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

本论文以高区域选择性取代的纤维素衍生物为研究对象，利用其自组装和金属配合物的形成能力，研究了新型纤维素三苯甲基化试剂4-烷氧基三苯甲基氯的合成方法，并通过三步反应，以较高的产率合成了4-烷氧基三苯甲基氯。以LiCl/DMAc为溶剂，在70℃下，纤维素与上述试剂反应，得到了一系列高取代度（0.94 ~ 0.99）的6-O-（4-烷氧基三苯甲基）纤维素，并制备了6-O-（4-硬脂氧基三苯甲基）纤维素醋酸酯LB膜。该纤维素衍生物形成Z型多层膜，尽管已经报道了Y型纤维素多层膜。另一方面，以葡萄糖原酸酯为原料，通过开环聚合反应合成了6-O-烷基纤维素，并将其与6-O-（4-硬脂酰氧基三苯甲基）纤维素制备成单层膜和多层膜。6-O-硬脂基纤维素也形成最稳定的单分子膜。最后，在6-O-（4-硬脂酰氧基三苯甲基）纤维素的C-2或C-3位引入了含金属的功能基，即3-二茂铁基丙酰基。制备的纤维素衍生物，得到X型多层膜。从膜在金电极上的循环伏安图，观察到纤维素膜和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