The reactions of ozone with cinnamic acids: formation and decay of 2-hydroperoxy-2-hydroxyacetic acid

Leitzke, Achim; Reisz, Erika; Flyunt, Roman; Sonntag, Clemens von

doi:10.1039/b009327k

Cited by 69 publications

(77 citation statements)

References 19 publications

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“…This first step is reversible, similar to the hydration of pyruvate or the formation of the hemiacetal 13 or the formation of 2-hydroperoxy-2-hydroxyacetate from glyoxylate and hydrogen peroxide. 11 …”

Section: Discussionmentioning

confidence: 99%

“…A comparable mechanism occurs when 2-hydroperoxy-2-hydroxyacetate yields formate, carbon dioxide, and water. 11 The decarboxylation step appears to be similar to the enzymatic decarboxylation of pyruvate through pyruvate dehydrogenase, to yield acetyl-CoA, or through pyruvate decarboxylase, yielding acetaldehyde. 32,33 For the enzymatic pathway, after a nucleophilic attack on the C2 position of pyruvate through the 4-amino-C2-carbanion thiamin pyrophosphate (TTP), 32 intermediate 4-imino-2-(2-hydroxypropionyl)-TTP is formed.…”

Section: Discussionmentioning

confidence: 99%

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Low-Temperature NMR Characterization of Reaction of Sodium Pyruvate with Hydrogen Peroxide

2015

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It was proposed that the reaction of sodium pyruvate and H2O2 generates the intermediate 2-hydroperoxy-2-hydroxypropanoate, which converts into acetate, CO2, and H2O (Aleksankin et al. Kernenergie 1962, 5, 362–365). These conclusions were based on the products generated in 18O-enriched water and H2O2 reacting with pyruvic acid at room temperature; however, the lifetime of 2-hydroperoxy-2-hydroxypropanoate at room temperature is too short for direct spectroscopic observation. Therefore, we applied the combination of low-temperature and 13C NMR techniques to verify, for the first time, the formation of 2-deuteroperoxy-2-deuteroxypropanoate in mixtures of D2O and methanol-d4 and to monitor directly each species involved in the reaction between D2O2 and 13C-enriched pyruvate. Our NMR results confirm the formation of 2-deuteroperoxy-2-deuteroxypropanoate, where the respective chemical shifts are supported by density functional theory (DFT) calculations. At near-neutral apparent pD (pD*) and −35 °C, the formation of 2-deuteroperoxy-2-deuteroxypropanoate occurred with k = 2.43 × 10−3 dm3·mol−1·s−1. The subsequent decomposition of 2-deuteroperoxy-2-deuteroxypropanoate into acetate, CO2, and D2O occurred with k = 2.58 × 10−4 s−1 at −35 °C. In order to provide a full kinetic analysis, we also monitored the equilibrium of pyruvate and methanol with the hemiacetal (2-deuteroxy-2-methoxypropanoate). The kinetics for the reaction of sodium pyruvate and D2O2 were fitted by taking into account all these equilibria and species.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Low-Temperature NMR Characterization of Reaction of Sodium Pyruvate with Hydrogen Peroxide

2015

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“…The liquid-phase reaction between the fumarate ions and ozone has been previously studied 70 and the direct products of the ozonolysis have been shown to be the glyoxylate anion and the 2-hydroperoxy-2-hydroxyacetate anion:…”

Section: Products and Mechanism Of Fumarate Oxidation By Ozonementioning

confidence: 99%

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

et al. 2008

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The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coefficients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic (alkane) solvent. The droplet was exposed to gas-phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha-pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic-like substances, HULIS; alpha-pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid-phase diffusion and reaction are the rate determining steps. Uptake coefficients, gamma, were found to be (1.1 +/- 0.7) x 10(-5), (1.5 +/- 0.7) x 10(-5) and (3.0-7.5) x 10(-3) for the reactions of ozone with the fumarate, benzoate and alpha-pinene containing droplets, respectively. Liquid-phase bimolecular rate coefficients for reactions of dissolved ozone molecules with fumarate, benzoate and alpha-pinene were also obtained: kfumarate = (2.7 +/- 2) x 10(5), kbenzoate = (3.5 +/- 3) x 10(5) and kalpha-pinene = (1-3) x 10(7) dm3 mol(-1) s(-1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS-proxies and for the oxidation of alpha-pinene in pentadecane. The study of the alpha-pinene/ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha-pinene suggest the formation of new species containing carbonyl groups.

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“…As appreciable ion signals are not usually generated for tri-or tetra-molecular clusters, the ion responsible for the signal at the m/z value of 91 is therefore not likely to be a non-covalent adduct. Alternatively, as glyoxylic acid can readily undergo hydration in aqueous solution (Leitzke et al 2001) to generate a di-alcohol of molecular mass 92 Da (Figure 4 B), such hydration would also be expected in the 12% aqueous ethanol medium. The ion at m/z 183 ( Figure 3) would then be explained by the non-covalent adduct formed between two of these hydrated glyoxylic acid species.…”

Section: Glyoxylic Acid Detection In Aqueous Ethanol Tartaric Acid Somentioning

confidence: 99%

“…For instance, Baraud (1954) suggested the oxidation of glyoxylic acid in the presence of molecular oxygen and iron(III). Furthermore, it is also known that hydrogen peroxide readily oxidises glyoxylic acid to formic acid (Leitzke et al 2001). To detect glyoxylic acid formed in the presence of hydrogen peroxide, the rate of glyoxylic acid production is required to be in excess of the rate of oxidative removal of glyoxylic acid.…”

Section: Tartaric Acid Solutions In Sunlight: Production Of Glyoxylicmentioning

confidence: 99%

Influence of light exposure, ethanol and copper(II) on the formation of a precursor for xanthylium cations from tartaric acid

Clark

Scollary

2003

Aust J Grape Wine Res

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The production of xanthylium cation pigments was greatly increased when an aged, tartaric acid buffered, 12% (v/v) aqueous ethanol solution was used in a model white wine system. This suggested the formation of a precursor to the pigments during the ageing of the tartaric acid solution. On examining factors responsible for the generation of tartaric acid oxidation products in wine-like solutions it was observed that on exposure of samples to sunlight, glyoxylic acid, a known precursor to xanthylium cations, was produced. The production of glyoxylic acid was achieved in both the absence and presence of ethanol and copper(II). Hydrogen peroxide was also detected in these solutions. The results were consistent with the presence of glyoxylic acid in the aged tartaric acid buffered, 12% (v/v) aqueous ethanol solution that had frequent aeration and periodic exposure to sunlight throughout its storage. Studies on the role of hydrogen peroxide in the production of glyoxylic acid were also investigated. On the addition of hydrogen peroxide to tartaric acid solutions, with heating at 45°C in darkness, glyoxylic acid was only determined in solutions without ethanol. Abbreviations HPLC/DAD high performance liquid chromatography/photodiode array detector;LC/MS liquid chromatography/mass spectrometry; MS mass spectrometry; UV ultra violet; VIS visible Formation of a xanthylium ion precursor 65Formation of a xanthylium ion precursor

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The reactions of ozone with cinnamic acids: formation and decay of 2-hydroperoxy-2-hydroxyacetic acid

Cited by 69 publications

References 19 publications

Low-Temperature NMR Characterization of Reaction of Sodium Pyruvate with Hydrogen Peroxide

Low-Temperature NMR Characterization of Reaction of Sodium Pyruvate with Hydrogen Peroxide

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

Influence of light exposure, ethanol and copper(II) on the formation of a precursor for xanthylium cations from tartaric acid

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