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XII Iberian Meeting of Electrochemistry XVI Meeting of the ...

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<strong>XII</strong> <strong>Iberian</strong> <strong>Meeting</strong> <strong>of</strong> <strong>Electrochemistry</strong> & <strong>XVI</strong> <strong>Meeting</strong> <strong>of</strong> <strong>the</strong> Portuguese Electrochemical Society K N 04<br />

Evaluation <strong>of</strong> antioxidant activity: a reagentless<br />

electrochemical approach<br />

Dulce Geraldo, Fátima Bento<br />

Departament <strong>of</strong> Chemistry, Universidade do Minho, 4710-057 Braga<br />

gdulce@quimica.uminho.pt<br />

The growing interest in <strong>the</strong> study <strong>of</strong> <strong>the</strong> action <strong>of</strong> antioxidants in health and<br />

biotechnology has led to <strong>the</strong> development <strong>of</strong> different analytical methods for <strong>the</strong><br />

evaluation <strong>of</strong> <strong>the</strong> antioxidant capacity <strong>of</strong> <strong>the</strong>se compounds.<br />

Cyclic voltammetry has been widely used in <strong>the</strong> analysis <strong>of</strong> samples containing mixtures<br />

<strong>of</strong> antioxidants. The analysis <strong>of</strong> voltammograms gives qualitative information, which<br />

relates to <strong>the</strong> identification <strong>of</strong> peaks, or waves resulting from overlapping voltammetric<br />

peaks. This information is usually used to evaluate <strong>the</strong> power <strong>of</strong> <strong>the</strong> antioxidants present<br />

in <strong>the</strong> sample. Quantitative information can be achieved by following two different<br />

approaches, consisting in measuring <strong>the</strong> current intensity at a fixed potential, or <strong>the</strong> area<br />

under <strong>the</strong> anodic scan <strong>of</strong> voltammograms. The values <strong>of</strong> current or area are converted to<br />

relative values <strong>of</strong> antioxidant activity against a model antioxidant. Besides cyclic<br />

voltammetry, electrochemical methods have been used as an alternative to optical<br />

methods for monitoring <strong>the</strong> consumption <strong>of</strong> reactive species, such as <strong>the</strong> DPPH [1] . O<strong>the</strong>r<br />

studies reported <strong>the</strong> use <strong>of</strong> coulometric titration at constant current to generate reactive<br />

species such as <strong>the</strong> cation radical ABTS [2] , Ce(IV) [3] , Cl 2<br />

[4, 5] and Br 2 [5] . As <strong>the</strong> reactivity<br />

<strong>of</strong> <strong>the</strong>se species is different from that <strong>of</strong> naturally ROS involved in oxidative damage /<br />

oxidative stress, <strong>the</strong> significance <strong>of</strong> <strong>the</strong>se results is ra<strong>the</strong>r limited and may lead to an<br />

underestimation or overestimation <strong>of</strong> <strong>the</strong> antioxidant activity according to <strong>the</strong> relative<br />

value <strong>of</strong> <strong>the</strong> reduction potential <strong>of</strong> reactive species. Likewise, <strong>the</strong> difference between <strong>the</strong><br />

reduction potentials <strong>of</strong> <strong>the</strong> reactive species used in <strong>the</strong> various methods difficult <strong>the</strong><br />

establishment <strong>of</strong> a parallelism between <strong>the</strong> results from <strong>the</strong>se methods.<br />

The direct analysis <strong>of</strong> electron transfer with <strong>the</strong> antioxidants using controlled potential<br />

exhaustive electrolysis can overcome <strong>the</strong>se limitations.<br />

In this work, we present a new analytical approach for evaluating <strong>the</strong> antioxidant<br />

activity <strong>of</strong> chemical species in syn<strong>the</strong>tic solutions or in natural systems, designed to<br />

measure <strong>the</strong>ir reactivity against specific ROS (from <strong>the</strong> O 2 to <strong>the</strong> HO • ) under defined<br />

experimental conditions (eg pH). The method is based on <strong>the</strong> response <strong>of</strong> antioxidants<br />

during electrolysis conducted at a fixed potential, simulating an oxidative attack by a<br />

natural ROS.<br />

References<br />

[1] Milardovic, S.; Ivekovic, D.; Grabaric B. S. Bioelectrochemistry, 2006, 68, 175.<br />

[2] Alonso, A. M.; Dominguez, C.; Guillén D. A.; Barroso, C. G. J. Agric. Food Chem., 2002, 50,<br />

3112.<br />

[3] Ferreira, R. Q.; Avaca, L. A. Electroanalysis 2008, 20, 1323.<br />

[4] Addullin, I. F.; Turova, E. N.; Ziyatdinova, G. K.; Budnikov, H. C. Journal <strong>of</strong> Analytical<br />

Chemistry , 2002, 57, 730.<br />

Talanta, 2006, 68, 800.<br />

September, 811, 2010. ISEL - Lisbon 21

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