Paramagnetic 19F Chemical Shift Probes that Respond Selectively to Calcium or Citrate Levels and Signal Ester Hydrolysis

Paramagnetic magnetic resonance chemical shift probes containing a proximal CF3 group have been characterised. Different systems have been created that report reversible changes in calcium ion concentrations in the millimolar regime, signal the presence of citrate selectively in competitive aqueous media and allow the monitoring of remote ester/amide hydrolysis in relayed, irreversible transformations. Chemical shift non-equivalence is amplified by the presence of the proximate lanthanide ion, with a mean separation between the CF3 group and the metal ion of 6.4 A found for a thulium complex, in an X-ray structure of the metal complex aqua adduct. The enhanced rate of longitudinal relaxation of the 19F nucleus allows faster data acquisition.