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.

Basic information

Original name

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

Authors

SZABLA, Rafal Kazimierz (203 Czech Republic), Judit ŠPONEROVÁ (203 Czech Republic, belonging to the institution), Jiří ŠPONER (203 Czech Republic, guarantor, belonging to the institution), Andrzej SOBOLEWSKI (616 Poland) and Robert W. GÓRA (616 Poland)

Edition

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

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10403 Physical chemistry

Country of publisher

United Kingdom of Great Britain and Northern Ireland

Confidentiality degree

není předmětem státního či obchodního tajemství

References:

URL

Impact factor

Impact factor: 4.493

RIV identification code

RIV/00216224:14740/14:00076674

Organization unit

Central European Institute of Technology

DOI

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

UT WoS

000341064800030

Keywords in English

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

Abstract

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.

Links

ED1.1.00/02.0068, research and development project

Name: CEITEC - central european institute of technology

Citovat

SZABLA, Rafal Kazimierz, Judit ŠPONEROVÁ, Jiří ŠPONER, Andrzej SOBOLEWSKI and 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, vol. 16, No 33, p. 17617-17626. ISSN 1463-9076. Available from: 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 and 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, vol.~16, No~33, p.~17617-17626. ISSN~1463-9076. Available from: https://dx.doi.org/10.1039/c4cp02074j.

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