Cyclen based lanthanide ion ribonuclease mimics: the effect of pyridine cofactors upon phosphodiester HPNP hydrolysis

The cyclen based pyridine complexes 1Ln-3Ln (Ln = La(III) and Eu(III)) were synthesised as metallo-ribonuclease mimics and their ability to hydrolytically cleave the phosphodiester of HPNP at 37 °C was investigated using UV-vis spectroscopy, whereas the binding of the substrate was evaluated using ³¹P NMR and Eu(III)-luminescent measurements. In contrast 2La gave rise to fast pH dependent hydrolysis of HPNP, with maximum efficiency at ca. pH 8.2, and with a half-lifetime of ∼1 h, the 1Ln and 3Ln complexes were found to be inactive, emphasizing the importance of the nature of the pyridine isomer as a cofactor in the hydrolytic process.