Artificial phosphatase upon premicellar nanoarchitectonics of lanthanum complexes with long-chained imidazole...

Four novel long chain-containing tridentate imidazole derivatives (Lⁿ, n = 1, 2, 3, 4) were synthesized for in situ formation of mononuclear lanthanum(III) complexes as artificial phosphodiesterases. These in-situ formed La(III) complexes (named LaLⁿ) were used to catalyze the transesterification of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP), a classic RNA model. Critical aggregation concentrations (CAC) were determined for the as-prepared tridentate imidazole derivatives as ligands and corresponding mixtures of equivalent ligand and La³⁺ ion with a mole rate of 1:1. It denotes that the introduction of La³⁺ ion increases the CAC values of imidazole derivatives by about 2 to 3 folds. Foaming test shows that the foam height is positively correlated with the length of hydrophobic chain. Transesterification of HPNP mediated by LaLⁿ nanoarchitectonics indicates that the introducing of hydrophobic chain benefits rate enhancement, showing excess three orders of magnitude acceleration under physiological conditions (pH 7.0, 25 °C). Moreover, catalytic reactivities of these La(III) complexes increased along with the increase in chain length: LaL¹ < LaL² < LaL³ < LaL⁴, suggesting a positive correlation to hydrophobic chain length.