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

质子耦合电子转移。

• 批准号: 1362481
• 负责人: Thomas Meyer
• 金额: $ 50万
• 依托单位: University of North Carolina at Chapel Hill
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-07-15 至 2017-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1362481&HistoricalAwards=false
• 关键词: Proton; Coupled; Electron; Transfer.; Redox

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.

在这个奖项中，化学部的化学催化项目支持查佩尔山的北卡罗来纳州大学的托马斯迈耶教授进行“质子耦合电子转移（PCET）”的研究。氧化还原辅因子、催化与光化学。“PCET是一个化学过程，涉及带负电荷的电子的运动，这是由带正电荷的氢离子的同时转移促进。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、能量转换以及生物功能和疾病的影响才刚刚开始被充分认识。事实上，在PCET的基本过程的充分理解尚未实现。该项目探讨了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正在向制备有价值的有机化学品的方向延伸。研究生和博士后研究员积极参与该项目，还有来自“气候飞跃”的本科生，这是一个针对代表性不足的群体的暑期项目。一个是研究PCET在生物学的关键氧化还原辅因子中的作用，着眼于阐明其在酶反应性的更大范围内的作用。在另一方面，最近发现的作用PCET在激发态化学正在扩展到映射其在分子光化学中的作用，并可能，其在化学合成和能量转换的作用。在第一，PCET机制将探讨与氧化还原酶蛋白质结构的功能分析与应用的计算协议的基础上的Rosetta能量函数。PCET和电子质子转移（EPT）将在醌/氢醌相互转化和异咯嗪功能团的黄素和二氢吡啶/吡啶功能团的烟酰胺。氧化还原辅因子的研究将扩展到修饰电极，以探索PCET/EPT在电极界面上的分析和电催化的可能应用。最后，激发态PCET将扩展到H-原子和photoEPT在溶液中的反应性和表面上的介观，纳米结构的氧化物膜，着眼于光电化学有机合成。