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Examining the reaction between antioxidant compounds and 2,2-diphenyl-1-picrylhydrazyl (DPPH) through a computational investigation

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Abstract

In this work, we present a computational investigation on the reactions between two well-known antioxidants (quercetin and morin) and 2,2-diphenyl-1-picrylhydrazyl (DPPH). A density functional theory (DFT) approach with the B3LYP functional and the 6-31G(d,p) basis set was used for the simulations. The structural and energetic parameters (Gibbs free-energy, ΔG, and Gibbs free-energy of activation, ΔG++) were determined to provide information on the antioxidant activity as well as to evaluate the contributions of each hydroxyl group to the referred property. According to the results obtained, quercetin presented three hydroxyls as being thermodynamically spontaneous in the reaction with DPPH (4\(^{\prime }\)-ArOH, 3\(^{\prime }\)-ArOH, and 3-ArOH, with ΔG = -4.93 kcal/mol, -2.89 kcal/mol, and -1.87 kcal/mol, respectively) against only two in the case of morin (2\(^{\prime }\)-ArOH and 3-ArOH, with ΔG = -7.56 kcal/mol and -4.57 kcal/mol, respectively). Hence, quercetin was found to be a more efficient antioxidant, which is in agreement with different experimental and computational investigations of bond dissociation enthalpies (BDEs). However, the order of contribution of the OH groups of each compound to the antioxidant potential present some differences when compared to what was seen in the previous investigations, especially for morin. These findings are in contrast to what was observed in studies based on the determinations of BDEs. Therefore, experimental investigations on the hydrogen-atom transfer mechanism (HAT) for both compounds are encouraged in order to clarify these observations.

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Acknowledgments

First of all, “Fora Temer!”. The Brazilian agency CNPq funded this work (Process number: 306266/2016-4). The authors thank Prof. Alex Brown from Department of Chemistry at University of Alberta for suggestions.

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Authors and Affiliations

  1. Departamento de Química, Universidade Federal de Mato Grosso, Cuiabá, Mato Grosso, 78060-900, Brazil

    Eduardo N. Maciel, Shawan K. C. Almeida, Sebastião C. da Silva & Gabriel L. C. de Souza

  2. Departamento de Ensino, Instituto Federal de Educação, Ciência e Tecnologia de Mato Grosso, Rondonópolis, Mato Grosso, 78721-520, Brazil

    Eduardo N. Maciel

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  1. Eduardo N. Maciel
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  2. Shawan K. C. Almeida
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Correspondence to Gabriel L. C. de Souza.

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This paper belongs to Topical Collection XIX - Brazilian Symposium of Theoretical Chemistry (SBQT2017)

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Maciel, E.N., Almeida, S.K.C., da Silva, S.C. et al. Examining the reaction between antioxidant compounds and 2,2-diphenyl-1-picrylhydrazyl (DPPH) through a computational investigation. J Mol Model 24, 218 (2018). https://doi.org/10.1007/s00894-018-3745-1

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