Evidence for Adduct Formation between ONOO<sup>-</sup> and CO<sub>2</sub> from High-Pressure Pulse Radiolysis

Goldstein, Sara; Meyerstein, Dan; Eldik, and Rudi van; Czapski, Gidon

doi:10.1021/jp002093c

Cited by 10 publications

(5 citation statements)

References 19 publications

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“…Calculations show that it decomposes to nitrate and carbon dioxide within a few vibrations; thus, its participation in bimolecular reactions is precluded (30). Formation of the adduct (ONOOCO 2 -) was suggested (1), confirmed experimentally (31), and shown to be theoretically feasible (32). It was concluded, however, that the adduct is also too short-lived to directly react with substrates (30,33,34).…”

Section: Discussionmentioning

confidence: 94%

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Two Pathways of Carbon Dioxide Catalyzed Oxidative Coupling of Phenol by Peroxynitrite

Papina

Koppenol

2006

Chem. Res. Toxicol.

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Carbon dioxide catalyzed oxidative coupling of phenol by peroxynitrite occurs by two pathways distinguished by the isomer ratio of 2,2'- to 4,4'-biphenols. As already established, at neutral pH and moderate phenol concentrations, both biphenols are formed in comparable yields by the coupling of two phenoxyl radicals. However, at high pH and phenol concentration, 2,2'-biphenol is the only identified coupled product, and its formation does not involve phenoxyl radicals. Instead, under these conditions, a previously unreported long-lived (t(1/2) approximately 10 s at pH 10 and 1 mM phenol) diamagnetic intermediate with an absorption maximum at 400 nm is observed. This intermediate is formed from phenolate concomitantly with the decay of peroxynitrite and disappears via reaction with phenol [k = (2.4 +/- 0.1) x 10 M(-)(1) s(-)(1) at pH 10.5] to form 2,2'-biphenol. We also find that para-benzoquinone, previously unreported, is formed in up to 5% yield relative to the initial peroxynitrite concentration. The appearance of an absorption band above 500 nm, which might be due to quinhydrone, indicates that hydroquinone is a likely para-benzoquinone precursor. The dependence of para-benzoquinone yields on pH and phenol concentration suggests that its formation is related to the nonradical pathway of 2,2'-biphenol formation. This novel nonradical pathway of 2,2'-biphenol formation might be relevant to the mechanisms of reaction of phenolic antioxidants with peroxynitrite. The existence of two distinct pathways of biphenol formation implies that, apart from a CO(3)(*)(-)/NO(2)(*) radical pair, another reactive intermediate is formed during the carbon dioxide catalyzed decay of peroxynitrite.

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Section: Discussionmentioning

confidence: 94%

“…Lifetime of the Peroxynitrite-Carbon Dioxide Adduct and Secondary Oxidants Derived from It. The following reaction sequence (reactions 1−4) has been suggested to take place during the carbon dioxide catalyzed isomerization of peroxynitrite ( , ) …”

Section: Discussionmentioning

confidence: 99%

Two Pathways of Carbon Dioxide Catalyzed Oxidative Coupling of Phenol by Peroxynitrite

Papina

Koppenol

2006

Chem. Res. Toxicol.

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“…19 Adduct formation is supported by a considerable negative activation volume of −22 cm 3 /mol. 36 As the rate of disappearance of ONOO − parallels formation of products, it was concluded that ONOOCO 2 − does not accumulate. Given its presumed short lifetime, which implies that ONOOCO 2 − could not be observed, equilibrium constants for reaction 1 were estimated on the basis of equilibria between analogous molecules.…”

Section: Adductmentioning

confidence: 99%

“…Based on the rate of decrease of the absorption at 302 nm in the presence of CO 2 , formation of the adduct formation, reaction : was reported to take place with rate constants k 2 of (2.9 ± 0.3) × 10 4 M –1 s –1 and (2.3 ± 0.2) × 10 4 M –1 s –1 at 25 °C and (5.8 ± 0.2) × 10 4 M –1 s –1 at 37 °C, which makes CO 2 a major, if not the largest, sink for ONOO – in a cell. ,− The activation parameters of reaction were reported as Δ ⧧ H ° = +45 kJ/mol and Δ ⧧ S ° = −27 J/(K mol) . Adduct formation is supported by a considerable negative activation volume of −22 cm 3 /mol . As the rate of disappearance of ONOO – parallels formation of products, it was concluded that ONOOCO 2 – does not accumulate.…”

Section: Adductmentioning

confidence: 99%

Thinking Outside the Cage: A New Hypothesis That Accounts for Variable Yields of Radicals from the Reaction of CO₂ with ONOO^–

Koppenol

Serrano-Luginbuehl

Nauser

et al. 2020

Chem. Res. Toxicol.

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In biology, the reaction of ONOO − with CO 2 is the main sink for ONOO − . This reaction yields CO 3•− , NO 2 • , NO 3 − , and CO 2 . There is a long-standing debate with respect to the yield of the radicals relative to ONOO − . The reaction of ONOO − with CO 2 results at first in ONOOCO 2− . According to one hypothesis, ONOOCO 2 − is extremely short-lived and devolves into a solvent cage that contains CO 3•− and NO 2 • . Of these solvent cages, approximately two/thirds result in NO 3 − and CO 2 , and approximately one/third release CO 3and NO 2• that oxidize the substrate. According to our hypothesis, ONOOCO 2 − is formed much faster, is relatively long-lived, and may also be an oxidant; the limited yield is the result of ONOOCO 2− being scavenged by a second CO 2 under conditions of a high CO 2 concentration. We disagree with the first hypothesis for three reasons: First, it is based on an estimated K for the reaction of ONOO − with CO 2 to form ONOOCO 2 − of ∼1 M −1 , while experiments yield a value of 4.5 × 10 3 M −1 . Second, we argue that the solvent cage as proposed is physically not realistic. Given the less than diffusion-controlled rate constant of CO 3•− with NO 2• , all radicals would escape from the solvent cage. Third, the reported ∼33% radical is not supported by an experiment where mass balance was established. We propose here a hybrid mechanism. After formation of ONOOCO 2 − , it undergoes homolysis to yield CO 3 •− with NO 2• , or, depending on [CO 2 ], it is scavenged by a second CO 2 ; CO 3 •− oxidizes ONOO − , if present. These reactions allow us to successfully simulate the reaction of ONOO − with CO 2 over a wide range of ONOO − /CO 2 ratios. At lower ratios, fewer radicals are formed, while at higher ratios, radical yields between 30% and 40% are predicted. The differences in radical yields reported may thus be traced to the experimental ONOO − /CO 2 ratios. Given a physiological [CO 2 ] of 1.3 mM, the yield of CO 3•− and NO 2• is 19%, and lower if ONOOCO 2 − has a significant reactivity of its own.

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“…The reaction between peroxynitrite anion and CO 2 presents a rate constant of 3.0 × 10 4 M −1 s −1 , leading to the formation of a postulated highly reactive short-lived secondary oxidant, the nitrosoperoxycarbonate anion (1-carboxylato-2-nitrosodioxidane anion, ONO 2 CO 2 − ) ( Figure 1). Nitrosoperoxycarbonate anion can be considered as the biologically active form of peroxynitrite that does not terminate the action of peroxynitrite but rather redirects its reactivity Goldstein et al 2000b •− (trioxidocarbonate(1 − )) has been detected by electron paramagnetic resonance spectroscopy at physiological pH (Bonini et al 1999) and is a strong one-electron oxidant that rapidly abstracts one electron, preferably from tyrosine, to yield tyrosyl radical, which recombines with NO 2…”

Section: : Chemistry and Biologymentioning

confidence: 99%

Peroxynitrite and nitrosoperoxycarbonate, a tightly connected oxidizing-nitrating couple in the reactive nitrogen-oxygen species family: new perspectives for protection from radical-promoted injury by flavonoids

Pavlović

Santaniello

2007

Journal of Pharmacy and Pharmacology

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Peroxynitrite is the product of the reaction of nitric oxide with superoxide radical and is implicated in the pathogenesis of a wide variety of human diseases, being responsible for in-vivo oxidation/nitration events. Nitrosoperoxycarbonate anion, formed by the interaction of peroxynitrite with CO(2)/bicarbonate at physiological concentrations, provides a new interpretation of oxidative/nitrative processes formerly attributed to peroxynitrite. The aim of this review is to summarize the chemistry and biology of peroxynitrite and radical species related to nitrosoperoxycarbonate anion, as well as the information available regarding the molecular mechanisms that determine and regulate radical-promoted injury by the two tightly connected species at physiological concentrations. Interception of carbonate and nitro radicals produced by interaction of peroxynitrite with CO(2)/bicarbonate, as in-vivo prevention of pathological events, creates new perspectives for the evaluation of safe scavengers of oxidative/nitrative stress at the physiological level. In this respect, natural products such as flavonoids hold a preeminent position among the vast array of compounds endowed with such properties.

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Evidence for Adduct Formation between ONOO^- and CO₂ from High-Pressure Pulse Radiolysis

Abstract: The activation volume for the reaction of CO2 with ONOO- has been determined to be −22 cm3 mol-1 using the high-pressure pulse radiolysis technique. The significant negative volume of activation provides conclusive evidence for a short-lived cyclo-adduct formation between ONOO- and CO2.

Cited by 10 publications

References 19 publications

Two Pathways of Carbon Dioxide Catalyzed Oxidative Coupling of Phenol by Peroxynitrite

Two Pathways of Carbon Dioxide Catalyzed Oxidative Coupling of Phenol by Peroxynitrite

Thinking Outside the Cage: A New Hypothesis That Accounts for Variable Yields of Radicals from the Reaction of CO₂ with ONOO^–

Peroxynitrite and nitrosoperoxycarbonate, a tightly connected oxidizing-nitrating couple in the reactive nitrogen-oxygen species family: new perspectives for protection from radical-promoted injury by flavonoids

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Evidence for Adduct Formation between ONOO- and CO2 from High-Pressure Pulse Radiolysis

Abstract: The activation volume for the reaction of CO2 with ONOO- has been determined to be −22 cm3 mol-1 using the high-pressure pulse radiolysis technique. The significant negative volume of activation provides conclusive evidence for a short-lived cyclo-adduct formation between ONOO- and CO2.

Cited by 10 publications

References 19 publications

Two Pathways of Carbon Dioxide Catalyzed Oxidative Coupling of Phenol by Peroxynitrite

Two Pathways of Carbon Dioxide Catalyzed Oxidative Coupling of Phenol by Peroxynitrite

Thinking Outside the Cage: A New Hypothesis That Accounts for Variable Yields of Radicals from the Reaction of CO2 with ONOO–

Peroxynitrite and nitrosoperoxycarbonate, a tightly connected oxidizing-nitrating couple in the reactive nitrogen-oxygen species family: new perspectives for protection from radical-promoted injury by flavonoids

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Evidence for Adduct Formation between ONOO^- and CO₂ from High-Pressure Pulse Radiolysis

Thinking Outside the Cage: A New Hypothesis That Accounts for Variable Yields of Radicals from the Reaction of CO₂ with ONOO^–