检测硝基芳烃用咔唑衍生物的合成及性能研究
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摘要
硝基芳烃是爆炸物的主要组成部分,并且硝基芳烃爆炸物对人们的生命、财产安全构成了严重的威胁。因此,快速检测大气、土壤、溶液中硝基芳烃引起了人们的普遍关注。目前,硝基芳烃的检测方法很多,如X射线法,质谱法、荧光法等。其中,荧光法具有选择性好、响应速度快、灵敏度高及设备简单等优点越来越受到人们的重视。目前，研究较多的主要是高分子聚合物作为硝基芳烃传感材料,传感高分子遇到硝基芳烃时,由于硝基芳烃中硝基的强拉电子作用,导致聚合物中电荷转移,聚合物荧光性质发生改变,实现对硝基芳烃的检测。但是,聚合高分子作为硝基芳烃传感材料普遍存在一个缺点：硝基芳烃在聚合物中不易扩散,致使荧光传感器响应速度慢。为了解决这一问题,并结合已有文献及我们课题组过去的工作,我们知道咔唑基团可以作为硝基芳烃的敏感基团,为此,我们设计合成对硝基芳烃具有高灵敏度、快速响应的分子荧光传感材料。
本论文合成了两系列作为硝基芳烃传感材料的化合物,并测试了他们的荧光性能及硝基芳烃对它们的荧光猝灭性能。
(1)利用Wittig、Heck反应合成了咔唑联三苯胺型、咔唑联均三嗪荧光传感材料：CB-1、CB-2、CB-3、CZ-1、CZ-3。
(2)研究了这两系列化合物在不同溶剂中的光学性质。随着溶剂极性的增大,所有化合物的线性吸收光谱变化都很小,但是荧光光谱变化比较明显,荧光发射波长都是随着溶剂极性的增加而出现红移,荧光强度逐渐降低。其中咔唑联均三嗪化合物CZ-1、CZ-3在乙醇中由于氢键的影响荧光强度几乎被完全猝灭。在这两系列化合物中,化合物的荧光发射波长都是随咔唑基团数目的增加而增大,荧光强度增强。
(3)用硝基甲烷、甲苯、对硝基甲苯、对硝基酚、邻硝基酚、2,4-二硝基甲苯、2,4，6-三硝基酚对这两系列化合物进行荧光猝灭性能测试,得出结论：这两系化合物对硝基芳烃具有很好的选择性,而硝基甲烷、甲苯对这两系列化合物硝基芳烃化合物没有猝灭性能；硝基芳烃对化合物的猝灭性能随咔唑数目的增加而减小；邻硝基酚对化合物的荧光猝灭率最大,将CB-1、CZ-1作为检测邻硝基酚的荧光传感材料时检测限最低,能达到10-6g/cm3。
Nitroaromatic compounds are the main constituent of explosives, which have been real threat to people's lives and properties. So developing a fast detection of nitroaromatic compounds in atmosphere, soil, and solvent has attracted great attention. At present, many analytical methods have been developped to monitoring nitroaromatic compounds, such as X-ray mass spectrometry, fluorescence method and so on. Fluorescent method attracts more and more attention because of its high selectivity, high sensitivity, quick response and facility. At present, the researches on nitroaromatic sensor materials were mainly focus on the polymer material. The fluorescent properties changed because of charge transport, which due to the strong electron-drawing group, nitro group, when the polymer faces nitroaromatic molecules. By this change, we can detect the nitroaromatic compound. But, using polymer as fluorescent sensor has many disadvantages. It is difficult for nitroaromatic compound to diffuse in polymer, which can slower the response. In order to solve this problem, we designed and synthesized single-molecular fluorescent sensor materials to detect nitroaromatic compounds, based on other studies and report and past work of our group.
In this paper, two series of fluorescent compounds were synthesized. Their optical properties were studied. Their fluorescence quenching properties faced different nitroaromatics were researched.
First, we synthesized two series of fluorescent compound containing carbazole groups, as fluorescence sensor, through Wittig reaction and Heck reaction. The compounds are CB-1, CB-2, CB-3, CZ-1 and CZ-3.
Second, the optical properties of these compounds in different solvents were studied. The absorption spectra of all compounds have nothing to do with the solvent polarity. However, with the increasing of solvent polarity, the emission wavelengths appear red-shift, and the fluorescence intensity become lower. Especially to deserve to be mentioned, in ethanol, the fluorescence of CZ-1 and CZ-3 were totally quenched, which is probably due to hydrogen bonding of ethanol to the fluorescent groups. In the two series of compounds, the emission wavelength and fluorescence intensity both increase with the increase of carbazole groups.
Third, the fluorescence quenching properties of all compounds to nitromethane. toluene, 1-methyl-4-nitrobenzene,4-nitrophenol,1-methyl-2,4-dinitrobenzene 2-nitrophenol, and picric acid were studied. We got the conclusions are as follows:As fluorescence sensor materials for nitroaromatic compounds, they all showed good selectivity. Nitromethane and toluene had little impact on the fluorescence spectra. With the increase of carbazole groups, the fluorescent quenching constant decreased. Among all the quenchers,2-nitrophenol has the biggest fluorescent quenching constant. We got a very low detection limit of 10-6 g/cm3, when we use CB-1,CZ-1 as fluorescent sensor to detect 2-nitrophenol.
本论文合成了两系列作为硝基芳烃传感材料的化合物,并测试了他们的荧光性能及硝基芳烃对它们的荧光猝灭性能。
(1)利用Wittig、Heck反应合成了咔唑联三苯胺型、咔唑联均三嗪荧光传感材料：CB-1、CB-2、CB-3、CZ-1、CZ-3。
(2)研究了这两系列化合物在不同溶剂中的光学性质。随着溶剂极性的增大,所有化合物的线性吸收光谱变化都很小,但是荧光光谱变化比较明显,荧光发射波长都是随着溶剂极性的增加而出现红移,荧光强度逐渐降低。其中咔唑联均三嗪化合物CZ-1、CZ-3在乙醇中由于氢键的影响荧光强度几乎被完全猝灭。在这两系列化合物中,化合物的荧光发射波长都是随咔唑基团数目的增加而增大,荧光强度增强。
(3)用硝基甲烷、甲苯、对硝基甲苯、对硝基酚、邻硝基酚、2,4-二硝基甲苯、2,4，6-三硝基酚对这两系列化合物进行荧光猝灭性能测试,得出结论：这两系化合物对硝基芳烃具有很好的选择性,而硝基甲烷、甲苯对这两系列化合物硝基芳烃化合物没有猝灭性能；硝基芳烃对化合物的猝灭性能随咔唑数目的增加而减小；邻硝基酚对化合物的荧光猝灭率最大,将CB-1、CZ-1作为检测邻硝基酚的荧光传感材料时检测限最低,能达到10-6g/cm3。
Nitroaromatic compounds are the main constituent of explosives, which have been real threat to people's lives and properties. So developing a fast detection of nitroaromatic compounds in atmosphere, soil, and solvent has attracted great attention. At present, many analytical methods have been developped to monitoring nitroaromatic compounds, such as X-ray mass spectrometry, fluorescence method and so on. Fluorescent method attracts more and more attention because of its high selectivity, high sensitivity, quick response and facility. At present, the researches on nitroaromatic sensor materials were mainly focus on the polymer material. The fluorescent properties changed because of charge transport, which due to the strong electron-drawing group, nitro group, when the polymer faces nitroaromatic molecules. By this change, we can detect the nitroaromatic compound. But, using polymer as fluorescent sensor has many disadvantages. It is difficult for nitroaromatic compound to diffuse in polymer, which can slower the response. In order to solve this problem, we designed and synthesized single-molecular fluorescent sensor materials to detect nitroaromatic compounds, based on other studies and report and past work of our group.
In this paper, two series of fluorescent compounds were synthesized. Their optical properties were studied. Their fluorescence quenching properties faced different nitroaromatics were researched.
First, we synthesized two series of fluorescent compound containing carbazole groups, as fluorescence sensor, through Wittig reaction and Heck reaction. The compounds are CB-1, CB-2, CB-3, CZ-1 and CZ-3.
Second, the optical properties of these compounds in different solvents were studied. The absorption spectra of all compounds have nothing to do with the solvent polarity. However, with the increasing of solvent polarity, the emission wavelengths appear red-shift, and the fluorescence intensity become lower. Especially to deserve to be mentioned, in ethanol, the fluorescence of CZ-1 and CZ-3 were totally quenched, which is probably due to hydrogen bonding of ethanol to the fluorescent groups. In the two series of compounds, the emission wavelength and fluorescence intensity both increase with the increase of carbazole groups.
Third, the fluorescence quenching properties of all compounds to nitromethane. toluene, 1-methyl-4-nitrobenzene,4-nitrophenol,1-methyl-2,4-dinitrobenzene 2-nitrophenol, and picric acid were studied. We got the conclusions are as follows:As fluorescence sensor materials for nitroaromatic compounds, they all showed good selectivity. Nitromethane and toluene had little impact on the fluorescence spectra. With the increase of carbazole groups, the fluorescent quenching constant decreased. Among all the quenchers,2-nitrophenol has the biggest fluorescent quenching constant. We got a very low detection limit of 10-6 g/cm3, when we use CB-1,CZ-1 as fluorescent sensor to detect 2-nitrophenol.
引文
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[2]Krausa M.,Rezne A. A..Vapor and trance detection of explosive for anti-terrorism purpose[M]. Kluwer Academic publishers, Dordrecht, The Netherland,2004
[3]孟祥承.爆炸物及毒品的探测技术[J].核电子学与探测技术,2003,23(4)：371-379
[4]Holmgren E., et al. Determination and characterization of organic explosives using porous graphitic carbon and liquid chromatography-atmospheric pressure chemical ionization mass spectrometry[J]. Journal of Chromatography A,2005,1099: 127-135.
[5]Rivera F. M.. Beaulieu C., Deschamps S., et al. J. Chromatogr. A[M],2004,1048: 213-221
[6]Patra D., Mishra, A.K.. Fluorescence quenching of benzo[k]fluoranthene in poly (vinyl alcoho) film:a possible optical sensor for nitro aromatic compounds[J]. Sensors and Actuators B,2001,80:278-282
[7]John V., Victoria L., et al.Fluorescence Quenching as an Indirect Detection Method for Nitrated Explosives[J].Anal. Chem,2001.73:2004-2011
[8]Ellen R., Goldman T. J., et al. Detection of 2,4,6-Trinitrotoluene in Environmental Samples Using a Homogeneous Fluoroimmunoassay[J]. Environ Sci. Technol., 2003,37:4733-4736
[9]唐江宏,胡娟，侯延民,等.荧光光纤传感器测定废水中邻硝基酚[J].环境污染与防治,2000,22(5)：37-40
[10]Keith J.,David R.. High-Speed Fluorescence Detection of Explosives-like Vapors[J]. Anai. Chem.,2000(72):1947-1955
[11]Stefano B.,Howard M. C., Barnaby W. G., et al. Pyrene-Functionalised, Alternating Copolyimide for Sensing itroaromatic Compounds [J]. Macromolecular Rapid Communications,2009,30:459-463
[12]高莉宁，吕凤婷,房喻.薄膜荧光传感器研究进展[J].物理化学学报：2007,23(2)：274-284
[13]Yang J. S., Swager, T. M.. Fluorescent porous polymer films as TNT chemosensors: electronic and structural effects [J]. Journal of American Chemical Society,1998, 120(46):11864-11873
[14]贺庆国,程建功,封松林.一种对硝基化合物有传感功能的荧光共轭聚合物及应用[p].中国专利：200710047742.2008-10-15
[15]任韦华,刘峰,胡军,等.含三苯胺单元的超支化共轭聚合物的合成、表征及应用[J].影响科学与光化学,2008,26：318-326.
[16]Zhao D. H., Swager T. M..Sensory responses in solution vs solid state:a fluorescence quenching study of poly(i-ptycenebutadiyny-2-lene)s[J]. Macromolecules,2005,38 (22):9377-9384
[17]Naddo T., Che Y. K.,Zhang W., et al. Detection of explosiveswith afluorescent nanofibril film. Journal of American Chemical Society,2007,129 (22):6978-6979.
[18]Liu F.,Zhang L., Xiao J. H., et al. A mesoporous silica modified conjugated polymer film:Preparation and detection nitroaromatics in aqueous phase [J]. Frontiers of Materials Science in China,2010,4(2):158-163
[19]Tao S,, Li G.. Porphyrin-doped mesoporous silica films for rapid TNT detection[J]. Colloid Polym Sci.,2007,285:721-728
[20]He G., Zhang G. F., Lu F. T., et al. Fluorescent Film Sensor for Vapor-Phase Nitroaromatic Explosives via Monolayer Assembly of Oligo(diphenylsilane) on Glass Plate Surfaces[J]. Chemistry of Materials,2009.21:1494-1499
[21]Liu Y., Mills R. C., Boncella J. M., et al. Fluorescent polyacetylene thin film sensor for nitroaromatics[J]. Langmuir 2001,17:7452-7455
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