摘要：在医学、冶金和环境领域中，氰根离子起着极其重要的作用。最近几年以来，对氰根离子的发展具有特定的识别效果的荧光受体已渐渐成为了超分子化工领域的研究的热点之一。萘酰亚胺类衍生物具有显著荧光特性，因此被广泛应用于染料、荧光探针等领域。以N-丁基-4-溴-6-硝基-1，8-萘酰亚胺与邻炔基苯甲醛经Sonogashira偶联反应合成了1种具有高度选择性的氰根离子荧光探针4。在乙腈溶液中，探针4对于氰根离子具有荧光双重响应和比色。加入氰根离子后，探针4的紫外-可见光谱在540nm处产生新吸收峰，溶液由无色变成浅紫色，其他阴离子对探针4的紫外-可见光谱几乎无影响。没有CN存在时，探针4的荧光光谱在484nm附件产生强的荧光，加入CN-后，在484nm处的发射带在慢慢的消失，就在此时，在400nm的附近产生了强荧光，浅绿色的荧光逐渐变成了浅棕色。这归因于CN-对不饱和醛基进行加成，进而通过共轭炔基影响萘酰亚胺荧光团上的电荷转移。同时，探针4在乙腈/水（体积比9：1）混合体系对阴离子的干扰实验进行了详细的研究。58166

毕业论文关键词：  1，8-萘酰亚胺；阴离子识别；氰根离子；亲核加成；荧光探针

A selective colorimetric and fluorescent diphenylacetylene-based naphthalimide for sensing of cyanide

Abstract  A high selective fluorescent probe (4) for cyanides was developed based on the sonogashira reaction between N-butyl-4-bromo-1,8-naphthalimide and 2-ethynylbenzaldehyde. In CH3CN solution, the probe 4 shows moderate colorimetric and fluorescent response to the cyanides. Upon the addition of TBACN, a new peak at 540 nm appeared in the UV-visible spectra accompanied by an instant colorimetric change from colorless to light violet. No change in the spectral pattern of chemosensor 4 was observed in the presence of other anions. Further, chemosensor 4 showed strong fluorescence with the maxima at 484 nm (λex = 390 nm) in a mixture of CH3CN; however, in presence of [CN–], a new emission band (λem = 400 nm, light brown fluorescence) appeared along with a decrease in the emission intensity at 484 nm. Therefore, this process clearly demonstrates that chemosensor 4 can selectively detect cyanide ions by a fluorogenic “on–off” response, which may be attributed to the fact that the electron transfer in 1,8-naphthalimide is affected by the formation of adducts of anion with carbonyl groups. Moreover, the detailed interference experiments of chemosensor 4 in the mixed solvents were also investigated. 

Keywords 1,8-naphlimide; Anion recognition; Cyanides; Nucleophilic addition; Fluorescent probe;

1前言 1

  1.1  在生命科学，环境科学及医学领域中阴离子的重要作用 1

  1.2  荧光探针的简介及其应用价值 1

2文献综述 3

  2.1  Michael加成反应 3

    2.1.1  CN—加成至吡啶环 3

    2.1.2  CN—加成至α，β不饱和羰基部分 3

    2.1.3  基于对CN—转换发光能量转移的荧光探针 4

  2.2  亲核加成反应 6

    2.2.1  CN—与三氟甲基活化的羰基的亲核加成反应 6

    2.2.2  分子内氢键辅助的亲核加成 7

    2.2.3  有吲哚鎓基团的CN—亲核加成