Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective

doi:10.1039/c9cp00868c

	Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective
	Chai, Jun; Zheng, Zhaoyang; Pan, Hui; Zhang, Shengbai; Lakshmi, K. V.; Sun, Yi-Yang
刊名	PHYSICAL CHEMISTRY CHEMICAL PHYSICS
	2019-05-07
卷号	21 期号:17 页码:8721
ISSN号	1463-9076
DOI	10.1039/c9cp00868c
文献子类	Article
英文摘要	The photosynthetic protein complex, photosystem II (PSII), conducts the light-driven water-splitting reaction with unrivaled efficiency. Proton-coupled electron transfer (PCET) reactions at the redox-active tyrosine residues are thought to play a critical role in the water-splitting chemistry. Addressing the fundamental question as to why the tyrosine residue, Y-Z, is kinetically competent in comparison to a symmetrically placed tyrosine residue, Y-D, is important for the elucidation of the mechanism of PCET in the water-splitting reaction of PSII. Here, using all-quantum-mechanical calculations we study PCET at the Y-Z and Y-D residues of PSII. We find that when Y-Z is in its protein matrix under physiological conditions, the HOMO of Y-Z constitutes the HOMO of the whole system. In contrast, the HOMO of Y-D is buried under the electronic states localized elsewhere in the protein matrix and PCET at Y-D requires the transfer of the phenolic proton, which elevates the HOMO of Y-D to become the HOMO of the whole system. This leads to the oxidation of Y-D, albeit on a slower timescale. Our study reveals that the key differences between the electronic structure of Y-Z and Y-D are primarily determined by the protonation state of the respective hydrogen-bonding partners, D1-His190 and D2-His189, or more generally by the H-bonding network of the protein matrix.
WOS研究方向	Chemistry ; Physics
语种	英语
出版者	ROYAL SOC CHEMISTRY
内容类型	期刊论文
源URL	[http://ir.sic.ac.cn/handle/331005/27123]
专题	中国科学院上海硅酸盐研究所
推荐引用方式 GB/T 7714	Chai, Jun,Zheng, Zhaoyang,Pan, Hui,et al. Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2019,21(17):8721.
APA	Chai, Jun,Zheng, Zhaoyang,Pan, Hui,Zhang, Shengbai,Lakshmi, K. V.,&Sun, Yi-Yang.(2019).Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,21(17),8721.
MLA	Chai, Jun,et al."Significance of hydrogen bonding networks in the proton-coupled electron transfer reactions of photosystem II from a quantum-mechanics perspective".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 21.17(2019):8721.