title: Bioinspired heme, heme/nonheme diiron, heme/copper, and inorganic NOx chemistry: *NO((g)) oxidation, peroxynitrite-metal chemistry, and *NO((g)) reductive coupling.
abstract: The focus of this Forum Article highlights work from our own laboratories and those of others in the area of biochemical and biologically inspired inorganic chemistry dealing with nitric oxide [nitrogen monoxide, *NO((g))] and its biological roles and reactions. The latter focus is on (i) oxidation of *NO((g)) to nitrate by nitric oxide dioxygenases (NODs) and (ii) reductive coupling of two molecules of *NO((g)) to give N(2)O(g). In the former case, NODs are described, and the highlighting of possible peroxynitrite/heme intermediates and the consequences of this are given by a discussion of recent works with myoglobin and a synthetic heme model system for NOD action. Summaries of recent copper complex chemistries with *NO((g)) and O(2)(g), leading to peroxynitrite species, are given. The coverage of biological reductive coupling of *NO((g)) deals with bacterial nitric oxide reductases (NORs) with heme/nonheme diiron active sites and on heme/copper oxidases such as cytochrome c oxidase, which can mediate the same chemistry. Recently designed protein and synthetic model compounds (heme/nonheme/diiron or heme/copper) as functional mimics are discussed in some detail. We also highlight examples from the chemical literature, not necessarily involving biologically relevant metal ions, that describe the oxidation of *NO((g)) to nitrate (or nitrite) and possible peroxynitrite intermediates or reductive coupling of *NO((g)) to give nitrous oxide.
authors.affiliation: Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA.
authors.forename: Mark P
authors.initials: MP
authors.lastname: Schopfer
authors.forename: Jun
authors.initials: J
authors.lastname: Wang
authors.forename: Kenneth D
authors.initials: KD
authors.lastname: Karlin
mesh_terms: D003300:Copper / Q000737:chemistry*; D006418:Heme / Q000737:chemistry*; D008958:Models, Molecular; D009569:Nitric Oxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D010105:Oxygenases / Q000737:chemistry / Q000378:metabolism; D030421:Peroxynitrous Acid / Q000737:chemistry*
chemical_list: D030421:Peroxynitrous Acid; D009569:Nitric Oxide; D006418:Heme; D003300:Copper; D010105:Oxygenases; C114415:nitric oxide dioxygenase