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Concerted HO2 elimination from alpha-aminoalkylperoxyl free radicals: experimental and theoretical evidence from the gas-phase NH2 CHCO2 - + O2 reaction
Faculty of Science - Papers (Archive)
  • Gabriel da Silva, University Of Melbourne
  • Benjamin B Kirk, University of Wollongong
  • Celli Lloyd, University of Wollongong
  • Adam J Trevitt, University of Wollongong
  • Stephen J Blanksby, University of Wollongong
RIS ID
55675
Publication Date
1-1-2012
Publication Details

da Silva, G., Kirk, B. B., Lloyd, C., Trevitt, A. J. , Blanksby, S. J. (2012). Concerted HO2 elimination from alpha-aminoalkylperoxyl free radicals: experimental and theoretical evidence from the gas-phase NH 2 CHCO 2 - + O 2 reaction. Journal of Physical Chemistry Letters, 3 (7), 805-811.

Abstract

We have investigated the gas-phase reaction of the α- aminoacetate (glycyl) radical anion (NH2 •CHCO2−) with O2 using ion trap mass spectrometry, quantum chemistry, and statistical reaction rate theory. This radical is found to undergo a remarkably rapid reaction with O2 to form the hydroperoxyl radical (HO2 •) and an even-electron imine (NHCHCO2−), with experiments and master equation simulations revealing that reaction proceeds at the ion−molecule collision rate. This reaction is facilitated by a low-energy concerted HO2 • elimination mechanism in the NH2CH(OO•)CO2− peroxyl radical. These findings can explain the widely observed free-radical-mediated oxidation of simple amino acids to amides plus α-keto acids (their imine hydrolysis products). This work also suggests that imines will be the main intermediates in the atmospheric oxidation of primary and secondary amines, including amine carbon capture solvents such as 2-aminoethanol (commonly known as monoethanolamine, or MEA), in a process that avoids the ozone-promoting conversion of •NO to •NO2 commonly encountered in peroxyl radical chemistry.

Grant Number
ARC/DP0986738
Citation Information
Gabriel da Silva, Benjamin B Kirk, Celli Lloyd, Adam J Trevitt, et al.. "Concerted HO2 elimination from alpha-aminoalkylperoxyl free radicals: experimental and theoretical evidence from the gas-phase NH2 CHCO2 - + O2 reaction" (2012) p. 805 - 811
Available at: http://works.bepress.com/adam_trevitt/25/