Journal of Physical Chemistry Letters
Journal of Physical Chemistry Letters
5 years ago

Excited-State Dynamics of Isocytosine: A Hybrid Case of Canonical Nucleobase Photodynamics

Excited-State Dynamics of Isocytosine: A Hybrid Case of Canonical Nucleobase Photodynamics
Trevor Cohen, Briana Aboulache, Gregory Gate, Jacob A. Berenbeim, Michael R. Haggmark, Faady M. Siouri, Mattanjah S. de Vries, Samuel Boldissar
We present resonant two-photon ionization (R2PI) spectra of isocytosine (isoC) and pump–probe results on two of its tautomers. IsoC is one of a handful of alternative bases that have been proposed in scenarios of prebiotic chemistry. It is structurally similar to both cytosine (C) and guanine (G). We compare the excited-state dynamics with the Watson–Crick (WC) C and G tautomeric forms. These results suggest that the excited-state dynamics of WC form of G may primarily depend on the heterocyclic substructure of the pyrimidine moiety, which is chemically identical to isoC. For WC isoC we find a single excited-state decay with a rate of ∼1010 s–1, while the enol form has multiple decay rates, the fastest of which is 7 times slower than for WC isoC. The excited-state dynamics of isoC exhibits striking similarities with that of G, more so than with the photodynamics of C.

Publisher URL: http://dx.doi.org/10.1021/acs.jpclett.7b02032

DOI: 10.1021/acs.jpclett.7b02032

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