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Paramagnetic 19 F Chemical Shift Probes that Respond Selectively to Calcium or Citrate Levels and Signal Ester Hydrolysis
Author(s) -
Harvey Peter,
Chalmers Kirsten H.,
De Luca Elena,
Mishra Anurag,
Parker David
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201200737
Subject(s) - thulium , chemistry , amide , hydrolysis , lanthanide , adduct , aqueous solution , paramagnetism , ion , calcium , inorganic chemistry , metal , molar concentration , metal ions in aqueous solution , organic chemistry , materials science , doping , quantum mechanics , physics , optoelectronics
Paramagnetic magnetic resonance chemical shift probes containing a proximal CF 3 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 CF 3 group and the metal ion of 6.4 Å found for a thulium complex, in an X‐ray structure of the metal complex aqua adduct. The enhanced rate of longitudinal relaxation of the 19 F nucleus allows faster data acquisition.