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. |
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@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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