Construction of Artificial photosynthetic Reaction Center on Protein Surface: Toward Chemical Design of Photosynthetic-type Semisynthetic Enzyme

对于血红蛋白结构和/或功能的工程，预计将非自然分子纳入血红蛋白的方法可以极大地扩展我们合理和系统地操纵其结构和功能的能力。哪些合成分子可以被纳入血红蛋白？我们可以从这种半合成的血红蛋白中产生哪些类型的新功能？蛋白质或酶与光电子分子的杂交对于合成复杂的生物材料（如光生物催化剂、生物电子或光生物电子器件和生物传感器）是有希望的。在本文中，我们描述了我们最近在构建新的基于血红蛋白的功能分子及其性质方面的努力，包括蛋白质功能的光控制和光诱导电荷分离。采用辅因子重构法，在氧化还原活性血红蛋白支架中构建了超分子ET体系。我们的研究可以被认为是蛋白质工程和超分子化学的十字路口。

Toward engineering of hemoprotein structure and/or function, it is anticipated that a methodology to incorporate unnatural molecules into hemoproteins can greatly expand our ability to rationally and systematically manipulate their structure and function. What sorts of synthetic molecules can be incorporated into hemoproteins? What types of new functions can we produce from such semisynthetic hemoproteins? Hybridization of proteins or enzymes with photoelectronic molecules is promising for the synthesis of sophisticated biomaterials such as photo-biocatalysts, bioelectronic or optobioelectronic devices, and biosensors. In this paper, we describe our recent efforts to construct novel hemoprotein-based functional molecules and their properties, including topics of photo-control of the protein function, and photoinduced charge separation. Using cofactor reconstitution method, supramolecular ET systems were built in redox-active hemoprotein scaffold. Our research can be considered as a crossroad of protein engineering and supramolecular chemistry.