Fluorine-19 magnetic resonance methods offer advantages for molecular or cellular imaging in vivo due to the absence of radioactivity, lack of naturally occurring background signal, and the ability to easily combine measurements with anatomical MRI. Previous studies have shown that (19) F-MRI sensitivity is limited to millimolar concentrations by slow… (More)
The construction of lanthanide(III) chelates that exhibit superior photophysical properties holds great importance in biological and materials science. One strategy to increase the luminescence properties of lanthanide(III) chelates is to hinder competitive non-radiative decay processes through perfluorination of the chelating ligands. Here, the synthesis… (More)
Yb⋅DTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [Yb⋅DTMA⋅F](2+) and [Yb⋅DTMA⋅OH2 ](3+) are in slow exchange on the relevant NMR timescale (<2000 s(-1) ), and profound differences are observed in their respective NMR and EPR spectra of these species. The observed… (More)
A series of lanthanide complexes have been synthesized from 1,4,7,10-tetrakis(2-pyridylmethyl)-1,4,7,10-tetraazacyclododecane. Crystallographic studies indicate that, in the solid phase, all of the lanthanide ions are 9-coordinate and are bound to eight N atoms from the donor ligand, with the ninth site being filled by a counterion or solvent molecule. In… (More)
Experimental measurements and theoretical analysis of magnetic properties, structural dynamics and acid-base equilibria for several lanthanide(III) complexes with tetraazacyclododecane derivatives as 19F NMR chemical shift pH probes are presented; pKa values vary between 6.9 and 7.7, with 18 to 40 ppm chemical shift differences between the acidic and basic… (More)
The Ugi reaction offers an effective method for preparing chromophore-appended DOTA-monoamide ligands, which can readily be elaborated to their lanthanide complexes.
The introduction of CF(3) reporter groups close to the paramagnetic centre in macrocyclic lanthanide(iii) complexes allows faster acquisition of (19)F magnetic resonance data, and amplifies chemical shift non-equivalence, as exemplified by the definition of ratiometric chemical shift probes for pH and, in principle, enzyme activity.