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

对于血蛋白结构和/或功能的工程化，可以预期将非天然分子结合到血蛋白中的方法学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。什么样的人工合成分子可以被掺入到血球蛋白中？我们可以从这种半合成的血球蛋白中产生什么类型的新功能？蛋白质或酶与光电分子的杂交在合成复杂的生物材料如光生物催化剂、生物电子学或光电电子器件、生物传感器等方面具有广阔的应用前景。在这篇文章中，我们描述了我们最近在构建基于血红蛋白的新型功能分子及其性质方面所做的努力，包括蛋白质功能的光控制和光致电荷分离。利用辅因子重组法，在氧化还原活性的血红蛋白支架上构建了超分子内质网。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.