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Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study

Cordier, Christine and Pierre, Valérie C. and Barton, Jacqueline K. (2007) Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch: An NMR Solution Study. Journal of the American Chemical Society, 129 (40). pp. 12287-12295. ISSN 0002-7863. PMCID PMC2748819. doi:10.1021/ja0739436. https://resolver.caltech.edu/CaltechAUTHORS:20160226-135926826

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Abstract

The bulky octahedral complex Rh(bpy)_2chrysi^(3+) (chrysi = 5,6-chrysenequinonediimine) binds single-base mismatches in a DNA duplex with micromolar binding affinities and high selectivity. Here we present an NMR solution study to characterize the binding mode of this bulky metal complex with its target CC mismatch in the oligonucleotide duplex (5‘-CGGACTCCG-3‘)_2. Both NOESY and COSY studies indicate that Rh(bpy)_2chrysi^(3+) inserts deeply in the DNA at the mismatch site via the minor groove and with ejection of both destabilized cytosines into the opposite major groove. The insertion only minimally distorts the conformation of the oligonucleotide local to the binding site. Both flanking, well-matched base pairs remain tightly hydrogen-bonded to each other, and 2D DQF-COSY experiments indicate that all sugars maintain their original C_2‘-endo conformation. Remarkably, ^(31)P NMR reveals that opening of the phosphate angles from a B_I to a B_(II) conformation is sufficient for insertion of the bulky metal complex. These results corroborate those obtained crystallographically and, importantly, provide structural evidence for this specific insertion mode in solution.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja0739436DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja0739436PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja0739436PublisherSupporting Information
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2748819/PubMed CentralArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2007 American Chemical Society. Received May 31, 2007. Publication Date (Web): September 18, 2007. We are grateful to the National Institutes of Health (Grant GM33309) for their financial support. We also thank the Université Denis Diderot, Paris VII, for sabbatical support to C.C. Additionally we thank P. K. Bhattacharya, K. Crowhurst, M. Shahgholi, and S. Ross for helpful discussions.
Funders:
Funding AgencyGrant Number
NIHGM33309
Université Denis Diderot, Paris VIIUNSPECIFIED
Issue or Number:40
PubMed Central ID:PMC2748819
DOI:10.1021/ja0739436
Record Number:CaltechAUTHORS:20160226-135926826
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160226-135926826
Official Citation:Insertion of a Bulky Rhodium Complex into a DNA Cytosine−Cytosine Mismatch:  An NMR Solution Study Christine Cordier, Valérie C. Pierre, and Jacqueline K. Barton Journal of the American Chemical Society 2007 129 (40), 12287-12295 DOI: 10.1021/ja0739436
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64809
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:29 Feb 2016 18:19
Last Modified:10 Nov 2021 23:35

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