Theoretical study of proton coupled electron transfer reaction in the light state of the AppA BLUF photoreceptor,Journal of Computational Chemistry

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Theoretical study of proton coupled electron transfer reaction in the light state of the AppA BLUF photoreceptor
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2018-10-20 , DOI: 10.1002/jcc.25561
Yang Xu _{1,

2} , Peng Bao _{1,

2} , Kai Song _{1,

2} , Qiang Shi _{1,

2}

Affiliation

The BLUF (blue light sensor using flavin adenine dinucleotide) domain is widely studied as a prototype for proton coupled electron transfer (PCET) reactions in biological systems. In this work, the photo‐induced concerted PCET reaction from the light state of the AppA BLUF domain is investigated. To model the simultaneous transfer of two protons in the reaction, two‐dimensional potential energy surfaces for the double proton transfer are first calculated for the locally excited and charge transfer states, which are then used to obtain the vibrational wave function overlaps and the vibrational energy levels. Contributions to the PCET rate constant from each pair of vibronic states are then analyzed using the theory based on the Fermi's golden rule. We show that, the recently proposed light state structure of the BLUF domain with a tautomerized Gln63 residue is consistent with the concerted transfer of one electron and two protons. It is also found that, thermal fluctuations of the protein structure, especially the proton donor‐acceptor distances, play an important role in determining the PCET reaction rate. © 2018 Wiley Periodicals, Inc.

中文翻译：

AppA BLUF光感受器光态下质子耦合电子转移反应的理论研究

BLUF（使用黄素腺嘌呤二核苷酸的蓝光传感器）域作为生物系统中质子耦合电子转移 (PCET) 反应的原型被广泛研究。在这项工作中，研究了来自 AppA BLUF 域的光态的光诱导协同 PCET 反应。为了模拟反应中两个质子的同时转移，首先计算局部激发态和电荷转移态的双质子转移的二维势能面，然后用于获得振动波函数重叠和振动能量水平。然后使用基于费米黄金法则的理论分析每对振动态对 PCET 速率常数的贡献。我们表明，最近提出的具有互变异构化 Gln63 残基的 BLUF 结构域的光态结构与一个电子和两个质子的协同转移一致。还发现，蛋白质结构的热波动，尤其是质子供体-受体距离，在决定 PCET 反应速率方面起着重要作用。© 2018 Wiley Periodicals, Inc.

更新日期：2018-10-20

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