当前位置: X-MOL 学术ACS Energy Lett. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Crystallographic Data Support the Carousel Mechanism of Water Supply to the Oxygen-Evolving Complex of Photosystem II
ACS Energy Letters ( IF 22.0 ) Pub Date : 2017-09-12 00:00:00 , DOI: 10.1021/acsenergylett.7b00750
Jimin Wang 1 , Mikhail Askerka 2 , Gary W. Brudvig 2 , Victor S. Batista 2
Affiliation  

Photosystem II (PSII) oxidizes water to produce oxygen through a four-step photocatalytic cycle. Understanding PSII structure–function relations is important for the development of biomimetic photocatalytic systems. The quantum mechanics/molecular mechanics (QM/MM) analysis of substrate water binding to the oxygen-evolving complex (OEC) has suggested a rearrangement of water ligands in a carousel mechanism around a key Mn center. Here, we find that the most recently reported X-ray free-electron laser (XFEL) crystallographic data obtained for the dark-stable S1 state and the doubly flashed S3 state at 2.25 Å resolution support the carousel mechanism. The features in the XFEL data and QM/MM model-simulated difference Fourier maps suggest that water displacement may occur from the so-called “narrow” channel, resulting in binding of a new water molecule to the OEC, and thus provide new insights into the nature of rearrangements of water ligands along the catalytic cycle before O═O bond formation.

中文翻译:

晶体学数据支持向光系统II的放氧复合物供水的旋转传送带机制

光系统II(PSII)通过四步光催化循环将水氧化生成氧气。理解PSII结构与功能的关系对于仿生光催化系统的开发很重要。底物水与析氧复合物(OEC)结合的量子力学/分子力学(QM / MM)分析表明,在关键的Mn中心周围的旋转木马机理中,水配体发生了重排。在这里,我们发现针对暗稳定S 1状态和双闪S 3获得的最新报道的X射线自由电子激光(XFEL)晶体学数据状态在2.25Å分辨率下支持轮播机制。XFEL数据和QM / MM模型模拟的差异傅立叶图的特征表明,水的驱替可能是从所谓的“窄”通道发生的,从而导致新的水分子与OEC结合,从而提供了新的见解O═O键形成之前,水配体沿催化循环的重排性质。
更新日期:2017-09-12
down
wechat
bug