Tryptophan to Tryptophan Hole Hopping in an Azurin Construct
The result's identifiers
Result code in 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>
Alternative codes found
RIV/00216208:11320/23:10476165
Result on the web
<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>
Alternative languages
Result language
angličtina
Original language name
Tryptophan to Tryptophan Hole Hopping in an Azurin Construct
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
Result was created during the realization of more than one project. More information in the Projects tab.
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry B
ISSN
1520-6106
e-ISSN
1520-5207
Volume of the periodical
128
Issue of the periodical within the volume
1
Country of publishing house
US - UNITED STATES
Number of pages
13
Pages from-to
96-108
UT code for WoS article
001141711200001
EID of the result in the Scopus database
2-s2.0-85181573648