The origin of efficient triplet state population in sulfur-substituted nucleobases
EntityUAM. Departamento de Química
PublisherNature Publishing Group
10.1038/ncomms13077Nature Communications 7 (2016): 13077
Funded byS.M., P.M. and L.G. thank the Austrian Science Fund (FWF) through project P25827, the COST action CM1204 (XLIC) and the Vienna Scientific Cluster (VSC) for the allocation of computational time. We also thank F. Plasser for assistance with the TheoDORE program. I.C. and L.M.-F. thank the Comunidad Autónoma de Madrid, the Ministerio de Economía y Competitividad (Spain) for an FPU (L.M.-F.) grant, the Projects FOTOCARBON-CM S2013/MIT-2841 and No. CTQ2015-63997-C2, and the ERA-Chemistry Project PIM2010EEC-00751 for financial support, as well as the Centro de Computación Científica UAM for generous allocation of computational time. M.P., N.D. and C.E.C.-H. acknowledge the CAREER program of the National Science Foundation (Grant No. CHE-1255084) for financial support
ProjectComunidad de Madrid. S2013/MIT-2841/FOTOCARBON; Gobierno de España. CTQ2015-63997-C2
SubjectsSulfur-substituted; Nucleobases; Química
Rights© The Author(s) 2016
Esta obra está bajo una Licencia Creative Commons Atribución 4.0 Internacional.
Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo-and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, the molecular factors underlying this efficiency are poorly understood. Herein we combine femtosecond transient absorption experiments with quantum chemistry and nonadiabatic dynamics simulations to investigate 2-thiocytosine as a necessary step to unravel the electronic and structural elements that lead to ultrafast and near-unity triplet-state population in thiobases in general. We show that different parts of the potential energy surfaces are stabilized to different extents via thionation, quenching the intrinsic photostability of canonical DNA and RNA nucleobases. These findings satisfactorily explain why thiobases exhibit the fastest intersystem crossing lifetimes measured to date among bio-organic molecules and have near-unity triplet yields, whereas the triplet yields of canonical nucleobases are nearly zero
Google Scholar:Mai, Sebastian - Pollum, Marvin - Martínez-Fernández, Lara - Dunn, Nicholas - Marquetand, Philipp - Corral, Inés - Crespo-Hernández, Carlos E. - González, Leticia
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