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

本文主要研究了高区域选择性取代纤维素衍生物的合成及利用其自组装和形成金属配合物的能力制备新型材料。首先，通过三个反应步骤合成了纤维素三甲基化的新试剂——不同烷基链的4-烷氧基三烷基氯。纤维素与这些试剂在LiCl/DMAc中70℃反应，得到一系列取代度高（0.94 ~ 0.99）、产率高的6-O-（4-烷氧三烯基）纤维素。其次，制备了6-O-（4-硬脂氧基三烷基）醋酸纤维素Langmuir-Blodgett薄膜并对其进行了表征。这种纤维素衍生物形成了z型多层膜，尽管y型纤维素多层膜已有报道。原子力显微镜和椭偏测量表明，LB膜中的长烷基链具有折叠结构。采用葡萄糖正构酯衍生物开环聚合法制备6-O-烷基纤维素，制备单层膜和多层膜，并与6-O-（4-硬脂氧基三烷基）纤维素进行比较。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-硬脂氧基三烷基基）纤维素的C-2或C-3位置上引入了含金属的官能团3-二茂铁基丙基。制备的纤维素衍生物，得到了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。该纤维素衍生物制备的LB膜可用于电致发光

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