The Importance of Mesomerism in the Termination ofα-Carboxymethyl Radicals from Aqueous Malonic and Acetic Acids

Wang, Wenfeng; Schuchmann, Man Nien; Schuchmann, Heinz‐Peter; Sonntag, Clemens von

doi:10.1002/1521-3765(20010216)7:4<791::aid-chem791>3.0.co;2-2

Cited by 18 publications

(11 citation statements)

References 20 publications

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“…The Å CH 2 COO À radical is comparatively stable (Wang et al, 2001). The organic P compounds are broadly grouped into three sets: the P-acetyl compounds, the P-CH 2 compounds, and phosphonoformate (Fig.…”

Section: Proposed Organic Phosphorus Reaction Pathwaysupporting

confidence: 73%

A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

Pasek¹,

Dworkin²,

Лауретта³

2007

Geochimica et Cosmochimica Acta

120

123

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Section: Proposed Organic Phosphorus Reaction Pathwaysupporting

confidence: 73%

A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

Pasek¹,

Dworkin²,

Лауретта³

2007

Geochimica et Cosmochimica Acta

120

123

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“…Abstraction of a hydrogen atom from glycolate 5 by a sulfite radical generates the hydroxy-carboxymethyl radical 24 whilst redox compensatory reduction of 5 generates the carboxymethyl radical 25 . Dimerization of 24 produces the tartrates 9 whereas dimerization of 25 produces succinate 32 as well as acetate 6 and glycolate 5 37 . Recombination of radicals 24 and 25 provides one route to malate 31 , a second would be from reduction of 9 .…”

Section: Resultsmentioning

confidence: 99%

“…Dimerization of 24 produces the tartrates 9 whereas dimerization of 25 produces succinate 32 as well as acetate 6 and glycolate 5 32 . Recombination of radicals 24 and 25 provides one route to malate 31, a second would be from reduction of 9.…”

Section: S19 -S23)mentioning

confidence: 99%

Prebiotic photoredox synthesis from carbon dioxide and sulfite

Liu

Kufner

et al. 2021

Nat. Chem.

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Carbon dioxide (CO2) is the major carbonaceous component of many planetary atmospheres including the Earth throughout its history, and prebiological chemistry that reduces this C1 feedstock to organics has accordingly been sought. Carbon fixation chemistry utilizing hydrogen as stoichiometric reductant tends to require high pressures and temperatures, and yields of products of potential use to nascent biology are low 1 . Here we demonstrate efficient ultraviolet (UV) photoredox chemistry between CO2 and sulfite (SO3 2-) that generates organics and sulfate (SO4 2-). The chemistry is initiated by electron photodetachment from SO3 2giving sulfite radicals and hydrated electrons, which reduce CO2 to its radical anion. By subjecting individual products and putative intermediates to the reaction conditions and analyzing the resultant mixtures, a network of ensuing reactions that can rationalize the products was revealed. In this way it was further discovered that citrate, malate, succinate, and tartrate can be generated by irradiation of glycolate in the presence of SO3 2-. The simplicity of this carboxysulfitic chemistry and the widespread occurrence and abundance of its feedstocks suggest that it could have readily taken place on the early Earth as well as on the surfaces of many rocky planets. The environmental availability of the carboxylate products on Earth could have driven the development of central carbon metabolism before the advent of biological CO2 fixation.

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“…Studies have shown that acetic acid, one of the products for the reaction between Hg II and malonic acid (Table 2), could be produced from the recombination of acetic acid radical followed by hydrolysis at acidic conditions (29).…”

Section: Reaction Mechanismmentioning

confidence: 99%

Reduction of Oxidized Mercury Species by Dicarboxylic Acids (C₂−C₄): Kinetic and Product Studies

Ariya

2008

Environ. Sci. Technol.

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Mercury is an environmental contaminant of global concern. The reduction of oxidized mercury species (Hg(II)) by organic acids to elemental mercury (Hg0) is significant for understanding the cycling of mercury between the atmosphere and aqueous systems. This study focused on the reduction of Hg(II) by small, semivolatile dicarboxylic acids (C2-C4). The reaction kinetics was studied using cold vapor atomic fluorescence spectroscopy (CVAFS), and the products of the reaction were analyzed using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and nuclear magnetic resonance (NMR) spectrometry. The effects of light, dissolved oxygen and chloride ion on reaction rates were also investigated. The highest reaction rates were observed in systems free of both oxygen and chloride ion with the second-order apparent rate constants of 1.2 x 10(4), 4.9 x 10(3), and 2.8 x 10(3) (L x mol(-1) x s(-1)) for oxalic, malonic, and succinic acids at pH 3.0 and T = 296 +/- 2 K, respectively. The photoreduction of Hg(II) was mediated by the complexes formed between Hg" and dicarboxylic acids, and the identified products were Hg0, hydroxycarboxylic acids and monocarboxylic acids. Our results also indicated that the presence of chloride ion significantly reduced the reduction rate by competing with the complexation of Hg" with dicarboxylic acids, while dissolved oxygen retarded the production of Hg0 by involving in the reoxidation of reduced Hg species to Hg(II). Based on our experimental results, a tentative mechanism is proposed and the potential environmental implications are discussed.

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The Importance of Mesomerism in the Termination ofα-Carboxymethyl Radicals from Aqueous Malonic and Acetic Acids

Cited by 18 publications

References 20 publications

A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

Prebiotic photoredox synthesis from carbon dioxide and sulfite

Reduction of Oxidized Mercury Species by Dicarboxylic Acids (C₂−C₄): Kinetic and Product Studies

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The Importance of Mesomerism in the Termination ofα-Carboxymethyl Radicals from Aqueous Malonic and Acetic Acids

Cited by 18 publications

References 20 publications

A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

A radical pathway for organic phosphorylation during schreibersite corrosion with implications for the origin of life

Prebiotic photoredox synthesis from carbon dioxide and sulfite

Reduction of Oxidized Mercury Species by Dicarboxylic Acids (C2−C4): Kinetic and Product Studies

Contact Info

Product

Resources

About

Reduction of Oxidized Mercury Species by Dicarboxylic Acids (C₂−C₄): Kinetic and Product Studies