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Bicarbonate and alkyl carbonate radicals: structural integrity and reactions with lipid components

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Michael Buehl, Peter DaBell, David Manley, Rory McCaughan, John Christopher Walton

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Abstract

The elusive neutral bicarbonate radical and the carbonate radical anion form an acid/conjugate base pair. We now report experimental studies for a model of bicarbonate radical, namely methyl carbonate (methoxycarbonyloxyl) radical, complemented by DFT computations at the CAM-B3LYP level applied to the bicarbonate radical itself. Methyl carbonate radicals were generated by UV irradiation of oxime carbonate precursors. Kinetic EPR was employed to measure rate constants and Arrhenius parameters for their dissociation to CO2 and methoxyl radicals. With oleate and cholesterol lipid components methyl carbonate radicals preferentially added to their double bonds; with linoleate and linolenate substrates abstraction of the bis-allylic H-atoms competed with addition. This contrasts with the behavior of ROS such as hydroxyl radicals that selectively abstract allylic and/or bis-allylic H-atoms. The thermodynamic and activation parameters for bicarbonate radical dissociation, obtained from DFT computations, predicted it would indeed have substantial lifetime in gas and non-polar solvents. The acidity of bicarbonate radicals was also examined by DFT methods. A noteworthy linear relationship was discovered between the known pKas of strong acids and the computed numbers of microsolvating water molecules needed to bring about their ionization. DFT computations with bicarbonate radicals, solvated with up to 8 water molecules, predicted that only 5 water molecules were needed to bring about its complete ionization. On comparing with the correlation, this indicated a pKa of about -2 units. This marks the bicarbonate radical as the strongest known carboxylic acid.
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Original languageEnglish
Pages (from-to)16153–16162
JournalJournal of the American Chemical Society
Volume137
Issue number51
Early online date1 Dec 2015
DOIs
StatePublished - 30 Dec 2015

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