A comparative DFT Study of the Schiff base formation from Acetaldehyde and Butylamine, Glycine and Phosphatidylethanolamine

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dc.contributor.author Solís-Calero, Christian
dc.contributor.author Ortega-Castro, Joaquín
dc.contributor.author Hernández-Laguna, Alfonso
dc.contributor.author Muñoz Izquierdo, Francisco
dc.date.accessioned 2018-10-22T11:18:35Z
dc.identifier.uri http://hdl.handle.net/11201/148204
dc.description.abstract [eng] Mechanisms for the formation of the Schiff base from acetaldehyde and butylamine, glycine and phosphatidylethanolamine based on Dmol3/DFT calculations were realized. For the case of phosphatidylethanolamine, calculations were done under periodic boundary conditions, in an amine-phospholipid monolayer model with two molecules of phosphatidylethanolamine by cell. All models contained explicit aqueous solvent. In the three cases, a neutral amino group is used to model the nucleophilic attack on the carbonyl group of acetaldehyde, and water molecules form hydrogen bond networks. These networks were involved in the reactions by performing as proton-transfer carriers, important in some steps of reactions, and stabilizing reaction intermediates. In all the studied reactions, they take place in two steps, namely: (1) formation of a carbinolamine and (2) its dehydration to the Schiff base, being the dehydration the rate-determining step of the process, consistent with available experimental evidence for similar reactions. The main difference between the studied reactions is found in the value for relative free energy for the intermediates and transition states in the second step; these values are lower in the cases of glycine and phosphatidylethanolamine in comparison with butylamine, due the influence of their molecular environments. Based on the results, the aminophospholipid surface environment and carboxylic group of glycine may boost Schiff base formation via a neighboring catalyst effect.
dc.format application/pdf
dc.relation.isformatof Versió postprint del document publicat a: https://doi.org/10.1007/s00214-012-1263-2
dc.relation.ispartof Theoretical Chemistry Accounts, 2012, vol. 131, p. 1263-1275
dc.subject.classification 54 - Química
dc.subject.other 54 - Chemistry. Crystallography. Mineralogy
dc.title A comparative DFT Study of the Schiff base formation from Acetaldehyde and Butylamine, Glycine and Phosphatidylethanolamine
dc.type info:eu-repo/semantics/article
dc.type info:eu-repo/semantics/acceptedVersion
dc.date.updated 2018-10-22T11:18:36Z
dc.date.embargoEndDate info:eu-repo/date/embargoEnd/2075-01-01
dc.embargo 2075-01-01
dc.subject.keywords Cálculos teóricos
dc.subject.keywords Density functional calculations
dc.subject.keywords Amino-Phospholipid
dc.rights.accessRights info:eu-repo/semantics/embargoedAccess
dc.identifier.doi https://doi.org/10.1007/s00214-012-1263-2

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