新型次氯酸、硫化氢荧光探针研制及其在环境分析中的应用

发布时间：2018-01-15 17:32

本文关键词：新型次氯酸、硫化氢荧光探针研制及其在环境分析中的应用　出处：《江苏大学》2017年硕士论文　论文类型：学位论文

【摘要】：目前,环境中一些污染物如次氯酸(HOCl)和硫化氢(H2S)等对环境和人类的危害性逐渐被人们所认识。HOCl是一种仅存在于溶液中的极不稳定的弱酸,是细胞内氧化还原反应中的重要参与者之一;人体内的HOCl浓度过高或过低都会影响人体的健康。H2S在生物体内是一种具有生理作用的内源性气体,但同时其具有极强的毒性,即使环境中浓度极低也会造成人体损伤。研制具有高性能的HOCl和H2S荧光探针仍是一个具有挑战和充满活力的领域。本论文中,我们合成并研究了三种以香豆素作为平台分子的荧光探针并分别用于HOCl和H2S的检测。在第二章中,我们以7-二乙胺基香豆素为荧光母体键联强淬灭基团二硝基苯肼得到荧光探针分子Cou-HOCl-1并用于自来水和细胞内HOCl的检测。该探针分子由于二硝基苯肼的强淬灭荧光作用和乙酰肼中N-N单键的旋转作用共同导致了其荧光背景非常弱,加入10倍当量的次氯酸时荧光强度增加了134倍,灵敏度显著提高。探针对HOCl响应线性范围为0.1~40μM,检测下限为0.052μM;探针对HOCl响应快,选择性高。最后,该探针被成功用于自来水和细胞内HOCl的检测。在第三章中,我们利用香豆素衍生物与巯基乙醇反应合成了荧光淬灭型次氯酸比色探针Cou-HOCl-2。加入次氯酸前后,探针分子紫外吸收光谱发生了显著的波长变化,波长红移了44 nm;同时溶液颜色从无色变为黄色。当加入100μM次氯酸钠时,探针分子的荧光淬灭了20.27倍。在次氯酸浓度为0.8~9μM范围内,442 nm和398 nm处紫外吸光强度的比值和次氯酸浓度呈现良好的线性关系,检测下限达到0.667μM。最后,该探针被用于自来水中HOCl的检测,结果令人满意。在第四章中,我们同样以香豆素作为荧光母体研制了一种硫化氢(H2S)荧光探针Cou-H2S。当存在H2S时,叠氮基结构遭到破坏转化为氨基结构,探针Cou-H2S被激发出荧光。相对于其他活性硫化物(RSS)探针,Cou-H2S对H2S表现出很高的灵敏性和选择性。当加入100μM的硫化氢(H2S)后,探针荧光强度增强了28.72倍。荧光光谱显示,探针分子与H2S在1~10μM的浓度范围内呈现出良好的线性关系,检测下限为0.427μM,有望用于细胞内H2S荧光成像。
[Abstract]:Right now. Some pollutants in the environment, such as Hocl) and H2S), have been recognized as a very unstable weak acid only in solution. It is one of the important participants in intracellular redox reaction. Too high or too low concentration of HOCl in human body will affect the health of human body. H2S is an endogenous gas with physiological effect in vivo, but at the same time, it has very strong toxicity. The development of high performance HOCl and H2S fluorescent probes is still a challenging and dynamic field. We have synthesized and studied three fluorescent probes using coumarin as a platform molecule for the detection of HOCl and H2S respectively. The fluorescence probe molecule Cou-HOCl-1 was obtained by using 7-diethylaminocoumarin as the fluorescence mother with strong quenching group dinitrophenylhydrazine. The probe molecule was used for the detection of HOCl in tap water and in cells. The fluorescence background of dinitrophenylhydrazine is very weak due to the strong quenching of fluorescence and the rotation of N-N single bond in acetyl hydrazine. When 10 times equivalent hypochlorite was added, the fluorescence intensity increased by 134-fold and the sensitivity was improved significantly. The linear range of the HOCl response of the probe was 0.1 渭 m and the detection limit was 0.052 渭 M. The probe is fast in response to HOCl and highly selective. Finally, the probe has been successfully used for the detection of HOCl in tap water and cells. In Chapter 3. Cou-HOCl-2was synthesized by the reaction of coumarin derivatives with mercaptoethanol. The fluorescence quenching hypochloric acid colorimetric probe Cou-HOCl-2 was synthesized before and after the addition of hypochloric acid. The UV absorption spectrum of the probe molecule changed obviously, and the wavelength shifted to 44 nm. At the same time, the color of the solution changed from colorless to yellow. When 100 渭 M sodium hypochlorite was added, the fluorescence of the probe molecule quenched 20.27 times. The ratio of UV absorptivity to hypochloric acid concentration at 442 nm and 398 nm showed a good linear relationship, and the detection limit was 0.667 渭 M. finally. The probe was used to detect HOCl in tap water with satisfactory results. In Chapter 4th. We have also developed a novel fluorescence probe Cou-H2Swith coumarin as the fluorescence mother. In the presence of H2S, the azido group structure was destroyed and converted into amino structure. The probe Cou-H2S was stimulated by fluorescence, compared with other active sulphide probes. Cou-H2S showed high sensitivity and selectivity to H2S. The fluorescence intensity of the probe was increased by 28.72 times when 100 渭 M H2S was added. The probe molecule has a good linear relationship with H _ 2S in the concentration range of 1 ~ 10 渭 m, and the detection limit is 0.427 渭 M, which is expected to be used in intracellular H _ 2S fluorescence imaging.
【学位授予单位】：江苏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X830

【参考文献】