Theoretical Calculations of the Multistep Reaction Mechanism Involved in Asparagine Pyrolysis Supported by Degree of Rate Control and Thermodynamic Control Analyses

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dc.contributor.authorCervantes, Cristian
dc.contributor.authorMora, Jose R.
dc.contributor.authorMarquez, Edgar
dc.contributor.authorTorres, Javier
dc.contributor.authorRincon, Luis
dc.contributor.authorMendez, Miguel A.
dc.contributor.authorAlcazar, Jackson J.
dc.date.accessioned2025-01-23T21:08:59Z
dc.date.available2025-01-23T21:08:59Z
dc.date.issued2019
dc.description.abstractA computational study on the mechanisms of reaction for the pyrolysis of asparagine is presented. A density functional theory (DFT) study at the <mml:semantics>omega</mml:semantics> B97XD/6-311G(d,p) level was performed to analyze the differences in two reaction mechanisms: (i) the formation of five-membered cyclic products: maleimide and succinimide, and (ii) the more classical, six-membered cyclic products (diketopiperazine species) which are common in the pyrolysis of many other amino acids. The effect of temperature was included in the calculations at 300 degrees C or 625 degrees C, as required. Moreover, a detailed study based on the degree of rate control and thermodynamic control of the proposed mechanism for the formation of maleimide and succinimide is also presented. Results show that, for asparagine, the five-membered ring formation is the preferred process instead of the six-membered cycle (32 kJ/mol of Gibbs free energy difference between them at the first cyclization step); therefore, the polymerization is favored. On the other hand, the rupture of the polymer represents the highest energetic barrier (Delta G(double dagger) = 281 kJ/mol) and the most influential process in the overall rate of the reaction. These results are in good agreement with the experimental evidence.
dc.fuente.origenWOS
dc.identifier.doi10.3390/app9224847
dc.identifier.eissn2076-3417
dc.identifier.urihttps://doi.org/10.3390/app9224847
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/100784
dc.identifier.wosidWOS:000502570800124
dc.issue.numero22
dc.language.isoen
dc.revistaApplied sciences-basel
dc.rightsacceso restringido
dc.subjectpyrolysis
dc.subjectbiomass pyrolysis
dc.subjectasparagine
dc.subjectreaction mechanism
dc.titleTheoretical Calculations of the Multistep Reaction Mechanism Involved in Asparagine Pyrolysis Supported by Degree of Rate Control and Thermodynamic Control Analyses
dc.typeartículo
dc.volumen9
sipa.indexWOS
sipa.trazabilidadWOS;2025-01-12
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