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Concentration-dependent HAT/ET mechanism of the reaction of phenols with 2,2-diphenyl-1-picrylhydrazyl (dpph˙) in methanol

The reaction of a 2,2-diphenyl-1-picrylhydrazyl radical (dpph˙) with phenols carried out in alcohols is a frequently used assay for estimation of the antiradical activity of phenolic compounds. The rates of reactions of dpph˙ with five phenols (ArOH: unsubstituted phenol, 4-hydroxyacetophenone, two...

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Detalles Bibliográficos
Autores principales: Przybylski, Paweł, Konopko, Adrian, Łętowski, Piotr, Jodko-Piórecka, Katarzyna, Litwinienko, Grzegorz
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8982332/
https://www.ncbi.nlm.nih.gov/pubmed/35424731
http://dx.doi.org/10.1039/d2ra01033j
Descripción
Sumario:The reaction of a 2,2-diphenyl-1-picrylhydrazyl radical (dpph˙) with phenols carried out in alcohols is a frequently used assay for estimation of the antiradical activity of phenolic compounds. The rates of reactions of dpph˙ with five phenols (ArOH: unsubstituted phenol, 4-hydroxyacetophenone, two calix[4]resorcinarenes and baicalein) measured in methanol indicate the different kinetics of the process for very diluted phenols compared to their non-diluted solutions. This effect was explained as dependent on the ratio [ArO(−)]/[ArOH] and for diluted ArOH corresponds to an increased contribution of much faster electron transfer (ET, ArO(−)/dpph˙) over the Hydrogen Atom Transfer (HAT, ArOH/dpph˙). Simplified analysis of the reaction kinetics resulted in estimation of k(ET)/k(HAT) ratios for each studied ArOH, and in calculation of the rate constants k(ET). Described results are cautionary examples of how the concentration of a phenol might change the reaction mechanism and the overall kinetics of the observed process.