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Enantiomeric Conformation Controls Rate and Yield of Photoinduced Electron Transfer in DNA Sensitized by Ru(II) Dipyridophenazine Complexes

DOI: 10.1021/jz502743q DOI Help

Authors: Paraic M. Keane (Trinity College, Dublin) , Fergus E. Poynton (Trinity College, Dublin) , James P. Hall (University of Reading) , Ian P. Clark (Research Complex at Harwell) , Igor V. Sazanovich (Research Complex at Harwell) , Michael Towrie (Research Complex at Harwell) , Thorfinnur Gunnlaugsson (Trinity College, Dublin) , Susan J. Quinn (University College Dublin) , Christine J. Cardin (University of Reading) , John M. Kelly (Trinity College, Dublin)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: The Journal Of Physical Chemistry Letters , VOL 6 (4) , PAGES 734 - 738

State: Published (Approved)
Published: February 2015

Abstract: Photosensitized oxidation of guanine is an important route to DNA damage. Ruthenium polypyridyls are very useful photosensitizers, as their reactivity and DNA-binding properties are readily tunable. Here we show a strong difference in the reactivity of the two enantiomers of [Ru(TAP)2(dppz)]2+, by using time-resolved visible and IR spectroscopy. This reveals that the photosensitized one-electron oxidation of guanine in three oligonucleotide sequences proceeds with similar rates and yields for bound Δ-[Ru(TAP)2(dppz)]2+, whereas those for the Λ enantiomer are very sensitive to base sequence. It is proposed that these differences are due to preferences of each enantiomer for different binding sites in the duplex.

Journal Keywords: photo-oxidation; transient spectroscopy; nucleic acids; metal complexes; guanine

Subject Areas: Physics, Chemistry

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Added On: 08/02/2016 15:00

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