多酰胺基荧光小分子的合成与表征

发布时间：2018-03-06 05:12

本文选题：多酰胺基　切入点：荧光小分子　出处：《济南大学》2016年硕士论文　论文类型：学位论文

【摘要】：一般认为,典型的有机荧光分子都具有刚性结构和离域电子双键共轭体系,芳环或具有共轭不饱和基团的存在有利于提高荧光效率,从而产生强烈的荧光。但是近些年来,研究者发现一些只含有伯胺、仲胺、叔胺和酰胺等简单官能团的含氮类枝状聚合物具有荧光。含氮枝状聚合物具有非典型性荧光生色团,其荧光性质和生物学应用很快得到了广泛关注,但是由于含氮类聚合物的体系相对复杂,荧光中心结构及其相互位置、相互作用难以确定,进而造成影响荧光性质的结构因素较多,因此对含氮类枝状聚合物发光机理的研究相对困难。与含氮类聚合物相比,含氮类小分子化合物的体系相对简单,制备方法多样、分子结构简单,便于系统研究多元羧酸和氨基试剂的结构与产物发光机理、发光性能等之间的对应关系,有利于明确荧光发光中心,进而深入研究含氮小分子的荧光发光机理。由于含氮小分子的结构简单,影响因素较少。具有明确的简单结构的荧光含氮小分子的发现,无论从理论计算还是实验方面都为最终探索含氮有机分子的发光机理提供了有效的途径。本文具体研究工作如下:1、采用酰氯法制备了荧光多元酰胺,探索了适合的反应条件;先用二氯亚砜活化有机酸中的羧基,再与有机胺反应的反应路线,使羧基和氨基通过简单的官能团反应生成酰胺小分子。2、改变羧酸的结构,探索羧酸结构对多元酰胺荧光量子产率的影响;3、改变有机胺的结构,探索有机胺结构对多元酰胺荧光量子产率的影响;4、改变多酰胺基荧光小分子外部条件,探索温度、溶剂、紫外光照时间、离子等对多元酰胺基荧光量子产率的影响。某些多酰胺键荧光分子(如柠檬酸酰胺)的QY可高达70.2%(硫酸奎宁为参比),分子体积小,在荧光示踪、呈像方面具有潜在的用途。另外如与多元酸反应的氨基试剂中含有其他官能团(如烷氧基),则有利于进一步构建多用途的复合材料。综上所述,初步研究结果表明,该类分子有望成为是一类新型的发光材料,也将为新型发光机理研究提供有效支撑。
[Abstract]:It is generally believed that typical organic fluorescent molecules have rigid structures and delocalized electron double bond conjugation systems. The existence of aromatic rings or conjugated unsaturated groups is conducive to improving the fluorescence efficiency and thus producing strong fluorescence. The researchers found that some nitrogen-containing dendritic polymers containing only simple functional groups such as primary amine, secondary amine, tertiary amine and amides have fluorescence, while nitrogen-containing dendritic polymers have atypical fluorescent chromophore. Its fluorescence properties and biological applications have been paid more and more attention. However, due to the relatively complex system of nitrogen-containing polymers, the fluorescence center structure and its mutual position are difficult to determine. Therefore, it is difficult to study the luminescence mechanism of nitrogen-containing dendritic polymers. Compared with nitrogen-containing polymers, the system of nitrogen-containing small molecular compounds is relatively simple, and the preparation methods are various. The molecular structure is simple, and it is convenient to systematically study the corresponding relationship between the structure of polycarboxylic acid and amino reagent and the luminescence mechanism of the product, the luminescent property, etc. The fluorescence luminescence mechanism of nitrogen-containing small molecules is further studied. Because the structure of nitrogen-containing small molecules is simple, there are few influencing factors, and the discovery of fluorescent nitrogen-containing small molecules with clear and simple structure, Both theoretical and experimental results provide an effective way to explore the luminescence mechanism of nitrogen-containing organic molecules. In this paper, the specific research work is as follows: 1. Fluorescence polyamides were prepared by acyl chloride method, and suitable reaction conditions were explored. The carboxyl group in organic acid was activated by dichloro sulfoxide and then reacted with organic amine. The carboxyl group and amino group reacted with simple functional groups to form small amide molecule. 2, which changed the structure of carboxylic acid. To explore the effect of carboxylic acid structure on the fluorescence quantum yield of polyamides, to change the structure of organic amines, to explore the effects of the structure of organic amines on the fluorescence quantum yields of polyamides, to change the external conditions of polyamide-based fluorescent small molecules, to explore the temperature and solvent, The effects of UV irradiation time, ions and so on on the quantum yield of polyamide-based fluorescence. The QY of some polyamide bond fluorescent molecules (such as citric acid amide) can be as high as 70.2%. In addition, the amino reagents that react with polyacids contain other functional groups (such as alkoxy), which are conducive to the further construction of multipurpose composite materials. This kind of molecule is expected to be a new kind of luminescent material, and it will provide an effective support for the study of new luminescence mechanism.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.22

【参考文献】