Untersuchungen zu einkernigen Kupfer- und Eisenkomplexen mit biomimetischer Relevanz zur Reaktionsweise von Radikalen in biologischen Prozessen

• Applicant: Professor Hans-Jörg Krüger, Ph.D.
• Subject Area: Microbiology, Virology and Immunology
• Term: from 1999 to 2008
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 5183438

In recent years radicals have gained more and more importance in the discussion of biological processes. Objectives of this proposal are the synthesis of biomimetic complexes for the active sites in the copper-containing enzymes galactose oxidase and copper amine oxidase and in the iron-containing enzyme intradiol-cleaving catechol dioxygenase - all enzymes for which radicals are either known or believed to be involved in the reaction mechanisms - and the investigation of the structural and electronic properties as well as of the reactivity of these complexes. Thus, novel copper(II) phenoxyl radical complexes will be synthesized to serve as functional model complexes for the reactivity of the active site in galactose oxidase. The reproduction of the reactivity of copper amine oxidase and especially the modelling of the intramolecular redox reaction occurring between the copper ion and the 4-aminoresorcine cofactor in the active site are the objectives of a study focusing on copper complexes in which a 2-hydroxy-1,4-quinone unit or derivatives thereof are either directly coordinated to the copper ion or only placed in the proximity of the copper ion. The last part of this proposal concentrates on functional model complexes which address the reasons why the reaction of molecular oxygen with an iron(III) catecholate species occurs during catalytic turnovers of intradiol-cleaving catechol dioxygenases.

• DFG Programme: Priority Programmes
• Subproject of: SPP 1071: Radikale in der enzymatischen Katalyse