CN111518134A - Dynamic resonance aggregation-induced emission material for explosive detection and preparation method and application thereof - Google Patents
Dynamic resonance aggregation-induced emission material for explosive detection and preparation method and application thereof Download PDFInfo
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- 239000002360 explosive Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000001514 detection method Methods 0.000 title claims abstract description 54
- 238000004220 aggregation Methods 0.000 title claims abstract description 50
- 230000002776 aggregation Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000000171 quenching effect Effects 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000010791 quenching Methods 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007850 fluorescent dye Substances 0.000 claims description 17
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- VCDOOGZTWDOHEB-UHFFFAOYSA-N 1-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C(Br)=CC=C2 VCDOOGZTWDOHEB-UHFFFAOYSA-N 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- VUQVJIUBUPPCDB-UHFFFAOYSA-N (1-bromo-2,2-diphenylethenyl)benzene Chemical group C=1C=CC=CC=1C(Br)=C(C=1C=CC=CC=1)C1=CC=CC=C1 VUQVJIUBUPPCDB-UHFFFAOYSA-N 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 claims description 4
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 claims description 4
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 claims description 4
- -1 boric acid ester Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 4
- PJRGCJBBXGNEGD-UHFFFAOYSA-N 2-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC=C(Br)C=C3NC2=C1 PJRGCJBBXGNEGD-UHFFFAOYSA-N 0.000 claims description 3
- CBJHFGQCHKNNJY-UHFFFAOYSA-N 4-bromo-9h-carbazole Chemical compound N1C2=CC=CC=C2C2=C1C=CC=C2Br CBJHFGQCHKNNJY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000000243 solution Substances 0.000 description 44
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000005284 excitation Effects 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000012491 analyte Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical compound CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 description 1
- BYUXGASCTZKHRN-UHFFFAOYSA-N 9h-carbazol-1-yloxyboronic acid Chemical class C12=CC=CC=C2NC2=C1C=CC=C2OB(O)O BYUXGASCTZKHRN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000954 titration curve Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a dynamic resonance aggregation-induced emission material for explosive detection and a preparation method and application thereof. The dynamic resonance aggregation-induced emission material for explosive detection provided by the invention is based on an N-P = X dynamic resonance structural system, and introduces a typical aggregation-induced emission group-tetraphenylethylene, so that the material has the advantages of simple synthesis, high yield, high quantum efficiency and the like.
Description
Technical Field
The invention relates to a novel resonance aggregation-induced emission material, in particular to a dynamic resonance aggregation-induced emission material for explosive detection and a preparation method and application thereof, belonging to the technical field of organic photoelectric materials.
Background
Nitroaromatic explosive (NAC) is an environmental pollutant that is highly toxic and difficult to degrade, and poses a great hazard to human health and even the overall ecological balance, and common such substances include 2,4, 6-trinitrophenol (PA), 2, 4-Dinitrophenol (DNP), o-Nitroaniline (NA), 2, 4-Dinitrotoluene (DNT), and the like. In view of the above material properties, such substances are often found in recent years in the world of increasing terrorist explosion attacks. Therefore, effective detection of nitroaromatic explosives in the environment is currently a hot research topic.
In the conventional technology, detection of the nitro-aromatic explosives generally requires the use of expensive large-scale instruments such as liquid chromatography and mass spectrometry, so that the detection operation is only suitable for being carried out in a laboratory, and the detection of the nitro-aromatic explosives in the environment cannot be completed in real time, on the spot and on the spot.
In view of the above technical defects, many industry people are now focusing on developing and exploring new detection methods for nitroaromatic explosives, wherein the fluorescence detection method is receiving wide attention due to its advantages of low cost, high efficiency, simplicity, easy implementation, and sensitivity. Especially since the aggregation-induced emission (AIE) phenomenon discovered by Down's loyal courtyard, many of the aggregation-induced emission (AIE) materials are used as fluorescent probes for the rapid detection of nitroaromatic explosives due to their good quantum efficiency. For example, the typical AIE group-tetraphenylethylene can reach the lowest detection limit of 0.276mM [ He T, Gu Z, Yin S.Univ.chem.2019,34(1):48-53] as a fluorescent probe for PA explosive molecules.
The dynamic resonance material with single-double bond alternation has dynamic redistribution property to electron cloud, has good electrical property, and has wide application in the fields of OLED host materials and the like [ Tao Y, Xi ao J, Zheng C, Zhang Z, YanM, Chen R, ZHou X, Li H, An Z, Wang Z, Xu H, Huang W.Angew Chem Int Ed Engl,2013,52(40): 10491-. However, at present, various literature documents do not mention that the material is used as a fluorescent detection reagent for micro-trace nitro-aromatic explosives and is used for realizing rapid screening and detection of the nitro-aromatic explosives.
In summary, how to find and prepare a novel dynamic resonance aggregation-induced emission material and apply the material as a fluorescence detection reagent for trace nitro-aromatic explosives is a technical problem that those skilled in the art expect to solve.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a dynamic resonance aggregation-induced emission material for explosive detection, and a preparation method and an application thereof, which are described below.
A dynamic resonance aggregation-induced emission material for explosive detection has a molecular structural formula as follows:
wherein X is not present or is any one of oxygen atom, sulfur atom and selenium atom.
Preferably, the connection mode between two groups in the molecule is any one of para connection, ortho connection and meta connection.
A preparation method of a dynamic resonance aggregation-induced emission material for explosive detection comprises the following steps:
s11, taking bromocarbazole and diboron acid pinacol ester as raw materials, taking potassium acetate and palladium catalysts as catalysts, taking anhydrous 1, 4-dioxane or toluene as a solvent, reacting in a dark place, and extracting and purifying after the reaction is finished to obtain a compound with a terminal group of boric acid ester, wherein the compound is taken as an intermediate I;
s12, taking the intermediate I and 2-bromo-1, 1, 2-triphenylethylene prepared in S11 as raw materials, taking potassium carbonate and palladium tetratriphenylphosphine as catalysts, taking toluene as a solvent, carrying out Suzuki coupling reaction, and extracting and purifying after the reaction is finished to obtain a tetraphenyl vinyl derivative as an intermediate II;
s13, dissolving the intermediate II prepared in the S12 in anhydrous tetrahydrofuran or anhydrous dimethylformamide, adding n-butyllithium at a low temperature for reaction, adding diphenyl phosphorus chloride into a reaction system, heating to room temperature for reaction, and extracting and purifying after the reaction is finished to obtain an aggregation-induced luminescent material containing tetraphenyl vinyl derivatives, namely an intermediate III;
and S14, dissolving the intermediate III prepared in the S13 in dichloromethane, adding any one of hydrogen peroxide, sulfur powder and selenium powder, controlling equivalent weight, and extracting and purifying after reaction is finished to obtain the dynamic resonance aggregation-induced emission material for explosive detection.
Preferably, in S11, the bromocarbazole is any one of 1-bromocarbazole, 2-bromocarbazole, 3-bromocarbazole, and 4-bromocarbazole.
Preferably, in S12, the molar ratio of the first intermediate to 2-bromo-1, 1, 2-triphenylethylene is 1:1 to 1:1.5, the molar ratio of the first intermediate to potassium carbonate is 1:8 to 1:10, and the molar ratio of the first intermediate to palladium tetratriphenylphosphine is 1:0.03 to 1: 0.08.
Preferably, in S12, the Suzuki coupling reaction temperature is 80-100 ℃, and the reaction time is 24-48 h.
Preferably, in S14, when the added substance is hydrogen peroxide, the molar ratio of the intermediate III to the hydrogen peroxide is 1: 5-1: 10; when the added substance is sulfur powder, the molar ratio of the intermediate III to the sulfur powder is 1: 3-1: 10; when the added substance is selenium powder, the molar ratio of the intermediate III to the selenium powder is 1: 3-1: 10.
Preferably, in S14, the reaction time is 12h to 24 h.
The application of dynamic resonance aggregation-induced emission material for explosive detection comprises the following steps:
s21, dissolving the dynamic resonance aggregation-induced emission material for explosive detection in tetrahydrofuran, and adding water to prepare a quenching type fluorescent probe solution, wherein the water content of the quenching type fluorescent probe solution is 70-98%;
s22, dissolving the explosive to be detected in tetrahydrofuran to prepare a solution to be detected;
s23, adding the solution to be detected into the quenching type fluorescent probe solution, measuring the fluorescence intensity of the quenching type fluorescent probe solution, and drawing a fluorescence curve with a scanning wavelength range as a horizontal coordinate and the fluorescence intensity as a vertical coordinate;
then adding the same amount of the solution to be detected in batches for multiple times, measuring the fluorescence intensity of the quenching type fluorescent probe solution after adding the solution to be detected each time, and drawing a corresponding fluorescence curve with the scanning wavelength range as the abscissa and the fluorescence intensity as the ordinate;
and finally, judging whether fluorescence quenching occurs or not according to all the drawn fluorescence curves.
Preferably, in S22, the explosives to be detected include 2,4, 6-trinitrophenol, 2, 4-dinitrophenol, o-nitroaniline and 2, 4-dinitrotoluene.
Compared with the prior art, the invention has the advantages that:
the invention provides a dynamic resonance aggregation-induced emission material for explosive detection. The material is based on an N-P ═ X dynamic resonance structural system, and a typical aggregation-induced emission group-tetraphenylethylene is introduced, so that the material has the advantages of simplicity in synthesis, high yield, high quantum efficiency and the like.
The material of the invention is used as a sensing molecule for detecting explosives, and the material of the resonance structure has certain regulation and control capability on electron distribution, so that the combination between the sensing molecule and the target detection molecule can be more sensitive, and compared with the material without the resonance structure in the prior art, the material of the invention has better detection effect and higher detection sensitivity5M-1The lowest detection limit can reach 31 nM.
In addition, the invention also provides a new design idea for the preparation of the novel organic photoelectric material, provides reference for other related problems in the same field, can be expanded and extended on the basis of the design idea, and has very wide application prospect.
The following detailed description of the embodiments of the present invention is provided in connection with the accompanying drawings for the purpose of facilitating understanding and understanding of the technical solutions of the present invention.
Drawings
FIG. 1 is a graph showing the relationship between the scanning wavelength and the fluorescence intensity of T-CZPO prepared in example 1 of the present invention in tetrahydrofuran-water solutions with different water contents.
FIG. 2 is a graph showing the relationship between water content and fluorescence intensity of T-CZPO prepared in example 1 of the present invention in tetrahydrofuran-water solutions with different water contents.
FIG. 3 is a graph of the fluorescence titration curve of T-CzPO versus PA prepared in example 1 of the present invention.
FIG. 4 shows the I-time of detecting PA by T-CZPO prepared in example 1 of the present invention0I-PA concentration profile.
FIG. 5 is a Stern-Volmer graph of the T-CzPO prepared in example 1 of the present invention in detecting PA.
FIG. 6 is a graph showing the variation of fluorescence intensity with PA concentration when detecting PA by T-CZPO prepared in example 1 of the present invention.
FIG. 7 is a graph showing the relationship between the fluorescence intensity and the scanning wavelength of the T-CZPS prepared in example 2 of the present invention in tetrahydrofuran-water solutions with different water contents.
FIG. 8 is a graph showing the relationship between water content and fluorescence intensity of T-CZPS prepared in example 2 of the present invention in tetrahydrofuran-water solutions with different water contents.
FIG. 9 is a graph of the fluorescence titration of T-CzPS versus PA made in example 2 of the present invention.
FIG. 10 shows the I time of detecting PA by T-CZPS prepared in example 2 of the present invention0I-PA concentration profile.
FIG. 11 is a Stern-Volmer graph of the T-CZPS prepared in example 2 of the present invention in detecting PA.
FIG. 12 is a graph showing the variation of the fluorescence intensity with the PA concentration when detecting PA by T-CZPS prepared in example 2 of the present invention.
Detailed Description
The invention discloses a dynamic resonance aggregation-induced emission material for explosive detection and a preparation method and application thereof, and particularly relates to the following.
A dynamic resonance aggregation-induced emission material for explosive detection has a molecular structural formula shown in formula 1.
In formula 1, X is not present or is any of an oxygen atom, a sulfur atom, and a selenium atom.
In the molecular structural formula, the connection mode between two groups in a molecule is any one of para connection, ortho connection and meta connection.
A method for preparing the dynamic resonance aggregation-induced emission material for explosive detection as described above, comprising the following steps:
s11, taking bromo nitrogen heterocyclic compound and boronic acid pinacol ester as raw materials, taking potassium acetate and palladium catalyst as catalysts, taking anhydrous 1, 4-dioxane or toluene as a solvent, reacting in a dark place, and extracting and purifying after the reaction is finished to obtain a compound with a terminal group of boric acid ester, which is used as an intermediate I.
In this step, the bromocarbazole is any one of 1-bromocarbazole, 2-bromocarbazole, 3-bromocarbazole, and 4-bromocarbazole.
S12, taking the intermediate I and 2-bromo-1, 1, 2-triphenylethylene prepared in S11 as raw materials, taking potassium carbonate and palladium tetratriphenylphosphine as catalysts, taking toluene as a solvent, carrying out Suzuki coupling reaction, and extracting and purifying after the reaction is finished to obtain the tetraphenyl vinyl derivative as an intermediate II.
In the step, the molar ratio of the intermediate I to 2-bromo-1, 1, 2-triphenylethylene is 1: 1-1: 1.5, the molar ratio of the intermediate I to potassium carbonate is 1: 8-1: 10, and the molar ratio of the intermediate I to tetratriphenylphosphine palladium is 1: 0.03-1: 0.08.
The Suzuki coupling reaction temperature is 80-100 ℃, and the reaction time is 24-48 h.
S13, dissolving the intermediate II prepared in the S12 in anhydrous Tetrahydrofuran (THF) or anhydrous Dimethylformamide (DMF), adding n-butyllithium at low temperature for reaction, adding diphenyl phosphorus chloride into a reaction system, heating to room temperature for reaction, and extracting and purifying after the reaction is finished to obtain an aggregation-induced luminescent material containing tetraphenyl vinyl derivatives, namely an intermediate III.
And S14, dissolving the intermediate III prepared in the S13 in dichloromethane, adding any one of hydrogen peroxide, sulfur powder and selenium powder, controlling equivalent weight, reacting for 12-24 h, and extracting and purifying after the reaction is finished to obtain the aggregation-induced luminescent material containing the N-P-X resonance structure, namely the dynamic resonance aggregation-induced luminescent material for explosive detection.
In the step, when the added substance is hydrogen peroxide, the molar ratio of the intermediate III to the hydrogen peroxide is 1: 5-1: 10; when the added substance is sulfur powder, the molar ratio of the intermediate III to the sulfur powder is 1: 3-1: 10; when the added substance is selenium powder, the molar ratio of the intermediate III to the selenium powder is 1: 3-1: 10.
Use of a dynamic resonance aggregation-inducing luminescent material as described above for explosives detection, comprising the steps of:
s21, dissolving the dynamic resonance aggregation-induced emission material for explosive detection in tetrahydrofuran, and adding water to prepare a quenching type fluorescent probe solution, wherein the water content of the quenching type fluorescent probe solution is 70-98%.
And S22, dissolving the explosive to be detected in tetrahydrofuran to prepare a solution to be detected. The explosives to be detected comprise 2,4, 6-trinitrophenol (PA), 2, 4-dinitrophenol, o-nitroaniline, 2, 4-dinitrotoluene and the like.
S23, adding the solution to be detected into the quenching type fluorescent probe solution, measuring the fluorescence intensity of the quenching type fluorescent probe solution, and drawing a fluorescence curve with the scanning wavelength range as the abscissa and the fluorescence intensity as the ordinate.
And then adding the same amount of the solution to be detected in batches for multiple times, measuring the fluorescence intensity of the quenching type fluorescent probe solution after adding the solution to be detected each time, and drawing a corresponding fluorescence curve with the scanning wavelength range as an abscissa and the fluorescence intensity as an ordinate.
And finally, judging whether fluorescence quenching occurs or not according to all the drawn fluorescence curves.
The above-described embodiments of the present invention are further illustrated by two specific examples. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example one
1. Synthesis of Compound T-CzPO
(1) Synthesis of intermediate one
Adding 4.00g of 3-bromocarbazole, 6.32g of pinacol diboron diboride, 9.56g of methyl acetate and 0.60g of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex into a 250mL two-port bottle, sealing, protecting the tinfoil from light, vacuumizing and blowing nitrogen for three times, injecting 100mL of 1, 4-dioxane into the bottle under the atmosphere of nitrogen for dissolving, and heating the device to 80 ℃ for reacting for 48 hours. Extracting, drying and purifying to obtain the carbazolyl borate derivative, namely the intermediate I.
(2) Synthesis of intermediate II
A250 mL two-neck flask is taken, 4.00g of intermediate I, 5.95g of 2-bromo-1, 1, 2-triphenylethylene, 0.47g of tetratriphenylphosphine palladium and two drops of phase transfer catalyst methyl trioctyl ammonium chloride (Aliquat336) are added, the flask is sealed, vacuum blowing is carried out for three times, 100mL of toluene is injected and dissolved under the nitrogen atmosphere, then potassium carbonate aqueous solution (68.22mL, 2M) is injected, and the device is heated to 80 ℃ for reaction for 48 hours. And extracting, drying and purifying to obtain an intermediate II.
(3) Synthesis of intermediate III
And taking a 100mL single-neck bottle, putting 2.00g of the intermediate II into the single-neck bottle, vacuumizing and blowing nitrogen for three times, dissolving the intermediate II by using 20mL of THF solution, measuring 0.36mL of n-hexane solution of n-butyllithium by using a syringe, dropwise adding the n-hexane solution into the reaction bottle, and reacting at-78 ℃ for 1.5 hours under the protection of nitrogen to obtain a reaction system. 0.12mL of diphenylphosphoryl chloride was added to the reaction system, and the mixture was warmed to room temperature to react for 12 hours. And extracting, drying and purifying to obtain a compound T-CzP, namely an intermediate III.
(4) Synthesis of Compound T-CzPO
Dissolving the intermediate III (2.00g) in 50mL of dichloromethane solution, weighing 0.81mL of 30% hydrogen peroxide solution for oxidation, and reacting at normal temperature overnight. The dichloromethane solution was spun off using a rotary evaporator. The crude product was then dissolved in 50mL of dichloromethane and silica gel powder added and the solvent spun dry and purified by column chromatography to give 1.85g of a white solid in 90% yield.1HNMR(400MHz,DMSO)7.92(d,J＝8.4Hz,1H),7.74(dd,J＝8.0,6.6Hz,3H),7.68(m,8H),7.23(m,19H),6.86(dd,J＝8.7,1.8Hz,1H)；13CNMR(101MHz,CDCl3)143.88,143.82,141.97,141.94,140.93,140.86,140.31,140.28,137.63,133.13,133.10,132.18,132.07,131.50,131.48,131.38,130.25,130.07,129.08,128.95,127.66,127.64,126.57,126.51,126.45,126.36,126.34,126.16,126.08,126.02,122.63,121.87,119.86,115.06,114.13；HRMS(EI):m/zcalcdforC44H32NPSNa[M+Na]+:644.2119；found:644.2113。
The molecular structural formula of the finally prepared compound T-CzPO is as follows.
2. Determination of aggregation-induced emission property of compound T-CzPO
Dissolving the compound T-CzPO in tetrahydrofuran solution, adding a certain amount of water, and preparing into tetrahydrofuran-water (THF-H) containing compound T-CzPO at a concentration of 10 μ M and a total volume of 5mL according to water content (0%, 20%, 40%, 60%, 80%, 85%, 90%, 95%, 98%)2O) solution, and the fluorescence intensity of tetrahydrofuran-water solution of the series of compounds T-CzPO was measured by fluorescence spectrometer (test conditions: excitation wavelength 315nm, scanning wavelength range 330-700 nm), and drawing a fluorescence intensity change curve with the excitation wavelength as abscissa and the fluorescence intensity as ordinate. The results are shown in FIG. 1, which is a fluorescence quenching curve under excitation at 315nM excitation wavelength after dropping PA in tetrahydrofuran-water solution (5: 95 by volume ratio). Then drawing the water content (f)w) On the abscissa, fluorescence intensityThe peak value of the intensity is a fluorescence intensity curve on the ordinate, and the result is shown in FIG. 2.
As can be seen from FIG. 1, the fluorescence intensity of the tetrahydrofuran-water solution of the compound T-CzPO gradually increased with the increase of the water content, indicating that the compound T-CzPO has aggregation-induced emission properties. As can be seen from FIG. 2, the compound T-CzPO shows typical aggregation-induced emission properties in tetrahydrofuran-water solution.
3. Fluorescence titration of explosive molecule PA by compound T-CzPO
In a tetrahydrofuran-water solution (5: 95 volume ratio) of T-CzPO (10 μ M), PA dissolved in tetrahydrofuran was added dropwise, and the effect of PA on the fluorescence property of T-CzPO was tested by light excitation at 315nm, and the result is shown in FIG. 3. Taking the concentration of PA molecules as the abscissa, the ratio (I) of the initial fluorescence intensity to the real-time fluorescence intensity after adding PA0I) as abscissa, plotted as graph, the results are shown in FIG. 4.
As can be seen from FIG. 3, the fluorescence of T-CzPO was gradually quenched with the gradual addition of PA; the quenching effect is obvious. As can be seen from FIG. 4, the detection of PA by T-CzPO molecules shows signal amplification quenching effect with the increase of PA concentration, and an exponential curve formula is obtained by fitting a quenching curve:
I0/I＝1.128e6.728[PA]-0.135。
according to the formula, the quantitative detection of the explosives can be realized.
4. Determination of detection limit and quenching constant of compound T-CzPO on explosive molecule PA
According to Stern-Volmer equation "I0/I＝1+Ksv[Q]"quench constant (Ksv) can be determined. Plotting the ratio of fluorescence intensities (I)0/I，I0And I is the initial fluorescence intensity of T-CzPO and the fluorescence intensity in the presence of the analyte, respectively, and the concentration of the analyte ([ Q ]]) The K value obtained by linear fitting of the relation graph is Ksv, and the quenching constant of T-CzPO to explosive molecule PA is 9.752 × 10 as can be seen from the combination of FIG. 54M-1. The calculation method of the limit of detection (LOD) comprises the following steps: LOD is 3/K. In the formula, the fluorescence intensity is calculated after the solution of T-CzPO (10 MuM) in tetrahydrofuran-water solution (volume ratio 5:95) is scanned for 20 times3.4211; k is the slope of the fitted line. The relationship between the fluorescence intensity corresponding to the maximum luminescence wavelength and the concentration of the analyte in the low concentration range was plotted, and the result is shown in FIG. 6. And linear fitting is carried out on the obtained product to obtain a K value, LOD can be obtained by substituting LOD (Lod) 3/K, and LOD is 45nM by calculation.
Example two
1. Synthesis of Compound T-CzPS
T-CzP (2.00g) obtained in example 1 was dissolved in 50mL of methylene chloride solution, and then 1.68g of sulfur powder was added thereto to carry out vulcanization, followed by reaction overnight at normal temperature. The dichloromethane solution was spun off using a rotary evaporator. The crude product was then dissolved in 50mL of dichloromethane, silica gel powder was added and the solvent was spun off and purified by column chromatography to give 1.83g of a white solid in 87% yield.1HNMR(400MHz,DMSO)8.02(m,5H),7.73(dd,J＝11.3,9.4Hz,3H),7.62(td,J＝7.7,3.8Hz,4H),7.23(m,17H),6.69(dd,J＝8.7,2.0Hz,1H),6.53(d,J＝8.5Hz,1H),6.16(d,J＝8.7Hz,1H).13CNMR(101MHz,CDCl3)143.91,143.79,141.55,141.52,140.88,140.73,140.04,137.40,132.92,132.68,132.63,132.51,131.91,131.49,131.37,131.33,129.53,129.07,128.93,127.70,127.65,126.96,126.91,126.43,126.36,125.63,122.68,121.78,119.88,115.47,114.29；HRMS(EI):m/zcalcdforC44H32OPS[M+H]+:637.1993；found:637.1992。
The molecular structural formula of the finally prepared compound T-CZPS is as follows.
2. Determination of aggregation-induced emission Properties of Compound T-CzPS
The aggregation-induced emission properties of the compound T-CzPS were examined in the same manner as in the example. The fluorescence intensity curve with the excitation wavelength on the abscissa and the fluorescence intensity on the ordinate was plotted, and the result is shown in FIG. 7, which is a fluorescence quenching curve under the excitation of 315nM excitation wavelength after dropping PA in tetrahydrofuran-water solution (5: 95 by volume). Then drawing the water content (f)w) As abscissa, peak of fluorescence intensityThe results are shown in FIG. 8, which shows the change in fluorescence intensity on the ordinate.
As can be seen from FIG. 7, the aggregation-induced emission property of the compound T-CzPS is similar to that of T-CzPO, and the fluorescence intensity of the solution gradually increases with the increase of the water content of the tetrahydrofuran-water solution of the compound T-CzPS, which indicates that the compound T-CzPS has the aggregation-induced emission property. As can be seen from fig. 8, the compound T-CzPS showed typical aggregation-induced emission properties in tetrahydrofuran-water solution.
3. Fluorometric titration of the explosive molecule PA of the compound T-CzPS
The effect of PA on the fluorescence performance of T-CzPS was tested by fluorescence titration of the compound T-CzPS on the explosive molecule PA in the same manner as in the example, and the results are shown in FIG. 9. Taking the concentration of PA molecules as the abscissa, the ratio of the initial fluorescence intensity to the real-time fluorescence intensity after the addition of PA (I)0I) as the abscissa, the results are shown in fig. 10.
As can be seen from FIG. 9, the fluorescence of T-CzPS was gradually quenched with the gradual addition of PA, and the quenching effect was significant. As can be seen from FIG. 10, the detection of PA by T-CzPS molecules shows signal amplification quenching effect with increasing PA concentration, and by fitting the quenching curve, an exponential curve formula is obtained:
I0/I＝0.915e6.093[PA]+0.456。
according to the formula, the quantitative detection of the explosives can be realized.
4. Determination of detection limit and quenching constant of compound T-CzPS on explosive molecule PA
According to Stern-Volmer equation "I0/I＝1+Ksv[Q]"quench constant (Ksv) can be determined. Plotting the ratio of fluorescence intensities (I)0/I，I0And I is the initial fluorescence intensity of T-CzPS and the fluorescence intensity in the presence of the analyte, respectively, and the concentration of the analyte ([ Q ]]) The K value obtained by linear fitting of the relation graph is Ksv, and the quenching constant of T-CzPS to explosive molecule PA is 1.332 × 10, which can be seen from the combination of FIG. 115M-1. The calculation method of the limit of detection (LOD) comprises the following steps: LOD is 3/K. In the formula, scanning is performed by using a tetrahydrofuran-water solution (volume ratio of 5:95) of T-CzPS (10 μ M)After 20 times, the standard deviation of fluorescence intensity was calculated as 2.54221; k is the slope of the fitted line. And (3) drawing a relation graph of the fluorescence intensity corresponding to the maximum luminescence wavelength and the concentration of the measured object in a low concentration range, wherein the result is shown in fig. 12, performing linear fitting on the relation graph to obtain a K value, substituting LOD (log intensity) into 3/K to obtain LOD, and calculating to obtain the LOD of 31 nM.
In summary, the present invention provides a dynamic resonance aggregation-induced emission material for detecting explosives. The material is based on an N-P ═ X dynamic resonance structural system, and a typical aggregation-induced emission group-tetraphenylethylene is introduced, so that the material has the advantages of simplicity in synthesis, high yield, high quantum efficiency and the like.
The material of the invention is used as a sensing molecule to detect explosives, and the resonance structure material has certain regulation and control capability on electron distribution, so that the combination between the sensing molecule and the target detection molecule is more sensitive.
The data analysis shows that compared with the prior art which does not introduce a resonance structure, the material of the invention has obviously improved test effect on the typical nitroaromatic explosive PA molecule, lower detection limit, larger quenching constant and shows a quenching effect of signal amplification5M-1The lowest detection limit can reach 31 nM.
In addition, the invention also provides a new design idea for the preparation of the novel organic photoelectric material, provides reference for other related problems in the same field, can be expanded and extended on the basis of the design idea, and has very wide application prospect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A dynamic resonance aggregation-induced emission material for explosive detection is characterized in that the molecular structural formula is as follows:
wherein X is not present or is any one of oxygen atom, sulfur atom and selenium atom.
2. The dynamic resonance aggregation-induced emission material for explosive detection according to claim 1, wherein: the connection mode between two groups in the molecule is any one of para connection, ortho connection and meta connection.
3. The method for preparing dynamic resonance aggregation-induced emission material for explosive detection according to claim 1, comprising the following steps:
s11, taking bromocarbazole and diboron acid pinacol ester as raw materials, taking potassium acetate and palladium catalysts as catalysts, taking anhydrous 1, 4-dioxane or toluene as a solvent, reacting in a dark place, and extracting and purifying after the reaction is finished to obtain a compound with a terminal group of boric acid ester, wherein the compound is taken as an intermediate I;
s12, taking the intermediate I and 2-bromo-1, 1, 2-triphenylethylene prepared in S11 as raw materials, taking potassium carbonate and palladium tetratriphenylphosphine as catalysts, taking toluene as a solvent, carrying out Suzuki coupling reaction, and extracting and purifying after the reaction is finished to obtain a tetraphenyl vinyl derivative as an intermediate II;
s13, dissolving the intermediate II prepared in the S12 in anhydrous tetrahydrofuran or anhydrous dimethylformamide, adding n-butyllithium at a low temperature for reaction, adding diphenyl phosphorus chloride into a reaction system, heating to room temperature for reaction, and extracting and purifying after the reaction is finished to obtain an aggregation-induced luminescent material containing tetraphenyl vinyl derivatives, namely an intermediate III;
and S14, dissolving the intermediate III prepared in the S13 in dichloromethane, adding any one of hydrogen peroxide, sulfur powder and selenium powder, controlling equivalent weight, and extracting and purifying after reaction is finished to obtain the dynamic resonance aggregation-induced emission material for explosive detection.
4. The method for preparing dynamic resonance aggregation-induced emission material for explosive detection according to claim 3, wherein: in S11, the bromocarbazole is any one of 1-bromocarbazole, 2-bromocarbazole, 3-bromocarbazole, and 4-bromocarbazole.
5. The method for preparing dynamic resonance aggregation-induced emission material for explosive detection according to claim 3, wherein: in S12, the molar ratio of the intermediate I to 2-bromo-1, 1, 2-triphenylethylene is 1: 1-1: 1.5, the molar ratio of the intermediate I to potassium carbonate is 1: 8-1: 10, and the molar ratio of the intermediate I to tetratriphenylphosphine palladium is 1: 0.03-1: 0.08.
6. The method for preparing dynamic resonance aggregation-induced emission material for explosive detection according to claim 3, wherein: in S12, the Suzuki coupling reaction temperature is 80-100 ℃, and the reaction time is 24-48 h.
7. The method for preparing dynamic resonance aggregation-induced emission material for explosive detection according to claim 3, wherein: in S14, when the added substance is hydrogen peroxide, the molar ratio of the intermediate III to the hydrogen peroxide is 1: 5-1: 10; when the added substance is sulfur powder, the molar ratio of the intermediate III to the sulfur powder is 1: 3-1: 10; when the added substance is selenium powder, the molar ratio of the intermediate III to the selenium powder is 1: 3-1: 10.
8. The method for preparing dynamic resonance aggregation-induced emission material for explosive detection according to claim 3, wherein: in S14, the reaction time is 12 to 24 hours.
9. The use of the dynamic resonance aggregation-induced emission material for explosive detection according to claim 1, comprising the steps of:
s21, dissolving the dynamic resonance aggregation-induced emission material for explosive detection in tetrahydrofuran, and adding water to prepare a quenching type fluorescent probe solution, wherein the water content of the quenching type fluorescent probe solution is 70-98%;
s22, dissolving the explosive to be detected in tetrahydrofuran to prepare a solution to be detected;
s23, adding the solution to be detected into the quenching type fluorescent probe solution, measuring the fluorescence intensity of the quenching type fluorescent probe solution, and drawing a fluorescence curve with a scanning wavelength range as a horizontal coordinate and the fluorescence intensity as a vertical coordinate;
then adding the same amount of the solution to be detected in batches for multiple times, measuring the fluorescence intensity of the quenching type fluorescent probe solution after adding the solution to be detected each time, and drawing a corresponding fluorescence curve with the scanning wavelength range as the abscissa and the fluorescence intensity as the ordinate;
and finally, judging whether fluorescence quenching occurs or not according to all the drawn fluorescence curves.
10. The use of the dynamic resonance aggregation-induced emission material for explosives detection according to claim 9, wherein: in S22, the explosive to be tested includes 2,4, 6-trinitrophenol, 2, 4-dinitrophenol, o-nitroaniline, and 2, 4-dinitrotoluene.
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