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^1H NMR Studies of Tris(phenanthroline) Metal Complexes Bound to Oligonucleotides: Structural Characterizations via Selective Paramagnetic Relaxation

Rehmann, Jill P. and Barton, Jacqueline K. (1990) ^1H NMR Studies of Tris(phenanthroline) Metal Complexes Bound to Oligonucleotides: Structural Characterizations via Selective Paramagnetic Relaxation. Biochemistry, 29 (7). pp. 1710-1717. ISSN 0006-2960. https://resolver.caltech.edu/CaltechAUTHORS:20160516-112834153

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Abstract

The selective paramagnetic relaxation of oligonucleotide protons of d(GTGCAC)_2 by Δ- and Λ-Ni(phen)_3^(3+) and Δ- and Λ-Cr(phen)_3^(3+) has been examined to obtain some structural insight into the noncovalent binding of tris(phenanthroline) metal complexes to DNA. The experiments demonstrate that the relative rate of relaxation of different oligonucleotide protons by the paramagnetic metal complex varies with the chirality of the metal complex and, to a lesser extent, the metal charge. The proton most efficiently relaxed in all cases is the adenosine AH2, which is situated in the minor groove of the oligonucleotide helix. For both Λ-Ni(phen)_3^(2+) and Λ-Cr(phen)_3^(3+), the order of relaxation rates varies as AH2 » AH8 > G3H8 = TMe = C4H5. For Δ-Ni(phen)_3^(2+) it varies as AH2 > G3H8 > AH8 > TMe = C4H5 and for Δ-Cr(phen)_3^(3+) as AH2 > TMe = G3H8 = AH8 > C4H5. Distances between the metal center and oligonucleotide protons were calculated on the basis of the relaxation data, and these distances were used to generate a set of models to describe the interactions of the rigid metal complex with the helix. For A-isomers, the data are consistent with a predominant surface-bound association in the minor groove of the DNA helix. The results for A-isomers correlate better with models that incorporate also a major groove intercalative mode. Despite the absence of hydrogen-bonding groups in the metal complex, the surface-bound model of the phenanthroline complex in the minor groove of DNA resembles the noncovalent association seen with other DNA groove binding molecules.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/bi00459a007DOIArticle
http://pubs.acs.org/doi/abs/10.1021/bi00459a007PublisherArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Alternate Title:Proton NMR studies of tris(phenanthroline) metal complexes bound to oligonucleotides: structural characterizations via selective paramagnetic relaxation
Additional Information:© 1990 American Chemical Society. Received June 30, 1989; Revised Manuscript Received October 19, 1989. This work was supported by NIH Grant GM33309. We thank Dr. Christopher Turner for his expert technical assistance in these experiments.
Funders:
Funding AgencyGrant Number
NIHGM33309
Issue or Number:7
Record Number:CaltechAUTHORS:20160516-112834153
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160516-112834153
Official Citation:Proton NMR studies of tris(phenanthroline) metal complexes bound to oligonucleotides: structural characterizations via selective paramagnetic relaxation Jill P. Rehmann and Jacqueline K. Barton Biochemistry 1990 29 (7), 1710-1717 DOI: 10.1021/bi00459a007
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:67131
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:16 May 2016 19:15
Last Modified:03 Oct 2019 10:03

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