PMID- 16172644 OWN - NLM STAT- MEDLINE DCOM- 20070405 LR - 20131121 IS - 1477-9226 (Print) IS - 1477-9226 (Linking) IP - 19 DP - 2005 Oct 7 TI - Solution chemical properties and catecholase-like activity of the copper(II)-Ac-His-His-Gly-His-OH system, a relevant functional model for copper containing oxidases. PG - 3187-94 AB - The solution chemical properties, superoxide dismutase and catecholase activity of the copper(ii)-Ac-His-His-Gly-His-OH (hhgh) complexes were studied to identify functional and structural models of copper-containing oxidases. The solution speciation was determined in the pH range 3-11 by two independent methods (potentiometry and pH-dependent EPR measurements). The results obtained by the two methods agree very well with each other and show the formation of differently protonated CuH(x)L complexes (where x= 2 ,1, 0, -1, -2, -3) in aqueous solution. The spectroscopic (UV-Vis, CD, EPR) data indicate that the coordination of the imidazole rings is a determinant factor in all these complexes. Amide coordinated complexes are dominant only above pH 8. This offers excellent possibilities for structural/functional modelling of copper(ii) containing metalloenzymes. Indeed, the 3N(im) coordinated CuL species (pH = 6-7) has efficient superoxide dismutase-like activity. The 3N(im),OH(-) coordinated CuH(-1)L possesses outstanding activity to catalyze the oxidation of 3,5-di-tert-butylcatechol (H(2)dtbc) by dioxygen in 86 wt% methanol-water, providing the first example that copper(ii)-peptide complexes are able to mimic copper containing oxidases. FAU - Jancso, A AU - Jancso A AD - Department of Chemistry, University of Turku, FIN-20014 Turku, Finland. FAU - Paksi, Z AU - Paksi Z FAU - Jakab, N AU - Jakab N FAU - Gyurcsik, B AU - Gyurcsik B FAU - Rockenbauer, A AU - Rockenbauer A FAU - Gajda, T AU - Gajda T LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't DEP - 20050819 PL - England TA - Dalton Trans JT - Dalton transactions (Cambridge, England : 2003) JID - 101176026 RN - 0 (Catechols) RN - 0 (Oligopeptides) RN - 0 (Solutions) RN - 789U1901C5 (Copper) RN - EC 1.- (Oxidoreductases) RN - EC 1.16.- (copper oxidase) RN - LF3AJ089DQ (catechol) SB - IM MH - Biomimetic Materials/*chemistry MH - Catechols/metabolism MH - Copper/*chemistry MH - Electrochemistry MH - Electron Spin Resonance Spectroscopy MH - Hydrogen-Ion Concentration MH - *Models, Molecular MH - Oligopeptides/*chemistry MH - Oxidoreductases/*chemistry MH - Solutions EDAT- 2005/09/21 09:00 MHDA- 2007/04/06 09:00 CRDT- 2005/09/21 09:00 PHST- 2005/09/21 09:00 [pubmed] PHST- 2007/04/06 09:00 [medline] PHST- 2005/09/21 09:00 [entrez] AID - 10.1039/b507655b [doi] PST - ppublish SO - Dalton Trans. 2005 Oct 7;(19):3187-94. doi: 10.1039/b507655b. Epub 2005 Aug 19.