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Free radicals produced by the oxidation of gallic acid: An electron paramagnetic resonance study
Journal article   Open access

Free radicals produced by the oxidation of gallic acid: An electron paramagnetic resonance study

Angelique C Eslami, Wanvimol Pasanphan, Brett A Wagner and Garry R Buettner
Chemistry Central journal, Vol.4(1), pp.15-15
12/2010
DOI: 10.1186/1752-153X-4-15
PMCID: PMC2924338
PMID: 20687941
url
https://doi.org/10.1186/1752-153X-4-15View
Published (Version of record) Open Access

Abstract

Background: Gallic acid (3,4,5-trihydroxybenzoic acid) is found in a wide variety of plants; it is extensively used in tanning, ink dyes, as well as in the manufacturing of paper. The gallate moiety is a key component of many functional phytochemicals. In this work electron paramagnetic spectroscopy (EPR) was used to detect the free radicals generated by the air-oxidation of gallic acid. Results: We found that gallic acid produces two different radicals as a function of pH. In the pH range between 7-10, the spectrum of the gallate free radical is a doublet of triplets (aH = 1.00 G, aH = 0.23 G, aH = 0.28 G). This is consistent with three hydrogens providing hyperfine splitting. However, in a more alkaline environment, pH >10, the hyperfine splitting pattern transforms into a 1:2:1 pattern (aH (2) = 1.07 G). Using D2O as a solvent, we demonstrate that the third hydrogen (i.e. aH = 0.28 G) at lower pH is a slowly exchanging hydron, participating in hydrogen bonding with two oxygens in ortho position on the gallate ring. The pKa of this proton has been determined to be 10. Conclusions: This simple and novel approach permitted the understanding of the prototropic equilibrium of the semiquinone radicals generated by gallic acid, a ubiquitous compound, allowing new insights into its oxidation and subsequent reactions.

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