title: Dinuclear ZnIIand mixed CuII-ZnIIcomplexes of artificial patellamides as phosphatase models.
abstract: The patellamides (cyclic pseudo-octapeptides) are produced by Prochloron, a symbiont of the ascidians, marine invertebrate filter feeders. These pseudo-octapeptides are present in the cytoplasm and a possible natural function of putative metal complexes of these compounds is hydrolase activity, however the true biological role is still unknown. The dinuclear CuIIcomplexes of synthetic patellamide derivatives have been shown in in vitro experiments to be efficient hydrolase model catalysts. Many hydrolase enzymes, specifically phosphatases and carboanhydrases, are ZnII-based enzymes and therefore, we have studied the ZnIIand mixed ZnII/CuIIsolution chemistry of a series of synthetic patellamide derivatives, including solution structural and computational work, with the special focus on model phosphatase chemistry with bis-(2,4-dinitrophenyl)phosphate (BDNPP) as the substrate. The ZnIIcomplexes of a series of ligands are shown to form complexes of similar structure and stability compared to the well-studied CuIIanalogues and the phosphatase reactivities are also similar. Since the complex stabilities and phosphatase activities are generally a little lower compared to those of CuIIand since the concentration of ZnIIin Prochloron cells is slightly smaller, we conclude that the CuIIcomplexes of the patellamides are more likely to be of biological importance.
authors.affiliation: Universität Heidelberg, Anorganisch-Chemisches Institut und Interdisziplinäres Zentrum für Wissenschaftliches Rechnen (IWR), INF 270, D-69120 Heidelberg, Germany. peter.comba@aci.uni-heidelberg.de.
authors.forename: Peter
authors.initials: P
authors.lastname: Comba
authors.forename: Annika
authors.initials: A
authors.lastname: Eisenschmidt
authors.forename: Lawrence R
authors.initials: LR
authors.lastname: Gahan
authors.forename: Graeme R
authors.initials: GR
authors.lastname: Hanson
authors.forename: Nina
authors.initials: N
authors.lastname: Mehrkens
authors.forename: Michael
authors.initials: M
authors.lastname: Westphal
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D008958:Models, Molecular; D010755:Organophosphates / Q000737:chemistry*; D010456:Peptides, Cyclic / Q000737:chemistry*; D010744:Phosphoric Monoester Hydrolases / Q000737:chemistry*; D015032:Zinc / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D010755:Organophosphates; D010456:Peptides, Cyclic; C546103:bis(2,4-dinitrophenyl) phosphate; D003300:Copper; D010744:Phosphoric Monoester Hydrolases; D015032:Zinc