Potentiodynamically fabricated poly(alizarin red s) modified GCE was characterized using CV and EIS techniques. In contrast to the cyclic voltammetric response of the unmodified GCE for metronidazole, an irreversible reduction peak with three-folds of current enhancement and reduced overpotential at the poly(alizarin red s) modified GCE showed the catalytic effect of the modifier towards reduction of metronidazole. While observed peak potential shift with increasing pH (4.0–10.0) indicated the involvement of protons during the reduction of metronidazole, peak potential shift with scan rate (20–300 mV s-1) confirmed the irreversibility of the reduction reaction of metronidazole at the modified GCE. A better correlation for the dependence of peak current on scan rate (r2 = 0.9883) than on square root of scan rate (r2 = 0.9740) supplemented by slope value of 0.38 for plot of log(current) versus log(scan rate) indicated the reduction reaction of metronidazole at the surface of the modified electrode was predominantly adsorption controlled. Under the optimized method and solution parameters, reductive current response of tablet sample showed linear dependence on spiked standard concentration in a wide range (0–125 μM) with excellent determination coefficient r2, LoD and LoQ of 0.9991, 0.38, and 1.25 μM, respectively. Spike recovery of 97.9% and interference recovery of 96.2–97.5% in the presence of 21.28 and 31.92 μM of uric acid and ascorbic acid validated the applicability of the present method for determination of metronidazole in tablet formulation. The metronidazole content of the tested tablet formulation using standard addition method was found to be 97.6% of what is claimed by the tablet manufacturer making the developed method an excellent potential candidate for its applicability to determine metronidazole in real samples with complex matrix.

A selective and sensitive electrochemical method based on glassy carbon electrode modified with poly(malachite green) was developed for determination of tetracycline in pharmaceutical capsule formulation. Cyclic voltammetry and electrochemical impedance spectroscopy using [Fe(CN) 6 ] 3-/4- as a probe were used to characterize the potentiodynamiclly deposited poly(malachite green) on the surface of glassy carbon electrode. In contrast to the unmodified glassy carbon electrode, the fabricated poly(malachite green) modified glassy carbon electrode showed catalytic property towards two steps irreversible oxidation of tetracycline. Better correlation of the oxidative peak current with the scan rate than with the square root of scan rate supported by slope of 0.60 for log(current) versus log(scan rate) indicated that the oxidation reaction of tetracycline at the modified electrode was predominantly controlled by electron exchange step at the solution polymer interface. Under optimized solution pH, and accumulation parameters, the square wave adsorptive anodic striping peak current response of the modified electrode showed linear dependence on concentration of tetracycline in the range 5–100 μM with determination coefficient, method detection limit, and quantification limit of 0.99588, 1.6 μM, and 5.3 μM, respectively. The tetracycline content of a capsule sample claimed to have 250 mg/capsule was found to be 250.53 mg/capsule with 0.21% deviation. Excellent spike recovery result of 99.80%, and 98.49–99.78% recovery of tetracycline in capsule sample in the presence of 50–200% of UA, AA, and ampicillin validated the applicability of the method for determination of tetracycline in real samples with complex matrix like capsule formulations.

In this study, a square wave voltammetric method for determination of theophylline in tablet formulation based on EDTA salt modified carbon paste electrode is presented. CV, FT-IR, and EIS results confirmed modification of the carbon paste with EDTA salt. In contrast to the unmodified carbon paste electrode, the modified carbon paste electrode showed irreversible oxidation of theophylline with considerable current enhancement. Investigation of the effect of scan rate on the Ip and Ep response of the modified electrode for theophylline revealed predominantly diffusion controlled oxidation kinetics. Under the optimized conditions, square wave oxidative peak current of theophylline in pH 7.0 PBS showed linear dependence on concentration in the range 10–200 μM with determination coefficient (R2), limit of detection, and limit of quantification of 0.99782, 0.0257 μM, and 0.0857 μM, respectively. Detection of an amount of theophylline in the analyzed tablet formulation with 1.85% error from its nominal content (120 mg/tablet) confirmed the accuracy of the developed method. Spike and interference recovery results of 98.59%, and 95.7–100%, respectively validated the applicability of the developed method for determination of theophylline content in tablet samples.