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Monitoring guanine photo-oxidation by enantiomerically resolved Ru(II) dipyridophenazine complexes using inosine-substituted oligonucleotides

DOI: 10.1039/C5FD00085H DOI Help
PMID: 26426601 PMID Help

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

Type: Journal Paper
Journal: Faraday Discussions

State: Published (Approved)
Published: October 2015

Abstract: The intercalating [Ru(TAP)2(dppz)]2+ complex can photo-oxidise guanine in DNA, although in mixed-sequence DNA it can be difficult to understand the precise mechanism due to uncertainties in where and how the complex is bound. Replacement of guanine with the less oxidisable inosine (I) base can be used to understand the mechanism of electron transfer (ET). Here the ET has been compared for both Λ- and Δ-enantiomers of [Ru(TAP)2(dppz)]2+ in a set of sequences where guanines in the readily oxidisable GG step in {TCGGCGCCGA}2 have been replaced with I. The ET has been monitored using picosecond and nanosecond transient absorption and picosecond time-resolved IR spectroscopy. In both cases inosine replacement leads to a diminished yield, but the trends are strikingly different for Λ- and Δ-complexes.

Subject Areas: Chemistry


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