Electrochimica Acta, Vol.98, 54-65, 2013
Phosphomolybdic acid nano-aggregates immobilized nafion membrane modified electrode for selective cysteine electrocatalytic oxidation and anti-dermatophytic activity
Phosphomolybdic acid (PMo12) stabilized Nafion (NO membrane colloidal solution ({Nf-PMo12}) modified glassy carbon electrode (GCE/{Nf-PMo12}-CME) has been demonstrated as a new and efficient electrocatalyst for cysteine (CySH) oxidation in pH 7 phosphate buffer solution. Physico-chemical characterizations of the {Nf-PMo12} by TEM, XRD, ET-IR and UV-vis spectroscopy techniques revealed stabilization of the PMo12 as 5-60 nm sized nano-aggregates within the sulphonic acid micro-channels of Nafion without any changes in the crystal structure. Electrochemical characterization of the GCE/{Nf-PMo12}-CME with Fe(CN)(6)(3-) and Ru(bpy)(3)(2+) indicates metal like surface feature of the working electrode. The GCE/{Nf-PMo12}-CME showed highly stable CySH electrochemical oxidation current signal at 0.58 +/- 0.02 V vs. Ag/AgCl in pH 7 with 150 mV reduction in the response and about 8 times higher the peak current than that of the respective unmodified electrode. Amperometric i-t response of CySH at an applied potential of 0.58 V vs. Ag/AgCl yielded current sensitivity and regression coefficient values of 0.011 mu A/mu M and 0.9998 respectively without any interference from xanthine, hypoxanthine, nitrite, uric acid and other sulphur containing biochemicals; methionine and taurine, except ascorbic acid. Calculated detection limit value is (signal-to-noise ratio, S/N = 3) 25 mu M. In particular, the PMo12 and {Nf-PMo12} systems showed marked anti-dermatophytic activity against Trichophyton rubrum organism, and the activity is comparable with standard fluconazole drug. Crown Copyright (C) 2013 Published by Elsevier Ltd. All rights reserved.