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Theoretical study on the excited-state π-stacking versus intermolecular hydrogen-transfer processes in the guanine–cytosine/cytosine trimer

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Abstract

Understanding the complex events that take place in nucleic acids upon UV light exposure constitutes a key step in the comprehension of life evolution, as well as in the determination of the mechanisms that can originate genetic mutations and lead to the development of diseases like skin cancer. Over the last decade, intra- and inter-strand processes that depend on the relative movements of the DNA strands have been proposed as photochemical pathways capable to deactivate the excess of energy provided by UV light. In order to elucidate the relative importance of both types of photochemical routes, high-level ab initio quantum chemical computations have been conducted on a model formed by the guanine–cytosine base pair and an additional π-stacked cytosine yielding a GC/C trimeric system. The effect of the π-stacking has been evaluated along the reaction coordinate of the stepwise double-hydrogen-transfer (SDHT) mechanism reported in a previous study (Sauri et al. in J Chem Theory Comput 9: 481–496, 2013). It becomes apparent from the present findings that the SDHT process is available at a wide range of cytosine–cytosine intermolecular distances. At a face-to-face orientation of the two cytosine molecules with an intermolecular distance of 3.4 Å, the highly effective π-stacking interaction favours the formation of the CC excimer of the canonical nucleobases. Nevertheless, no barriers are found for the inter-strand mechanism. At larger interacting distances (4.0 Å), both intra-strand photochemistry and inter-strand photochemistry have to be simultaneously considered, whereas at very short distances (2.8 Å) the SDHT process is significantly hindered. The present work confirms the availability of the intermolecular hydrogen transfer in a wide region of the distinct hypersurfaces explored. As compared to the canonical WC base pair, the tautomeric form has more favourable SDHT channels.

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Acknowledgments

Paper dedicated to the UNESCO International Year of Light and Light-based Technologies (IYL 2015). TCA special Issue on Health & Energy from the Sun: a Computational Perspective. This research was supported by Projects CTQ2014-58624-P of the Spanish MINECO/FEDER and GV2015-057 of the Generalitat Valenciana. D.R.-S. thanks the “Juan de la Cierva” program of the Spanish MINECO (Ref. JCI-2012-13431). A.F.-M. thanks BES-2011-048326 FPI grant (MINECO).

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  1. Javier Segarra-Martí

    Present address: Dipartimento di Chimica “G. Ciamician”, Via Selmi 2, 40126, Bologna, Italy

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  1. Institut de Ciència Molecular, Universitat de València, P.O. Box 22085, 46071, Valencia, Spain

    Antonio Francés-Monerris, Javier Segarra-Martí, Manuela Merchán & Daniel Roca-Sanjuán

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Francés-Monerris, A., Segarra-Martí, J., Merchán, M. et al. Theoretical study on the excited-state π-stacking versus intermolecular hydrogen-transfer processes in the guanine–cytosine/cytosine trimer. Theor Chem Acc 135, 31 (2016). https://doi.org/10.1007/s00214-015-1762-z

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