Zumft WG, Kroneck PMH
Respiratory transformation of nitrous oxide (N₂O) to dinitrogen by Bacteria and Archaea

Adv. Microb. Physiol. 52:107-227 (2006)

N₂O is a potent greenhouse gas and stratospheric reactant that has been steadily on the rise since the beginning of industrialization. It is an obligatory inorganic metabolite of denitrifying bacteria, and some production of N₂O is found also in nitrifying and methanotrophic bacteria. We focus this review on the respiratory aspect of N₂O transformation catalysed by the multicopper enzyme nitrous oxide reductase (N₂OR) that provides the bacterial cell with an electron sink for anaerobic growth. Two types of Cu centers discovered in N₂OR were both novel structures among the Cu proteins: the mixed-valent dinuclear Cu_A species at the electron entry site of the enzyme, and the tetranuclear Cu_Z center as the first catalytically active Cu-sulfur complex known. Several accessory proteins function as Cu chaperone and ABC transporter system for the biogenesis of the catalytic centre. We describe here the paradigm of Z-type N₂OR, whose characteristics have been studied in most detail in the genera Pseudomonas and Paracoccus. Sequenced bacterial genomes now provide an invaluable additional source of information. New strains harbouring nos genes and capability of N₂O utilization are being uncovered. This reveals previously unknown relationships and allows pattern recognition and predictions. The core nos genes, nosZDFYL, share a common phylogeny. Most principal taxonomic lineages follow the same biochemical and genetic pattern and share the Z-type enzyme. A modified N₂OR is found in Wolinella succinogenes, and circumstantial evidence also indicates for certain Archaea another type of N₂OR. The current picture supports the view of evolution of N₂O respiration prior to the separation of the domains Bacteria and Archaea. Lateral nos gene transfer from an e-proteobacterium as donor is suggested for Magnetospirillum magnetotacticum and Dechloromonas aromatica. In a few cases nos gene clusters are plasmid borne. Inorganic N₂O metabolism is associated with a diversity of physiological traits and biochemically challenging metabolic modes or habitats, including halorespiration, diazotrophy, symbiosis, pathogenicity, psychrophily, thermophily, extreme halophily, and the marine habitat down to the greatest depth. Components for N₂O respiration cover topologically the periplasm and the inner and outer membranes. The Sec and Tat translocons share the task of exporting Nos components to their functional sites. Electron donation to N₂OR follows pathways with modifications depending on the host organism. A short chronology of the field is also presented.