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- W3107888074 abstract "Abstract DNA owes its remarkable photostability to the ability of its building blocks – the nucleosides – to efficiently dissipate the excess electronic energy acquired upon photoexcitation with ultraviolet light. The exact mechanism occurring on a sub-picosecond time scale has been a matter of intense debate. Here we combine sub-30-fs transient absorption spectroscopy with broad spectral coverage and state-of-the-art quantum dynamics simulations to resolve the early steps of the deactivation mechanisms of uridine (Urd) and 5-methyluridine (5mUrd) in aqueous solution. For both nucleosides we track the wave packet motion from the Franck-Condon region to the conical intersection (CI) with to the ground state and observe a direct spectral signature of an excited-state vibrational mode leading to the CI. We find that 5mUrd exhibits an order of magnitude longer excited state lifetime with respect to Urd and assign it to the larger inertia of the methyl group involved in the ring puckering mode leading to the CI. We argue that this longer lifetime enables the activation of potentially lesion-inducing coordinates such as ring opening, elucidating the origin of the susceptibility of thymine-containing DNA strands to photodamage." @default.
- W3107888074 created "2020-12-07" @default.
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- W3107888074 date "2020-11-18" @default.
- W3107888074 modified "2023-10-18" @default.
- W3107888074 title "Tracking excited state decay mechanisms of pyrimidine nucleosides in real time" @default.
- W3107888074 doi "https://doi.org/10.21203/rs.3.rs-97259/v1" @default.
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