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Monitoring guanine photo-oxidation by enantiomerically resolved Ru(II) dipyridophenazine complexes using inosine-substituted oligonucleotides
Keane, Páraic M.; Poynton, Fergus E.; Hall, James P.; Quinn, Susan J.; et al.
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. Irish Research Council Science Foundation Ireland Royal Irish Academy/Royal Society exchange programme UK Biotechnology and Biological Sciences Research Council UK Science and Technology Facilities Council School of Chemistry and Chemical Biology, UCD
Keyword(s): Ruthenium; Organometallic compounds; Guanine; Inosine; Oligonucleotides; Oxidation-reduction; Stereoisomerism; Photochemistry
Publication Date:
2020
Type: Journal article
Peer-Reviewed: Unknown
Language(s): English
Institution: University College Dublin
Publisher(s): Royal Society of Chemistry
File Format(s): other
First Indexed: 2020-10-01 06:22:19 Last Updated: 2020-10-01 06:22:19