title: 17O nuclear quadrupole coupling constants of water bound to a metal ion: a gadolinium(III) case study.
abstract: Rotational correlation times of metal ion aqua complexes can be determined from 17O NMR relaxation rates if the quadrupole coupling constant of the bound water oxygen-17 nucleus is known. The rotational correlation time is an important parameter for the efficiency of Gd3+ complexes as magnetic resonance imaging contrast agents. Using a combination of density functional theory with classical and Car-Parrinello molecular dynamics simulations we performed a computational study of the 17O quadrupole coupling constants in model aqua ions and the [Gd(DOTA)(H2O)]- complex used in clinical diagnostics. For the inner sphere water molecule in the [Gd(DOTA)(H2O)]- complex the determined quadrupole coupling parameter chi square root of (1 + eta2/3) of 8.7 MHz is very similar to that of the liquid water (9.0 MHz). Very close values were also predicted for the the homoleptic aqua ions of Gd3+ and Ca2+. We conclude that the 17O quadrupole coupling parameters of water molecules coordinated to closed shell and lanthanide metal ions are similar to water molecules in the liquid state.
authors.affiliation: Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland.
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Yazyev
authors.forename: Lothar
authors.initials: L
authors.lastname: Helm