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X-ray crystal structures show DNA stacking advantage of terminal nitrile substitution in Ru-dppz complexes

McQuaid, K., Hall, J. P., Brazier, J. A., Cardin, D. J. and Cardin, C. J. (2018) X-ray crystal structures show DNA stacking advantage of terminal nitrile substitution in Ru-dppz complexes. Chemistry- A European Journal, 24 (59). pp. 15859-15867. ISSN 1521-3765

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To link to this item DOI: 10.1002/chem.201803021

Abstract/Summary

The new complexes [Ru(TAP)2(11-CN-dppz)]2+, [Ru(TAP)2(11-Br-dppz)]2+and [Ru(TAP)2(11,12-diCN-dppz)]2+ are reported. The addition of nitrile substituents to the dppz ligand of the DNA photooxidising complex [Ru(TAP)2(dppz)]2+ promote π-stacking interactions and ordered binding to DNA, as shown by X-ray crystallography. The structure of -[Ru(TAP)2(11-CN-dppz)]2+ with the DNA duplex d(TCGGCGCCGA)2 shows, for the first time with this class of complex, a closed intercalation cavity with an AT base pair at the terminus. The structure obtained is compared to that formed with the 11-Br and 11,12-dinitrile derivatives, highlighting the stabilization of syn guanine by this enantiomer when the terminal basepair is GC. In contrast the AT basepair has the normal Watson-Crick orientation, highlighting the difference in charge distribution between the two purine bases and the complementarity of the dppz-purine interaction. The asymmetry of the cavity highlights the importance of the purine-dppz-purine stacking interaction.

Item Type:Article
Refereed:Yes
Divisions:Interdisciplinary centres and themes > Chemical Analysis Facility (CAF)
Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > NMR (CAF)
Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > School of Pharmacy > Division of Pharmacology
ID Code:78413
Publisher:Wiley

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