中文题名: | 典型芳香胺污染物的光学传感研究 |
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保密级别: | 公开 |
论文语种: | 中文 |
学科代码: | 070304 |
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学生类型: | 硕士 |
学位: | 理学硕士 |
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学位年度: | 2018 |
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研究方向: | 环境污染物检测 |
第一导师姓名: | |
第一导师单位: | |
提交日期: | 2018-05-01 |
答辩日期: | 2018-05-31 |
外文题名: | Optical Sensing Studies of Typical Aromatic Amines |
中文关键词: | |
中文摘要: |
芳香胺(Aromatic amines)是一类具有“致癌”、“致畸”和“致突变”三致作用性的环境污染物,它的来源广泛,主要作为生产塑料、医药、农药、染料等的中间体被合成出来。环境中的芳香胺性质比较稳定,难以被生物降解,因此会对环境造成持久的影响。芳香胺能够进入环境循环并随着生物链迁移,并且多数芳香胺具有强亲脂性,可以透过生物细胞膜在生物体的脂类有机物中浓缩富集,对人类的生命健康构成极大的威胁。作为典型的芳香胺,2-氨基蒽是一种直接有效的致癌物,在真核和原核细胞中引发突变;1-氨基蒽醌被证实可以诱发生物体癌变、畸变。基于芳香胺来源的广泛性、影响的持久性和对生物体的高毒性,发展更加高效、灵敏的分析方法来检测真实环境中的芳香胺具有重要意义。本论文主要研究了芳香胺的荧光性质,并引入两种新型纳米材料分别实现了水体系中2-氨基蒽、1-氨基蒽醌的高灵敏、高选择性的光学传感。
1、基于Ag@SiO2纳米粒子(Ag@SiO2 NPs)的金属增强荧光检测2-氨基蒽。制备的Ag@SiO2纳米粒子可以有效增强2-氨基蒽的荧光,利用这一新现象开发出一种高灵敏、高选择性检测环境污染物2-氨基蒽的方法。我们合成了一系列具有不同Ag核尺寸和SiO2壳厚度的Ag@SiO2纳米粒子,发现当纳米粒子的Ag核尺寸为40 nm,SiO2壳厚度为7 nm(Ag(40 nm)@SiO2(7 nm))时,Ag@SiO2纳米粒子对2-氨基蒽的荧光强度有最佳的增强效果。该现象的解释是Ag(40 nm)@SiO2(7 nm)的局域表面等离子共振(LSPR)峰与2-氨基蒽的吸收峰有最大的光谱重叠,以及2-氨基蒽与SiO2壳之间有高效的氢键作用。因为水体系里的其他共存物质(芳香胺、金属离子等)的吸收峰和Ag(40 nm)@SiO2(7 nm)的LSPR峰不匹配,所以这种金属增强荧光(MEF)效应对2-氨基蒽具有高选择性。混合溶液在2分钟内可以获得2-氨基蒽的MEF效应。基于此,我们实现了水体系中2-氨基蒽的荧光法检测,检测限低至1 nM。最后,这一新开发的检测方法被成功应用于真实水体系中2-氨基蒽的检测。
2、基于硼掺杂石墨烯量子点(B-GQDs)与1-氨基蒽醌的荧光共振能量转移(FRET)检测1-氨基蒽醌。制备的硼掺杂石墨烯量子点的荧光光谱和1-氨基蒽醌的激发光谱重叠,硼掺杂石墨烯量子点结构中的芳香骨架可以和1-氨基蒽醌发生π-π堆积作用,硼掺杂石墨烯量子点结构中的羟基、羧基可以和1-氨基蒽醌的氨基发生氢键作用,多重作用力拉近了硼掺杂石墨烯量子点和1-氨基蒽醌的距离,为实现两者之间的荧光共振能量转移提供了条件。硼掺杂石墨烯量子点和1-氨基蒽醌的混合体系可以在370 nm光激发下,收集到有460 nm和610 nm的两处特征发射峰的荧光光谱,即两者之间发生FRET,响应时间为5分钟。基于此,我们实现了水体系中1-氨基蒽醌的荧光法检测,检测限低至3 nM。
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外文摘要: |
Aromatic amines are well-known persistent organic pollutants due to their high mutagenicity, teratogenicity and carcinogenicity. They are widely sourced and mainly synthesized as intermediates for plastics, pharmaceuticals, pesticides and dyes. They are relatively stable and difficult to be biodegraded, which have long-lasting effects on the environment. They can enter the environmental cycle and migrate along with the biologic chain. Most of aromatic amines are lipophilic; they can penetrate biological cell membranes and concentrate in the lipid organic matter of organisms, which poses a great threat to human life and health. As a typical aromatic amine, 2-aminoanthracene is an effective direct carcinogen, triggering mutation in eukaryotic and prokaryotic cells; 1-aminoanthraquinone is proved carcinogenic and teratogenic in organisms. It is of great significance to develop more efficient and sensitive methods for the detection of aromatic amines in the real environment, based on their extensive sources, persistent effects and high toxicity to organisms. In this paper, we studied the fluorescence properties of aromatic amines, and introduced two suitable nanomaterials to realize highly sensitive and highly selective optical sensing for 2-aminoanthracene and 1-aminoanthraquinone in aqueous systems respectively.
1. Metal-enhanced fluorescence detection of 2-aminoanthracene based on Ag@SiO2 nanoparticles (Ag@SiO2 NPs). The prepared Ag@SiO2 NPs could effectively enhance the fluorescence of 2-aminoanthracene. And a highly sensitive and highly selective method for the detection of 2-aminoanthracene was developed by this new phenomenon. We synthesized a series of Ag@SiO2 NPs with different sizes of Ag core and thickness of SiO2 shell. It was found that when the size of Ag core was 40 nm and the thickness of SiO2 shell was 7 nm (Ag(40 nm)@SiO2(7 nm)), Ag@SiO2 NPs had the best enhancement effect on 2-aminoanthracene. The explanation was that the Localized Surface Plasmon Resonance (LSPR) band of Ag(40 nm)@SiO2(7 nm) had the maximum spectral overlap with the absorption band of 2-aminoanthracene, and there were hydrogen bonds between 2-aminoanthracene and the SiO2 shell. Because the absorption peaks of other possible interferers in water (aromatic amines, metal ions) were not matched with the LSPR peak of Ag(40 nm)@SiO2(7 nm), the metal-enhanced fluorescence (MEF) effect was highly selective for the 2-aminoanthracene. In addition, the MEF effect of 2-aminoanthracene could be obtained in mixed solution within 2 minutes. Based on this, we realized the fluorescence detection of 2-aminoanthracene in water with a detection limit as low as 1 nM. Finally, the newly developed detection method has been successfully applied to the detection of 2-aminoanthracene in four real water systems.
2. 1-Aminoanthraquinone was detected based on the fluorescence resonance energy transfer (FRET) between boron-doped graphene quantum dots (B-GQDs) and 1-aminoanthraquinone. The fluorescence spectrum of B-GQDs overlaped well with the excitation spectrum of 1-aminoanthraquinone. In addition, the aromatic skeletons of B-GQDs had π-π stacking effect with 1-aminoanthraquinone, the hydroxyl, carboxyl of B-GQDs had hydrogen bonding with 1-aminoanthraquinone. Multiple forces narrowed the distance between B-GQDs and 1-aminoanthraquinone, providing a good distance for FRET between them. The mixture of B-GQDs and 1-aminoanthraquinone could be excited at 370 nm and collected at 460 nm and 610 nm within 5 minutes, which meant FRET occured between them. Based on the FRET, we realized the detection of 1-aminoanthraquinone in water with a detection limit as low as 3 nM.
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参考文献总数: | 0 |
馆藏号: | 硕070304/18020 |
开放日期: | 2019-07-09 |