NDLI: Direct evidence of singlet molecular oxygen generation from peroxynitrate, a decomposition product of peroxynitrite

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Direct evidence of singlet molecular oxygen generation from peroxynitrate, a decomposition product of peroxynitrite

Content Provider	Royal Society of Chemistry (RSC)
Author	Miyamoto, Sayuri Ronsein, Graziella E. Medeiros, Marisa H. G. Martinez, Glaucia R. Corrêa, Thaís C. Mascio, Paolo Di
Copyright Year	2009
Abstract	The decomposition of peroxynitrite to nitrite and dioxygen at neutral pH follows complex kinetics, compared to its isomerization to nitrate at low pH. Decomposition may involve radicals or proceed by way of the classical peracid decomposition mechanism. Peroxynitrite (ONOOH/ONOO−) decomposition has been proposed to involve formation of peroxynitrate (O2NOOH/O2NOO−) at neutral pH (D. Gupta, B. Harish, R. Kissner and W. H. Koppenol, Dalton Trans., 2009, DOI: 10.1039/b905535e, see accompanying paper in this issue). Peroxynitrate is unstable and decomposes to nitrite and dioxygen. This study aimed to investigate whether O2NOO− formed upon ONOOH/ONOO−decomposition generates singlet molecular oxygen [O2 (1Δg)]. As unequivocally revealed by the measurement of monomol light emission in the near infrared region at 1270 nm and by chemical trapping experiments, the decomposition of ONOO− or O2NOOH at neutral to alkaline pH generates O2 (1Δg) at a yield of ca. 1% and 2–10%, respectively. Characteristic light emission, corresponding to O2 (1Δg) monomolecular decay was observed for ONOO− and for O2NOOH prepared by reaction of H2O2 with NO2BF4 and of H2O2 with NO2− in HClO4. The generation of O2 (1Δg) from ONOO− increased in a concentration-dependent manner in the range of 0.1–2.5 mM and was dependent on pH, giving a sigmoid profile with an apparent pKa around pD 8.1 (pH 7.7). Taken together, our results clearly identify the generation of O2 (1Δg) from peroxynitrate [O2NOO−→ NO2− + O2 (1Δg)] generated from peroxynitrite and also from the reactions of H2O2 with either NO2BF4 or NO2− in acidic media.
Starting Page	5720
Ending Page	5729
Page Count	10
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	0
Issue Number	29
Journal	Dalton Transactions
DOI	10.1039/b905560f
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Dalton ONOO Gupta Harish Kissner Koppenol Peroxynitrite Nitrite Oxygen Acid Isomerization Nitrate Classical mechanics Peroxy acid Dalton Transactions Infrared spectroscopy Hydrogen peroxide Acid dissociation constant
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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