Urate hydroperoxide is a strong oxidant generated by the combination of urate free radical and superoxide. The formation of urate hydroperoxide as an intermediate in urate oxidation is potentially responsible for the pro-oxidant effects of urate in inflammatory disorders, protein degradation, and food decomposition. To understand the molecular mechanisms that sustain the harmful effects of urate in inflammatory and oxidative stress related conditions, we report a detailed structural characterization and reactivity of urate hydroperoxide toward biomolecules. Urate hydroperoxide was synthesized by photo-oxidation and by a myeloperoxidase/hydrogen peroxide/superoxide system. Multiple reaction monitoring (MRM) and MS(3) ion fragmentation revealed that urate hydroperoxide from both sources has the same chemical structure. Urate hydroperoxide has a maximum absorption at 308 nm, ε308nm = 6.54 ± 0.38 × 10(3) M(-1) cm(-1). This peroxide decays spontaneously with a rate constant of k = 2.80 ± 0.18 × 10(-4) s(-1) and a half-life of 41 min at 22 °C. Urate hydroperoxide undergoes electrochemical reduction at potential values less negative than -0.5 V (versus Ag/AgCl). When incubated with taurine, histidine, tryptophan, lysine, methionine, cysteine, or glutathione, urate hydroperoxide reacted only with methionine, cysteine, and glutathione. The oxidation of these molecules occurred by a two-electron mechanism, generating the alcohol, hydroxyisourate. No adduct between cysteine or glutathione and urate hydroperoxide was detected. The second-order rate constant for the oxidation of glutathione by urate hydroperoxide was 13.7 ± 0.8 M(-1) s(-1). In conclusion, the oxidation of sulfur-containing biomolecules by urate hydroperoxide is likely to be a mechanism by which the pro-oxidant and damaging effects of urate are mediated in inflammatory and photo-oxidizing processes.
This study describes the electrochemical preparation of the electrocatalytic oxidation/reduction of noradrenaline in modified glassy carbon of cobalt ferrite nanoparticles and carbon nanotubes (GC/MWCNT/FCo98). The cobalt ferrite powder was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optimum conditions found in an electrode composition were 4 μL of cobalt ferrite and 10 μL of carbon nanotubes in 0.1 mol L−1 PBS at pH 7.0. The electrode displays electrochemical behavior in a wide potential range (−0.4 to 1.0 V vs. Ag/AgCl), high conductivity, and electrode stability/durability in 0.1 mol L−1 PBS. Catalytic oxidation of noradrenaline was performed at the unmodified GC electrode at +0.60 V vs. Ag/AgCl and current of 0.17 μA and modified GC with cobalt ferrite nanoparticles and carbon nanotubes at +0.54 V vs. Ag/AgCl and current of 0.23 mA. With regard to the anodic peak current (Ipa) versus noradrenaline concentration by means of the amperometric method at the modified electrode, (which is linear in the 0.16 and 1.91 mmol L−1 concentration range), the concentration limit was 0.76 μmol L−1. In this way, the modified electrode GC/MWCNT/FCo98 was found to be a promising application for the determination of this neurotransmitter in the area of neuroscience.
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