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Development of metal complex/electron-transfer composite system realizing enzyme-like function

开发实现类酶功能的金属配合物/电子转移复合系统

基本信息

批准号：
07305062
负责人：
FUNABIKI Takuzo
金额：
$ 1.86万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

In the aim of development of new types homogeneous catalysis by metal complexes which works in the similar fashion to metalloenzymes, the effective combination between metal complexes and electron-transfer systems has been studied. As electron-transfer and electron-donor systems, organic and inorganic reductants, electrochemical and photochemical systems have been used in the various catalytic systems involving oxygenations, oxygen generation from water, etc.in both enzymatic and model systems.1)Selective oxygenations by metal complexesOxygenations by heme and nonheme iron complexes have been extensively studied, and developed new types of oxygenations, e.g., ortho-hydroxylation of phenols in the similar way to tyrosine hydroxylases, aromatic ring cleavage of chlorocatechols as the first model reaction for chlorocatechol dioxygenase, and oxygenation of ortho-aminophenols.2)Biocatalytic reactions other than oxygenationsVarious types of catalytic reactions were performed, e.g.functional catalytic antibody, biological NO generation, oxo-transfer reaction by molybdenum enzymes and model conplexes, modeling of the active center of cytochrome C oxidase and oxygen generation by model complexes.3)Development of model systems for bioinorganicelectron-transfer processModeling of the skillful biological electron-transfer mechanisms has been developed, e.g.photo-excited intramolecular electron-transfer bybiologen-bound porphirins, electron-transfer process by artificial mioglobin, selective oxidation by electrochemical processes.

为了开发与金属酶类似的金属配合物的新型均相催化作用，研究了金属配合物与电子转移体系之间的有效结合。作为电子转移和电子给体系统，有机和无机还原剂、电化学和光化学系统已被用于涉及氧化、从水中产生氧的各种催化系统，酶系统和模型系统两者。1）通过金属络合物的选择性氧化通过血红素和非血红素铁络合物的氧化已被广泛研究，并开发了新类型的氧化，例如，etc.in以类似于酪氨酸羟化酶的方式进行的酚的邻位羟基化，作为氯邻苯二酚双加氧酶的第一模型反应的氯邻苯二酚的芳环断裂，以及邻位氨基酚的氧化。2）除氧化反应之外的生物催化反应进行了各种类型的催化反应，例如功能催化抗体，生物NO生成，通过钼酶和模型络合物的氧代转移反应，生物无机电子转移过程模型体系的建立生物电子转移机制的模型已经建立起来，如生物素结合的卟啉的光激发分子内电子转移，人工肌红蛋白的电子转移过程，通过电化学过程进行选择性氧化。