Nitric oxide, chemical reactions

Although much of the biological literature focuses on nitrosating reactions of nitric oxide, chemically nitric oxide is a moderate one-electron oxidant, making formation of nitroxyl anion feasible under physiological conditions. The reduction potential to reduce nitric oxide to nitroxyl anion is +0.39 V, whereas it requires +1.2 V to oxidize nitric oxide to nitrosonium ion. Nitrosating reactions of nitric oxide are often mediated by conversion of nitric oxide to another nitrogen oxide species or by direct reaction with transition metals (Wade and Castro, 1990). 

Sodium nitrite has been synthesized by a number of chemical reactions involving the reduction of sodium nitrate [7631-99-4] NaNO. These include exposure to heat, light, and ionizing radiation (2), addition of lead metal to fused sodium nitrate at 400—450°C (2), reaction of the nitrate in the presence of sodium ferrate and nitric oxide at - 400° C (2), contacting molten sodium nitrate with hydrogen (7), and electrolytic reduction of sodium nitrate in a cell having a cation-exchange membrane, rhodium-plated titanium anode, and lead cathode (8). 

Chemiluminescence. Chemiluminescence (262—265) is the emission of light duting an exothermic chemical reaction, generaUy as fluorescence. It often occurs ia oxidation processes, and enzyme-mediated bioluminescence has important analytical appHcations (241,262). Chemiluminescence analysis is highly specific and can reach ppb detection limits with relatively simple iastmmentation. Nitric oxide has been so analyzed from reaction with ozone (266—268), and ozone can be detected by the emission at 585 nm from reaction with ethylene. 

Here a chemical reaction produces a molecule with electrons in an excited state. Upon decay to the ground state the liberated radiation is detected. One such example is the reaction between ozone and nitric oxide to form nitrogen dioxide emitting radiation in the near infra-red in the 0.5-3/t region. The technique flnds use for measuring nitric oxide in ambient air or stack emissions. 

Denitrification involves the sequential formation of nitrite, nitric oxide, and nitrous oxide. Two aspects of nitric oxide have attracted attention (a) chemical oxidation of biogenic nitric oxide to Nq, in the context of increased ozone formation (Stohl et al. 1996) and (b) the physiological role in mammalian systems (Feldman et al. 1993 Stuehr et al. 2004), in parasitic infections (James 1995), and in the inhibition of bacterial respiration (Nagata et al. 1998). Nitric oxide may be produced microbiologically in widely different reactions such as... 

As another example from chemical kinetics, we consider the catalytic reduction of nitric oxide (NO) by hydrogen which was studied using a flow reactor operated differentially at atmospheric pressure (Ayen and Peters, 1962). The following reaction was considered to be important... 

Chromate conversion coatings for aluminum are carried out in acidic solutions. These solutions usually contain one chromium salt, such as sodium chromate or chromic acid and a strong oxidizing agent such as hydrofluoric acid or nitric acid. The final film usually contains both products and reactants and water of hydration. Chromate films are formed by the chemical reaction of hexavalent chromium with a metal surface in the presence of accelerators such as cyanides, acetates, formates, sulfates, chlorides, fluorides, nitrates, phosphates, and sulfamates. 

N02 plays a major role in the chemical reactions which generate photochemical smog and ground-level ozone, as well as contributes to the acid rain effect. Nitrogen dioxide is a strong oxidizing agent, which reacts in the air to form corrosive nitric acid, as well as... 

The discovery of nitric oxide in living organisms was a great event in the development of free radical studies in biology. NO is a gaseous neutral free radical with relatively long lifetime and at the same time is an active species capable of participating in many chemical reactions. 

At present, new developments challenge previous ideas concerning the role of nitric oxide in oxidative processes. The capacity of nitric oxide to oxidize substrates by a one-electron transfer mechanism was supported by the suggestion that its reduction potential is positive and relatively high. However, recent determinations based on the combination of quantum mechanical calculations, cyclic voltammetry, and chemical experiments suggest that °(NO/ NO-) = —0.8 0.2 V [56]. This new value of the NO reduction potential apparently denies the possibility for NO to react as a one-electron oxidant with biomolecules. However, it should be noted that such reactions are described in several studies. Thus, Sharpe and Cooper [57] showed that nitric oxide oxidized ferrocytochrome c to ferricytochrome c to form nitroxyl anion. These authors also proposed that the nitroxyl anion formed subsequently reacted with dioxygen, yielding peroxynitrite. If it is true, then Reactions (24) and (25) may represent a new pathway of peroxynitrite formation in mitochondria without the participation of superoxide. 

Some derivatization methods mentioned in other sections of this review include chemical ionization by nitric oxide (MS) or epoxidation (MS), formation of jr-complexes for NMR (shift agents) etc. Also, the Diels-Alder reaction, which was mentioned several times as a tool for derivatization of conjugated dienes and polyenes, was extensively described and reviewed in the literature. 

Nitric oxide formation from hydroxyurea requires a three-electron oxidation (Scheme 7.15) [114]. Treatment of hydroxyurea with a variety of chemical oxidants produces NO or NO-related species , including nitroxyl (HNO), and these reactions have recently been extensively reviewed [114]. Many of these reactions proceed either through the nitroxide radical (25) or a C-nitroso intermediate (26, Scheme 7.15) [114]. The remainder of the hydroxyurea molecule may decompose into formamide or carbon dioxide and ammonia, depending on the conditions and type of oxidant (one-electron vs. two electron) employed. 

Despite intense study of the chemical reactivity of the inorganic NO donor SNP with a number of electrophiles and nucleophiles (in particular thiols), the mechanism of NO release from this drug also remains incompletely understood. In biological systems, both enzymatic and non-enzymatic pathways appear to be involved [28]. Nitric oxide release is thought to be preceded by a one-electron reduction step followed by release of cyanide, and an inner-sphere charge transfer reaction between the ni-trosonium ion (NO+) and the ferrous iron (Fe2+). Upon addition of SNP to tissues, formation of iron nitrosyl complexes, which are in equilibrium with S-nitrosothiols, has been observed. A membrane-bound enzyme may be involved in the generation of NO from SNP in vascular tissue [35], but the exact nature of this reducing activity is unknown. 

Flagan, R. C. and J. P. Appleton (1974). A stochastic model of turbulent mixing with chemical reaction Nitric oxide formation in a plug-flow burner. Combustion and Flame 23, 249-267. 

Nitration Chemical reaction of a substance in which the nitro group (-N02) is introduced into the molecule often accomplished under highly reactive conditions using mixtures of nitric and sulfuric acids at high temperatures. Byproducts of the reaction may have explosive properties if reaction control is lost, may lead to vigorous and strongly exothermic runaway reactions due to oxidation of the reactants. 

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