Molecular design of hybrid inorganic-organic nanocomposite cellulose materials for their utilization

本论文主要研究了具有高区域选择性的取代纤维素衍生物的合成及其自组装新材料的开发和金属络合物的形成能力。首先，通过三步反应，高产率地合成了具有不同烷基链的新型纤维素三叔丁基化试剂4-烷氧基三甲基氯化物。在LiC l/DMAc中，在70℃的条件下，纤维素与这些试剂反应得到一系列高取代度(0.94~0.99)的6-O-(4-烷氧基三苯基)纤维素。其次，制备了6-O-(4-硬脂氧基三丁基)纤维素醋酸酯朗缪尔-布洛杰特薄膜。这种纤维素衍生物形成了Z型多层膜，尽管已有Y型纤维素多层膜的报道。原子力显微镜和椭圆偏振光谱仪的测量结果表明，6-O-烷基纤维素在LB膜中具有折叠结构。另一方面，利用葡萄糖邻酯衍生物开环聚合合成了6-O-烷基纤维素，并与6-O-(4-硬脂氧基三苯基)纤维素进行了单层和多层膜的制备。6-O-硬脂基纤维素也形成了最稳定的单层膜。最后，在6-O-(4-硬脂氧基三苯基)纤维素的C-2或C-3位引入了一个含金属的官能团，即3-二茂铁酰丙酰基。制得的纤维素衍生物制备了X型多层膜。从膜在金电极上的循环伏安图可以观察到纤维素膜与电极表面之间的电子转移。这种纤维素衍生物的LB膜可能用于电致发光

In this study, the syntheses of highly regio-selective substituted cellulose derivative and the development of the advanced material from them using their self assembly and their ability for the metal complex formation were investigated.First, novel reagents for tritylation of cellulose, 4-alkoxytrityl chlorides with different, alkyl chains, were synthesized by three reaction steps in high yields. Cellulose was reacted with theses reagents in LiCl/DMAc at 70℃ to afford a series of 6-O-(4-alkoxytrityl)celluloses with a high degree of substitution (0.94〜0.99) in high yield.Next, 6-O-(4-stearyloxytrityl) cellulose acetate Langmuir-Blodgett films were prepared and characterized. This cellulose derivative formed Z-type multilayer films, although Y-type cellulose multilayer films have been reported. From AFM and ellipsometry measurements, it was suggested that long alkyl chain of it in LB film has a folding structure.On the other hand, 6-O-alkylcelluloses, which were synthesized by a ring-opening polymerization using glucose orthoester derivative, were subject to prepare monolayer and multilayer film to compare with 6-O-(4-stearyloxytrityl) cellulose. 6-O-stearylcellulose also formed most stable monolayer film. This indicates that trityl group in the monoalkylated tritylcellulose was not essential to a form monolayer film,Finally, a fnctional group containing metal, that is, 3-ferrocenoylpropanoyl group, was introduced at C-2 or C-3 position in 6-O-(4-stearyloxytrityl) cellulose. The cellulose derivative prepared, gave X-type multilayer films. From cyclic voltammogram of the film on a gold electrode, electron transfer between the cellulose film and the electrode surface was observed. The LB films from this cellulose derivative might be useful for an electroluminescence