Electrochemical preparation of brilliant-blue-modified poly(diallyldimethylammonium chloride) and Nafion-coated glassy carbon electrodes and their electrocatalytic behavior towards oxygen and L-cysteine

Brilliant blue FCF-modified glassy carbon electrodes have been prepared by cycling the Nafion (or poly(diallyldimethylammonium chloride) (PDDAC)) coated electrodes repeatedly 15 cycles in brilliant blue FCF (BB FCF) dye solution. The BB FCF molecules are incorporated into Nafion coating by cycling the film-covered electrode between +0.3 to 1.2 V (vs. Ag/AgCl) in pH 1.5 BB FCF solution while PDDAC-coated electrode cycled between 0 to - 1.0 V (vs. Ag/AgCl) in pH 6.5 BB FCF solution to immobilize the dye. Electrostatic interaction between dye molecule and PDDAC was predominant in PDDAC coating whereas immobilization of dye in Nafion film attributed to the combined effect of electrostatic and hydrophobic interactions. ne voltammetric features of BB FCF-modified electrodes resemble that of surf ace-confined redox couples. The peak potentials of BB FCF-incorporated PDDAC-coated electrode were shifted to more positive potential region with decreasing pH of contacting solution. BB FCF-modified electrodes showed electrocatalytic activity towards reduction of oxygen and oxidation of L-cysteine with significant decease of overvoltage compared to unmodified electrode. The BB FCF-modified Nafion-coated electrode was tested for its analytical applications toward determination of L-cysteine. The linear range of calibration plot at BB FCF-modified Nafion-coated electrode is 10 to 100 mu M, which coincides with L-cysteine levels in biological fluids. Sensitivity and detection limit of the electrode are 111 nA mu M-1 and 0.5 mu M, respectively.