H-naphtho [2, 3-d)]Imidazol-2-yl) - [1,1' -binaphthyl]The synthesis of the 2,2' -diol was indeed successful.
(d) Fluorescent probe 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] oxasila-8-onium structural characterization
As shown in figures 3-6 of the drawings, 1 H NMR(DMSO-d 6 ,400MHz):δ＝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. 13 C NMR(DMSO-d 6 ,100MHz):δ＝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 C 43 H 29 N 2 O 2 Si + [M+H 2 O] + :651.2098,found:651.2100.
(e) Fluorescent probe 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] oxasiladin-8-ium spectral Properties
1) Fluorescence response of probes in different solvents
The fluorescent probe presents different fluorescent colors in different solvents, four common organic solvents (ACT, DCM, DMSO and DMF) are selected for better research of the luminescence performance, and fluorescence tests are respectively carried out under the optimal excitation. FIG. 7 is a graph showing 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 the probe luminescence intensity is higher, whereas in DCM and ACT, the fluorescence intensity is lower overall and the emission wavelength is shorter. Considering the practical application of the later period, finally, DMF solvent with longer emission wavelength and higher fluorescence intensity is selected as the test environment of the probe molecule.
2) Fluorescence response studies of probes to different warfare agent mimics
After choosing 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 Cyanomethylphosphonate (DCMP), and Diethyl Chlorophosphate (DCP). As shown in fig. 8, the test results found that the fluorescent probe molecules exhibited fluorescence quenching response only to diethyl chlorophosphate, while hardly exhibited fluorescence change to the other three common warfare agent mimics. This is a fluorescence quenching probe, which exhibits a fluorescence quenching effect at 565nm when reacted with diethyl chlorophosphate, and the color of the solution changes from green to pale green under irradiation of an ultraviolet lamp having an excitation wavelength of 365 nm. These results indicate that the fluorescent probe has excellent selectivity for diethyl chlorophosphate and that a macroscopic color change can be observed under uv lamp irradiation. And the fluorescent probes have larger Stokes shift.
3) Competition and interference experiments of probes
In order to study the specific recognition of diethyl chlorophosphate by the fluorescent probe in the presence of different warfare agent mimics, four common warfare agent mimics, DMMP, DCNP, DCMP and DCP, were selected to interfere with the fluorescent probe. As shown in FIG. 9, the red bar graph shows the fluorescence intensity of the fluorescent probe after addition of diethyl chlorophosphate and the black bar graph shows the fluorescence intensity of the fluorescent probe after addition of other warfare agent mimics (DMMP, DCNP and DCMP, respectively, 1-3). In the presence of the other warfare agent mimics described above, no quenching effect of the fluorescent probe occurred at 565nm, but no significant quenching of the fluorescence occurred after the addition of diethyl chlorophosphate. This phenomenon suggests that the fluorescent probe can still achieve efficient recognition of diethyl chlorophosphate even in the presence of other warfare agent mimics.
4) Probe fluorescence titration study
To further investigate the relationship between the concentration of diethyl chlorophosphate and the fluorescence of the fluorescent probe, a fluorescence titration experiment of diethyl chlorophosphate molecules was performed. As shown in FIG. 10, fluorescence spectra of fluorescent probes reacted with different concentrations of 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. Mu.M). As a result of the test, it was found that when the concentration of diethyl chlorophosphate reached 10.0. Mu.M (1.0 eq), 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 values of the fluorescent probe at 565nm were plotted against different concentrations of 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. Mu.M), the fluorescent probe exhibited a good linear relationship with the concentration of diethyl chlorophosphate added (0.0-10.0. Mu.M), and the R value of the reaction of the fluorescent probe with diethyl chlorophosphate by linear fitting was 0.9989 over the range of the concentration of diethyl chlorophosphate added. So that 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, the probe can realize the specific identification of the warfare agent simulative diethyl chlorophosphate, has the advantages of high sensitivity and short reaction time, and has a good detection effect on the diethyl chlorophosphate.
(3) A fluorescent probe application method for detecting diethyl chlorophosphate comprises the following steps:
in recent years, many subject groups have designed and synthesized a number of fluorescent probes that can be used to detect warfare agent mimics. However, many probes have been reported to have limitations in application, such as a test paper or a silica gel plate for detecting diethyl chlorophosphate vapor. These probes lack a degree of practicality and high precision of accurate real-time detection capabilities. And the means currently used for gas detection analysis, for example: gas chromatography, infrared absorption, thermal conductivity analysis and the like all have the problem of poor on-site real-time detection mobility. Therefore, it is important to find a gas sensor that is cost effective, highly sensitive, and portable.
Because the probe has good fluorescence performance, and the F-4600FL Spectrophotometer micro spectrum analyzer of Ocean Optics company is finally selected as a component of the optical fiber sensor in consideration of portability of the sensor, the 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: excitation light source (380 nm, which is relatively close to the silicon compound-containing fluorescent probe, is selected as excitation light wavelength because the portable light source wavelength only has part of fixed wavelength of each wave band and cannot be selected arbitrarily), optical fiber probe for transmitting and receiving optical signal, micro spectrum analyzer and 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 variation degree of the fluorescence emitted by the sensitive film are important indexes for judging the performance of the optical fiber sensor. Because the prepared probe belongs to organic micromolecules and has very good compatibility with organic solvents, only 10.0 mu M fluorescent probe is dissolved in 10.0mL acetone, after the fluorescent probe is fully dissolved, the fluorescent probe is uniformly coated on an optical fiber probe part, and then an organic sensitive film can be respectively formed after the fluorescent probe is naturally volatilized. The microstructure of the optical fiber probe is shown in fig. 12, the optical fiber 2 at the center of the probe is an optical fiber for providing an excitation light source, the 6 optical fibers 1 around are optical fibers for absorbing fluorescent signals of a sensitive film, and the whole element has the capability of providing excitation light and absorbing emitted light signals at the same time, and only the fluorescent probe is coated on the surface of the optical fiber probe to directly manufacture the sensitive element for detecting the diethyl chlorophosphate steam.
The application method of the fluorescent probe for detecting the diethyl chlorophosphate comprises the following steps:
(1) Dissolving 10.0 mu mol of fluorescent probe 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] oxasilaling-8-onium in 10.0mL of acetone, uniformly coating the solution after the solution is fully dissolved on an optical fiber probe part of an F-4600FL Spectrophotometer micro spectrum analyzer of Ocean Optics company, and forming a fluorescent probe film after the solution is naturally volatilized, wherein an excitation light source and a computer perform signal transmission through a signal transmission optical fiber, the signal is luminous intensity and fluorescent intensity, and the optical fiber probe comprises an incident optical fiber and a fluorescent absorption type optical fiber;
(2) Using 380nm excitation light as excitation light source, performing fluorescence excitation by optical fiber probe part of micro spectrum analyzer, and recording original luminous intensity I by computer 0 102a.u;
(3) Proportioning diethyl chlorophosphate steam and nitrogen by using a gas collecting bag, wherein the proportions of the diethyl chlorophosphate steam to be detected are respectively 0.0125ppm,0.025ppm,0.05ppm,0.1ppm,0.2ppm,0.4ppm,0.8ppm,1.6ppm,3.2ppm,6.5ppm,12.9ppm,25.7ppm,51.4ppm and 103ppm;
(4) The method for carrying out normalization treatment on the change degree of the optimal emission fluorescence intensity data comprises the steps of inserting an optical fiber probe part of a micro spectrum analyzer into gas collecting bags of diethyl chlorophosphate steam with different concentrations for testing, recording the optimal emission fluorescence intensity I, carrying out normalization treatment on the change degree of the optimal emission fluorescence intensity data, and subtracting the original luminous intensity I of a fluorescent probe film from the optimal emission fluorescence intensity I of the diethyl chlorophosphate steam with different concentrations in real time, which is obtained by testing 0 Dividing by the original luminous intensity I of the fluorescent probe film 0 Obtaining normalized data representing the degree of variation of the best emitted fluorescence intensity data;
(5) Performing linear fitting by using origin software to obtain a fitting function between the concentration of diethyl chlorophosphate vapor and the normalized data of the change degree of the best emission fluorescence intensity data, and obtaining a fitting function Y=0.3983X+0.00175, wherein X is the concentration of diethyl chlorophosphate vapor (unit: ppm), and Y is the normalized data of the change degree of the best emission fluorescence intensity data;
(6) When diethyl chlorophosphate steam with unknown concentration is detected, after diethyl chlorophosphate steam with unknown concentration is detected, calculating normalized data of the change degree of the best emission fluorescence intensity data under the concentration, and carrying the normalized data into the fitting function obtained in the step (5), so that the concentration of the diethyl chlorophosphate steam can be obtained;
(7) When the theoretical value of the low detection limit of the fluorescent probe for the diethyl chlorophosphate is detected, the signal-to-noise value of the micro spectrum analyzer is brought into the fitting function obtained in the step (5), so that the theoretical value of the low detection limit of the fluorescent probe for the diethyl chlorophosphate is obtained. For example, the spectrum analyzer signal-to-noise ratio y=1: 300, the resulting fitting function was carried over to give a theoretical value of x=6.5 ppb for the low detection limit of the fluorescent probe for diethyl chlorophosphate.
In conclusion, experiments prove that the prepared optical fiber sensor can realize the low-concentration real-time detection of diethyl chlorophosphate steam, and the detection limit can be theoretically as low as 6.5ppb which is lower than 7.0ppb which causes direct danger to life health. The optical fiber gas sensor for detecting the diethyl chlorophosphate steam is also designed and synthesized, and has the advantages of electromagnetic interference resistance, high detection accuracy, 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 minimum detection limit of diethyl chlorophosphate steam reaches 6.5ppb which is far lower than the IDLH (life health hazard) concentration of Sarin by 7.0ppb. The method combines the optical fiber sensing technology with the fluorescent probe for the first time, so that the low-concentration detection of the diethyl chlorophosphate vapor is realized.
The invention discloses a fluorescent probe for detecting diethyl chlorophosphate and application thereof, which synthesizes a silicon compound fluorescent probe based on a 1,1' -binaphthol structure, the silicon compound fluorescent probe can realize the specific detection of the diethyl chlorophosphate as a warfare agent simulant, has the advantages of high response speed, low detection limit, longer luminous 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 diethyl chlorophosphate based on normalized processing data, which comprises a micro spectrum analyzer, an excitation light source and a computer, wherein the micro spectrum analyzer, the excitation light source and the computer perform signal transmission through a signal transmission optical fiber, and the optical fiber probe has the unique electromagnetic interference resistance advantage, and has the characteristic of higher detection accuracy of diethyl chlorophosphate vapor because of the accuracy of optical signals, which is different from the conventional naked eye observation.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any person skilled in the art can make some changes or modifications to the equivalent embodiments without departing from the scope of the technical solution of the present invention, but any simple modification, equivalent changes and modifications to the above-mentioned embodiments according to the technical substance of the present invention are still within the scope of the technical solution of the present invention.
Claims (2)
1. A method for synthesizing a fluorescent probe for detecting diethyl chlorophosphate, which is characterized by comprising the following steps of:
(1) Under the protection of inert gas atmosphere, placing 2,2 '-dihydroxyl- [1,1' -binaphthyl ] -3-formaldehyde into a round bottom flask, and adding a certain amount of ultra-dry ethanol to fully dissolve the 2,2 '-dihydroxyl- [1,1' -binaphthyl ] -3-formaldehyde;
(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, removing a solvent by rotary evaporation, extracting with ethyl acetate for multiple times, washing an organic phase, drying with anhydrous sodium sulfate, rotary evaporating to obtain a brown solid crude product, purifying by column chromatography, and vacuum drying to obtain 3- (1H-naphtho [2,3-d ] imidazol-2-yl) - [1,1 '-binaphthyl ] -2,2' -diol;
(4) 3- (1H-naphtho [2,3-d ] imidazol-2-yl) - [1,
1 '-binaphthyl ] -2,2' -diol is put into a round bottom flask, and then a certain amount of redistilled tetrahydrofuran is added to fully dissolve the 1 '-binaphthyl ] -2,2' -diol;
(5) Dropwise adding redistilled triethylamine at room temperature, and changing the reaction system from yellow to brown; (6) After a certain period of time, ph is added dropwise 2 SiCl 2 The color of the reaction system becomes light;
(7) After a certain time, TLC detection is carried out, after the raw materials are basically completely reacted, ethyl acetate is used for multiple extraction, an organic phase is washed, anhydrous sodium sulfate is dried, rotary evaporation is carried out to obtain a yellow solid crude product, column chromatography purification is carried out, and vacuum drying is carried out to obtain 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] oxasilalin-8-onium;
the inert gas in the step (1) and the step (4) is argon, the dosage of 2,2 '-dihydroxyl- [1,1' -binaphthyl ] -3-formaldehyde in the step (1) is 1mmol, the dosage of ultra-dry ethanol is 30mL, the proper temperature in the step (3) is 85 ℃, the certain time is 3h, the extraction times of ethyl acetate are 2 times, the organic phase washing process is distilled water and saturated saline water in sequence, and the volume ratio of the elution phase of column chromatography purification is petroleum ether: ethyl acetate=3:1;
in the step (1) and the step (2), 2 '-dihydroxy- [1,1' -binaphthyl ] -3-formaldehyde: 2, 3-diaminonaphthalene: sodium metabisulfite has a molar ratio of 1mmol:1.2mmol:1.2mmol;
the 3- (1H-naphtho [2,3-d ] imidazol-2-yl) - [1,1 '-binaphthyl ] -2,2' -diol in the step (4) is 0.5mmol, and the amount of redistilled tetrahydrofuran is 30mL; in the step (7), the extraction times of ethyl acetate are 2, the washing process of the organic phase is sequentially distilled water and saturated saline water, and the volume ratio of the elution phase of column chromatography purification is petroleum ether: ethyl acetate=3:1;
3- (1H-naphtho [2, 3-d) in said step (4) -step (6)]Imidazol-2-yl) - [1,1' -binaphthyl]-2,2' -diol: re-steaming triethylamine: ph (Ph) 2 SiCl 2 Molar ratio of 0.5 mmol): 1.5mmol:1.3mmol;
the certain time in the step (6) is 5min, and the certain time in the step (7) is 30min.
2. The application of the fluorescent probe for detecting diethyl chlorophosphate is characterized by comprising the following application steps of:
(1) Dissolving 10.0 mu mol of fluorescent probe 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] oxasila-8-onium in 10.0mL of acetone, uniformly coating the solution on an optical fiber probe part of a miniature spectrum analyzer after the solution is fully dissolved, and forming a fluorescent probe film after the solution is naturally volatilized;
(2) Using excitation light with a certain wavelength as an excitation light source, performing fluorescence excitation through an optical fiber probe part of a micro spectrum analyzer, and recording the original luminous intensity I through a computer 0 ；
(3) Proportioning diethyl chlorophosphate steam and nitrogen by using a gas collecting bag, and proportioning diethyl chlorophosphate steam to be detected with different concentrations;
(4) Inserting an optical fiber probe part of a micro spectrum analyzer into gas collecting bags of diethyl chlorophosphate steam with different concentrations for testing, recording the optimal emitted fluorescence intensity I, and carrying out normalization treatment on the variation degree of the optimal emitted fluorescence intensity data;
(5) Performing linear fitting by software to obtain a fitting function between the concentration of diethyl chlorophosphate vapor and the normalized data of the variation degree of the optimal emitted fluorescence intensity data;
(6) Detecting diethyl chlorophosphate vapor with unknown concentration, calculating to obtain normalized data of the change degree of the best emitted fluorescence intensity data under the concentration, and carrying the normalized data into the fitting function obtained in the step (5) to obtain the concentration of the diethyl chlorophosphate vapor;
(7) Bringing the signal-to-noise value of the micro spectrum analyzer into the fitting function obtained in the step (5) to obtain a theoretical value of the fluorescent probe for the low detection limit of diethyl chlorophosphate;
the wavelength of excitation light with a certain wavelength in the step (2) is 380nm, and the fitting software in the step (5) is origin software;
the miniature spectrum analyzer, the excitation light source and the computer perform signal transmission through a signal transmission optical fiber, 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;
the method for normalizing the change degree of the optimal fluorescence intensity data in the step (4) is to test the obtained real-time optimal fluorescence intensity I of the diethyl chlorophosphate vapor with different concentrations minus the original luminescence intensity I of the fluorescent probe film 0 Dividing by the original luminous intensity I of the fluorescent probe film 0 Normalized data representing the degree of variation of the best emitted fluorescence intensity data can be obtained.
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| WO2017146400A1 (en) * | 2016-02-24 | 2017-08-31 | Ewha University - Industry Collaboration Foundation | Compound and composition for detecting phosgene and diethyl chlorophosphate |
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| CN104478915A (en) * | 2014-12-29 | 2015-04-01 | 华东理工大学 | Boranil compounds based on binaphthol frameworks, and preparation method and application thereof |
| WO2017146400A1 (en) * | 2016-02-24 | 2017-08-31 | Ewha University - Industry Collaboration Foundation | Compound and composition for detecting phosgene and diethyl chlorophosphate |
| CN109734622A (en) * | 2019-01-09 | 2019-05-10 | 中国工程物理研究院材料研究所 | A method of preparation method containing oxime compound and use the compound test organophosphorus compounds |
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