Effective heterogeneous hydrolysis of phosphodiester by pyridine-containing metallopolymers

The copper (II) complex of a simple pyridine- and amide-containing copolymer serves as an effective catalyst for heterogeneous hydrolysis of the prototypical phosphodiester substrate bis(p-nitrophenyl)phosphate at pH 8.0 and 25 °C. The catalysis has a first-order rate constant of k_cat = 8.3 × 10⁻⁶ s⁻¹, corresponding to a catalytic proficiency of 75-thousand folds relative to the uncatalyzed hydrolysis with a rate constant of k₀ = 1.1 × 10⁻¹⁰ s⁻¹ in aqueous buffer solution at pH 8.0. This observation suggests that polymers can be designed to include various functional groups feasible for effective metal-centered catalysis of phosphodiester hydrolysis.