Southwest university of science and technology
本科毕业设计（论文）
刚性杂环香豆素荧光探针的合成及性能研究
学院名称 理学院
专业名称 学生姓名 学
号
光信息科学与技术
周为浩 20112833 任洪波
二〇一六年六月
指导教师
西南科技大学本科生毕业论文
I
刚性杂环香豆素荧光探针的合成
及性能研究
摘要：自然界中存在着各种金属，包括碱土金属、碱金属、过渡金属和重金属，而这些金属与环境、生物、医学和化学学科密切相关，生命体中金属离子的浓度在一定范围内有利于生物的健康，浓度过大则会对生物体产生严重的危害。因此设计及合成具有高选择性和高灵敏度的荧光探针越来越受到人们重视。
近些年来，香豆素母体被广泛应用于生物、医药、香料、化妆品及荧光染料等领域。由于其具有荧光量子产率高、Stokes位移大、光物理和光化学性质可调以及光稳定性好等优点，香豆素类化合物已成为荧光传感器分子设计中的优秀候选荧光团。[18]本文通过改良的Knoevenagel反应，将2,4-二羟基苯甲醛、氰乙酸乙酯分别与邻苯二胺、邻氨基苯酚、邻氨基硫酚反应，合成了三种刚性含氮杂环的单齿香豆素衍生物，并利用红外、核磁等方法对目标化合物进行了结构表征鉴定。考察了它们对常见阳离子的响应，发现探针可以高选择性识别水溶液中的Pd2+。另外，我们研究了这三种配体和Pd2+的自组装行为，成功制备了一种新型金属-有机凝胶材料。
关键词：香豆素； 荧光探针； 分子识别
西南科技大学本科生毕业论文
II
Synthesis and Property Research of Rigid Heterocyclic Coumarin Fluorescent Probe
Abstract: There are various metals, including alkaline earth metals, alkali metals, transition metals and heavy metals in nature. These metals are closely related with the environment, biology, medicine and chemistry. The concentration of metal ions within a certain range is useful to the life of the body, but it will lead to many serious detriment when the concentration is too maximum. So design and synthesis high selective and sensitive fluorescent probe is getting more and more attention.
Recent years, coumairn and its derivative have been found to be widely used in the fields of biology, medicine, perfumes, cosmetics and dyes etc. Due to its unique optical properties such as high fluorescence quantum yield, large stokes shifts, excellent light stabilities and less toxicity. Coumairns have received considerable attention in construction of fluorescence chemosensors. In this study, through the improved Knoevenagel reaction, the 2,4-dihydroxybenzaldehyde, ethyl cyanoacetate was
respectively
reactioned
with
o-phenylenediamine,
o-aminophenol,
oro-aminothiophenol, to get a kind of rigid N-heterocyclic coumarin derivatives. The structures of the new compounds were characterized by NMR and IR spectra. We studied the fluorescent properties of this class of compounds and found that they could serve as candidates for fluorescent Pd2+ sensing in aqueous solutions. Moreover, we explored the assembly of the structurally simple and conformationally rigid N-heterocyclic coumarin derivatives with Pd2+ to creat a new type of metal-organic gel.
Key words：coumarin; fluorescent probes; molecular recognition
西南科技大学本科生毕业论文
III
目录
第一章 绪论......................................................... 1
1.1.1 荧光现象....................................................................................................... 1 1.1.2 荧光的发光原理........................................................................................... 1 1.1.3 荧光传感器（荧光探针）........................................................................... 3 1.1.4 荧光外部影响因素及其排除办法............................................................... 4 1.2 香豆素类化合物性质及用途.......................................................................... 6 1.3 香豆素类化合物的主要合成方法.................................................................. 7 1.4 香豆素类荧光探针的近期研究...................................................................... 8 1.5 本课题的提出.................................................................................................. 9 第二章 实验与结果...................................................................................................... 1
2.1 实验概述.......................................................................................................... 1 2.2 实验试剂、仪器及表征方法.......................................................................... 1
2.2.1实验试剂................................................................................................. 2 2.2.2实验仪器................................................................................................. 3 2.2.3分析测试................................................................................................. 3 2.2.3.1 傅里叶变换红外光谱（FT-IR）分析 ............................................... 3 2.2.3.2 核磁共振（NMR）分析 ................................................................... 3 2.2.3.3 荧光光谱分析..................................................................................... 4 2.2.3.4 场发射扫描电镜分析......................................................................... 4 2.2.3.5 透射电镜分析..................................................................................... 4 2.3 实验内容.......................................................................................................... 4
2.3.1 3-苯并咪唑基-7-羟基香豆素（CIM）的合成 ..................................... 4 2.3.2 3-苯并噁唑基-7-羟基香豆素（COM）的合成 ................................... 5 2.3.3 3-苯并噻唑基-7-羟基香豆素（CSM）的合成 .................................... 7 2.4 结果与讨论...................................................................................................... 9
2.4.1 探针的荧光光谱分析............................................................................ 9 2.4.2 探针对金属阳离子荧光识别作用的研究............................................ 9
2.4.2.1 探针CIM对金属阳离子荧光识别作用的研究 ...................... 10 2.4.2.2 探针COM对金属阳离子荧光识别作用的研究 .................... 11 2.4.2.3 探针CSM对金属阳离子荧光识别作用的研究 ..................... 12
西南科技大学本科生毕业论文
IV
2.4.3 Pd2+浓度对探针CIM、COM、CSM荧光强度的影响 .................... 13 2.4.4 不同溶剂对荧光探针的影响.............................................................. 15 2.4.5 荧光探针的竞争性研究...................................................................... 15 2.4.6 探针与Pd2+可能的作用机理 ............................................................. 16 2.4.7 配体与Pd2+的自组装行为研究 ......................................................... 17
2.4.7.1 配体与不同金属盐在DMF中的凝胶化实验结果 ................. 17 2.4.7.2 溶剂对CIM和Pd(OAc)2自组装行为的影响......................... 17 2.4.7.3 凝胶的形貌图............................................................................ 18 2.4.7.4 阴离子对CIM和Pd2+自组装行为的影响 .............................. 18 2.4.7.5 凝胶的性质................................................................................ 19
结论............................................................... 21 致谢................................................................ 1 文献................................................................ 2