Proton-exchange in a paramagnetic chemical exchange saturation transfer agent from experimental studies and ab initio metadynamics simulation

Rodolphe Pollet (1) , Celia ́ Bonnet (2) , Pascal ́ Retailleau (3) , Philippe ́ Durand (3) , Éva Tóth (2)

1 LSDRM - Laboratoire Structure et Dynamique par Résonance Magnétique (LCF)
2 CBM - Centre de biophysique moléculaire
3 ICSN - Institut de Chimie des Substances Naturelles

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 $T_1$ MRI 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 $\it ab initio$ simulation in aqueous solution sheds light on the reaction mechanism for this proton exchange, which involves structural Grotthuss diffusion.

Domains: Chemical Sciences; Material chemistry

Rodolphe Pollet, Celia ́ Bonnet, Pascal ́ Retailleau, Philippe ́ Durand, Éva Tóth. Proton-exchange in a paramagnetic chemical exchange saturation transfer agent from experimental studies and ab initio metadynamics simulation. Inorganic Chemistry, 2017, 56, pp.4317-4323. ⟨10.1021/acs.inorgchem.6b02773⟩. ⟨cea-01496904⟩