The structure of metallo-DNA with consecutive thymine-Hg-II-thymine base pairs explains positive entropy for the metallo base pair formation

0428654 - ÚOCHB 2015 RIV GB eng J - Journal Article
Yamaguchi, H. - Šebera, Jakub - Kondo, J. - Oda, S. - Komuro, T. - Kawamura, T. - Dairaku, T. - Kondo, Y. - Okamoto, I. - Ono, A. - Burda, J. V. - Kojima, C. - Sychrovský, Vladimír - Tanaka, Y.
The structure of metallo-DNA with consecutive thymine-Hg-II-thymine base pairs explains positive entropy for the metallo base pair formation.
Nucleic Acids Research. Roč. 42, č. 6 (2014), s. 4094-4099. ISSN 0305-1048. E-ISSN 1362-4962
R&D Projects: GA ČR GAP205/10/0228
Institutional support: RVO:61388963
Keywords : NMR structures * mercury * metalation * metal-DNA binding * DFT
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 9.112, year: 2014
http://nar.oxfordjournals.org/content/42/6/4094.full

We have determined the three-dimensional (3D) structure of DNA duplex that includes tandem Hg-II-mediated T-T base pairs (thymine-Hg-II-thymine, T-Hg-II-T) with NMR spectroscopy in solution. This is the first 3D structure of metallo-DNA (covalently metallated DNA) composed exclusively of 'NATURAL' bases. The T-Hg-II-T base pairs whose chemical structure was determined with the N-15 NMR spectroscopy were well accommodated in a B-form double helix, mimicking normal Watson-Crick base pairs. The Hg atoms aligned along DNA helical axis were shielded from the bulk water. The complete dehydration of Hg atoms inside DNA explained the positive reaction entropy (delta S) for the T-Hg-II-T base pair formation. The positive delta S value arises owing to the Hg-II dehydration, which was approved with the 3D structure. The 3D structure explained extraordinary affinity of thymine towards Hg-II and revealed arrangement of T-Hg-II-T base pairs in metallo-DNA.
Permanent Link: http://hdl.handle.net/11104/0233994