The discovery of a new non-toxic metal complex with biological activity represents a very active area of research. Two Cu⁺² complexes, [Cu₄(L1)₄(OH)₄(DMF)₂(H₂O)] (C1) (HL1 = N-(5-ethyl-[1,3,4]–thiadiazole–2-yl)-benzenesulfonamide) and [Cu(L2)₂(phen)(H₂O)] (C2) (HL2 = N-(5-(4-methylphenyl)-[1,3,4]–thiadiazole–2-yl)-naphtalenesulfonamide), with two new ligands were synthesized. The X-ray crystal structures of the complexes were determined. In both complexes, Cu⁺² is five-coordinated, forming a CuN₂O₃ and CuN₄O chromophore, respectively. The ligands act as monodentate, coordinating the metal ion through a single N_thiadiazole atom; for the two complexes, the molecules from the reaction medium (phenantroline, dimethylformamide and water) are also involved in the coordination of Cu⁺². The complexes have a distorted square pyramidal square-planar geometry. The compounds were characterized by FT-IR and UV-Vis spectroscopy. Using the microdilution method, the antibacterial activity of the complexes was determined against four Gram-positive and two Gram-negative bacteria, with Gentamicin as the positive control. Cytotoxicity studies were carried out on two tumor cell lines (HeLa, DLD-1) and on a normal cell line (HFL1) using the MTT method and Cisplatin as a positive control. Flow cytometric assessment of apoptosis induced by the complexes on the three cell lines was also performed. Both complexes present in vitro biological activities but complex C2 is more active.

The excellent adsorption properties of clay minerals make the optimization of heavy metal removal the subject of numerous research projects. In the present study, ASLAVITAL cosmetic clay (ACC) powder was applied for the removal of Cd²⁺ from water. The main deposit of ACC clay is the Pădurea Craiului Mountains in Romania. A wide range of morpho-structural approaches (SEM, EDX, FTIR, Raman, XRD) were used to characterize the morphology and elemental composition of the adsorbent. As expected for clay minerals, Al (Wt(%) = 11.4 ± 0.9) and Si (Wt(%) = 13.7 ± 1.4) are the main constituents of ACC. After adsorption, Wt(%) = 0.2 ± 0.01 Cd²⁺ was detected in the sample. As proved before, the initial metal concentration is the primary influencing factor; therefore, batch adsorption of 10–160 mg/L Cd²⁺ was investigated. After 190 min, an efficiency of 99% was reached, and the quantity in equilibrium increased from 1–8 mg/g. The best fit in linear form was obtained for the Langmuir II. model, where R² = 0.954 (R_L = 0.037–0.027). Based on linear isotherm models, physical bonds formed between ACC and Cd²⁺ during the favorable adsorption. For the non-linear fits, the Liu model proved to be the best R² = 0.965, χ² = 1.101. Pseudo-II-order kinetic model described the experimental data R² = 0.988–0.999; q_exp and q_calc were almost identical (the differences ranged 0.03–0.34).

N-doped graphene-ZnO hybrid materials with different N-doped graphene:ZnO wt% ratios (1:10; 1:20; 1:30) were prepared by a simple and inexpensive sol-gel method. The materials denoted NGr-ZnO-1 (1:10), NGr-ZnO-2 (1:20), and NGr-ZnO-3 (1:30) were investigated with advanced techniques and their morpho-structural, photocatalytic, and electrocatalytic properties were reported. Hence, pure N-doped graphene sample contains flakes with the size ranging from hundreds of nanometers to micrometers. In the case of all NGr-ZnO hybrid materials, the flakes appear heavily decorated with ZnO nanoparticles, having a cauliflower-like morphology. The X-ray powder diffraction (XRD) investigation of N-doped graphene sample revealed that it was formed by a mixture of graphene oxide, few-and multi-layer graphene. After the ZnO nanoparticles were attached to graphene, major diffraction peaks corresponding to crystalline planes of ZnO were seen. The qualitative and quantitative compositions of the samples were further evidenced by X-ray photoelectron spectroscopy (XPS). In addition, UV photoelectron spectroscopy (UPS) spectra allowed the determination of the ionization energy and valence band maxima. The energy band alignment of the hybrid materials was established by combining UV–Vis with UPS results. A high photocatalytic activity of NGr-ZnO samples against rhodamine B solution was observed. The associated reactive oxygen species (ROS) generation was monitored by electron paramagnetic resonance (EPR)-spin trapping technique. In accordance with bands alignment and identification of radical species, the photocatalytic mechanism was elucidated.

Nitrogen-doped graphene (NGr) was synthesized by the hydrothermal method using urea as a reducing and doping agent for graphene oxide (GO). The crystalline structure of GO was revealed by the XRD intense peak recorded at 2θ = 11.4°, indicating that the interlayer distance within the structure was large (d = 0.77 nm), and the number of layers (n) was 9. Further, the transformation of GO in NGr also led to the decrease in the interlayer distance and number of layers (d = 0.387 nm; n = 3). As indicated by elemental analysis, the concentration of nitrogen in the NGr sample was 6 wt%. Next, the comparison between the performance of bare GC and the graphene-modified electrode (NGr/GC) towards piroxicam (PIR) detection was studied. Significant differences were observed between the two electrodes. Hence, in the case of bare GC, the oxidation signal of PIR was very broad and appeared at a high potential (+0.7 V). In contrast, the signal recorded with the NGr/GC electrode was significantly higher (four times) and shifted towards lower potentials (+0.54 V), proving the electro-catalytic effect of nitrogen-doped graphene. The NGr/GC electrode was also tested for its ability to detect piroxicam in pharmaceutical drugs (Flamexin), giving excellent recoveries.

Three-dimensional printing by fused deposition modeling (FDM) coupled with hot-melt extrusion (HME) is a point of convergence of research efforts directed toward the development of personalized dosage forms. In addition to the customization in terms of shapes, sizes, or delivered drug doses, the modulation of drug release profiles is crucial to ensure the superior efficacy and safety of modern 3D-printed medications compared to those of conventional ones. Our work aims to solidify the groundwork for the preparation of 3D-printed tablets that ensure the sustained release of diclofenac sodium. Specifically, we achieved the fast release of a diclofenac sodium dose to allow for the prompt onset of its pharmacological effect, further sustaining by the slow release of another dose to maintain the effect over a prolonged timeframe. In this regard, proper formulation and design strategies (a honeycomb structure for the immediate-release layer and a completely filled structure for the sustained-release layer) were applied. Secondarily, the potential of polyvinyl alcohol to function as a multifaceted polymeric matrix for both the immediate and slow-release layers was explored, with the objective of promoting the real-life applicability of the technique by downsizing the number of materials required to obtain versatile pharmaceutical products. The present study is a step forward in the translation of HME-FDM-3DP into a pharmaceutical manufacturing methodology.