Construction of Silica-Based Ordered Nanostructured Materials from Precisely Designed Building Units

有序硅基纳米结构材料是由精确设计的结构单元自组织合成的。二氧化硅是地球上储量最丰富的材料之一，在吸附、催化等方面有着优异的应用。硅基材料与有机物的杂化是材料化学中的一个重要问题。我们重点研究了有机和无机杂化分子的自组织形成纳米结构，并研究了原料的结构与产物的功能之间的关系。特别地，研究了利用有限空间和界面各向异性的宏观结构控制。本研究项目的完成分为以下四个部分：1)具有可聚合官能团的有机烷氧基硅烷多层杂化膜的形成及其光刻成型学研究；2)两亲性硅氧烷低聚物在密闭空间内的自组装行为研究及层次化结构设计；3)孔壁上具有光学官能团的单轴排列介孔有机硅膜的合成及其光学性能表征；4)采用精确设计的聚合物模板并将模板固定在孔壁表面合成介孔二氧化硅。1-3)的研究是以新型两亲性硅氧烷基分子和桥式有机烷氧基硅氧烷为起始材料。这些精确设计的建筑单元利用宏观技术来控制纳米结构的层次结构和排列。研究4)提出了一种新型介孔二氧化硅模板聚合物，该模板聚合物被设计为作为改性分子固定在二氧化硅壁上。通过对起始分子的精确设计，我们成功地对其结构和功能进行了详细控制。应用宏观调控技术对硅基纳米材料的层次结构和取向进行调控，开辟了一个新的研究领域。少

Ordered silica-based nanostructured materials have been synthesized by the self-organization of precisely designed building units. Silica, one of the most abundant materials on the earth, is excellent for the applications including adsorption, catalysis, and so on. Hybridization of silica-based materials and organic substances is an important issue in materials chemistry. We have focused on the formation of nanostructures by the self-organization of hybrid molecules having both inorganic and organic parts within the structures, and studied the relations between the structures of the starting materials and the functions of the products. In particular, macroscopic structural control utilizing both a confined space and anisotropy of interface was investigated.The accomplishment of this research project consists of four parts as follows : 1) The formation of multilayered hybrid films from organoalkoxysilanes with polymerizable functional groups and the patterning by photolithography techni … More que, 2) the investigation of the self-assembly behavior of amphiphilic siloxane oligomers in a confined space and the design of hierarchical structures, 3) the synthesis of uniaxially aligned mesoporous organosilica films with optical functional groups in the pore walls and the characterization of the optical properties, and 4) the synthesis of mesoporous silica by using a precisely designed polymer template and immobilization of the template onto the pore wall surface. The researches of 1-3) are based on the use of novel amphiphilic siloxane-based molecules and the bridged-organoalkoxysilane as the starting materials. These precisely designed building units were utilized with macroscopic techniques to control the hierarchical structures and the alignment of nanostructures. The research 4) has shown the novel template polymer of mesoporous silica designed to be immobilized in a silica wall as a modifier molecule.We have succeeded in controlling the structures and the functions in detail by the precise design of starting molecules. A novel field on the controls of both hierarchical structures and alignment of silica-based nanomaterials has been developed by applying macroscopically controlled techniques. Less