Laboratoire d'Electrochimie Moléculaire, UMR CNRS 7591, Univ Paris Diderot, Sorbonne Paris Cité, 15 rue Jean-Antoine de Baïf, F-75205 Paris Cedex 13, France.
Photochem Photobiol. 2011 Nov-Dec;87(6):1190-203. doi: 10.1111/j.1751-1097.2011.00996.x. Epub 2011 Oct 3.
Proton-coupled electron transfer (PCET) reactions have received much attention over the past 10 years, from an experimental as well as from a theoretical point of view. At the heart of many chemical and biological processes, such reactions are of particular interest in energy conversion and enzymatic processes. Among the numerous examples of PCET reactions, photosynthesis and particularly reactions inside the Photosystem II (PSII) subunit, involving a global four electrons and four protons process to perform water oxidation and respiration, is the most emblematic one. This review focuses on the photochemical approaches of PCET reactions involving phenolic molecules. Indeed, a significant part of photochemical PCET studies were conducted on tyrosine or phenol relevant to PSII and charge transport in enzymes. The mechanisms of these reactions, sequential or concerted, with particular emphasis on the influence of pH, temperature, solvent nature and H-bonding pattern are presented based on photochemical techniques and related theoretical analysis.
质子耦合电子转移 (PCET) 反应在过去 10 年中受到了广泛关注，无论是从实验角度还是理论角度来看。作为许多化学和生物过程的核心，这类反应在能量转换和酶促过程中特别重要。在众多 PCET 反应的实例中，光合作用，特别是光合作用系统 II (PSII) 亚基内的反应，涉及一个全球的四电子和四质子过程，以进行水氧化和呼吸作用，是最具代表性的一个。本综述重点介绍了涉及酚类分子的光化学 PCET 反应。事实上，很大一部分光化学 PCET 研究是针对与 PSII 和酶中的电荷转移相关的酪氨酸或苯酚进行的。基于光化学技术和相关的理论分析，介绍了这些反应的机制，包括顺序或协同反应，特别强调了 pH、温度、溶剂性质和氢键模式的影响。
