Catalytic Zinc Complexes for Phosphate Diester Hydrolysis
2014 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 53, no 31, 8246-8250 p.Article in journal (Refereed) Published
Creating efficient artificial catalysts that can compete with biocatalysis has been an enduring challenge which has yet to be met. Reported herein is the synthesis and characterization of a series of zinc complexes designed to catalyze the hydrolysis of phosphate diesters. By introducing a hydrated aldehyde into the ligand we achieve turnover for DNA-like substrates which, combined with ligand methylation, increases reactivity by two orders of magnitude. In contrast to current orthodoxy and mechanistic explanations, we propose a mechanism where the nucleophile is not coordinated to the metal ion, but involves a tautomer with a more effective Lewis acid and more reactive nucleophile. This data suggests a new strategy for creating more efficient metal ion based catalysts, and highlights a possible mode of action for metalloenzymes.
Place, publisher, year, edition, pages
2014. Vol. 53, no 31, 8246-8250 p.
bioinorganic chemistry, DNA cleavage, enzyme models, kinetics, zinc
IdentifiersURN: urn:nbn:se:uu:diva-232071DOI: 10.1002/anie.201400335ISI: 000340520700050OAI: oai:DiVA.org:uu-232071DiVA: diva2:746600