基于联二萘酚新型聚集诱导发光分子的设计合成及其性能研究

发布时间：2018-10-10 17:38

【摘要】：荧光材料由于在光电器件、环境传感器、生物科学等领域具有重要的应用价值,近年来引起了科学家们的广泛关注。但是许多传统的荧光物质都具有聚集诱导荧光淬灭(ACQ)效应,限制了荧光物质在固体或聚集状态的应用。2001年,唐本忠教授课题组提出了聚集诱导发光(AIE)现象,即荧光物质在稀溶液中没有荧光或荧光微弱,而在聚集或固体状态则呈现很强的荧光。AIE现象的提出进一步拓宽了有机荧光化合物在固体或聚集状态的应用。联二萘酚(BINOL)作为一类被广泛应用的手性发色团,由于其结构多样性和优良的发光性能,在荧光分子检测领域体现出了极大的优越性。但是BINOL本身是一个ACQ分子,限制了其作为手性荧光材料的应用范围。近年来,科学家们为了改变BINOL的ACQ性质,通过将典型的AIE单元TPE基团引入BINOL分子中获得了手性AIE分子。但是从BINOL分子本身出发,采用一种简单且有效的方法构建手性AIE分子仍是一个挑战。金属离子对生物体的生理功能和新陈代谢的调节起着非常重要的作用。铜是生物体内含量第三的重金属元素,参与多种酶的催化反应,但当生物体内的铜离子水平超过一定含量,则会导致一系列的疾病,如阿兹海默症、威尔逊氏症、帕金森综合症等。因此对铜离子水平的监测近年来越来越受到研究者的重视。为了克服BINOL的ACQ效应,合成基于BINOL骨架的聚集诱导发光分子,并将其用于离子检测。本论文开展了以下工作：(1)本论文以手性BINOL为骨架,以二氰基亚甲基为电子受体,通过简单的缩合反应得到一系列具有AIE特性的BINOL衍生物,同时该类化合物显示出反常的聚集诱导CD信号淬灭现象。通过核磁、质谱、荧光等对中间体和目标产物进行了表征。本文提供了一种简单有效的构筑手性AIE分子的方法,并为基于BINOL的手性传感器的构筑提供了新途径。(2)本论文以BINOL为骨架,合成了一种新型的铜离子荧光化学传感器(BINOP-CN),它对铜离子的检测不受其它金属离子的干扰。另外,化合物BINOP-CN与铜离子的单晶结构表明了配合物的形成：通过扫描电镜发现化合物BINOP-CN在聚集态形成纳米多面体颗粒,而铜离子的加入,诱导体系自组装成枝状结构。
[Abstract]:Fluorescent materials have attracted wide attention of scientists in recent years because of their important application value in the fields of optoelectronic devices, environmental sensors, biosciences and so on. However, many traditional fluorescent substances have the effect of agglomeration induced fluorescence quenching of (ACQ), which limits the application of fluorescent substances in solid or aggregate state. In 2001, Professor Tang Benzhong's research group proposed the phenomenon of aggregation induced luminescence (AIE). There is no fluorescence or weak fluorescence in dilute solution, but strong fluorescence in aggregate or solid state. The introduction of AIE phenomenon further broadens the application of organic fluorescent compounds in solid or aggregate state. As a kind of chiral chromophore, binaphthol (BINOL) has shown great superiority in the field of fluorescent molecular detection because of its diversity in structure and excellent luminescence properties. However, BINOL itself is a ACQ molecule, limiting its application as a chiral fluorescent material. In recent years, in order to change the ACQ properties of BINOL, the chiral AIE molecules were obtained by introducing typical TPE groups of AIE units into BINOL molecules. However, it is still a challenge to construct chiral AIE molecules using a simple and effective method based on the BINOL molecule itself. Metal ions play an important role in the regulation of biological function and metabolism. Copper is the third most abundant heavy metal in organisms, which is involved in the catalytic reaction of many enzymes, but when the copper ion level exceeds a certain level, it can lead to a series of diseases such as Alzheimer's disease and Wilson's disease. Parkinson's syndrome, etc. Therefore, more and more attention has been paid to the monitoring of copper ion level in recent years. In order to overcome the ACQ effect of BINOL, the aggregation induced luminescent molecules based on BINOL skeleton were synthesized and used for ion detection. In this thesis, the following works were carried out: (1) A series of BINOL derivatives with AIE properties were obtained by simple condensation reaction with chiral BINOL as the skeleton and dicyanomethyl as the electron receptor. At the same time, the compounds showed abnormal agglomeration induced quenching of CD signals. The intermediates and target products were characterized by NMR, MS and fluorescence. This paper provides a simple and effective method for the construction of chiral AIE molecules, and provides a new way for the construction of chiral sensors based on BINOL. (2) in this thesis, BINOL is used as the skeleton. A novel copper ion fluorescent chemical sensor (BINOP-CN) was synthesized, and its detection of copper ion was not interfered with by other metal ions. In addition, the single crystal structure of compound BINOP-CN and copper ion indicates the formation of the complex. It is found by scanning electron microscope that the compound BINOP-CN forms nano-polyhedron particles in the aggregate state, and the addition of copper ion induces the self-assembly into dendritic structure.
【学位授予单位】：陕西师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O644.1

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