Voltammetric, spectroscopic, and cellular characterization of redox functionality of eckol and phlorofucofuroeckol-A:...

Interest in phlorotannins has increased in recent years largely due to antioxidant capacity, however, the redox mechanism of phlorotannins is still obscure. In the present study, the electrochemical oxidation mechanisms of eckol (EL) and phlorofucofuroeckol-A (PFF-A), two representative phlorotannin compounds, were comparatively analyzed in a wide pH range using cyclic and differential pulse voltammetry as well as spectroscopic assay. The voltammetric study revealed that EL and PFF-A were successively oxidized in three pH-dependent steps. Moreover, it was found that the PFF-A presented a stronger proton and electron transferring activity as compared to EL since PFF-A exhibited lower acid-base dissociation constant (pK_a ) value and higher heterogeneous rate constant (k_bh ) value in the first oxidation step. These property were further evidenced by comparison of direct antioxidant activity (i.e., superoxide anion and peroxide radicals) as well as indirect antioxidant activity (i.e., mRNA expression of two phase II enzymes) between EL and PFF-A. PRACTICAL APPLICATIONS: Phlorotannins from edible algae have been regarded as novel antioxidants those presented high application potential in food industry. Even though antioxidant activity of phlorotannin compounds have been widely investigated in both in vitro and in vivo studies, very few reports focused on electron transferring functionality which is chemical basis for antioxidant process. Herein, the oxidative mechanisms of two representative phlorotannins were comparatively analyzed using multiple electrochemical methods. This is hopefully to give information on the chemical meaning behind the antioxidant activity of dietary phlorotannins.