title: Fast ferrous heme-NO oxidation in nitric oxide synthases.
abstract: During catalysis, the heme in nitric oxide synthase (NOS) binds NO before releasing it to the environment. Oxidation of the NOS ferrous heme-NO complex by O2 is key for catalytic cycling, but the mechanism is unclear. We utilized stopped-flow methods to study the reaction of O2 with ferrous heme-NO complexes of inducible and neuronal NOS enzymes. We found that the reaction does not involve heme-NO dissociation, but instead proceeds by a rapid direct reaction of O2 with the ferrous heme-NO complex. This behavior is novel and may distinguish heme-thiolate enzymes, such as NOS, from related heme proteins.
authors.affiliation: Department of Pathobiology, The Cleveland Clinic Foundation, Lerner Research Institute, 9500 Euclid Ave., Cleveland, OH 44195, USA.
authors.forename: Jesús
authors.initials: J
authors.lastname: Tejero
authors.forename: Jérôme
authors.initials: J
authors.lastname: Santolini
authors.forename: Dennis J
authors.initials: DJ
authors.lastname: Stuehr
mesh_terms: D000818:Animals; D055598:Chemical Phenomena; D006418:Heme / Q000737:chemistry*; D051379:Mice; D009569:Nitric Oxide / Q000737:chemistry*; D019001:Nitric Oxide Synthase / Q000737:chemistry*; D052248:Nitric Oxide Synthase Type I; D052247:Nitric Oxide Synthase Type II / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D051381:Rats
chemical_list: D009569:Nitric Oxide; D006418:Heme; D019001:Nitric Oxide Synthase; D052248:Nitric Oxide Synthase Type I; D052247:Nitric Oxide Synthase Type II; C496322:Nos1 protein, rat; C496317:Nos2 protein, mouse; D010100:Oxygen
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