The origin of efficient triplet state population in sulfur-substituted nucleobases

Sebastian Mai, Marvin Pollum, Lara Martínez-Fernández, Nicholas Dunn, Philipp Marquetand, Inés Corral (), Carlos E. Crespo-Hernández () and Leticia González ()
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Sebastian Mai: Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna
Marvin Pollum: Case Western Reserve University
Lara Martínez-Fernández: Universidad Autónoma de Madrid
Nicholas Dunn: Case Western Reserve University
Philipp Marquetand: Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna
Inés Corral: Universidad Autónoma de Madrid
Carlos E. Crespo-Hernández: Case Western Reserve University
Leticia González: Institute of Theoretical Chemistry, Faculty of Chemistry, University of Vienna

Nature Communications, 2016, vol. 7, issue 1, 1-8

Abstract: Abstract 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.

Date: 2016
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DOI: 10.1038/ncomms13077

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