Proton Coupled Electron Transfer. Redox Cofactors, Catalysis, and Photochemistry

在这个奖项中，化学部化学催化项目支持北卡罗来纳大学教堂山分校的Thomas Meyer教授对“质子耦合电子转移（PCET）”的研究。氧化还原辅助因子，催化和光化学。”PCET是一种化学过程，它涉及到一个带负电的电子的移动，同时一个带正电的氢离子的转移促进了电子的移动。这一过程在化学和生物系统中都起着重要作用。然而，它对催化、能量转换、生物功能和疾病的影响才刚刚开始得到充分认识。事实上，对PCET的基本过程还没有完全了解。本项目探讨了PCET机制的细节，这些机制有助于决定生物功能，并涉及实验和理论研究。此外，PCET正在向有价值的有机化学品的制备领域扩展。研究生和博士后研究人员积极参与该项目，来自“气候飞跃”（Climate LEAP）的本科生也积极参与该项目，这是一个针对代表性不足群体的暑期项目。这项研究集中在两个重要主题上。一项是对ppet在生物学关键氧化还原辅助因子中的作用的研究，旨在阐明其在更广泛的酶反应性中的作用。另一方面，最近发现的PCET在激发态化学中的作用正在扩展到分子光化学中的作用，并且可能在化学合成和能量转换中发挥作用。首先，PCET机制将与氧化还原酶蛋白结构的功能分析相结合，应用基于Rosetta能量函数的计算协议进行探索。研究了醌/对苯二酚相互转化、黄酮类化合物的异alloxazine官能团和烟酰胺类化合物的二氢吡啶/吡啶官能团中的PCET和电子质子转移（EPT）。对氧化还原辅助因子的研究将扩展到修饰电极，以探索PCET/EPT在电极界面上的应用，并可能在分析和电催化中得到应用。最后，激发态PCET将扩展到溶液和介观纳米结构氧化膜表面的h原子和光电ept反应性，并着眼于光电化学有机合成。

In this award, the Chemical Catalysis program of the Chemistry Division supports Professor Thomas Meyer of The University of North Carolina at Chapel Hill for the research on "Proton Coupled Electron Transfer (PCET). Redox Cofactors, Catalysis, and Photochemistry." PCET is a chemical process that involves movement of a negatively charged electron that is facilitated by the simultaneous transfer of a positively charged hydrogen ion. This process plays an important role in both chemical and biological systems. However, its implications for catalysis, energy conversion, and for biological function and disease are only beginning to be fully appreciated. In fact, a full understanding of the elementary processes in PCET has not been achieved. This project explores the details of the PCET mechanisms that help dictate biological function and involves both experimental and theoretical studies. In addition, PCET is being extended toward the preparation of valuable organic chemicals. Graduate students and postdoctoral research fellows are actively involved in the project as are undergraduate students from "Climate LEAP," a summer program that targets underrepresented groups.The research focuses on two important themes. One is an investigation of the role of PCET in key redox cofactors of biology with an eye toward elucidating its role in the larger sweep of enzymatic reactivity. In the other, recently uncovered roles for PCET in excited state chemistry are being extended to map its role in molecular photochemistry, and, potentially, its role in chemical synthesis and energy conversion. In the first, the PCET mechanism will be explored in concert with functional analysis of oxido-reductase protein structures with application of a computational protocol based on the Rosetta energy function. PCET and electron proton transfer (EPT) will be investigated in quinone/hydroquinone interconversion and in the isoalloxazine functional group of flavins and the dihydropyridine/pyridinium functional group of nictotinamides. Investigations on redox cofactors will be extended to modified electrodes to explore PCET/EPT at electrode interfaces with possible applications in analysis and electrocatalysis. Finally, excited state PCET will be extended to H-atom and photoEPT reactivity in solution and on the surfaces of mesoscopic, nanostructured oxide films with an eye toward photoelectrochemical organic synthesis.