title: Theoretical study of hydrated copper(II) interactions with guanine: a computational density functional theory study.
abstract: Optimization of the hydrated Cu(II)(N7-guanine) structures revealed a number of minima on the potential energy surface. For selected structures, energy decompositions together with the determination of electronic properties (partial charges and electron spin densities) were performed. In the complexes of guanine with the bare copper cation and that with the monoaqua ligated cation, an electron transfer from guanine to Cu(II) was observed, resulting in a Cu(I)-guanine(+) type of complex. Conformers with two aqua ligands are borderline systems characterized by a Cu partial charge of +0.7e and a similar value of the spin density (0.6e) localized on guanine. When tetracoordination of copper was achieved, only then the prevailing electron spin density is unambiguously localized on copper. The energetic preference of diaqua-Cu-(N7,O6-guanine) over triaqua-Cu-(N7-guanine) was found for the four-coordinate structures. However, the energy difference between these two conformations decreases with the number of water molecules present in the systems, and in complexes with five water molecules this preference is preserved only at DeltaG level where thermal and entropy terms are included.
authors: Department of Chemical Physics and Optics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 3, 121 16 Prague 2, Czech Republic.
authors: Matej
authors: M
authors: Pavelka
authors: Manoj K
authors: MK
authors: Shukla
authors: Jerzy
authors: J
authors: Leszczynski
authors: Jaroslav V
authors: JV
authors: Burda
mesh_terms: D003198:Computer Simulation; D003300:Copper / Q000737:chemistry*; D006147:Guanine / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D014867:Water / Q000737:chemistry*
chemical_list: D008024:Ligands; D014867:Water; D006147:Guanine; D003300:Copper