Bicarbonate and Alkyl Carbonate Radicals: Structural Integrity and Reactions with Lipid Components

详细信息    查看全文

• 作者：Michael Bühl ; Peter DaBell ; David W. Manley ; Rory P. McCaughan ; John C. Walton
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：December 30, 2015
• 年：2015
• 卷：137
• 期：51
• 页码：16153-16162
• 全文大小：550K
• ISSN：1520-5126

文摘

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 nonpolar solvents. The acidity of bicarbonate radicals was also examined by DFT methods. A noteworthy linear relationship was discovered between the known pK_a’s 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 eight water molecules, predicted that only five water molecules were needed to bring about its complete ionization. On comparing with the correlation, this indicated a pK_a of about ?2 units. This marks the bicarbonate radical as the strongest known carboxylic acid.