Antioxidant activity represents one of the important features of phenolic acids, such as hydroxyderivatives of cinnamic acid. However, in the case of cis-cinnamic acid derivatives, corresponding thermochemistry data can be still considered scarce. This work is focused on the two most relevant mechanisms of primary antioxidant action in gas-phase, non-polar benzene and in aqueous solution. Reaction enthalpies describing thermodynamics of Hydrogen Atom Transfer (HAT) and Sequential Proton-Loss – Electron Transfer (SPLET) mechanisms were theoretically investigated using (SMD) M06-2X/6-311++G(d,p) method for cis-ortho-coumaric, cis-meta-coumaric, cis-para-coumaric, cis-ferulic, cis-sinapic and cis-caffeic acid and their carboxylate anions. The effect of carboxyl COOH group deprotonation on the thermodynamics of studied mechanisms was assessed for the three environments.
Amić A, Marković Z, Marković D, Milenković J, Stepanić D, V. Antioxidative potential of ferulic acid phenoxyl radical. Phytochemistry. 2020;112218.
2.
Amić A, Marković Z, Klein E, Marković D, Milenković J, D. Theoretical study of the thermodynamics of the mechanisms underlying antiradical activity of cinnamic acid derivatives. Food Chem. 2018;481–9.
3.
Chen Y, Xiao H, Zheng J, Liang G. Structure-thermodynamics-antioxidant activity relationships of selected natural phenolic acids and derivatives: An experimental and theoretical evaluation. PLoS ONE. 2015;121276.
4.
Dávalos J, Lima C, F R A C, Silva AMS, Santos LMNBF, Erra-Balsells R, et al. Energetics of neutral and deprotonated (Z)-cinnamic acid. J Chem Thermodyn. 2016;195–201.
5.
Meo D, Lemaur F, Cornil V, Lazzaroni J, Duroux R, Olivier JL, et al. Free radical scavenging by natural polyphenols: Atom versus electron transfer. J Phys Chem A. 2013;2082–92.
6.
Estevéz L, Otero N, Mosquera R. A computational study on the acidity dependence of radical-scavenging mechanisms of anthocyanidins. J Phys Chem B. 2010;9706–12.
7.
Filipović M, Marković Z, Ðorović J, Marković JD, Lučić B, Amić D. QSAR of the free radical scavenging potency of selected hydroxybenzoic acids and simple phenolics. C R Chimie. 2015;492–8.
8.
Frisch M, Trucks G, Schlegel HB, Scuseria G, Robb MA, Cheeseman JR. 2013;
9.
Galano A, Mazzone A, Alvarez-Diduk R, Marino T, Aalvarez-Idaboy R, Russo J, et al. Food Antioxidants: Chemical insights at the Molecular Level. Annu Rev Food Sci Technol. 2016;15–6.
10.
Hariharan P, Pople J. The influence of polarization functions on molecular orbital hydrogenation energies. Theor Chim Acta. 1973;213–22.
11.
Heleno S, Martins A, Queiroz MJRP, Ferreira I, C F R. Food Chem. 2015;501–213.
12.
Klein E, Lukeš V, Rimarčík J, Kleinová A. Theoretical study of primary antioxidant action thermodynamics. J Serbian Soc Comput Mech. 2017;130–8.
13.
Klein E, Rimarčík J, Senajová E, Vagánek A, Lengyel J. Deprotonation of flavonoids severely alters the thermodynamics of the hydrogen atom transfer. Comp Theor Chem. 2016;7–17.
14.
Koroleva O, Torkova A, Nikolaev I, Khrameeva E, Fedorova T, Tsentalovich M, et al. Evaluation of the antiradical properties of phenolic acids. Int J Mol Sci. 2014;16351–80.
15.
Lemańska K, Szymusiak H, Tyrakowska B, Zieliński R, Soffers AEMF, Rietjens IMCM. The influence of pH on antioxidant properties and the mechanism of antioxidant action of hydroxyflavones, Free Radic. Biol Med. 2001;869–81.
16.
Lengyel J, Rimarčík J, Vagánek A, Klein E. On the radical scavenging activity of isoflavones: Thermodynamics of O-H bond cleavage. Phys Chem Chem Phys. 2013;10895–903.
17.
Marenich V, Cramer CJ, Truhlar D. Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions. J Phys Chem B. 2009;6378–96.
18.
Marković Z, Ðorović J, Marković D, Biočanin J, Amić R, D. Comparative density functional study of antioxidative activity of the hydroxybenzoic acids and their anions. Turk J Chem. 2016;499–509.
19.
Marković S, Tošović J. Comparative study of the antioxidative activities of caffeoylquinic and caffeic acids. Food Chem. 2016;585–92.
20.
Mazzone G, Russo N, Toscano M. Antioxidant properties comparative study of natural hydroxycinnamic acids and structurally modified derivatives: Computational insights. Comp Theor Chem. 2016;39–47.
21.
Michalík M, Poliak P, Lukeš V, Klein E. From phenols to quinones: Thermodynamics of radical scavenging activity of para-substituted phenols. Phytochemistry. 2019;112077.
22.
Milenković D, Ðorović J, Jeremić S, Marković D, Avdović J, Marković E, et al. Free Radical Scavenging Potency of Dihydroxybenzoic Acids. J Chem. 2017;5936239.
23.
Ozkorucuklu S, Beltrán J, Fonrodona G, Barrón D, Alsancak G, Barbosa J. Determination of dissociation constants of some hydroxylated benzoic and cinnamic acids in water from mobility and spectroscopic data obtained by CE-DAD. J Chem Eng Data. 2009;807–11.
24.
Rassolov V, Pople J, Ratner M, Windus T. 6-31G* basis set for atoms K through Zn. J Chem Phys. 1998;1223–9.
25.
Saxena M, Saxena J, Pradhan A. Flavonoids and phenolic acids as antioxidants in plants and human health. Int J Pharm Sci Rev Res. 2012;130–4.
26.
Škorňa P, Michalík M, Klein E. Gallic acid: thermodynamics of the homolytic and heterolytic phenolic O-H bonds splitting-off. Acta Chimica Slovaca. 2016;114–23.
27.
Škorňa P, Rimarčík J, Poliak P, Lukeš V, Klein E. Thermodynamic study of vitamin B6 antioxidant potential. Comp Theor Chem. 2016;32–8.
28.
Urbaniak A, Szeląg M, Molski M. Theoretical investigation of stereochemistry and solvent influence on antioxidant activity of ferulic acid. Comp Theor Chem. 2013;33–40.
29.
Zhao Y, Truhlar D. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor Chem Acc. 2008;215–41.
The statements, opinions and data contained in the journal are solely those of the individual authors and contributors and not of the publisher and the editor(s). We stay neutral with regard to jurisdictional claims in published maps and institutional affiliations.
