Photoinduced hole hopping through tryptophans in proteins

Kód výsledku v IS VaVaI

RIV/61388955:_____/21:00541310 - isvavai.cz

Nalezeny alternativní kódy

RIV/60461373:22340/21:43922688

Výsledek na webu

http://hdl.handle.net/11104/0318888

DOI - Digital Object Identifier

10.1073/pnas.2024627118

Jazyk výsledku

angličtina

Název v původním jazyce

Photoinduced hole hopping through tryptophans in proteins

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

Photoinduced hole hopping through tryptophans in proteins

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

LTAUSA18026: Fotochemická aktivace redox center v proteinech

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Proceedings of the National Academy of Sciences of the United States of America

ISSN

0027-8424

e-ISSN

—

Svazek periodika

118

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

e2024627118

Kód UT WoS článku

000629635100086

EID výsledku v databázi Scopus

2-s2.0-85102389679