Synthesis and antioxidant activities of transition metal complexes based 3-hydroxysalicylaldehyde-S-methylthiosemicarbazone.

The nickel(II), iron(III), oxovanadium(IV) complexes of the 3-hydroxysalicylidene-S-methyl-thiosemicarbazone (L) were obtained from the 3-hydroxysalicyldehyde-S-methylthiosemicarbazone with the R1-substituted-salicylaldehyde (R1: H, 3-OH) in the presence of Ni(II), Fe(III), VO(IV) as template ion. The ligand and its complexes were characterized by elemental analysis, electronic, UV/Vis., (1)HNMR, EPR and IR studies. The free ligand and its metal complexes have been tested for in vitro antioxidant capacity by reduction of copper(II) neocuproine (Cu(II)-Nc) using the CUPRAC method. The ligand exhibited more potent in vitro antioxidant capacity than its complexes. The obtained trolox equivalent antioxidant capacity (TEAC) value of the iron(III) complex (TEACCUPRAC=3.27) was higher than those of other complexes. Furthermore, the antioxidant activity of the free ligand and its complexes were determined by in vitro methods measuring the scavenging activity of reactive oxygen species (ROS) including hydroxyl radical (OH), superoxide anion radical (O2(-)), and hydrogen peroxide (H2O2), showing that especially the V(IV) and Fe(III) complexes had significant scavenging activity for ROS.

Synthesis, antioxidant activities of the nickel(II), iron(III) and oxovanadium(IV) complexes with N2O2 chelating thiosemicarbazones.

The nickel(II), iron(III) and oxovanadium(IV) complexes of the N2O2 chelating thiosemicarbazones were synthesized using 4-hydroxysalicyladehyde-S-methylthiosemicarbazone and R1-substitute-salicylaldehyde (R1: 4-OH, H) in the presence of Ni(II), Fe(III), VO(IV) ions by the template reaction. The structures of the thiosemicarbazone complexes were characterized by FT-IR, (1)H NMR, elemental, ESI-MS and APCI-MS analysis. The synthesized compounds were screened for their antioxidant capacity by using the cupric reducing antioxidant capacity (CUPRAC) method. Trolox equivalent antioxidant capacity (TEAC) of iron(III) complex, 1c, was measured to be higher than that of the other complexes. Other parameters of antioxidant activity (scavenging effects on •OH, O2(•-) and H2O2) of these compounds were also determined. All the compounds have shown encouraging ROS scavenging activities.

Novel pro-oxidant activity assay for polyphenols, vitamins C and E using a modified CUPRAC method.

In this study, a direct assay, a modified CUPRAC (Cupric Ion Reducing Antioxidant Capacity) method, is developed to determine transition metal ion (Cu(II))-catalyzed pro-oxidant activity of polyphenolic compounds, vitamins C and E, and herbal samples in the presence of proteins containing thiol groups. Since transition metal ion-catalyzed pro-oxidant activity of phenolics is usually initiated with the reduction of the metal to lower oxidation states (as a prerequisite of Fenton-type reactions), this method involves the reduction of copper(II) ions to copper(I) by polyphenolic compounds (simultaneously giving rise to reactive species), binding of the formed Cu(I) to egg white protein -SH groups, and liberation of copper(I)-neocuproine (Cu(I)-Nc) chelate (showing maximum absorbance at 450 nm) by treating the incubation product with a neocuproine-ammonium acetate mixture. The proposed method is validated against atomic absorption spectrometric (AAS) determination of protein-bound copper and protein carbonyl assay of oxidative stress. The proposed assay is faster and more specific than the carbonyl assay, and uses low-cost reagents and equipment. Pro-oxidant activity (i.e. proportional to absorbance) varies linearly over a relatively wide range with concentration, as opposed to the reciprocal correlations (i.e. linear regression of 1/(pro-oxidant activity) versus 1/concentration) of other similar assays. The pro-oxidant activity order of the tested antioxidant compounds in terms of 'Quercetin Equivalent Pro-oxidant Activity' (QREPA) coefficients is: gallic acid > epicatechin > quercetin ≈ catechin > α-tocopherol > rosmarinic acid > trolox > caffeic acid > ascorbic acid.