Reversibility and Diffusion in Mandelythiamin Decarboxylation. Searching Dynamical Effects in Decarboxylation Reactions
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Title
Reversibility and Diffusion in Mandelythiamin Decarboxylation. Searching Dynamical Effects in Decarboxylation ReactionsDate
2012-06xmlui.dri2xhtml.METS-1.0.item-edition
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American Chemical SocietyBibliographic citation
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.Type
info:eu-repo/semantics/articlePublisher version
http://pubs.acs.org/doi/abs/10.1021/ja3026455Version
info:eu-repo/semantics/publishedVersionAbstract
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. [-]
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Journal of the American Chemical Society, 2012, vol. 134, no 25Rights
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