Chronoamperometric estimation of cognac and brandy antioxidant capacity using MWNT modified glassy carbon electrode.

Cognac and brandy components are electrochemically oxidized on multi-walled carbon nanotube modified glassy carbon electrode at 0.44 and 0.59 V in 0.1 М phosphate buffer solution pH 3.0. Voltammetric behavior of the main antioxidant constituents of cognac (ellagic and gallic acids, syringaldehyde, coniferaldehyde, vanillin, 5-hydroxymethylfurfural and furfural) has been investigated. The peak at the less positive potential of cognacs is caused by oxidation of gallic acid as well as syringaldehyde- and coniferaldehyde. The second peak corresponds to ellagic acid oxidation. One-step chronoamperometry at 0.59 V for 75 s has been applied for the cognac and brandy antioxidant capacity (AOC) evaluation. Ellagic acid, being the main antioxidant of cognac, has been used as a reference substance. The chronoamperometric response of ellagic acid is linear in the range of 0.66-52.8 µM with the limit of detection and quantification at 0.19 and 0.63 µM, respectively. AOC in ellagic acid equivalents per 100mL of cognac and brandy for different denominations (11 cognacs and 11 ordinary and vintage brandies) has been estimated. AOC of cognacs and brandies increases with the age of the beverages. Positive correlations (r=0.9134-0.9703) with common parameters characterizing antioxidant properties of beverages, in particular antiradical activity, total phenolics content, total antioxidant capacity and ferric reducing power have been observed.

Coulometric titration with electrogenerated oxidants as a tool for evaluation of cognac and brandy antioxidant properties.

Stoichiometric coefficients for reactions of cognac antioxidants with coulometric titrants (electrogenerated bromine and hexacyanoferrate(III) ions) have been found. Ellagic and gallic acids react with both titrants while aldehydes (vanillin, syringic and coniferaldehyde) - with electrogenerated bromine only. Furfurals do not show significant reactivity toward both oxidants. Cognac and brandy total antioxidant capacity (TAC) and ferric reducing power (FRP) based on reactions with electrogenerated bromine and hexacyanoferrate(III) ions, respectively, have been evaluated. Both parameters for cognacs are statistically significant higher than for brandies and grow with the age increase. Beverages under investigation has shown relatively high antiradical activity toward 2,2-diphenyl-1-picrylhydrazyl (7-92% and 5-93% for cognacs and brandies, respectively). Total phenolics content has been evaluated by Folin-Ciocalteu method. Older beverages represent the higher phenolics content caused by more time of extraction from oak barrels. Positive correlations (r=0.8077-0.9617) have been observed for TAC and FRP with antiradical activity and total phenolics content.