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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13650860/
• 关键词: PHOTOSYNTHESIS; PHOTOSYSTEM II; MANGANESE COMPLEXES; AMPHIPHILIC COMPLEX; DIOXYGEN EVOLUTION; ZINC-CHLORIN; SELF-AGGREGATION; ARTIFICIAL PHOTOSYNTHESIS; マンガンシッフ塩基錯体; シッフ塩基配位子

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.

这个项目是为了在绿色植物中制备光系统II的仿生材料，在绿色植物中，水被氧化，通过四核锰簇(OEC，放氧中心)和捕光天线叶绿素之间的合作产生二氧化氧。本研究制备了新型锰络合物，对其进行了表征，并对其作为OEC模型的功能进行了评价。研究结果总结如下。1.用X-射线衍射法测定了三齿席夫碱三核锰(II)配合物的分子结构。2.合成了同时带有亲水和疏水基团的席夫碱配体的两亲性锰(III)配合物。这些络合物在接近临界胶束浓度(CMC)或超过临界胶束浓度(CMC)时都能有效地分解H_2O_2，这可以用浓度效应来解释。3.用DO计和电化学方法研究了含酯基席夫碱与二氯锰(IV)形成的新型配合物氧化H_2O生成氧气的反应。然而，要用H_2^&lt；18&gt；O_2进行质谱学测定，还有待于证实。4.合成了含烷基锌的氯化锌化合物，发现它在卵磷脂存在下能溶于水，并具有强烈的荧光。根据这些结果，人工光合作用系统(PSII)可以通过放氧的锰配合物和锌-氯素结合来创建。

项目成果

H.Asadaら: "Preparation and structures of novel trinuclear manganese(II) complexes with N-2-pyridiylmethylidene-2-hydroxy-5-substituted-phenylamine"Inorg.Chem.Commun.. 6. 193-196 (2003)

H. Asada 等人：“N-2-吡啶基亚甲基-2-羟基-5-取代-苯胺新型三核锰 (II) 配合物的制备和结构” Inorg.Chem.Commun.. 6. 193-196 (2003 ）

S.Negoroら: "Preparation and characterization of three types of dinuclear iron(III) complexes with H_2salbn, N,N'-disalicylidene-1,4-diaminobutane"Inorg.Chem.Commun.. 6. 357-360 (2003)

S. Negoro 等人：“三种类型的双核铁 (III) 配合物与 H_2salbn、N,N-disalicylidene-1,4-diaminobutane 的制备和表征”Inorg.Chem.Commun.. 6. 357-360 ( 2003）

T.Matsushita et al.: "Preparation and characterization of manganese(III) and iron(III) complexes with Schiff base ligands and their reactions with active oxygen species(^tBuOOH, H_2O_2 and O_2^-)"J.Inorg.Biochem.. 96. 187 (2003)

T.Matsushita 等人：“席夫碱配体的锰 (III) 和铁 (III) 配合物的制备和表征及其与活性氧物质 (^tBuOOH、H_2O_2 和 O_2^-) 的反应”J.Inorg.Biochem。

S.Negoro et al.: "Preparation and Characterization of Three Types of Dinuclear Iron(III) Complexes with H_2salbn, N,N'-disalicylidene-1,4-diaminobutane"Inorg.Chem.Commun.. 6. 357-360 (2003)

S.Negoro 等人：“三种类型的双核铁 (III) 配合物与 H_2salbn、N,N-disalicylidene-1,4-diaminobutane 的制备和表征”Inorg.Chem.Commun.. 6. 357-360 (

S.Negoro ら: "Preparation and characterization of dinuclear iron(III) and vanadiumu(IV) complexes with bridging salbn or salpentn ligands"J.Inorg.Biochem.. 96. 200-200 (2003)

S. Negoro 等人：“具有桥接 salbn 或 salpentn 配体的双核铁 (III) 和钒 (IV) 配合物的制备和表征” J.Inorg.Biochem.. 96. 200-200 (2003)