title: Photophysics and photochemistry of a DNA-protein cross-linking model: a synergistic approach combining experiments and theory.
abstract: The photophysical and photochemical properties of 5-benzyluracil and 5,6-benzyluracil, the latter produced by photocyclization of the former through irradiation with femtosecond UV laser pulses, are investigated both experimentally and theoretically. The absorption spectra of the two molecules are compared, and the principal electronic transitions involved are discussed, with particular emphasis on the perturbation induced on the two chromophore species (uracil and benzene) by their proximity. The photoproduct formation for different irradiation times was verified with high-performance liquid chromatography and nuclear magnetic resonance measurements. The steady-state fluorescence demonstrates that the fluorescence is a distinctive physical observable for detection and selective identification of 5- and 5,6-benzyluracil. The principal electronic decay paths of the two molecules, obtained through TDDFT calculations, explain the features observed in the emission spectra and the photoreactivity of 5-benzyluracil. The order of magnitude of the lifetime of the excited states is derived with steady-state fluorescence anisotropy measurements and rationalized with the help of the computational findings. Finally, the spectroscopic data collected are used to derive the photocyclization and fluorescence quantum yields. In obtaining a global picture of the photophysical and photochemical properties of the two molecules, our findings demonstrates that the use of 5-benzyluracil as a model system to study the proximity relations of a DNA base with a close-lying aromatic amino acid is valid at a local level since the main characteristics of the decay processes from the excited states of the uracil/thymine molecules remain almost unchanged in 5-benzyluracil, the main perturbation arising from the presence of the close-lying aromatic group.
authors.affiliation: Department of Physics, University of Naples Federico II , Via Cintia, 26, 80126 Napoli, Italy.
authors.forename: Marco
authors.initials: M
authors.lastname: Micciarelli
authors.forename: Mohammadhassan
authors.initials: M
authors.lastname: Valadan
authors.forename: Bartolomeo
authors.initials: B
authors.lastname: Della Ventura
authors.forename: Giovanni
authors.initials: G
authors.lastname: Di Fabio
authors.forename: Lorenzo
authors.initials: L
authors.lastname: De Napoli
authors.forename: Sara
authors.initials: S
authors.lastname: Bonella
authors.forename: Ursula
authors.initials: U
authors.lastname: Röthlisberger
authors.forename: Ivano
authors.initials: I
authors.lastname: Tavernelli
authors.forename: Carlo
authors.initials: C
authors.lastname: Altucci
authors.forename: Raffaele
authors.initials: R
authors.lastname: Velotta
mesh_terms: D003500:Cyclization; D004247:DNA / Q000737:chemistry*; D004583:Electrons; D008956:Models, Chemical; D055668:Photochemical Processes; D011789:Quantum Theory; D013050:Spectrometry, Fluorescence; D014466:Ultraviolet Rays; D014498:Uracil / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: C403911:5-benzyluracil; D014498:Uracil; D004247:DNA