胶体界面调控组装苯并咪唑和卟啉衍生物超分子及性质

发布时间：2018-03-27 06:39

本文选题：胶体界面　切入点：可控超分子组装　出处：《郑州大学》2017年硕士论文

【摘要】：胶体与界面体系的各种构筑手段,例如气/液界面组装和表面活性剂辅助的组装,作为实现有机功能材料可控构筑及性能调控的有效途径,引起了诸多领域研究者的关注。本研究以上述方法为基本平台,分别系统地研究了苯并咪唑和卟啉衍生物在气/液界面以及油/水界面的有序超分子组装,并对聚集体的结构、性能及其规律展开了探究,主要工作如下:(1)我们采用气/液界面Langmuir-Blodgett(LB)膜技术,制备了2-萘-苯并咪唑(α-NpBz)分子的有序超分子薄膜。结果表明,其组装体的光学活性具有一定的随机性,也就是说左螺旋或者右螺旋的特征不明确。研究还发现手性分子L-或D-十八烷酰基-组氨酸甲酯(L-C18His或D-C18His)经气/液界面组装,稳定成Langmuir-Schaefer(LS)膜的原因和超分子光学活性产生的机理。此外,我们也制备出不同摩尔比下的C18His与α-NpBz的复合LS膜。研究发现,由非手性分子α-NpBz形成的LS膜光学活性在一定程度上能够被手性掺杂剂控制,即L-或D-C18His和α-NpBz的摩尔比为1:30时,混合体系表现出单一的圆二色性吸收,并且与手性分子的手性一致。根据上述结果,我们合理地解释了基于分子间氢键的手性与非手性组装机理,同时提出一种可以有效控制由非手性基元组装成的超分子光学活性的重要策略。(2)气/液界面组装的各种材料由于大量固体基片的使用,在一定程度上限制了其普遍应用,因而如何可控构筑基于free-standing组装材料引起了相关催化领域研究者的关注。我们通过表面活性剂CTAB辅助的油/水体系实现了ZnTPyP纳米结构的可控构筑。研究发现,陈化15 min的锌卟啉纳米结构为表面光滑的纳米球,而陈化20 d时则形成一维棒状。有意思的是,在无其他底物的条件下,我们对一维棒状纳米结构在可见光环境中光照120 min后发现,一维棒状纳米结构实现了向一维纳米管状结构的转变。可见光催化降解中性红分子的结果表明,具有各向异性的一维纳米棒和纳米管结构的锌卟啉表现出更为优良的光催化性能。这些研究现象为实现卟啉纳米结构的可控构筑和高性能光催化剂的开发提供了创新方向。
[Abstract]:Various construction methods of colloid and interface system, such as gas / liquid interface assembly and surfactant assisted assembly, are effective ways to realize controllable construction and performance control of organic functional materials. In this study, the ordered supramolecular assembly of benzimidazole and porphyrin derivatives at the gas / liquid interface and the oil / water interface were systematically studied based on the above methods. The main work is as follows: (1) the ordered supramolecular films of 伪 -NpBzole molecules were prepared by gas / liquid interface Langmuir-Blodgetttt-LB film technique. The optical activity of the assembly is random, that is, the characteristics of left helix or right helix are not clear. It is also found that the chiral molecule L- or D- octadecanoacyl-histidine methyl ester L-C18His or D-C18Hisis is assembled through the air-liquid interface. The reason of the formation of Langmuir-Schaeferian LSfilm and the mechanism of supramolecular optical activity. In addition, we also prepared the composite LS films of C18His and 伪 -NpBz at different molar ratios. The optical activity of LS film formed by non-chiral molecule 伪 -NpBz can be controlled by chiral dopant to some extent, that is, when the molar ratio of L- or D-C18His and 伪 -NpBz is 1:30, the mixed system exhibits a single circular dichroism absorption. And the chirality of chiral molecules is consistent with that of chiral molecules. According to the above results, we reasonably explain the mechanism of chiral and non-chiral groups based on intermolecular hydrogen bonds. At the same time, an important strategy for controlling the optical activity of supramolecular molecules assembled by non-chiral units is proposed. The gas / liquid interface assembly of various kinds of materials is limited to a certain extent due to the use of a large number of solid substrates. Therefore, the controllable construction of ZnTPyP nanostructures based on free-standing has attracted the attention of researchers in the field of catalysis. We have realized the controllable construction of ZnTPyP nanostructures by surfactant CTAB assisted oil / water system. The zinc porphyrin nanostructures aged for 15 min are nanospheres with smooth surface, and after 20 days of aging, they form one-dimensional rod shape. Interestingly, without other substrates, We found that the one-dimensional rod-like nanostructures were transformed to one-dimensional nanotubes after illumination in visible light for 120 min. The results of visible photocatalytic degradation of neutral red molecules showed that, Zinc porphyrins with anisotropic one-dimensional nanorods and nanotube structures exhibit better photocatalytic properties, which provide an innovative direction for the controllable construction of porphyrin nanostructures and the development of high performance photocatalysts.
【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626;O641.3

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