Solvent effects on the photochemistry of
4-aminoimidazole-5-carbonitrile, a prebiotically plausible
precursor of purines

J 2014

Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines

SZABLA, Rafal Kazimierz, Judit ŠPONEROVÁ, Jiří ŠPONER, Andrzej SOBOLEWSKI, Robert W. GÓRA et. al.

Základní údaje

Originální název

Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines

Autoři

SZABLA, Rafal Kazimierz (203 Česká republika), Judit ŠPONEROVÁ (203 Česká republika, domácí), Jiří ŠPONER (203 Česká republika, garant, domácí), Andrzej SOBOLEWSKI (616 Polsko) a Robert W. GÓRA (616 Polsko)

Vydání

Physical Chemistry Chemical Physics, Cambridge, Royal Society of Chemistry, 2014, 1463-9076

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Velká Británie a Severní Irsko

Utajení

není předmětem státního či obchodního tajemství

Odkazy

URL

Impakt faktor

Impact factor: 4.493

Kód RIV

RIV/00216224:14740/14:00076674

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1039/c4cp02074j

UT WoS

000341064800030

Klíčová slova anglicky

PROTON-TRANSFER PROCESSES; INDOLE-WATER CLUSTERS; CHEMICAL EVOLUTION; PROGRAM SYSTEM; GAS-PHASE; ULTRAFAST DYNAMICS; BUILDING-BLOCKS; EXCITED-STATES; EARLY EARTH; PYRROLE

Štítky

kontrola MP, MP, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 3. 10. 2014 09:03, Olga Křížová

Anotace

V originále

4-Aminoimidazole-5-carbonitrile (AICN) was suggested as a prebiotically plausible precursor of purine nucleobases and nucleotides. Although it can be formed in a sequence of photoreactions, AICN is immune to further irradiation with UV-light. We present state-of-the-art multi-reference quantum-chemical calculations of potential energy surface cuts and conical intersection optimizations to explain the molecular mechanisms underlying the photostability of this compound. We have identified the N-H bond stretching and ring-puckering mechanisms that should be responsible for the photochemistry of AICN in the gas phase. We have further considered the photochemistry of AICN-water clusters, while including up to six explicit water molecules. The calculations reveal charge transfer to solvent followed by formation of an H3O+ cation, both of which occur on the (1)pi sigma* hypersurface. Interestingly, a second proton transfer to an adjacent water molecule leads to a (1)pi sigma*/S-o conical intersection. We suggest that this electron-driven proton relay might be characteristic of low-lying lice states in chromophore water clusters. Owing to its nature, this mechanism might also be responsible for the photostability of analogous organic molecules in bulk water.

Návaznosti

ED1.1.00/02.0068, projekt VaV

Název: CEITEC - central european institute of technology

Citovat

SZABLA, Rafal Kazimierz, Judit ŠPONEROVÁ, Jiří ŠPONER, Andrzej SOBOLEWSKI a Robert W. GÓRA. Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines. Physical Chemistry Chemical Physics. Cambridge: Royal Society of Chemistry, 2014, roč. 16, č. 33, s. 17617-17626. ISSN 1463-9076. Dostupné z: https://dx.doi.org/10.1039/c4cp02074j.

@article{1200023,
   author = {Szabla, Rafal Kazimierz and Šponerová, Judit and Šponer, Jiří and Sobolewski, Andrzej and Góra, Robert W.},
   article_location = {Cambridge},
   article_number = {33},
   doi = {http://dx.doi.org/10.1039/c4cp02074j},
   keywords = {PROTON-TRANSFER PROCESSES; INDOLE-WATER CLUSTERS; CHEMICAL EVOLUTION; PROGRAM SYSTEM; GAS-PHASE; ULTRAFAST DYNAMICS; BUILDING-BLOCKS; EXCITED-STATES; EARLY EARTH; PYRROLE},
   language = {eng},
   issn = {1463-9076},
   journal = {Physical Chemistry Chemical Physics},
   title = {Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines},
   url = {http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP02074J#!divAbstract},
   volume = {16},
   year = {2014}
}

TY  - JOUR
ID  - 1200023
AU  - Szabla, Rafal Kazimierz - Šponerová, Judit - Šponer, Jiří - Sobolewski, Andrzej - Góra, Robert W.
PY  - 2014
TI  - Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines
JF  - Physical Chemistry Chemical Physics
VL  - 16
IS  - 33
SP  - 17617-17626
EP  - 17617-17626
PB  - Royal Society of Chemistry
SN  - 14639076
KW  - PROTON-TRANSFER PROCESSES
KW  - INDOLE-WATER CLUSTERS
KW  - CHEMICAL EVOLUTION
KW  - PROGRAM SYSTEM
KW  - GAS-PHASE
KW  - ULTRAFAST DYNAMICS
KW  - BUILDING-BLOCKS
KW  - EXCITED-STATES
KW  - EARLY EARTH
KW  - PYRROLE
UR  - http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP02074J#!divAbstract
L2  - http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/C4CP02074J#!divAbstract
N2  - 4-Aminoimidazole-5-carbonitrile (AICN) was suggested as a prebiotically plausible precursor of purine nucleobases and nucleotides. Although it can be formed in a sequence of photoreactions, AICN is immune to further irradiation with UV-light. We present state-of-the-art multi-reference quantum-chemical calculations of potential energy surface cuts and conical intersection optimizations to explain the molecular mechanisms underlying the photostability of this compound. We have identified the N-H bond stretching and ring-puckering mechanisms that should be responsible for the photochemistry of AICN in the gas phase. We have further considered the photochemistry of AICN-water clusters, while including up to six explicit water molecules. The calculations reveal charge transfer to solvent followed by formation of an H3O+ cation, both of which occur on the (1)pi sigma* hypersurface. Interestingly, a second proton transfer to an adjacent water molecule leads to a (1)pi sigma*/S-o conical intersection. We suggest that this electron-driven proton relay might be characteristic of low-lying lice states in chromophore water clusters. Owing to its nature, this mechanism might also be responsible for the photostability of analogous organic molecules in bulk water.
ER  -

SZABLA, Rafal Kazimierz, Judit ŠPONEROVÁ, Jiří ŠPONER, Andrzej SOBOLEWSKI a Robert W. GÓRA. Solvent effects on the photochemistry of 4-aminoimidazole-5-carbonitrile, a prebiotically plausible precursor of purines. \textit{Physical Chemistry Chemical Physics}. Cambridge: Royal Society of Chemistry, 2014, roč.~16, č.~33, s.~17617-17626. ISSN~1463-9076. Dostupné z: https://dx.doi.org/10.1039/c4cp02074j.

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