Understanding the function of non-heme iron enzimes from biomimetic metal-organic coordination networks

Stefano Fabris

Abstract:
The activation of dioxygen by metalloproteins and enzymes containing binuclear non-heme iron units is one of the fundamental processes allowing for aerobic life. A synthetic nanostructure that displays key structural and functional similarities with the carboxylate-rich active sites of these enzymes allow us to unveil a novel mechanism of dioxygen activation, which is controlled by the concerted catalytic action of metal centers in within the same active site. Cooordinatively unsaturated diiron units of a two-dimensional metal-organic coordination network are shown to be capable of activating and dissociating molecular oxygen. I will provide an atomic-level structural characterization of the active sites before and after reaction by combining high-resolution Scanning Tunneling Microscopy and Density Functional Theory calculations. Our simulations reveal a complex self-catalytic reaction mechanism governed by concerted dissociations occurring at neighboring metal centers.