Carbon dioxide-catalyzed peroxynitrite reactivity - The resilience of the radical mechanism after two decades of research

Augusto, OharaUniv Sao Paulo, Inst Quim, Dept Bioquim, BR-5508000 Sao Paulo, Brazil. (author)

QC 20190613
Peroxynitrite, ONOO-, formed in tissues that are simultaneously generating NO center dot and O-2(center dot-), is widely regarded as a major contributor to oxidative stress. Many of the reactions involved are catalyzed by CO2 via formation of an unstable adduct, ONOOC(O)O-, that undergoes O-O bond homolysis to produce NO2 center dot and CO3 center dot- radicals, whose yields are equal at about 0.33 with respect to the ONOO- reactant. Since its inception two decades ago, this radical-based mechanism has been frequently but unsuccessfully challenged. The most recent among these [Serrano-Luginbuehl et al. Chem. Res. Toxicol. 31: 721-730; 2018] claims that ONOOC(O)O- is stable, predicts a yield of NO2 center dot/CO3 center dot- of less than 0.01 under physiological conditions and, contrary to widely accepted viewpoints, suggests that radical generation is inconsequential to peroxynitrite-induced oxidative damage. Here we review the experimental and theoretical evidence that support the radical model and show this recently proposed alternative mechanism to be incorrect.

Goldstein, SaraHebrew Univ Jerusalem, Chem Inst, IL-91904 Jerusalem, Israel. (author)
Hurst, James K.Oregon State Univ, Dept Biochem & Biophys, Corvallis, OR 97331 USA. (author)
Lind, JohanKTH,Skolan för kemi, bioteknologi och hälsa (CBH)(Swepub:kth)u167ondn (author)
Lymar, Sergei, VBrookhaven Natl Lab, Dept Chem, Upton, NY 11973 USA. (author)
Merényi, GaborKTH,Tillämpad fysikalisk kemi(Swepub:kth)u12lteij (author)
Radi, RafaelUniv Republica, Dept Bioquim, Fac Med, Montevideo 11800, Uruguay.;Univ Republica, Ctr Free Rad & Biomed Res, Fac Med, Montevideo 11800, Uruguay. (author)
Univ Sao Paulo, Inst Quim, Dept Bioquim, BR-5508000 Sao Paulo, Brazil.Hebrew Univ Jerusalem, Chem Inst, IL-91904 Jerusalem, Israel. (creator_code:org_t)

In:Free Radical Biology & Medicine: ELSEVIER SCIENCE INC135, s. 210-2150891-58491873-4596

By the author/editor: Augusto, Ohara; Goldstein, Sara; Hurst, James K.; Lind, Johan; Lymar, Sergei, V; Merényi, Gabor; show more...; Radi, Rafael; show less...

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NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Physical Chemist ...

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