Mechanistic insights into the dehalogenation reaction of fluoroacetate/fluoroacetic acid

Sebastián Miranda-Rojas, Alejandro Toro-Labbé

Resultado de la investigación: Article

2 Citas (Scopus)

Resumen

Fluoroacetate is a toxic compound whose environmental accumulation may represent an important contamination problem, its elimination is therefore a challenging issue. Fluoroacetate dehalogenase catalyzes its degradation through a two step process initiated by an SN2 reaction in which the aspartate residue performs a nucleophilic attack on the carbon bonded to the fluorine; the second step is hydrolysis that releases the product as glycolate. In this paper, we present a study based on density functional theory calculations of the SN2 initiation reaction modeled through the interaction between the substrate and the propionate anion as the nucleophile. Results are analyzed within the framework of the reaction force and using the reaction electronic flux to identify and characterize the electronic activity that drives the reaction. Our results reveal that the selective protonation of the substrate catalyzes the reaction by decreasing the resistance of the structural and electronic reorganization needed to reach the transition state. Finally, the reaction energy is modulated by the degree of stabilization of the fluoride anion formed after the SN2 reaction. In this way, a site-induced partial protonation acts as a chemical switch in a key process that determines the output of the reaction.

Idioma originalEnglish
Número de artículo194301
PublicaciónJournal of Chemical Physics
Volumen142
N.º19
DOI
EstadoPublished - 1 ene 2015

Huella dactilar

Fluoroacetates
Dehalogenation
haloacetate dehalogenase
glycolic acid
Protonation
Anions
Nucleophiles
acids
Fluorine
Poisons
Propionates
Substrates
Fluorides
Aspartic Acid
Density functional theory
Hydrolysis
Contamination
Carbon
Stabilization
Switches

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Citar esto

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Mechanistic insights into the dehalogenation reaction of fluoroacetate/fluoroacetic acid. / Miranda-Rojas, Sebastián; Toro-Labbé, Alejandro.

En: Journal of Chemical Physics, Vol. 142, N.º 19, 194301, 01.01.2015.

Resultado de la investigación: Article

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