Thermodynamic study of lanthanide(iii) complexes with bifunctional monophosphinic acid analogues of H4dota and comparative kinetic study of yttrium(iii) complexes

Abstract

New bifunctional H₄dota-like ligands with three acetic acid and one phosphinic acid pendant arms and propionate (H₅do3ap^PrA) or 4-aminobenzyl (H₄do3ap^ABn) reactive groups bound to the phosphorus atom were investigated. Potentiometric studies showed that the ligands have a similar basicity to the parent H₄dota and the stability constants of their complexes with sodium(I) and selected lanthanide(III) ions are also similar. Formation and acid-assisted decomplexation kinetics of yttrium(III) complexes with a series of H₄dota-like ligands (H₄dota and its phosphinic/phosphonic acid analogues) were studied and the reactions are sensitive to a slight modification of the ligand structure. The (2-carboxyethyl)phosphinic acid derivative H₅do3ap^PrA and the phosphonic acid ligand H₅do3ap form complexes faster than H₄dota. The most kinetically inert complex is that with H₄do3ap^ABn. Rates of complexation and decomplexation can depend on the ability to transfer proton(s) outside/inside the complex cavity and, therefore, on the hydrophobicity of the ligands. The results demonstrate that the new bifunctional ligands are suitable for labelling biomolecules with yttrium(III) radioisotopes for utilization in nuclear medicine.