超分子自组装制备偶氮苯类光响应性材料

发布时间：2018-05-03 05:14

本文选题：超分子 + 自组装　；参考：《苏州大学》2015年硕士论文

【摘要】：偶氮苯在光和热的刺激下能够产生可逆顺反异构。这种光致异构性使偶氮苯成为许多分子器件和功能材料的理想选择。超分子自组装是制备纳米结构材料的重要途径之一。含有偶氮苯的两亲性分子不仅能够自组装形成具有不同纳米结构的胶束,而且形成的胶束具有光致形变、光致解离等光响应性,这在药物释放、光响应器件、生物识别等方面都有潜在的应用。虽然近年来两亲性偶氮苯聚合物和表面活性剂得到广泛关注和快速发展,然而两亲性偶氮苯聚合物仍然存在合成方法复杂、分子序列结构难以控制等不足。而且对于管状、螺旋带等重要胶束结构的形成机理和制备条件仍然处于不断的探索阶段。本论文旨在:一方面探索一种简单高效的方法制备具有规整接枝偶氮苯基团的聚合物,并研究其自组装和光响应性;另一方面制备一种具有光响应性的偶氮苯纳米结构,并研究其形成机理。首先,我们通过基于帕瑟里尼反应的多组分聚合法合成了具有规整接枝偶氮苯基团的聚合物MCP-azo-OH,并研究了其自组装性能和自组装结构的光致形变性。我们发现该分子在THF中能够形成球状结构。NMR和FTIR研究表明聚集体内分子间存在很强的氢键作用。通过将THF溶液在一定搅拌速度下滴加到水中,可以将微球根据粒径分开,高转速下可以得到较小的微球。另外,在紫外光照下,纳米球在液相中会形成团簇,而在干态条件下会融合成岛状结构。其次,我们合成了一种含有偶氮苯的长链脂肪酸,该分子在DMSO中可自组装形成具有统一直径的纳米管。TEM、XRD和FTIR数据表明纳米管是由双分子层构成的,羧酸基团之间的氢键是双分子层形成的主要驱动力。并且通过控制保温温度和时间,聚集体发生由膜、带、螺旋带到管的形貌演变。在由Selinger等提出的纳米管形成理论模型中的所有自组装结构都在这一体系中出现,并且演变过程也与该理论相符。所以这部分研究从实验上支持了该纳米管形成理论。
[Abstract]:Azobenzene can produce reversible cis-trans isomerization under the stimulation of light and heat. This photoisomerization makes azobenzene an ideal choice for many molecular devices and functional materials. Supramolecular self-assembly is one of the important ways to prepare nanostructured materials. Amphiphilic molecules containing azobenzene can not only self-assemble to form micelles with different nanostructures, but also form micelles with photoinduced deformation, photodissociation and photoresponse, which can be used in drug release and photoresponse devices. Biometrics have potential applications. Although amphiphilic azobenzene polymers and surfactants have received extensive attention and rapid development in recent years, there are still shortcomings in the synthesis of amphiphilic azobenzene polymers, such as complex synthesis methods and difficult control of molecular sequence structure. Moreover, the formation mechanism and preparation conditions of the important micelle structures such as tubular and spiral bands are still in the stage of continuous exploration. The aim of this thesis is to explore a simple and efficient method to prepare polymers with regular graft azobenzene groups and to study their self-assembly and photoresponse, on the other hand, to prepare a photoresponsive nanostructure of azobenzene. The formation mechanism was also studied. Firstly, we synthesized the polymer MCP-azo-OH with regular grafted azophenyl group by multicomponent polymerization based on the Pacerini reaction, and studied its self-assembly properties and photo-induced denaturation of self-assembled structure. We found that the molecule can form spherical structure in THF. NMR and FTIR studies show that there is a strong hydrogen bond between the molecules in the aggregation body. By adding THF solution into water at a certain stirring speed, the microspheres can be separated according to the particle size, and smaller microspheres can be obtained at high speed. In addition, the nanospheres formed clusters in liquid phase under ultraviolet light, and fused into island structures in dry state. Secondly, we synthesized a long chain fatty acid containing azobenzene, which can self-assemble in DMSO to form nanotubes with uniform diameter. The XRD and FTIR data show that nanotubes are composed of bimolecular layers. The hydrogen bond between carboxylic groups is the main driving force for the formation of bimolecular layer. By controlling the holding temperature and time, the aggregates evolved from the film, strip and spiral to the shape of the tube. All the self-assembled structures in the theoretical model of nanotube formation proposed by Selinger et al appear in this system and the evolution process is consistent with the theory. Therefore, this part of the study supports the theory of nanotube formation experimentally.
【学位授予单位】：苏州大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1

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