Effectiveness of Cyclic Voltammetry in Evaluation of the Synergistic Effect of Phenolic and Amino Acids Compounds on Antioxidant Activity: Optimization of Electrochemical Parameters.

Antioxidant activity can be evaluated using cyclic voltammetry (CV). The aim of this work is to verify the efficacy of CV in evaluating the synergistic effect of bioactive compounds, such as phenolic and amino acid compounds, on antioxidant activity. Therefore, three types of model solutions were prepared: individual model solution (phenol and amino acid), (b) binary model solutions (phenol-phenol and amino acid-amino acid) and (c) mixed phenol-amino acid solutions. Electrochemical measurement conditions were optimized for phenolic compounds (pH 3.0, 1.0 g/L and 100 mV/s) and for amino acids (pH 7.0, 2.0 g/L for amino acids and 100 mV/s), and, for each solution, the functional groups responsible of the anodic and cathodic peaks were established. The peak anodic potential (Epa) and the onset potential (Eon) were two parameters of great importance. The first one was used to classify the solutions according to their antioxidant potential. In general, all the binary and mixed solutions had lower values of Epa than the corresponding individual model solution, which indicates an improvement in the antioxidant potential. The second one was used to evaluate the synergistic effects of phenolic compounds and amino acids.

Oxidoperoxidomolybdenum(vi) complexes with acylpyrazolonate ligands: synthesis, structure and catalytic properties.

Oxidoperoxido-molybdenum(vi) complexes containing acylpyrazolonate ligands were obtained by reaction of [Mo(O)(O)2(H2O)n] with the corresponding acylpyrazolone compounds HQR. Complexes Ph4P[Mo(O)(O2)2(QR)] (R = neopentyl, 1; perfluoroethyl, 2; hexyl, 3; phenyl, 4; naphthyl, 5; methyl, 6; cyclohexyl, 7; ethylcyclopentyl, 8) were obtained if the reaction was carried out with one equivalent of HQR in the presence of Ph4PCl. Alternatively, neutral complexes [Mo(O)(O2)(QR)2] (R = neopentyl, 9; hexyl, 10; cyclohexyl, 11) were formed when two equivalents of HQR were used in the reaction. These complexes were isolated in good yields as yellow or yellow-orange crystalline solids and were spectroscopically (IR, 1H, 13C{1H} and 31P{1H} NMR), theoretically (DFT) and structurally characterised (X-ray for 1, 2, 9 and 10). Compounds 1 and 9 were selected to investigate their catalytic behaviour in epoxidation of selected alkenes and oxidation of selected sulphides, while 10 and 11 were tested as catalyst precursors in the deoxygenation of selected epoxide substrates to alkenes, using PPh3 as the oxygen-acceptor. Complexes Ph4P[Mo(O)(O2)2(QR)] were shown to be poor catalyst precursors in oxidation reactions, while the activity of [Mo(O)(O2)(QR)2] species is good in all the studied reactions and comparable to related oxidoperoxido-molybdenum(vi) complexes. Complex [Mo(O)2(QC6)2], 12, was obtained by treatment of 10 with one equivalent of PPh3, demonstrating that the first step in the epoxide deoxygenation mechanism was the oxygen atom transfer toward the phosphane.