Electron-driven proton transfer enables nonradiative photodeactivation in microhydrated 2-aminoimidazole

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68081707%3A_____%2F18%3A00501643" target="_blank" >RIV/68081707:_____/18:00501643 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1039/c8fd00086g" target="_blank" >http://dx.doi.org/10.1039/c8fd00086g</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c8fd00086g" target="_blank" >10.1039/c8fd00086g</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electron-driven proton transfer enables nonradiative photodeactivation in microhydrated 2-aminoimidazole

Popis výsledku v původním jazyce

2-Aminoimidazole (2-AIM) was proposed as a plausible nucleotide activating group in a nonenzymatic copying and polymerization of short RNA sequences under prebiotically plausible conditions. One of the key selection factors controlling the lifespan and importance of organic molecules on early Earth was ultraviolet radiation from the young Sun. Therefore, to assess the suitability of 2-AIM for prebiotic chemistry, we performed non-adiabatic molecular dynamics simulations and static explorations of potential energy surfaces of the photoexcited 2-AIM-(H2O)(5) model system by means of the algebraic diagrammatic construction method to the second order [ADC(2)]. Our quantum mechanical simulations demonstrate that (1)sigma* excited states play a crucial role in the radiationless deactivation of the UV-excited 2-AIM-(H2O)(5) system. More precisely, electron-driven proton transfer (EDPT) along water wires is the only photorelaxation pathway leading to the formation of (1)sigma*/S-0 conical intersections. The availability of this mechanism and the lack of destructive photochemistry indicate that microhydrated 2-AIM is characterized by substantial photostability and resistance to prolonged UV irradiation.

Název v anglickém jazyce

Electron-driven proton transfer enables nonradiative photodeactivation in microhydrated 2-aminoimidazole

Popis výsledku anglicky

2-Aminoimidazole (2-AIM) was proposed as a plausible nucleotide activating group in a nonenzymatic copying and polymerization of short RNA sequences under prebiotically plausible conditions. One of the key selection factors controlling the lifespan and importance of organic molecules on early Earth was ultraviolet radiation from the young Sun. Therefore, to assess the suitability of 2-AIM for prebiotic chemistry, we performed non-adiabatic molecular dynamics simulations and static explorations of potential energy surfaces of the photoexcited 2-AIM-(H2O)(5) model system by means of the algebraic diagrammatic construction method to the second order [ADC(2)]. Our quantum mechanical simulations demonstrate that (1)sigma* excited states play a crucial role in the radiationless deactivation of the UV-excited 2-AIM-(H2O)(5) system. More precisely, electron-driven proton transfer (EDPT) along water wires is the only photorelaxation pathway leading to the formation of (1)sigma*/S-0 conical intersections. The availability of this mechanism and the lack of destructive photochemistry indicate that microhydrated 2-AIM is characterized by substantial photostability and resistance to prolonged UV irradiation.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

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OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Faraday Discussions

ISSN

1359-6640

e-ISSN

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Svazek periodika

212

Číslo periodika v rámci svazku

DEC 1 2018

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

14

Strana od-do

345-358

Kód UT WoS článku

000455021000017

EID výsledku v databázi Scopus

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