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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

BO - Biofyzika

OECD FORD obor

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Projekt

<a href="/cs/project/GA14-12010S" target="_blank" >GA14-12010S: Teoretické a experimentální studie o původu života</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Faraday Discussions

ISSN

1364-5498

e-ISSN

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Svazek periodika

195

Číslo periodika v rámci svazku

2016

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

15

Strana od-do

237-251

Kód UT WoS článku

000392437000012

EID výsledku v databázi Scopus

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