Two graphene samples co-doped with nitrogen and sulfur were synthesized by the hydrothermal method using thiourea as doping and reducing agent for graphene oxide (GO). An appropriate amount of thiourea was added to the aqueous dispersion of GO, previously sonicated for 30 min. The mixture was poured into an autoclave and placed in the oven for 3 h, at 120 and 200 °C. The samples were denoted NSGr-120 and NSGr-200, respectively, in agreement with the reaction temperatures. They were next morphologically and structurally characterized by advanced techniques, such as SEM/TEM, XPS, XRD, and FTIR. According to XPS analysis, the NSGr-120 sample has higher amounts of heteroatoms in comparison with NSGr-200, indicating that the reaction temperature is a crucial factor that affects the doping degree. In order to reveal the influence of the doping degree on the electrochemical performances of graphene-modified electrodes, they were tested in solutions containing L-cysteine molecules. The electrode with the best electrocatalytic performances, GC/NSGr-120, was tested to detect L-cysteine in a pharmaceutical drug, proving its applicability in real sample analysis.

Easy and cost-efficient modifications of titanium dioxide nanoparticles that improve their efficiency in the visible light domain represent a continuous and challenging research topic. In addition, the effect of graphene on the overall photocatalytic process is still debated. Consequently, herein, we prepared a series of TiO₂ nanoparticle-based composites with different copper oxide mass content (1–3%) and co-doped with graphene of different oxidation degrees. Different characterization techniques were used to analyze the structural and physico-chemical properties of the obtained composites: Scanning Electron Microscopy (SEM)/Transmission Electron Microscopy (TEM)/Energy-dispersive X-ray spectroscopy (EDX) analysis, X-ray powder diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic performance was evaluated by the degradation of methylene blue under both UVA and visible light irradiation. The nanocomposites show very good photocatalytic activity independent of the presence of reduced graphene oxide, due to the Cu₂O/CuO-TiO₂ heterojunctions. This finding has been confirmed by the very efficient visible-light-driven degradation of amoxicillin and ciprofloxacin.

A graphene sample (EGr) was prepared by electrochemical exfoliation of graphite rods in solution containing 0.05 M (NH₄)₂SO₄ + 0.1 M H₃BO₃ + 0.05 M NaCl. The exfoliation was performed by applying a constant voltage (12 V) between the graphite rods, while the temperature was kept constant (18 °C) with a temperature-controlled cryostat. The structural investigation of the graphene sample, performed by X-ray powder diffraction (XRD), revealed that the sample consists of a mixture of few-layer (69%), multi-layer graphene (14%) and graphene oxide (17%). In addition, XPS analysis proved that the sample was triple-doped with heteroatoms such as nitrogen (1.7 at%), sulfur (2.5 at%), and boron (3 at%). The sample was deposited onto the surface of a clean, glassy carbon electrode (GC) and investigated for the non-enzymatic electrochemical detection of L-tryptophan (TRP). The electrocatalytic properties of the EGr/GC electrode led to a considerable decrease in the oxidation potential from +0.9 V (bare GC) to +0.72 V. In addition, the EGr/GC electrode has higher sensitivity (two times) and a lower detection limit (ten times) in comparison with the bare GC electrode.

Magnetic structures exhibiting large magnetic moments are sought after in theranostic approaches that combine magnetic hyperthermia treatment (MH) and diagnostic magnetic resonance imaging in oncology, since they offer an enhanced magnetic response to an external magnetic field. We report on the synthesized production of a core–shell magnetic structure using two types of magnetite nanoclusters (MNC) based on a magnetite core and polymer shell. This was achieved through an in situ solvothermal process, using, for the first time, 3,4-dihydroxybenzhydrazide (DHBH) and poly[3,4-dihydroxybenzhydrazide] (PDHBH) as stabilizers. Transmission electron microscopy (TEM) analysis showed the formation of spherical MNC, X-ray photoelectronic spectroscopy (XPS) and Fourier transformed infrared (FT-IR) analysis proved the existence of the polymer shell. Magnetization measurement showed saturation magnetization values of 50 emu/g for PDHBH@MNC and 60 emu/g for DHBH@MNC with very low coercive field and remanence, indicating that the MNC are in a superparamagnetic state at room temperature and are thus suitable for biomedical applications. MNCs were investigated in vitro, on human normal (dermal fibroblasts-BJ) and tumor (colon adenocarcinoma-CACO2, and melanoma-A375) cell lines, in view of toxicity, antitumor effectiveness and selectivity upon magnetic hyperthermia. MNCs exhibited good biocompatibility and were internalized by all cell lines (TEM), with minimal ultrastructural changes. By means of flowcytometry apoptosis detection, fluorimetry, spectrophotometry for mitochondrial membrane potential, oxidative stress, ELISA-caspases, and Western blot–p53 pathway, we show that MH efficiently induced apoptosis mostly via the membrane pathway and to a lower extent by the mitochondrial pathway, the latter mainly observed in melanoma. Contrarily, the apoptosis rate was above the toxicity limit in fibroblasts. Due to its coating, PDHBH@MNC showed selective antitumor efficacy and can be further used in theranostics since the PDHBH polymer provides multiple reaction sites for the attachment of therapeutic molecules.

Poly(tartaric acid) is a relatively recently described polymer that can be easily synthesized and scaled up from a readily available renewable material (tartaric acid). This article demonstrates its use in a green synthesis of gold nanoparticles, silver nanoparticles, copper particles, and magnetite nanoparticles. In this case poly(tartaric acid) acts both as a reductant and as a coating agent. To our knowledge this is the first green synthesis of several different types of nanoparticles using only one reagent (polytartrate) as both reductant and coating. The resulting particles were analyzed by XRD, TEM/SEM, EDX, FTIR, DLS, zeta-potential, XPS, and UV/VIS spectroscopy. Preliminary studies of the thermal behavior of mixtures of different types of particles with poly(tartaric acid) were also conducted. The obtained particles show different sizes depending on the material, and the coating allows for better dispersibility as well as potential further functionalization, making them potentially useful also for other applications, besides the inclusion in polymer composites.

Magnetite nanoparticles and clusters of nanoparticles have been of Increasing scientific interest in the past decades. In order to prepare nanoparticles and clusters that are stable in suspension, different coatings have been used. Phosphates and phosphonates are a preferred anchoring group for the coating of magnetite nanomaterials. However, poly(vinylphosphonates) have rarely been used as a coating agent for any nanoparticles. Here, poly(methylvinylphosphonate) and other substituted polyvinylphosphonates are described as new coatings for magnetite nanoparticles and clusters. They show great stability in aqueous suspension. This is also the first time phosphonate-coated magnetite clusters have been synthesized in a one-pot polyol reaction. The coated magnetite nanoparticles and clusters have been characterized by TEM, EDX, FTIR, magnetization measurement, XRD as well as XPS. It has been shown that substituted vinylphosphonates can be easily synthesized in one-step procedures and as a polymeric coating can imbue important properties such as stability in suspension, tight binding to the particle surface, the ability to be further functionalized or to tightly adsorb metal ions. For the synthesis of magnetite clusters the cluster formation, polymerization and coating are done in a one-pot reaction and the resulting magnetite clusters show a higher amount of phosphonate coating than with a three-step procedure including a ligand exchange.