Metal ions in non-complementary DNA base pairs: an ab initio study of Cu(I), Ag(I), and Au(I) complexes with the cytosine-adenine base pair |
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Authors: | Jiří Šponer Michal Sabat Jaroslav V Burda Jerzy Leszczynski Pavel Hobza Bernhard Lippert |
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Institution: | (1) J. Heyrovsky Institute of Physical Chemistry Academy of Sciences of the Czech Republic, Dolejškova 3, CZ-182 23 Prague, Czech Republic e-mail: sponer@indy.jh-inst.cas.cz Tel.: +420-2-66053776 Fax: +420-2-8582307,;(2) Department of Chemistry, University of Virginia Charlottesville, VA 22901, USA, US;(3) Department of Chemical Physics, Faculty of Mathematics and Physics, Charles University, CZ-121 16 Prague, Czech Republic,;(4) Department of Chemistry and Computational Center for Molecular Structure and Interactions, Jackson State University Jackson, MS 39217, USA, US;(5) Department of Chemistry, University of Dortmund D-44221 Dortmund, Germany, DE |
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Abstract: | Ab initio calculations have been carried out to characterize the structure and energetics of a silver(I) complex with the
cytosine-adenine DNA base pair and an aqua ligand in the coordination sphere of Ag. In addition, we have also studied analogous
complexes with Cu(I) and Au(I), and structures in which adenine has been replaced by purine in order to investigate the structural
role of the adenine amino group. The calculations revealed that all metal-modified structures are dominated by the metal-base
interactions, while the water-metal ion interaction and many-body interligand repulsion are less important contributions.
Nevertheless, the structural role of the water molecule in the complex is quite apparent and in agreement with an earlier
crystallographic study. The metal-modified base pairs exhibit large conformational flexibility toward out-of-plane motions
(propeller twist and buckle), comparable or, in some cases, even larger than that observed in the base pairs without metal
ions. All structures have been optimized within the Hartree-Fock approximation, while interaction energies were evaluated
with the inclusion of electron correlation.
Received: 25 March 1999 / Accepted: 10 June 1999 |
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Keywords: | Ab initio Silver Nucleobase Cytosine Adenine |
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