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A sensitive and facile electrochemical biosensor has been developed for monitoring the protein nitration damage affected by the nitro free radicals(NO2). The NO2 radicals is generated from hemin-catalyzed oxidation of nitrite (NO(-)2) in the presence of hydrogen peroxide (H2O2). In this work, nanocomposite films of graphene-gold nanoparticles (EG-AuNPs) were modified on the glassy carbon electrode by electropolymerization. Bovine serum albumin (BSA) was then further assembled on EG-AuNPs film through Au-S bond. The damage of BSA molecule was caused by the NO2 radicals which was generated from the NaNO2/hemin/H2O2 nitration reagent. The differential pulse voltammetry was used to detect the damage of BSA molecule. Fluorescence spectra and circular dichroism spectrum further confirmed the nitration damage of BSA. Moreover, the lowest concentration at which the BSA damage was detected is 28.9 µM NO(-)2 or H2O2, and the volume ratio of NO(-)2 and H2O2 was 1:1 in the hemin/NO(-)2/H2O2 nitration reagent. The results demonstrated that the proposed electrochemical method can be used to detect protein damage affected by nitration reagent. The developed electrochemical biosensor is envisioned to have promising applications in protein damage studies.
Raspberry-like composite spheres based on chemically-reactive poly(glycidyl methacrylate) (PGMA) colloids as the cores coated with tunable size of gold nanoparticles were synthesized via a controlled assembly method. Kinetic study of 4-nitrophenol reduction by NaBH4 in the presence of poly(allylamine hydrochloride)-modified PGMA composite with tunable size of AuNPs (PGMA@PAH@AuNPs) was demonstrated. Effects of gold nanoparticles size and PGMA colloid diameter on the reaction time, average reaction rate and average turnover frequency (TOF), order of reaction (n) and apparent rate constant (kapp) were systematically investigated. Experimental results of our study showed composites with 3.4 0.9 nm AuNPs have the best catalytic efficiency with the highest reaction order and apparent rate constant. The poisoning of product 4-aminophenol on PAH-modified PGMA colloid-supported gold nanocatalysts was evaluated using 4-nitrophenol/NaBH4 reduction reaction for the reaction time, average reaction rate, average TOF, order of reaction and apparent rate constant. 350c69d7ab