Fundamental Studies on Functionalization of Cellulosics by Control of Their Molecular Assemblies

本研究项目将讨论关于细胞衍生物的有机分子组装形成的基本研究，特别是关于液体晶体和Langmuir Blodgett（LB）电影形成的结构。到目前为止，我们已经准备了各种类型的新颖细胞衍生物，这些类型是通过传统聚合物反应来使用的。结果揭示了（1）细胞以太衍生物具有适当长度的灵活替代物可以形成胆固醇间相，并可能产生一个热诱导的螺旋状感在一个特征温度中的热诱导反转，取决于灵活替代物和主链的长度。（2）这种雌激素衍生物是细胞三聚氰胺，不能形成一种胆固醇间相，但一种新型的柱状液体晶体。（3）纤维素-寡链（包括纤维素）是非常有趣的中间体，作为LB薄膜、不同类型的氨酰胺和以太衍生物从纤维素和纤维素衍生物以及单和多层薄膜的精细结构中制备出来的LB薄膜、不同类型的氨酰胺和多层薄膜是由电子显微镜和荧光光谱学检验的。它发现了完全由同源单层和多层薄膜制成的完全同源单层薄膜，而其他衍生物包括三O-烷基纤维素不能形成同源单层薄膜。结果是从一个从蜂窝学的一种新颖功能化的观点出发的。

This research project concerns the fundamental studies on the formation of organized molecular assemblies by cellulose derivatives, especially on the formation of liquid crystals and Langmuir-Blodgett(LB) films. To this end, we have prepared various types of novel cellulose derivatives by utilizing conventional polymer reactions. The results revealed that(1) cellulose ether derivatives having a flexible substituent of appropriate length can form a cholesteric mesophase and undergo a thermally induced inversion of helicoidal sense at a characteristic temperature, depending on the length of flexible substituent and main chain.(2) The ester derivatives such as cellulose triacylates do not form a cholesteric mesophase but a new type of columnar liquid crystal.(3) Cello-oligosaccharides including cellobiose are very interesting mesogens.As to LB films, different types of amphiphilic ester and ether derivatives were prepared from cellulose and cellulose derivatives and the fine structure of mono- and multi-layer films was examined by electron microscopy and fluorescence spectroscopy. It was found that completely homogeneous mono- and multiーlayer films are formed with esters derived from cellulose, while other derivatives including tri-O-alkyl celluloses cannot form a homogeneous monoーlayer.The results were discussed from a viewpoint of novel functionalization of cellulosics.