Phosphoesterase activity of polyoxomolybdates: diffusion ordered NMR spectroscopy as a tool for obtaining insights into the reactivity of polyoxometalate clusters

Abstract

Diffusion ordered NMR spectroscopy (DOSY NMR) is shown to be an excellent tool for observing reactive transients in the hydrolysis of the phosphatase model substrate (p-nitrophenyl)phosphate (NPP) promoted by polyoxomolybdate.

Eu(III) luminescence and tryptophan fluorescence spectroscopy as a tool for understanding interactions between hen egg white lysozyme and metal-substituted Keggin type polyoxometalates

“…Initially, this was illustrated by the hydrolysis of the phospho(di)ester bonds in DNA and RNA model compounds by isopolyoxomolybdates [27][28][29][30][31], isopolyoxovanadates [32,33] and a series of metal-substituted POMs [34]. Encouraged by these results the hydrolysis of the highly inert peptide bond in dipeptides, oligopeptides and proteins in the presence of POMs has also been explored.…”

Understanding the Regioselective Hydrolysis of Human Serum Albumin by Zr(IV)-Substituted Polyoxotungstates Using Tryptophan Fluorescence Spectroscopy

“…It was previously reported by our research group that isopolyoxomolybdates [40][41][42][43], isopolyoxovandates [44,45] and metal-substituted POMs [46] are able to efficiently hydrolyze the phopho(di)ester bonds in DNA and RNA model compounds. Moreover, hydrolysis of the highly inert peptide bond in dipeptides [46][47][48][49][50], oligopeptides [51], and several model proteins [34,52,53] , was the first reported example of protein hydrolysis promoted by a POM [34].…”

Polyoxoniobates and Polyoxotantalates as Ligands—Revisited

“…Moreover, it is possible to estimate diffusion coefficients from 1 H NMR DOSY of the organic part that can be subsequently used to calculate molecular weight of a particular species. This 1 H DOSY NMR technique is becoming a powerful tool for the determination of the size (hydrodynamic radius) and the molecular weight of inorganic clusters [68][69][70]. This technique has not been virtually used in the chemistry of Nb and Ta POM prior to our work.…”