Reversibility and Diffusion in Mandelythiamin Decarboxylation. Searching Dynamical Effects in Decarboxylation Reactions
comunitat-uji-handle:10234/9
comunitat-uji-handle2:10234/7013
comunitat-uji-handle3:10234/8638
comunitat-uji-handle4:
INVESTIGACIONMetadatos
Título
Reversibility and Diffusion in Mandelythiamin Decarboxylation. Searching Dynamical Effects in Decarboxylation ReactionsFecha de publicación
2012-06xmlui.dri2xhtml.METS-1.0.item-edition
postprintEditor
American Chemical SocietyCita bibliográfica
ROCA, Maite; PASCUAL-AHUIR, Juan-Luis; TUÑÓN, Iñaki. Reversibility and diffusion in mandelythiamin decarboxylation. Searching dynamical effects in decarboxylation reactions. Journal of the American Chemical Society, 2012, vol. 134, no 25, p. 10509-10514.Tipo de documento
info:eu-repo/semantics/articleVersión de la editorial
http://pubs.acs.org/doi/abs/10.1021/ja3026455Versión
info:eu-repo/semantics/publishedVersionPalabras clave / Materias
Resumen
Decarboxylation of mandelylthiamin in aqueous solution is analyzed by means of quantum mechanics/molecular mechanics simulations including solvent effects. The free energy profile for the decarboxylation reaction was ... [+]
Decarboxylation of mandelylthiamin in aqueous solution is analyzed by means of quantum mechanics/molecular mechanics simulations including solvent effects. The free energy profile for the decarboxylation reaction was traced, assuming equilibrium solvation, while reaction trajectories allowed us to incorporate nonequilibrium effects due to the solvent degrees of freedom as well as to evaluate the rate of the diffusion process in competition with the backward reaction. Our calculations that reproduce the experimental rate constant show that decarboxylation takes place with a non-negligible free energy barrier for the backward reaction and that diffusion of carbon dioxide is very fast compared to the chemical step. According to these findings catalysts would not act by preventing the backward reaction. [-]
Publicado en
Journal of the American Chemical Society, 2012, vol. 134, no 25Derechos de acceso
info:eu-repo/semantics/openAccess
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