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Metal-catalyzed decarboxylation of oxaloacetic acid studied in silico and in vitro, implications for enzymatic and prebiotic catalysis

dc.contributor.authorYañez, Osvaldo
dc.contributor.authorCabrera, Ricardo
dc.contributor.authorPino-Rios, Ricardo
dc.contributor.authorSepúlveda, Carolina
dc.contributor.authorLópez-Cortés, Xaviera A.
dc.contributor.authorGonzález-Nilo, Fernando D.
dc.contributor.authorRavanal, María Cristina
dc.date.accessioned2025-04-02T14:46:05Z
dc.date.available2025-04-02T14:46:05Z
dc.date.issued2025
dc.identifier.urihttp://repositorio.ucm.cl/handle/ucm/5902
dc.description.abstractDuring the decarboxylation of oxaloacetic acid (OAA), an α-keto acid that participates in the central metabolic pathways of all organisms, its fourth carbon is released in the form of CO2 through a metal-catalyzed reaction. In the context of prebiotic chemistry, it is generally accepted that metalloenzymes catalyse reactions that could have originally occurred abiotically mediated by metals. In this study, we investigate the effect of various divalent cations (Ni2+, Co2+, Mn2+ and Mg2+) on the non-enzymatic decarboxylation rate of oxaloacetic acid (OAA) using both in silico quantum mechanical calculations and in vitro experimental analysis. Our experimental findings demonstrate that for the rate of OAA decarboxylation, the cations followed the order Ni2+ > Co2+ > Mg2+ > Mn2+. Theoretical results, utilizing the enolpyruvate metal complex as the final stage of the reaction, showed that the Ni2+ complex had the lowest decarboxylation energy and negative Gibbs free energy compared to other complexes. Additionally, it exhibited a lower HOMO-LUMO gap, indicating its potential to aid in the decarboxylation reaction. Given that decarboxylases in current metabolism primarily employ Mg2+ and Mn2+ but not Ni2+, we consider how the cation that performs better in the abiotic reaction was not selected as the catalytic centre of the enzyme-based reaction in current biochemistry.es_CL
dc.language.isoenes_CL
dc.rightsAtribución-NoComercial-SinDerivadas 3.0 Chile*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/cl/*
dc.sourceJournal of Molecular Structure, 1326, 141105es_CL
dc.subjectDivalent cationses_CL
dc.subjectDecarboxylation of oxaloacetic acides_CL
dc.subjectTransition statees_CL
dc.subjectDFT calculationes_CL
dc.subjectQuantum mechanical calculationses_CL
dc.subjectAbiotic reactiones_CL
dc.titleMetal-catalyzed decarboxylation of oxaloacetic acid studied in silico and in vitro, implications for enzymatic and prebiotic catalysises_CL
dc.typeArticlees_CL
dc.ucm.facultadFacultad de Ciencias de la Ingenieríaes_CL
dc.ucm.indexacionScopuses_CL
dc.ucm.indexacionIsies_CL
dc.ucm.urisciencedirect.ucm.elogim.com/science/article/pii/S0022286024036111?via%3Dihubes_CL
dc.ucm.doidoi.org/10.1016/j.molstruc.2024.141105es_CL


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