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Diastereomeric Crowding Effects in the Competitive DNA Intercalation of Ru(phenanthroline)2dipyridophenazine2+ Enantiomers

Lookup NU author(s): Dr Eimer TuiteORCiD



This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2019.

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The biexponential excited-state emission decay characteristic of DNA intercalated tris-bidentate dppz-based ruthenium complexes of the general form Ru(L)2dppz2+ has previously been explained by a binding model with two distinct geometry orientations of the bound ligands, with a distinct lifetime associated with each orientation. However, it has been found that upon DNA binding of Ru(phen)2dppz2+ the fractions of short and long lifetimes are strongly dependent on environmental factors such as salt concentration and, in particular, temperature. Analyzing isothermal titration calorimetry for competitive binding of Ru(phen)2dppz2+ enantiomers to poly(dAdT)2, we find that a consistent binding model must assume that the short and long lifetimes states of intercalated complexes are in equilibrium and that this equilibrium is altered when neighboring bound ligands affect each other. The degree of intercomplex binding is found to be a subtle manifestation of several attractive and repulsive factors that are highly likely to directly reflect the strong diastereomeric difference in the binding enthalpy and entropy values. In addition, as the titration progresses and the binding sites on the DNA lattice become increasingly occupied, a general resistance for the saturation of the binding sites is observed, suggesting diastereomeric crowding of the neighboring bound ligands.

Publication metadata

Author(s): MÃ¥rtensson AKF, Abrahamsson M, Tuite EM, Lincoln P

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2019

Volume: 58

Issue: 14

Pages: 9452-9459

Print publication date: 15/07/2019

Online publication date: 24/06/2019

Acceptance date: 03/05/2019

Date deposited: 19/07/2019

ISSN (print): 0020-1669

ISSN (electronic): 1520-510X

Publisher: American Chemical Society


DOI: 10.1021/acs.inorgchem.9b01298


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