MOLECULAR DESIGN OF BIOACTIVE HYBRID COMPLEXES

人类活动对地球生态系统产生了严重的不利影响。为了保持美丽的自然环境，化学家应该在许多方面发挥重要作用。从这个角度出发，我们多年来对绿色化学（我们称之为绿色地球化学）产生了浓厚的兴趣，并在配位化学的基础上研究了以下课题。制备了一组与碳水化合物相连的1,3-丙二胺衍生物。d -葡萄糖、d -甘露糖、d -半乳糖、d -木糖、d -核糖和d -麦芽糖被用作糖分子。二胺部分通过o -糖苷键连接到甘氨糖环的Cl碳上。除d -麦芽糖衍生物外，所有的异位构象和糖皱缩构象都是用x射线晶体学对重氮或二溴前体进行测定的。该方法已用于合成糖链二胺库，包括oh保护衍生物和N，N'-二异丙基取代衍生物。研究了这些糖链二胺的酸度常数，以及这些配体在溶液中与二价金属离子的稳定性常数。这些糖链二胺的有效抗肿瘤顺铂型配合物被开发出来。研究了四和八糖缀合的四苯基卟啉和富勒烯衍生物的糖依赖性光细胞毒性。观察了新制备的糖缀合物的有效光毒性。利用与非血红素二铁活性中心相关的铁和钌簇对金电极表面进行了功能修饰。

Human activity has serious and adverse effects on the Earth's ecosystems. To keep the beautiful natural environment, chemists should play an important role in much respect. From this viewpoint, we have hold a great interest in green chemistry (=we call green earth chemistry) over the past years and studied the following topics on the basis of coordination chemistry. A set of 1,3-propanediamine derivatives connected to carbohydrates has been prepared. D-Glucose, D-mannose, D-galactose, D-xylose, D-ribose, and D-maltose are utilized as sugar molecules in this work. The diamine moiety was connected to the Cl carbon of the glycopyranose ring via an O-glycoside bond. All the anomeric configurations and sugar puckering conformations, except in the D-maltose derivative, were determined by X-ray crystallography of the diazido or dibromo precursors. This method has been used to synthesize a library of sugar-pendant diamines including an OH-protected derivative, and an N,N'-diisopropyl-substituted derivative. Acidty constants of these sugar-pendant diamines have been examined, as have the stability constants of these ligands with the divalent metal ions in solution. The effective antitumor cisplatin type complexes of these sugar-pendant dimaines were developed. Sugar-dependent photocytotoxic property of tetra- and octa-glycoconjugated tetraphenylporphyrin and fullarene derivatives has been examined. Effective phototoxic property of newly prepared these glycoconjugated compounds was observed. Functional modification of surface of gold electrodes by utilizing Fe and Ru clusters relevant to non-heme diiron Active Centers has been carried out.