Metal centers, especially iron, constitute principal targets for nitric oxide in its various physiological roles, and for this reason, we have long been interested in defining the quantitative reactivities of NO and various other NOx with such species. For example, in a recent study we demonstrated that the water-soluble ferriheme model FeIII(TPPS) mediates O-atom transfer from nitrite to various reductants including cysteine and glutathione. The nitrosyl complex FeII(TPPS)(NO) is the dominant iron species while excess substrate is present. However, the system does not terminate at this stable ferrous nitrosyl but instead displays a matrix of redox transformations linking regeneration of FeIII(TPPS) to formation of both N2O and NO, the former apparently via the intermediacy of HNO. A key pathway to NO formation is nitrite reduction by FeII(TPPS), and the kinetics of this iron-mediated transformation will be discussed. Inorganic nitrite has protective roles during organ ischemia/reperfusion injury, so this result is relevant to potential mechanisms of such protection. We also will describe on-going studies probing the kinetics of the formation and transformations of dinitrosyl iron complexes (DNICs) in aqueous media.These studies were supported by the US National Science Foundation (CHE-1058794)

Mechanistic studies of NO and NO<sub>x</sub> reactions with heme and non-heme iron

248th National Meeting (2014)

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Mechanistic studies of NO and NOx reactions with heme and non-heme iron

Mechanistic studies of NO and NO_x reactions with heme and non-heme iron