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Journal of the Mexican Chemical Society
versión impresa ISSN 1870-249X
J. Mex. Chem. Soc vol.55 no.1 Ciudad de México ene./mar. 2011
Article
Computational Modeling of the Dehydrogenation of Methylamine
Kirsten Ivey, Belynda Sanders, Chris Estela, and Andrew L. Cooksy*
Department of Chemistry and Biochemistry; San Diego State University; San Diego, CA 921821030. *corresponding author; Department of Chemistry and Biochemistry; San Diego State University; San Diego, CA 921821030; email: acooksy@sciences.sdsu.edu; tel: +16195945571.
Received June 14, 2010.
Accepted October 12, 2010.
Abstract
The reaction sequence early in the metabolism of methylamine by the dehydrogenase cofactor tryptophan tryptophyl quinone (TTQ) is investigated by a large series of density functional theory calculations. Free energy corrections are calculated at the reactant and intermediate geometries, and solvation effects are estimated by use of the semiempirical COSMORS solvent model. Two competing reaction paths are found to have very similar reaction free energies, and the free energies of activation are found to depend heavily on adequate modeling of the solvent.
Keywords: Tryptophan tryptophyl quinine; TTQ; density functional theory; COSMORS; solvent model.
Resumen
Se investigaron las reacciones tempranas en el metabolismo de la metilamina por el cofactor quinontriptofiltriptofano (TTQ), mediante una larga serie de cálculos de la teoría de funcionales de la densidad. Las correcciones a las energías libres se calcularon en las geometrías del reactivo y de los intermediarios, así como los efectos del disolvente se estimaron por el modelo semiempírico COSMORS. Se encontró que dos caminos de reacción compiten, teniendo energías libres de reacción muy similares, y las energías libres de activación dependen mucho de un modelado adecuado del disolvente.
Palabras clave: quinontriptofiltriptofano; TTQ; teoría de funcionales de la densidad; COSMORS; modelo del disolvente.
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Acknowledgements
This work was originally supported by the Blasker Fund of the San Diego Foundation. Computer resources have been provided under US National Science Foundation Grant CHE0216563. B. Sanders, C. Estela, and K. Ivey were supported by NIW fellowships from the US National Institutes of Health.
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