Nitrite formation

Servent D, C Ducrorq, Y Henry, A Guissani, M Lenfant (1991) Nitroglycerin metabolism by Phanerochaete chrysosporium evidence for nitric oxide and nitrite formation. Biochim Biophys Acta 1074 320-325. 

Hydroperoxide groups react with NO to give only nitrates as the dominant products, with only traces (< 5%) of nitrite in both oxidized polyolefins and in concentrated solutions of model hydroperoxides (-OOH levels from iodometry -ONO and -ON02 levels by IR). As reported by Shelton and Kopczewski we have confirmed that both nitrate and nitrite result from NO reaction with dilute hydroperoxide solutions (24). Rather than the NO-induced 0-0 scission proposed by these authors, our evidence points to hydrogen abstraction by NO (reaction 4). (A similar scheme may explain nitrite formation from alcohols.) Both e.s.r. and FTIR evidence is... 

AT-Alkyl methanesulfonamides, 23 685 Alkyl monoperoxycarbonic acid, 18 466 Alkylnaphthalenes, 17 84-85 dispersant moieties, 8 706t Alkyl naphthalene sulfonates, 24 146 Alkylnickel, re-complexes of, 17 116 Alkyl nitrites, formation of, 17 165-166 Alkylonium salt hydrates, 14 171... 

Nitrite formation may lead to nitrous oxide (N O) emission. An example of such a process under reclaimed efQuent disposal on the land surface is reported by Master et al. (2004). Irrigating a grumosol (<60% clay content) with fresh and reclaimed effluent water, it was found that, under efQuent irrigation, the amount of nitrous oxide emissions was double the amount emitted under freshwater treatment, at 60% w/w. The N O emission from efQuent-freated bulk soil was more than double the amount formed from large aggregates. 

The breakthrough time observed in the NO, concentration profile indicates that during the initial part of the pulse the N O fed to the reactor is completely stored on the catalyst surface. As shown by FT-IR spectroscopy [inset (d) in Figure 13.12], the initial NO uptake occurs primarily in the form of nitrites, which are readily transformed into nitrates so that at the end of the NO pulse, at catalyst saturation, nitrates were the prevalent species. Notably, the rate of both nitrite formation and their oxidation to nitrates was higher on Pt-Ba/y-AbOj than on Ba/y-AbO, thus indicating a catalytic role of Pt. 

Water extract of the freeze-dried root, at a concentration of 2 pg/mL, was inactive. Nitrite formation was used as an index of the macrophage stimulating activity . 

J. D. Hoffmann, D. Reaction of nicotine and sodium nitrite Formation of nitrosamines and fragmentation of the pyrrolidine ring. J. Org. Chem.. 1978, 72-76. 

Hecht, S.S., Chen, C.B., Ornaf, R.M., Jacobs, E., Adams, J.D. and Hoffmann, D., "Reaction of Nicotine and Sodium Nitrite Formation of Nitrosamines and Fragmentation of the Pyrrolidine Ring",... 

Hanst, P. L., and E. R. Stephens, Infrared Analysis of Engine Exhausts Methyl Nitrite Formation from Methanol Fuel, Spectroscopy, 4, 33-38 (1989). 

Effects of lL 1/3 and NMMA on islet-cell mitochondrial aconitase activity. Islets were treated for 18 hr with 5 U/ml lL-1, 0.5 mM NMMA, or lL-1/3 and NMMA. The islets were isolated and aconitase activity and the simultaneous release of nitrite were determined as described previously (Corbett et al., 1992b). Treatment of islets with lL-1/3 results in an 80% inhibition of mitochondrial aconitase activity, which is completely prevented by NMMA. lL-1 also stimulates a twofold increase in the level of nitrite released by islets, and NMMA prevents this nitrite formation. Reproduced with permission from J. Clin, Invest. (Corbett et al., 1992b), by the American Society for Clinical Investigation. 

If jS-cell production of nitric oxide participates in IDDM, human islets must produce nitric oxide in response to cytokines. We have shown that a combination of cytokines (lL-1, IFN, and TNF) induce the formation of nitric oxide by isolated human islets (Corbett et al., 1993b). The formation of nitric oxide has been demonstrated by cytokine-induced cGMP accumulation, nitrite formation, and EPR-detectable iron-nitrosyl complex formation (Fig. 12), all of which were prevented by NMMA. The cytokine combination of IFN and lL-1 are required for nitrite production, while TTSIF potentiates IL-1 and IFN-induced nitrite formation by human islets. The cytokine combination of lL-1, TNF, and IFN also influences the physiological function of insulin secretion by human islets. Low concentrations of this cytokine combination slightly stimulate insulin secretion, while high concentrations inhibit insulin secretion, similar to the concentration-dependent effects of lL-1 on rat islet function. NMMA partially prevents the inhibitory effects of this cytokine combination on insulin secretion from human islets, suggesting that nitric oxide may participate in )3-cell dysfunction associated with IDDM. 

Amarger, N., and Alexander, M. (1968). Nitrite formation from hydroxylamine and oximes by Pseudomonas aeruginosa. ]. Bacteriol. 95, 1651-1657. 

For an example involving nitrite formation, see Aldrcd Williams Garley J. Chem. Soc.. Perkin Trans. 2 1982, 777. 

Thus, copper and platinum give similar results the nitrite formation is greater with iron, nickel, and cobalt, and the nitrate formation less. The gases were mainly nitrous oxide and nitrogen with a small proportion of oxygen. N. D. Zelinsky and S. G. Krapiwin showed that the decomposition of hydroxylamine into acid and base does not occur in soln. with methyl alcohol as solvent. J. Tafel showed that an aq. soln. of hydroxylamine sulphate in presence of 20-50 per cent, of sulphuric acid is not reduced at a copper cathode. O. Flaschner observed some reduction in dil. sulphuric acid soln. J. Tafel and H. Hahl found that reduction always takes place when the sulphuric acid cone, in the layer of electrolyte in contact with the cathode is reduced beyond a certain point, and when there is no excess of acid in other words, when hydroxylamine sulphate itself is electrolyzed, the reduction is quantitative. These results are most readily accounted for on the view that only free hydroxylamine (produced in this case by partial hydrolysis of the sulphate), but not the hydroxylammonium ion, NH3OH, is reduced at a copper... 

Table 1 Half-lives for CO release to myoglobin and measurements of cell viability, cytotoxicity and nitrite formation using murine RAW264.7 macrophages [193, 194]...

Hoffmann and co-workers [178,179] have studied the photolysis of nitrate and nitrite in both water and water ice over broad temperature ranges. In the case of nitrite formation from nitrate photolysis, the photochemical reaction reaches a steady state condition that can be described by the following rate expression ... 

Since anions less polarizable than the perfluorinated species represented in Figure 2.6 cannot be made, it would seem that if fluorinated species are to be avoided for economic reasons, the number of anions that can be used in acceptable ionic liquids is rather limited. Nitrates, thiocyanates, nitrites, formates, dicyanamides, chlorosulfonates, and methanesulfonates would seem to be acceptable. Dicyanamides have been shown to have high fluidities with imidazolium and pyrrolidinium cations [28, 43]. 

Since alcohols and carbohydrates readily form equilibrium concentrations of alkyl nitrites which are themselves inactive as direct nitrosating agents (see below), it is to be expected that the addition of alcohols and carbohydrates will inhibit N-nitrosation of amines. This has been shown to be the case for aniline derivatives, and the reduction in the measured first order rate constants can be accounted for quantitatively by such equilibria (Aldred and Williams, 1982). But since alkyl nitrite formation is a rapid equilibrium process, it is not possible, at least for the aniline derivatives studied, to suppress N-nitrosation completely this way. This is in contrast to the effect of thiols discussed in Section 9. In another study (Kurechi et al., 1980), the same effect was observed at pH 3 for the nitrosation of dialkylamines, whereas at pH 5 there was claimed to be a rate enhancement on addition of alcohols, an effect which was not explained. 

In basic solutions, NO and NO2 are absorbed to form nitrites. N2O3, which is responsible for the nitrite formation, is formed according to the equilibrium (166). 

Tannenbaum, S., Weisman, M, and Fett, D (1976). The effect of nitrate intake on nitrite formation in human saliva. Food Cosmet Toxicol 14(6) 549-552. 

C. M. Sharpless, M. A. Page, and K. G. Linden, Impact of hydrogen peroxide on nitrite formation during UV disinfection. Water Research 37, 4730-4736 (2003). 

E2. Elstner, E. F., and Heupel, A., Inhibition of nitrite formation from hydroxylammonium-chlor-ide A simple assay for superoxide dismutase. Anal. Biochem. 70, 616-620 (1976). 

Fig. 3.6. A schematic presentation of nitrite formation from hydroxylamine in the cell of Alcaligenes faecalis. Circled numbers 1, ammonia monooxygenase 2, pyruvic oxime...

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