Disposable stencil-printed carbon electrodes for electrochemical analysis of sildenafil citrate in commercial and adulterated tablets

Forensic studies are extremally important to investigate suspected adulterations of consumable products, such as Viagra®. This report describes the determination of sildenafil citrate (SC) in commercial and adulterated tablets based on square-wave voltammetry (SWV) measurements using disposable stencil-printed carbon electrodes. The conductive ink used for the manufacture of integrated electrodes was produced by combining graphite powder and glass varnish. To promote a reusable strategy for limiting the geometric area of the electrodes, a 3D-printed holder was constructed. Detailed morphological and electrochemical characterization studies revealed well-defined graphite flakes incorporated on the polymeric substrate and a faster heterogeneous electron-transfer rate constant (Ks = 1.3 × 10–3 cm s–1). Based on the analytical performance, a linear behavior was observed in a SC concentration range from 1 to 20 µmol L–1 with limit of detection equal to 0.2 µmol L–1. The selectivity of the proposed method was evaluated and the presence of potentially interfering compounds like phosphate, lactose, paracetamol and tadalafil and no difference higher than 15% was observed. The analysis of SC was performed in commercial and seized tablets and the achieved values were 50 ± 1 mg for Viagra® tablet, 54 ± 1 mg for generic formulations 38 ± 1 mg for seized tablet. In addition, the proposed method offered satisfactory accuracy (98.2 – 102.0%) no noticeable matrix effect. Lastly, considering the achieved results, the use of stencil-printed carbon electrodes and SWV has demonstrated to be a powerful and robust analytical tool for forensic investigations.

Electrochemiluminescence at 3D Printed Titanium Electrodes

The fabrication and electrochemical properties of a 3D printed titanium electrode array are described. The array comprises 25 round cylinders (0.015 cm radius, 0.3 cm high) that are evenly separated on a 0.48 × 0.48 cm square porous base (total geometric area of 1.32 cm2). The electrochemically active surface area consists of fused titanium particles and exhibits a large roughness factor ≈17. In acidic, oxygenated solution, the available potential window is from ~-0.3 to +1.2 V. The voltammetric response of ferrocyanide is quasi-reversible arising from slow heterogeneous electron transfer due to the presence of a native/oxidatively formed oxide. Unlike other metal electrodes, both [Ru(bpy)3]1+ and [Ru(bpy)3]3+ can be created in aqueous solutions which enables electrochemiluminescence to be generated by an annihilation mechanism. Depositing a thin gold layer significantly increases the standard heterogeneous electron transfer rate constant, ko, by a factor of ~80 to a value of 8.0 ± 0.4 × 10−3 cm s−1 and the voltammetry of ferrocyanide becomes reversible. The titanium and gold coated arrays generate electrochemiluminescence using tri-propyl amine as a co-reactant. However, the intensity of the gold-coated array is between 30 (high scan rate) and 100-fold (slow scan rates) higher at the gold coated arrays. Moreover, while the voltammetry of the luminophore is dominated by semi-infinite linear diffusion, the ECL response is significantly influenced by radial diffusion to the individual microcylinders of the array.

Redox Potential Tuning of s-Tetrazine by Substitution of Electron-Withdrawing/Donating Groups for Organic Electrode Materials

Herein, we tune the redox potential of 3,6-diphenyl-1,2,4,5-tetrazine (DPT) by introducing various electron-donating/withdrawing groups (methoxy, t-butyl, H, F, and trifluoromethyl) into its two peripheral benzene rings for use as electrode material in a Li-ion cell. By both the theoretical DFT calculations and the practical cyclic voltammetry (CV) measurements, it is shown that the redox potentials (E1/2) of the 1,2,4,5-tetrazines (s-tetrazines) have a strong correlation with the Hammett constant of the substituents. In Li-ion coin cells, the discharge voltages of the s-tetrazine electrodes are successfully tuned depending on the electron-donating/withdrawing capabilities of the substituents. Furthermore, it is found that the heterogeneous electron transfer rate (k0) of the s-tetrazine molecules and Li-ion diffusivity (DLi) in the s-tetrazine electrodes are much faster than conventional electrode active materials.

Biological and Electrochemical Studies of Macrocyclic Complexes of Iron and Cobalt

In this work, we synthesized two tetraaza [N4] macrocyclic complexes of FeIII and CoII metal ions. The synthesized macrocyclic complexes were fully characterized by using various analytical techniques IR, UV-Vis, and MS. The spectral analysis indicated an octahedral geometry for both macrocyclic complexes. The electrochemical behavior was carried out using cyclic voltammetry on the Pt dish (0.031 cm2) electrode. The complexes were shown to have unusual oxidation states for the metal ions. The “heterogeneous electron transfer rate constant” (Ko) was also calculated using “Nicholson and Kochi’s method” and observed in the order: KoCoII > KoFeIII. The antimicrobial activities of two complexes were computed against E. coli, P. aeruginosa, B. cereus, S. aureus, whereas antifungal activities against C. Albicans and were contrasted with the standard drug “Gentamycin”.