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

为了开发类似于金属酶的新型金属络合物均相催化，研究了金属络合物与电子转移体系的有效结合。作为电子传递体系和电子供体体系，有机和无机还原体系、电化学体系和光化学体系已被用于各种催化体系，包括氧化、水制氧等。在酶体系和模型体系中，1)金属络合物的选择性氧化已被广泛地研究了血红素和非血红素铁络合物的氧化反应，并发展了新的类型的氧化反应，如类似于酪氨酸羟基酶的苯酚的邻羟基化，氯代辛醇的芳环裂解作为氯代辛酚双加氧酶的第一模型反应，以及邻氨基苯酚的氧化。2)除氧合以外的生物催化反应，如功能性催化反应、抗体、抗体和邻氨基苯酚的氧化等3)生物无机物电子转移过程模型体系的建立对生物分子内电子转移机理进行了模拟，如生物素结合的卟啉的光激发分子内电子转移、人工高铁血红蛋白的电子转移过程、电化学选择性氧化等。

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.