Tryptophan to Tryptophan Hole Hopping in an Azurin Construct

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00582015" target="_blank" >RIV/61388955:_____/23:00582015 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11320/23:10476165

Výsledek na webu

<a href="https://hdl.handle.net/11104/0350145" target="_blank" >https://hdl.handle.net/11104/0350145</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcb.3c06568" target="_blank" >10.1021/acs.jpcb.3c06568</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Tryptophan to Tryptophan Hole Hopping in an Azurin Construct

Popis výsledku v původním jazyce

Electron transfer (ET) between neutral and cationic tryptophan residues in the azurin construct [Re-I(H126)(CO)(3)(dmp)](W124)(W122)Cu-I (dmp = 4,7-Me-2-1,10-phenanthroline) was investigated by Born-Oppenheimer quantum-mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) simulations. We focused on W124(center dot+) <- W122 ET, which is the middle step of the photochemical hole-hopping process *Re-II(CO)(3)(dmp(center dot-)) <- W124 <- W122 <- Cu-I, where sequential hopping amounts to nearly 10,000-fold acceleration over single-step tunneling (ACS Cent. Sci. 2019, 5, 192-200). In accordance with experiments, UKS-DFT QM/MM/MD simulations identified forward and reverse steps of W124(center dot+) <-> W122 ET equilibrium, as well as back ET Re-I(CO)(3)(dmp(center dot-))> W124(center dot+) that restores *Re-II(CO)(3)(dmp(center dot-)). Strong electronic coupling between the two indoles (>= 40 meV in the crossing region) makes the productive W124(center dot+) <- W122 ET adiabatic. Energies of the two redox states are driven to degeneracy by fluctuations of the electrostatic potential at the two indoles, mainly caused by water solvation, with contributions from the protein dynamics in the W122 vicinity. ET probability depends on the orientation of Re(CO)(3)(dmp) relative to W124 and its rotation diminishes the hopping yield. Comparison with hole hopping in natural systems reveals structural and dynamics factors that are important for designing efficient hole-hopping processes.

Název v anglickém jazyce

Tryptophan to Tryptophan Hole Hopping in an Azurin Construct

Popis výsledku anglicky

Electron transfer (ET) between neutral and cationic tryptophan residues in the azurin construct [Re-I(H126)(CO)(3)(dmp)](W124)(W122)Cu-I (dmp = 4,7-Me-2-1,10-phenanthroline) was investigated by Born-Oppenheimer quantum-mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) simulations. We focused on W124(center dot+) <- W122 ET, which is the middle step of the photochemical hole-hopping process *Re-II(CO)(3)(dmp(center dot-)) <- W124 <- W122 <- Cu-I, where sequential hopping amounts to nearly 10,000-fold acceleration over single-step tunneling (ACS Cent. Sci. 2019, 5, 192-200). In accordance with experiments, UKS-DFT QM/MM/MD simulations identified forward and reverse steps of W124(center dot+) <-> W122 ET equilibrium, as well as back ET Re-I(CO)(3)(dmp(center dot-))> W124(center dot+) that restores *Re-II(CO)(3)(dmp(center dot-)). Strong electronic coupling between the two indoles (>= 40 meV in the crossing region) makes the productive W124(center dot+) <- W122 ET adiabatic. Energies of the two redox states are driven to degeneracy by fluctuations of the electrostatic potential at the two indoles, mainly caused by water solvation, with contributions from the protein dynamics in the W122 vicinity. ET probability depends on the orientation of Re(CO)(3)(dmp) relative to W124 and its rotation diminishes the hopping yield. Comparison with hole hopping in natural systems reveals structural and dynamics factors that are important for designing efficient hole-hopping processes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry B

ISSN

1520-6106

e-ISSN

1520-5207

Svazek periodika

128

Číslo periodika v rámci svazku

1

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

96-108

Kód UT WoS článku

001141711200001

EID výsledku v databázi Scopus

2-s2.0-85181573648