Synthesis, Crystal Structure and Cyclic Voltammetric Behavior of N-aroyl-N′-(4′-cyanophenyl)thioureas

Herein, two title compounds, N-benzoyl-N′-(4′-cyanophenyl)thiourea (1) and N-(4-nitrobenzoyl)-N′-(4′-cyanophenyl)thiourea (2) were synthesized in a high yield, via different applications of aroyl isocyanate and 4-aminobenzonitrile. The structure of the prepared compounds was characterized by elemental analysis and FT-IR, 1H, and 13C-NMR spectroscopic methods. The crystal structure of the title compound 1 was determined by an X-ray single-crystal technique and an intramolecular C=O…H-N hydrogen bond and intermolecular C=S…H-N and C=S…H-C hydrogen interactions, which were observed for the crystal structure. The molecular electrostatic potential (MEP) and the Mulliken atomic charges of title compounds 1 and 2 were theoretically calculated and interpreted. Cyclic voltammetric (CV) experiments for the compounds were performed with the glassy carbon electrode. The reduction in potential values of the different functional groups such as nitro and cyano in title compounds were investigated using CV curves.

Disposable Pencil Graphite Electrode for Diosmin Voltammetric Analysis

Diosmin (DIO) is a naturally occurring flavonoid with multiple beneficial effects on human health. The presence of different hydroxyl groups in diosmin structure enables its electrochemical investigation and quantification. This work presents, for the first time, diosmin voltammetric behavior and quantification on the cost-effective, disposable pencil graphite electrode (PGE). Diosmin oxidation on PGE involves two irreversible steps, generating products with reversible redox behaviors. All electrode processes are pH-dependent and predominantly adsorption-controlled. Differential pulse (DPV) and adsorptive stripping differential pulse (AdSDPV) voltammetric methods have been optimized for diosmin quantification o an H-type PGE, in 0.100 mol/L H2SO4. The linear ranges and limits of detection were for DPV 1.00 × 10−6–1.00 × 10−5 mol/L and 2.76 × 10−7 mol/L DIO for DPV and 1.00 × 10−7–2.50 × 10−6 mol/L and 7.42 × 10−8 mol/L DIO for AdSDPV, respectively. The DPV method was successfully applied for diosmin quantification in dietary supplement tablets. The percentage recovery was 99.87 ± 4.88%.

Voltammetric Behavior, Flavanol and Anthocyanin Contents, and Antioxidant Capacity of Grape Skins and Seeds during Ripening (Vitis vinifera var. Merlot, Tannat, and Syrah)

Skin and seed grape extracts of three red varieties (Merlot, Tannat, and Syrah) at different stages of ripening were studied for their total phenolic content (TPC) by using the Folin-Ciocalteu assay and for their total antioxidant capacity (TAC) by using spectrophotometric and electrochemical assays. Flavanol and anthocyanin compositions were also investigated using Ultra Performance Liquid Chromatography coupled with Mass Spectrometry (UPLC-MS). Results showed that seeds had the highest phenolic content and the highest antioxidant potential compared to skins at all stages of ripening. The highest TPC and TAC values were measured in seeds at close to veraison and veraison ripening stages. In skins, the highest values were found at the green stage, it was in accordance with the flavanols content. The voltammetric measurements were carried out using disposable single walled carbon nanotubes modified screen-printed carbon electrodes (SWCNT-SPCE). Three peaks on voltammograms were obtained at different oxidation potentials. The first anodic peak that oxidized at a low potential describes the oxidation of ortho-dihydroxy phenols and gallate groups, the second peak corresponds to the malvidin anthocyanins oxidation and the second oxidation of flavonoids. The third voltammetric peak could be due to phenolic acids such as p-coumaric acid and ferulic acid or the second oxidation of malvidin anthocyanins. The high linear correlation was observed between antioxidant tests and flavanols in skins (0.86 ≤ r ≤ 0.94), while in seeds, ‘r’ was higher between electrochemical parameters and flavanols (0.64 ≤ r ≤ 0.8).

Stochastic Analysis of Electron Transfer and Mass Transport in Confined Solid/Liquid Interfaces

Molecular-level understanding of electrified solid/liquid interfaces has recently been enabled thanks to the development of novel in situ/operando spectroscopic tools. Among those, ambient pressure photoelectron spectroscopy performed in the tender/hard X-ray region and coupled with the “dip and pull” method makes it possible to simultaneously interrogate the chemical composition of the interface and built-in electrical potentials. On the other hand, only thin liquid films (on the order of tens of nanometers at most) can be investigated, since the photo-emitted electrons must travel through the electrolyte layer to reach the photoelectron analyzer. Due to the challenging control and stability of nm-thick liquid films, a detailed experimental electrochemical investigation of such thin electrolyte layers is still lacking. This work therefore aims at characterizing the electrochemical behavior of solid/liquid interfaces when confined in nanometer-sized regions using a stochastic simulation approach. The investigation was performed by modeling (i) the electron transfer between a solid surface and a one-electron redox couple and (ii) its diffusion in solution. Our findings show that the well-known thin-layer voltammetry theory elaborated by Hubbard can be successfully applied to describe the voltammetric behavior of such nanometer-sized interfaces. We also provide an estimation of the current densities developed in these confined interfaces, resulting in values on the order of few hundreds of nA·cm−2. We believe that our results can contribute to the comprehension of the physical/chemical properties of nano-interfaces, thereby aiding to a better understanding of the capabilities and limitations of the “dip and pull” method.