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

对于血红素蛋白结构和/或功能的工程化，预期将非天然分子掺入血红素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。什么样的合成分子可以被整合到血红素蛋白中？我们可以从这些半合成血红素蛋白中产生什么样的新功能？蛋白质或酶与光电分子的杂交有望用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。在本文中，我们描述了我们最近的努力，以构建新型的血红素为基础的功能分子及其性质，包括主题的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，在具有氧化还原活性的血红素蛋白支架上构建了ET超分子体系。我们的研究可以被认为是蛋白质工程和超分子化学的交叉点。

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.