气候变化领域集成服务门户(CCPortal): Photoinduced hole hopping through tryptophans in proteins

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DOI	10.1073/pnas.2024627118
	Photoinduced hole hopping through tryptophans in proteins
	Záliš S.; Heyda J.; Šebesta F.; Winkler J.R.; Gray H.B.; Vlćek A.
发表日期	2021
ISSN	00278424
卷号	118 期号:11
英文摘要	Hole hopping through tryptophan/tyrosine chains enables rapid unidirectional charge transport over long distances. We have elucidated structural and dynamical factors controlling hopping speed and efficiency in two modified azurin constructs that include a rhenium(I) sensitizer, Re(His)(CO)3(dmp)+, and one or two tryptophans (W1, W2). Experimental kinetics investigations showed that the two closely spaced (3 to 4 Å) intervening tryptophans dramatically accelerated long-range electron transfer (ET) from CuIto the photoexcited sensitizer. In our theoretical work, we found that time-dependent density-functional theory (TDDFT) quantum mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) trajectories of low-lying triplet excited states of ReI(His)(CO)3(dmp)+--W1(-W2) exhibited crossings between sensitizer-localized (∗Re) and charge-separated [ReI(His)(CO)3(dmp•-)/(W1•+or W2•+)] (CS1 or CS2) states. Our analysis revealed that the distances, angles, and mutual orientations of ET-active cofactors fluctuate in a relatively narrow range in which the cofactors are strongly coupled, enabling adiabatic ET. Waterdominated electrostatic field fluctuations bring ∗Re and CS1 states to a crossing where ∗Re(CO)3(dmp)+←W1ET occurs, and CS1 becomes the lowest triplet state. ET is promoted by solvation dynamics around ∗Re(CO)3(dmp)+(W1); and CS1 is stabilized by Re(dmp•-)/W1•+electron/hole interaction and enhanced W1•+solvation. The second hop, W1•+←W2, is facilitated by water fluctuations near the W1/W2unit, taking place when the electrostatic potential at W2drops well below that at W1•+. Insufficient solvation and reorganization around W2make W1•+←W2ET endergonic, shifting the equilibrium toward W1•+and decreasing the charge-separation yield. We suggest that multiscale TDDFT/ MM/MD is a suitable technique to model the simultaneous evolution of photogenerated excited-state manifolds. © 2021 National Academy of Sciences. All rights reserved.
英文关键词	Azurin; Electron transfer; Hole hopping; Molecular dynamics; Tryptophan
语种	英语
scopus关键词	azurin; cryptochrome; deoxyribodipyrimidine photolyase; tryptophan; adiabaticity; Article; catalyst; chromatophore; density functional theory; electron transport; kinetics; light; molecular dynamics; molecular mechanics; oxidation; priority journal; quantum mechanics; solvation; static electricity; theoretical study
来源期刊	Proceedings of the National Academy of Sciences of the United States of America
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/180218
作者单位	J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague, CZ-182 23, Czech Republic; Department of Physical Chemistry, University of Chemistry and Technology, Prague, CZ-166 28, Czech Republic; School of Biological and Chemical Sciences, Queen Mary University of London, London, E1 4NS, United Kingdom; Beckman Institute, California Institute of Technology, Pasadena, CA 91125, United States
推荐引用方式 GB/T 7714	Záliš S.,Heyda J.,Šebesta F.,et al. Photoinduced hole hopping through tryptophans in proteins[J],2021,118(11).
APA	Záliš S.,Heyda J.,Šebesta F.,Winkler J.R.,Gray H.B.,&Vlćek A..(2021).Photoinduced hole hopping through tryptophans in proteins.Proceedings of the National Academy of Sciences of the United States of America,118(11).
MLA	Záliš S.,et al."Photoinduced hole hopping through tryptophans in proteins".Proceedings of the National Academy of Sciences of the United States of America 118.11(2021).