Understanding the factors controlling the photo-oxidation of natural DNA by enantiomerically pure intercalating ruthenium polypyridyl complexes through TA/TRIR studies with polydeoxynucleotides and mixed sequence oligodeoxynucleotides

Páraic M. Keane, Kyra O'Sullivan, Fergus E. Poynton, Bjørn C. Poulsen, Igor V. Sazanovich, Michael Towrie, Christine J. Cardin, Xue Zhong Sun, Michael W. George, Thorfinnur Gunnlaugsson, Susan J. Quinn, John M. Kelly

Research output: Journal PublicationArticlepeer-review

8 Citations (Scopus)
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Abstract

Ruthenium polypyridyl complexes which can sensitise the photo-oxidation of nucleic acids and other biological molecules show potential for photo-therapeutic applications. In this article a combination of transient visible absorption (TrA) and time-resolved infra-red (TRIR) spectroscopy are used to compare the photo-oxidation of guanine by the enantiomers of [Ru(TAP)2(dppz)]2+ in both polymeric {poly(dG-dC), poly(dA-dT) and natural DNA} and small mixed-sequence duplex-forming oligodeoxynucleotides. The products of electron transfer are readily monitored by the appearance of a characteristic TRIR band centred at ca. 1700 cm-1 for the guanine radical cation and a band centered at ca. 515 nm in the TrA for the reduced ruthenium complex. It is found that efficient electron transfer requires that the complex be intercalated at a G-C base-pair containing site. Significantly, changes in the nucleobase vibrations of the TRIR spectra induced by the bound excited state before electron transfer takes place are used to identify preferred intercalation sites in mixed-sequence oligodeoxynucleotides and natural DNA. Interestingly, with natural DNA, while it is found that quenching is inefficient in the picosecond range, a slower electron transfer process occurs, which is not found with the mixed-sequence duplex-forming oligodeoxynucleotides studied.

Original languageEnglish
Pages (from-to)8600-8609
Number of pages10
JournalChemical Science
Volume11
Issue number32
DOIs
Publication statusPublished - 28 Aug 2020

ASJC Scopus subject areas

  • Chemistry (all)

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