Albany 2001

category image Biomolecular
SUNY at Albany
June 19-23, 2001

The Effects of Nucleobase Metalation on the Electronic Structure of DNA Bases, Their Acidity, Basicity, Tautomeric Equilibria, and Proton Transfer Processes. Comparison of Intrinsic Gas Phase Trends With Solution and Solid State Data.

Interaction of metal cations with DNA bases can significantly influence the electronic structure of nucleobases. These effects can these days be successfully studied using quantum chemical approaches. We have been carrying out a systematic computational analysis of these effects complemented by a careful evaluation of available experimental data. Our results show that the intrinsic gas phase trends, as revealed by modern quantum chemical calculations, are highly relevant to the situation encountered in the solution and solid state experiments. Understanding of the correlation between intrinsic gas phase trends and solution studies is of primary importance for a correct interpretation of both computed and experimental results with respect to the role of metal ions in nucleic acids.

References and Footnotes

  1. J. Sponer, J.E. Sponer, L. Gorb, J. Leszczynski, B. Lippert: Metal-stabilized rare tautomers and mispairs of DNA bases: N6-metalated adenine and N4-metalated cytosine. Theoretical and experimental views. J. Phys. Chem. A 103, 1999, 11406.
  2. J.V.Burda, J. Sponer, J. Leszczynski: The interactions of square platinum(II) complexes with guanine and adenine: a quantum-chemical ab initio study of metalated tautomeric forms. J. Biol. Inorganic Chem. 5, 2000, 178.
  3. J. Sponer, J.E. Sponer, J. Leszczynski: Cation ? pi and amino-acceptor interactions between hydrated metal cations and DNA bases. Quantum-chemical view. J. Biomol. Struct. Dyn. 17, 2000, 1087.
  4. J. Sponer, M. Sabat, L. Gorb, J. Leszczynski, B. Lippert, P. Hobza: The effect of metal binding to the N7 site of purine nucleotides on their structure, energy, and involvement in base pairing. J. Phys. Chem. B 104, 2000, 7535.
  5. J.E. Sponer, F. Glahe, J. Leszczynski, B. Lippert, J. Sponer: The effect of metalation on adenine protonation. Gas phase vs. condensed phase picture. Submitted to Inorg. Chem.

J. Sponer(1), J. E. Sponer(1), J. Leszczynski(2) and B. Lippert(3)

(1)J. Heyrovsky Inst./Phys. Chem., Acad./Sciences/Czech Republic, Dolejykova 3, 182 23 Prague, Czech Republic (2)Dep./Chem./Comput. Ct./ Mol. Struct./Inter., Jackson State Univ., Jackson, MS 39217 (3)Dep./Chem., Univ./Dortmund, 44221 Dortmund, Germany