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Oxidative Damage by Ruthenium Complexes Containing the Dipyridophenazine Ligand or Its Derivatives: A Focus on Intercalation

Delaney, Sarah and Pascaly, Matthias and Bhattacharya, Pratip K. and Han, Koun and Barton, Jacqueline K. (2002) Oxidative Damage by Ruthenium Complexes Containing the Dipyridophenazine Ligand or Its Derivatives: A Focus on Intercalation. Inorganic Chemistry, 41 (7). pp. 1966-1974. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20160209-164250806

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Abstract

Interactions with DNA by a family of ruthenium(II) complexes bearing the dppz (dppz = dipyridophenazine) ligand or its derivatives have been examined. The complexes include Ru(bpy)_2(dppx)^(2+) (dppx = 7,8-dimethyldipyridophenazine), Ru(bpy)_2(dpq)^(2+) (dpq = dipyridoquinoxaline), and Ru(bpy)_2(dpqC)^(2+) (dpqC = dipyrido-6,7,8,9-tetrahydrophenazine). Their ground and excited state oxidation/reduction potentials have been determined using cyclic voltammetry and fluorescence spectroscopy. An intercalative binding mode has been established on the basis of luminescence enhancements in the presence of DNA, excited state quenching, fluorescence polarization values, and enantioselectivity. Oxidative damage to DNA by these complexes using the flash/quench method has been examined. A direct correlation between the amount of guanine oxidation obtained via DNA charge transport and the strength of intercalative binding was observed. Oxidative damage to DNA through DNA-mediated charge transport was also compared directly for two DNA-tethered ruthenium complexes. One contains the dppz ligand that binds avidly by intercalation, and the other contains only bpy ligands, that, while bound covalently, can only associate with the base pairs through groove binding. Long range oxidative damage was observed only with the tethered, intercalating complex. These results, taken together, all support the importance of close association and intercalation for DNA-mediated charge transport. Electronic access to the DNA base pairs, provided by intercalation of the oxidant, is a prerequisite for efficient charge transport through the DNA π-stack.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ic0111738DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic0111738PublisherArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2002 American Chemical Society. Received November 15, 2001. Publication Date (Web): March 9, 2002. We gratefully acknowledge the National Institutes of Health for financial support of this work. We also thank the NIH for a predoctoral training grant (to S.D.), M.P. acknowledges the DAAD for a postdoctoral fellowship, and K.H. thanks the Caltech SURF office for a summer research fellowship.
Funders:
Funding AgencyGrant Number
NIH Predoctoral FellowshipUNSPECIFIED
Deutscher Akademischer Austauschdienst (DAAD)UNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Issue or Number:7
Record Number:CaltechAUTHORS:20160209-164250806
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160209-164250806
Official Citation:Oxidative Damage by Ruthenium Complexes Containing the Dipyridophenazine Ligand or Its Derivatives:  A Focus on Intercalation Sarah Delaney, Matthias Pascaly, Pratip K. Bhattacharya, Koun Han, and Jacqueline K. Barton Inorganic Chemistry 2002 41 (7), 1966-1974 DOI: 10.1021/ic0111738
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64361
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:10 Feb 2016 15:56
Last Modified:03 Oct 2019 09:37

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