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STUDIES ON PREPARATION OF MIMETICS FOR PHOTOSYSTEM II (PSII) IN PHOTOSYNTHESIS

光合成中光系统II（PSII）模拟物的制备研究

基本信息

批准号：
13650860
负责人：
MATSUSHITA Takayuki
金额：
$ 1.66万
依托单位：
Ryukoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

This project has been carried out in order to prepare biomimetics for photosystem II in green plants, where water is oxidized to generate dioxygen by cooperation between a tetranuclear manganese cluster (OEC, oxygen-evolving center) and light harvesting antenna chlorophylls. In this study novel manganese complexes have been prepared, characterized and estimated their functions as models for OEC. The results are summarized as follows. 1.The molecular structures of trinuclear manganese(II) complexes with tridentate Schiff base ligands have been determined by X-ray analysis. 2.Amphiphilic manganese(III) complexes with Schiff base ligands bearing both hydrophilic and hydrophobic groups have been prepared. These complexes have been found to decompose H_2O_2 effectively near at critical micelle concentration(CMC) and beyond, which can be explained in terms of concentration effect. 3.Novel dichloromanganese(IV) complexes with Schiff bases having ester groups have been found to generate dioxygen by oxidation of H_2O, which were detected by a DO meter and electrochemical measurements. However, it must be still remained to confirm ^<18>O_2 by MS measurements by using H_2^<18>O. 4.Zinc-chlorins bearing alkyl groups have been prepared and found to be soluble in water in the presence of lecithin and exhibit intense fluorescence. From these results artificial photosynthetic systems (PSII) can be created by combination between oxygen-evolving manganese complexes and Zn-chlorins.

在绿色植物中，水通过四核锰团簇（OEC，氧气进化中心）和光收集天线叶绿素之间的合作被氧化生成双氧，该项目旨在制备光系统II的仿生材料。本研究制备了新型锰配合物，并对其作为OEC模型的功能进行了表征和评价。结果总结如下：1.用x射线分析确定了三核希夫碱配合物的分子结构。2.制备了两亲性锰（III）配合物，其席夫碱配体同时具有亲疏水基团。这些配合物在临界胶束浓度（CMC）附近及以上都能有效分解H_2O_2，这可以用浓度效应来解释。3.采用DO计和电化学测量方法，发现了具有酯基席夫碱的新型二氯锰（IV）配合物通过h2o氧化生成二氧。但是，仍然必须用H_2^<18>O进行质谱测量来确认^<18>O。4.含烷基的氯代锌在卵磷脂存在下可溶于水，并表现出强烈的荧光。从这些结果可以创建人工光合系统（PSII）之间的进化氧锰配合物和锌氯结合。