Electrochemical oxidation of selenocystine (SeCys) and selenomethionine (SeMet), on a gold electrode was studied by cyclic voltammetry (CV), rotating disk electrode technique (RDE) and chronocoulometry (CC). In 0.2 mol/L HAc-NaAc (pH=3.90) supporting electrolyte, anodic peak I potential of SeCys and SeMet was 810 mV and 638 mV, respectively, and this electrode process was diffused controlled. The electrochemical oxidation process of SeCys, in which six electron-transfers were involved, yielded selenocystine selenoxide. The electrochemical oxidation process of SeMet, in which two electron-transfers were involved, yielded selemethionine selenoxide.
[Show abstract][Hide abstract] ABSTRACT: Copper and iron are two widely studied transition metals associated with hydroxyl radical (˙OH) generation, oxidative damage, and disease development. Because antioxidants ameliorate metal-mediated DNA damage, DNA gel electrophoresis assays were used to quantify the ability of ten selenium-containing compounds to inhibit metal-mediated DNA damage by hydroxyl radical. In the Cu(I)/H(2)O(2) system, selenocystine, selenomethionine, and methyl-selenocysteine inhibit DNA damage with IC(50) values ranging from 3.34 to 25.1 μM. Four selenium compounds also prevent DNA damage from Fe(II) and H(2)O(2). Additional gel electrophoresis experiments indicate that Cu(I) or Fe(II) coordination is responsible for the selenium antioxidant activity. Mass spectrometry studies show that a 1 : 1 stoichiometry is the most common for iron and copper complexes of the tested compounds, even if no antioxidant activity is observed, suggesting that metal coordination is necessary but not sufficient for selenium antioxidant activity. A majority of the selenium compounds are electroactive, regardless of antioxidant activity, and the glutathione peroxidase activities of the selenium compounds show no correlation to DNA damage inhibition. Thus, metal binding is a primary mechanism of selenium antioxidant activity, and both the chemical functionality of the selenium compound and the metal ion generating damaging hydroxyl radical significantly affect selenium antioxidant behavior.
[Show abstract][Hide abstract] ABSTRACT: The complexation of Se-aminoacids selenomethionine (SeMet) and selenocystine (SeCyst) with Hg2+ was investigated by differential pulsed voltammetry (DPV) on Au-disk electrode. Complexation processes are proposed from the Gaussian Peak Adjustment analysis of DPV titration data. Main complexes were both 1:1 Hg:SeMet and Hg:SeCyst, although the formation of 2:1 complexes can be also proposed for Hg:SeCyst. Elimination voltammetry with linear scan was applied to investigate the adsorption of the ligands and the complexes on the Au surface.
[Show abstract][Hide abstract] ABSTRACT: The formation and characterization of Selenocysteine (SeCys) Self-assembly monolayers (SAMs) was studied. It was found that SeCys SAMs revealed ion-gate response for the electron-transfer of Fe(CN)64-/3- probe ion in the presence of Cu2+ or Pb2+. The ion-gate response of SeCys SAMs resulted from the fact that the interaction between SeCys SAMs and Cu2+ (Pb2+), including the coordination and the electrostatic interaction, changed the conformation of SeCys SAMs.
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