Free radical yields from the homolysis of peroxynitrous acid

doi:10.1016/0891-5849(92)90120-6

Free Radical Biology and Medicine

Volume 12, Issue 4, 1992, Pages 327-330

https://doi.org/10.1016/0891-5849(92)90120-6 Get rights and content

Abstract

A recent study¹ reports discordant results for maximal free-radical yields from the decomposition of peroxynitrous acid using different assay reagents and a puzzling decrease (to zero) of the radical yields with increasing pH. An assay method using 2,2,′azino-bis(3-ethyl-benzthiazoline sulphonate) (ABTS) has been tested using stopped-flow kinetic studies, and the results imply that the assay is satisfactory when [HOONO] ⪢ [⁻OONO] but that reactions involving peroxynitrite anion interfere at higher pH. Evidence is presented that peroxynitrite was an interfering species in the earlier studies.

References (11)

R. Radi et al.
Peroxy-nitrate oxidation of sulfhydryls: The cytotoxic potential of superoxide and nitric oxide
J. Biol. Chem.
(1991)
M.G. Steiner et al.
Quantitation of the hydroxyl radical by reaction with dimethyl sulfoxide
Arch. Biochem. Biophys.
(1990)
J.S. Beckman et al.
Apparent hydroxyl production by peroxynitrite: Implications for endothelial injury from nitric oxide and superoxide
M. Saran et al.
Reaction of NO with O₂·⁻. Implications for the action of endothelium-derived relaxing factor (EDRF)
Free Rad Res. Comms.
(1990)
E. Halfpenny et al.
Pernitrous acid. The reaction between hydrogen peroxide and nitrous acid and the properties of an intermediate product
J. Chem. Soc.
(1952)

There are more references available in the full text version of this article.

Cited by (70)

Hyaluronan and Hyaluronan Fragments
2017, Advances in Carbohydrate Chemistry and Biochemistry
The glycosaminoglycan hyaluronan (HA) is a key component of the microenvironment surrounding cells. In healthy tissues, HA molecules have extremely high molecular mass and consequently large hydrodynamic volumes. Tethered to the cell surface by clustered receptor proteins, HA molecules crowd each other, as well as other macromolecular species. This leads to severe nonideality in physical properties of the biomatrix, because steric exclusion leads to an increase in effective concentration of the macromolecules. The excluded volume depends on both polymer concentration and hydrodynamic volume/molecular mass. The biomechanical properties of the extracellular matrix, tissue hydration, receptor clustering, and receptor–ligand interactions are strongly affected by the presence of HA and by its molecular mass. In inflammation, reactive oxygen and nitrogen species fragment the HA chains. Depending on the rate of chain degradation relative to the rates of new synthesis and removal of damaged chains, short fragments of the HA molecules can be present at significant levels. Not only are the physical properties of the extracellular matrix affected, but the HA fragments decluster their primary receptors and act as endogenous danger signals. Bioanalytical methods to isolate and quantify HA fragments have been developed to determine profiles of HA content and size in healthy and diseased biological fluids and tissues. These methods have potential use in medical diagnostic tests. Therapeutic agents that modulate signaling by HA fragments show promise in wound healing and tissue repair without fibrosis.
Antioxidant effect of diphenyl diselenide against sodium nitroprusside (SNP) induced lipid peroxidation in human platelets and erythrocyte membranes: An in vitro evaluation
2006, Chemico-Biological Interactions
Citation Excerpt :
High concentrations of NO are toxic and interact with superoxide (O2−) to form peroxynitrite (ONOO−) [4]. Peroxynitrite is a strong oxidant and, at physiological pH, is protonated to form peroxynitrous acid (HOONO), a relatively long-lived oxidant agent, which spontaneously decomposes to form another potent oxidant with the reactivity of a hydroxyl-like radical [5,6] which could initiate lipid peroxidation (LPO) [3]. NO can be released from vasodilators like sodium nitroprusside (SNP) which is a potent hypotensive agent used to control hypertension during surgery, in hypertension emergencies, and to improve heart function after myocardial infarction [7].
An in vitro evaluation on the antioxidant effect of diphenyl diselenide (PhSe)₂, an organochalcogenide, against sodium nitroprusside (SNP)-induced lipid peroxidation (LPO) was conduced. Human platelets and erythrocyte membranes (ghosts), as well as rat brain homogenates (S₁), were pre-incubated with different concentrations of SNP (0–10 μM). All SNP concentrations tested significantly increased LPO in human platelets and S₁. Platelets were more sensitive to SNP-induced peroxidative damage when compared to S₁. SNP 10 μM decreased glutathione peroxidase (GPx) activity and did not affect glutathione reductase (GR) and catalase (CAT) activities in human platelets. However, ghosts were insensitive to SNP-induced LPO and no changes on GPx, GR and CAT activities were observed. Diphenyl diselenide significantly protected human platelets against SNP-induced LPO and recovered GPx inactivation. This effect was more evident at (PhSe)₂ concentrations above 2 μM. The presented results indicate that (PhSe)₂ exerts protective effects on SNP-induced oxidative damage in human blood components and in rat brain. These phenomena seem to be related to its thiol peroxidase-like activity and to a possible direct interaction with SNP and derivatives. Based on our results and on literature, diphenyl diselenide can be pointed as a promising antioxidant molecule.
Chain scission of hyaluronan by peroxynitrite
2003, Archives of Biochemistry and Biophysics
The reaction of peroxynitrite with the biopolymer hyaluronan has been studied using stopped-flow techniques combined with detection of molecular weight changes using the combination of gel permeation chromatography and multiangle laser light scattering. From the effect of peroxynitrite on the yield of hyaluronan chain breaks, it was concluded that the chain breaks were caused by hydroxyl radicals which escape a cage containing the $^{} OH NO_{2}^{}$ radical pair. The yield of free hydroxyl radicals was determined as 5±1% (as a proportion of the total peroxynitrite concentration). At high peroxynitrite concentrations, it was observed that the yield of chain breaks leveled out, an effect largely attributable to the scavenging of hydroxyl radicals by nitrite ions present in the peroxynitrite preparation. These experiments also provided some support for a previous proposal that the adduct formed between ONOOH and ONOO⁻ might itself produce hydroxyl radicals. The rate of this reaction would have to be of the order of $0.05 s^{−1}$ to produce hydroxyl radical yields that would account quantitatively for chain break yields at high peroxynitrite concentrations. By carrying out experiments at higher hyaluronan concentrations, it was also concluded that an additional yield of chain breaks was produced by the bimolecular reaction of the polymer with ONOOH at a rate constant of about $10 dm^{3} mol^{−1} s^{−1}$ . At $5.3×10^{−3} mol dm^{−3}$ hyaluronan, this amounted to 3.5% chain breaks (per peroxynitrite concentration). These conclusions support the proposal that the yield of hydroxyl radicals arising from the isomerization of ONOOH to nitrate ions is relatively low.
Oxidations of iron(II)/(III) by hydrogen peroxide: From aquo to enzyme
2002, Coordination Chemistry Reviews
The mechanism of reaction of hexaquo iron(II) with hydrogen peroxide has been unresolved for 70 years. Most scientists, perhaps by default, have accepted the free radical chain mechanism of Barb et al. (Trans. Faraday Soc. 47 (1957) 462). However an earlier proposal involved formation of the ferryl ion, FeO²⁺ (J. Am. Chem. Soc. 54 (1932) 2124). Recent work has favored a mechanism involving FeO²⁺ and FeOFe⁵⁺ species. Similarly there are differences of opinion on the mechanism of reaction of iron(III), both hexaquo and chelated, with hydrogen peroxide. These differences have fostered a recent burst of activity, with claims on one hand that hydroxyl radicals play a key role, and on the other, that there is a non-free radical mechanism. In contrast, the mechanism of reaction of the heme-containing peroxidase and catalase enzymes with hydrogen peroxide, orders of magnitude faster than reactions of iron(II)/(III), now appears to be well established. In this paper I attempt, as objectively as possible, to delineate the proposed mechanisms, discuss their possible physiological relevance, and summarize the current state of knowledge.
Involvement of the perferryl complex of nitric oxide synthase in the catalysis of secondary free radical formation
2001, Biochimica et Biophysica Acta - General Subjects
Neuronal nitric oxide synthase (NOS I) has been shown to generate nitric oxide (NO^⋅) and superoxide (O^⋅−₂) during enzymatic cycling, and the ratio of each free radical is dependent upon the concentration of l-arginine. Using spin trapping and electron paramagnetic resonance spectroscopy, we detected α-hydroxyethyl radical (CH₃ ^⋅CHOH), produced during the NOS I metabolism of ethanol (EtOH). The generation of CH₃ ^⋅CHOH by NOS I was found to be Ca²⁺/calmodulin dependent. Superoxide dismutase prevented CH₃ ^⋅CHOH formation in the absence of l-arginine. However, in the presence of l-arginine, the production of CH₃ ^⋅CHOH was independent of O^⋅−₂ but dependent upon the concentration of l-arginine. Formation of CH₃ ^⋅CHOH was inhibited by substituting d-arginine for l-arginine, or inclusion of the NOS inhibitors N^G-nitro-l-arginine methyl ester, N^G-monomethyl-l-arginine and the heme blocker, sodium cyanide. The addition of potassium hydrogen persulfate to NOS I, generating the perferryl complex (NOS-[Fe⁵⁺=O]³⁺) in the absence of oxygen and Ca²⁺/calmodulin, and EtOH resulted in the formation of CH₃ ^⋅CHOH. NOS I was found to produce the corresponding α-hydroxyalkyl radical from 1-propanol and 2-propanol, but not from 2-methyl-2-propanol. Data demonstrated that the perferryl complex of NOS I in the presence of l-arginine was responsible for catalyses of these secondary reactions.
Nitration and hydroxylation of substituted phenols by peroxynitrite. Kinetic feature and an alternative mechanistic view
1999, Tetrahedron Letters
The reaction of peroxynitrite (ONOO⁻) with a series of para-substituted phenols has been examined in aqueous phosphate buffer and acetonitrile solutions. Major products were the corresponding 2-nitro derivative and the 4-substituted catechol. Kinetic study showed good correlation with Hammett σ_p⁺ parameters and reduction potentials, suggesting the possible one-electron transfer process involving the nitrosoniun ion (NO⁺) as initial electrophile generated from peroxynitrous acid.

View all citing articles on Scopus

View full text

Brief communicationFree radical yields from the homolysis of peroxynitrous acid

Abstract

J. Biol. Chem.

Arch. Biochem. Biophys.

Apparent hydroxyl production by peroxynitrite: Implications for endothelial injury from nitric oxide and superoxide

Reaction of NO with O2·−. Implications for the action of endothelium-derived relaxing factor (EDRF)

Free Rad Res. Comms.

Pernitrous acid. The reaction between hydrogen peroxide and nitrous acid and the properties of an intermediate product

J. Chem. Soc.

Brief communication
Free radical yields from the homolysis of peroxynitrous acid

Reaction of NO with O₂·⁻. Implications for the action of endothelium-derived relaxing factor (EDRF)