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Tryptophan to Tryptophan Hole Hopping in an Azurin Construct
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SYSNO ASEP 0582015 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Tryptophan to Tryptophan Hole Hopping in an Azurin Construct Author(s) Melčák, Martin (UFCH-W)
Šebesta, Filip (UFCH-W)
Heyda, Jan (UFCH-W) ORCID, RID
Gray, H. B. (US)
Záliš, Stanislav (UFCH-W) RID, ORCID
Vlček, Antonín (UFCH-W) RID, ORCIDSource Title Journal of Physical Chemistry B. - : American Chemical Society - ISSN 1520-6106
Roč. 128, č. 1 (2023), s. 96-108Number of pages 13 s. Language eng - English Country US - United States Keywords accelerated electron flow ; density-functional theory ; relaxation dynamics ; charge-transfer ; photolyase ; proteins ; cryptochromes ; transport Subject RIV CF - Physical ; Theoretical Chemistry OECD category Physical chemistry R&D Projects GA21-05180S GA ČR - Czech Science Foundation (CSF) LTAUSA18026 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Research Infrastructure e-INFRA CZ II - 90254 - CESNET, zájmové sdružení právnických osob Method of publishing Open access Institutional support UFCH-W - RVO:61388955 UT WOS 001141711200001 EID SCOPUS 85181573648 DOI 10.1021/acs.jpcb.3c06568 Annotation 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. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2024 Electronic address https://hdl.handle.net/11104/0350145
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