Non-haem iron-containing oxygenases involved in the microbial biodegradation of aromatic hydrocarbons

A wide variety of aromatic hydrocarbons can be degraded aerobically by micro-organisms. A large fraction of the metabolic pathways are initiated by oxygenases containing Fe(II) at the active sites, which participates in the oxygenation and activation of the hydrocarbons. Mono-oxygenations and dioxygenations are found in these pathways. Some of these enzymes can catalyse either or both reactions, depending on the nature of the substrate. Two general themes are found: mononuclear Fe(II) centres that must be reduced by one electron at a time, or di-iron centres that can be reduced by two electrons. The electrons from NAD(P)H can be delivered by either an electron-transfer chain consisting of a flavin and one or more [2Fe-2S] centres, or a pterin. Proposed mechanisms generally involve higher oxidation states of the iron (Fe=O), analogous to those for P450, and peroxidase systems. These strong oxidants are necessary to oxidize aromatic and aliphatic compounds. Mechanisms currently considered viable for these reactions require significant changes in ligation during catalysis. The structures of the non-haem iron centres may be particularly well-suited for such transformations.