The influence of pH on antioxidant properties and the mechanism of antioxidant action of hydroxyflavones.
The effect of the pH on antioxidant properties of a series of hydroxyflavones was investigated. The pKa of the individual hydroxyl moieties in the hydroxyflavones was compared to computer-calculated deprotonation energies. This resulted in a quantitative structure activity relationship (QSAR), which enables the estimation of pKa values of individual hydroxyl moieties, also in hydroxyflavones for which these pKa values are not available. Comparison of the pKa values to the pH-dependent antioxidant profiles, determined by the TEAC assay, reveals that for various hydroxyflavones the pH-dependent behavior is related to hydroxyl moiety deprotonation, resulting in an increase of the antioxidant potential upon formation of the deprotonated forms. Comparison of these experimental results to computer calculated O-H bond dissociation energies (BDE) and ionization potentials (IP) of the nondeprotonated and the deprotonated forms of the various hydroxyflavones indicates that especially the parameter reflecting the ease of electron donation, i.e., the IP, and not the BDE, is greatly influenced by the deprotonation. Based on these results it is concluded that upon deprotonation the TEAC value increases (radical scavenging capacity increases) because electron-, not H*-, donation becomes easier. Taking into account that the mechanism of radical scavenging antioxidant activity of the neutral form of the hydroxyflavones is generally considered to be hydrogen atom donation, this implies than not only the ease of radical scavenging, but also the mechanism of antioxidant action changes upon hydroxyflavone deprotonation.
Lemańska
K
K
Faculty of Commodity Science, Poznan University of Economics, al. Niepodleglości 10, 60-967 Poznań, Poland.
Szymusiak
H
H
Tyrakowska
B
B
Zieliński
R
R
Soffers
A E
AE
Rietjens
I M
IM
D000975:Antioxidants / Q000032:analysis / Q000737:chemistry* / Q000378:metabolism / Q000494:pharmacology*; D052160:Benzothiazoles; D002839:Chromans / Q000737:chemistry; D004579:Electron Transport; D005419:Flavonoids / Q000032:analysis / Q000737:chemistry* / Q000378:metabolism / Q000494:pharmacology*; D016166:Free Radical Scavengers / Q000032:analysis* / Q000737:chemistry / Q000378:metabolism; D006859:Hydrogen / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D017665:Hydroxyl Radical / Q000737:chemistry; D007700:Kinetics; D021281:Quantitative Structure-Activity Relationship; D013451:Sulfonic Acids / Q000737:chemistry; D013816:Thermodynamics
D000975:Antioxidants; D052160:Benzothiazoles; D002839:Chromans; D005419:Flavonoids; D016166:Free Radical Scavengers; D013451:Sulfonic Acids; C002502:2,2'-azino-di-(3-ethylbenzothiazoline)-6-sulfonic acid; D017665:Hydroxyl Radical; D006859:Hydrogen; C010643:6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid