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Calculated bond dissociation energies and enthalpy of formation of α-amino acid radicals

Uddin, K.M., Henry, D.J.ORCID: 0000-0002-9629-4423, Poirier, R.A. and Warburton, P.L. (2016) Calculated bond dissociation energies and enthalpy of formation of α-amino acid radicals. Theoretical Chemistry Accounts, 135 . Article number: 224.

Link to Published Version: http://dx.doi.org/10.1007/s00214-016-1975-9
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Abstract

Bond dissociation energies (BDEs), radical stabilization energies (RSEs) and the enthalpies of formation (Δf H°(AA∙)) for the Cα-centered radical of 20 common α-amino acids were calculated at the G3MP2 level of theory. In addition, BDEs and Δf H°(AA∙) for the Cα-centered radicals were calculated via atomization, homolytic, isogyric and isodesmic reactions using 31 reference compounds. RSEs for the α-amino acid radicals reveal a strong captodative effect due to the resonance stabilization. Intramolecular H-bonding and steric repulsion between the side chains and –NH2 and ‒COOH also have an effect on the stability of α-carbon-centered radicals. For the key small reference compounds investigated, the BDEs (Δf H°(AA∙)) computed with isodesmic reactions were found to be quite consistent with each other in terms of mean absolute deviations (MADs) and root-mean-square deviations between 2.0 (2.6) and 3.2 (4.4) kJ mol−1 from experimental data.

Item Type: Journal Article
Murdoch Affiliation: School of Engineering and Information Technology
Publisher: Springer New York
URI: http://researchrepository.murdoch.edu.au/id/eprint/32970
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