title: Proton Exchange in a Paramagnetic Chemical Exchange Saturation Transfer Agent from Experimental Studies and ab Initio Metadynamics Simulation.
abstract: The proton-exchange process between water and a carbamate has been studied experimentally and theoretically in a lanthanide-based paramagnetic chemical exchange saturation transfer agent endowed with potential multimodality detection capabilities (optical imaging, or T1MRI for the Gd(III) analogue). In addition to an in-depth structural analysis by a combined approach (using X-ray crystallography, NMR, and molecular dynamics), our ab initio simulation in aqueous solution sheds light on the reaction mechanism for this proton exchange, which involves structural Grotthuss diffusion.
authors.affiliation: NIMBE, CEA, CNRS, Université Paris-Saclay, CEA Saclay , 91191 Gif-sur-Yvette Cedex, France.
authors.forename: Rodolphe
authors.identifier: http://orcid.org/0000-0003-1081-3323
authors.initials: R
authors.lastname: Pollet
authors.affiliation: Centre de Biophysique Moléculaire, CNRS UPR 4301, Université d'Orléans , Rue Charles Sadron, 45071 Orléans 2, France.
authors.forename: Célia S
authors.initials: CS
authors.lastname: Bonnet
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Saclay , 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette, France.
authors.forename: Pascal
authors.initials: P
authors.lastname: Retailleau
authors.affiliation: Institut de Chimie des Substances Naturelles, CNRS UPR 2301, Université Paris-Saclay , 1 Avenue de la Terrasse, 91198 Gif-sur-Yvette, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Durand
authors.affiliation: Centre de Biophysique Moléculaire, CNRS UPR 4301, Université d'Orléans , Rue Charles Sadron, 45071 Orléans 2, France.
authors.forename: Éva
authors.initials: É
authors.lastname: Tóth