Structural investigation into the threading intercalation of a chiral dinuclear ruthenium(II) polypyridyl complex through a B‑DNA oligonucleotide

Fairbanks, Simon D., Robertson, Craig C., Keene, F. Richard, Thomas, Jim A., and Williamson, Mike P. (2019) Structural investigation into the threading intercalation of a chiral dinuclear ruthenium(II) polypyridyl complex through a B‑DNA oligonucleotide. Journal of the American Chemical Society, 141 (11). pp. 4644-4652.

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Abstract

Herein we report the separation of the three stereoisomers of the DNA light-switch compound [{Ru(bpy)2}2(tpphz)]4+ (tpphz = tetrapyrido[3,2-a:2',3'-c:3",2"-h:2‴,3‴-j]phenazine) by column chromatography and the characterization of each stereoisomer by X-ray crystallography. The interaction of these compounds with a DNA octanucleotide d(GCATATCG).d(CGATATGC) has been studied using NMR techniques. Selective deuteration of the bipyridyl rings was needed to provide sufficient spectral resolution to characterize structures. NMR-derived structures for these complexes show a threading intercalation binding mode with slow and chirality-dependent rates. This represents the first solution structure of an intercalated bis-ruthenium ligand. Intriguingly, we find that the binding site selectivity is dependent on the nature of the stereoisomer employed, with Λ RuII centers showing a better intercalation fit.

Item ID: 57307
Item Type: Article (Research - C1)
ISSN: 1520-5126
Keywords: DNA; intercalation; chirality; chiral resolution; ruthenium; NMR structure; dynamics
Copyright Information: Copyright © 2019 American Chemical Society
Date Deposited: 08 Mar 2019 04:42
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030201 Bioinorganic Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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