CrossRef enabled

PAC Archives

Archive →

Pure Appl. Chem., 2009, Vol. 81, No. 7, pp. 1229-1239

Published online 2009-06-29

Vanadium haloperoxidases as supramolecular hosts: Synthetic and computational models

Winfried Plass

Institut für Anorganische und Analytische Chemie, Friedrich-Schiller-Universität Jena, Carl-Zeiss-Promenade 10, D-07745 Jena, Germany

Abstract: In the active-site cavity of vanadium haloperoxidases vanadate as the prosthetic group is solely fixed by one covalent bond to a histidine residue and embedded in a supramolecular environment of extensive hydrogen bonds. Structural aspects of relevant vanadium complexes with supramolecular interactions, including assemblies with chiral hosts, are presented. The importance of hydrogen-bonding relays is presented together with relevant examples. The reactivity of related functional mimics containing vanadium and molybdenum toward the oxidation of thioethers is described. Computational modeling based on density functional theory (DFT) is used for the investigation of model systems. The resulting implications for structure and function of vanadium haloperoxidases, including their substrate and cofactor specificity, are discussed.