Photorelaxation of imidazole and adenine via electron-driven proton transfer along H2O wires

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68081707%3A_____%2F16%3A00471977" target="_blank" >RIV/68081707:_____/16:00471977 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1039/c6fd00131a" target="_blank" >http://dx.doi.org/10.1039/c6fd00131a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c6fd00131a" target="_blank" >10.1039/c6fd00131a</a>

Result language

angličtina

Original language name

Photorelaxation of imidazole and adenine via electron-driven proton transfer along H2O wires

Original language description

Photochemically created pi sigma* states were classified among the most prominent factors determining the ultrafast radiationless deactivation and photostability of many biomolecular building blocks. In the past two decades, the gas phase photochemistry of pi sigma* excitations was extensively investigated and was attributed to N-H and O-H bond fission processes. However, complete understanding of the complex photorelaxation pathways of pi sigma* states in the aqueous environment was very challenging, owing to the direct participation of solvent molecules in the excited-state deactivation. Here, we present non-adiabatic molecular dynamics simulations and potential energy surface calculations of the photoexcited imidazole-(H2O)(5) cluster using the algebraic diagrammatic construction method to the second-order [ADC(2)]. We show that electron driven proton transfer (EDPT) along a wire of at least two water molecules may lead to the formation of a pi sigma*/S-0 state crossing, similarly to what we suggested for 2-aminooxazole. We expand on our previous findings by direct comparison of the imidazole-(H2O)(5) cluster to non-adiabatic molecular dynamics simulations of imidazole in the gas phase, which reveal that the presence of water molecules extends the overall excited-state lifetime of the chromophore. To embed the results in a biological context, we provide calculations of potential energy surface cuts for the analogous photorelaxation mechanism present in adenine, which contains an imidazole ring in its structure.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

BO - Biophysics

OECD FORD branch

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Project

<a href="/en/project/GA14-12010S" target="_blank" >GA14-12010S: Theoretical and experimental studies on the origin of life</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2016

Confidentiality

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

Name of the periodical

Faraday Discussions

ISSN

1364-5498

e-ISSN

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Volume of the periodical

195

Issue of the periodical within the volume

2016

Country of publishing house

GB - UNITED KINGDOM

Number of pages

15

Pages from-to

237-251

UT code for WoS article

000392437000012

EID of the result in the Scopus database

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