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.jpg): Failed to open stream: No such file or directory in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 117 J+Biol+Chem
2014 ; 289
(51
): 35570-81
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Nitroxyl (HNO) reacts with molecular oxygen and forms peroxynitrite at
physiological pH Biological Implications
#MMPMID25378389
Smulik R
; D?bski D
; Zielonka J
; Micha?owski B
; Adamus J
; Marcinek A
; Kalyanaraman B
; Sikora A
J Biol Chem
2014[Dec]; 289
(51
): 35570-81
PMID25378389
show ga
Nitroxyl (HNO), the protonated one-electron reduction product of NO, remains an
enigmatic reactive nitrogen species. Its chemical reactivity and biological
activity are still not completely understood. HNO donors show biological effects
different from NO donors. Although HNO reactivity with molecular oxygen is
described in the literature, the product of this reaction has not yet been
unambiguously identified. Here we report that the decomposition of HNO donors
under aerobic conditions in aqueous solutions at physiological pH leads to the
formation of peroxynitrite (ONOO(-)) as a major intermediate. We have
specifically detected and quantified ONOO(-) with the aid of boronate probes,
e.g. coumarin-7-boronic acid or 4-boronobenzyl derivative of fluorescein methyl
ester. In addition to the major phenolic products, peroxynitrite-specific minor
products of oxidation of boronate probes were detected under these conditions.
Using the competition kinetics method and a set of HNO scavengers, the value of
the second order rate constant of the HNO reaction with oxygen (k = 1.8 × 10(4)
m(-1) s(-1)) was determined. The rate constant (k = 2 × 10(4) m(-1) s(-1)) was
also determined using kinetic simulations. The kinetic parameters of the
reactions of HNO with selected thiols, including cysteine, dithiothreitol,
N-acetylcysteine, captopril, bovine and human serum albumins, and hydrogen
sulfide, are reported. Biological and cardiovascular implications of nitroxyl
reactions are discussed.