The pH- and thermo-responsive behavior of polymeric hydrogels have been studied in detail using dynamic light scattering , scanning electron microscopy, nuclear magnetic resonance (1H NMR) and rheology to evaluate the conformational changes, swelling–shrinkage, stability, the ability to flow and the diffusion process of nanoparticles at several temperatures. Furthermore, polymeric systems functionalized with acrylic acid and acrylamide were subjected to a titration process with a calcium chloride solution to analyze its effect on the average particle diameter, polymer structure and the intra- and intermolecular interactions in order to provide a responsive polymer network that can be used as a possible nanocarrier for drug delivery with several benefits. The results confirmed that the structural changes in the sensitive hydrogels are highly dependent on the corresponding critical solution temperature of the carboxylic (–COOH) and amide (–CONH2) functional groups and the influence of calcium ions on the formation or breaking of hydrogen bonds, as well as the decrease in electrostatic repulsions generated between the polymer chains contributing to a particle agglomeration phenomenon. The temperature leads to a re-arrangement of the polymer chains, affecting the viscoelastic properties of the hydrogels. In addition, the diffusion coefficients of nanoparticles were evaluated, showing a closeness among with the morphology, shape, size and temperature, resulting in slower diffusions for larger particles size and, conversely, the diffusion in the medium increasing as the polymer size is reduced. Therefore, the hydrogels exhibited a remarkable response to pH and temperature variations in the environment. During this research, the functionality and behavior of the polymeric nanoparticles were observed under different analysis conditions, which revealed notable structural changes and further demonstrated the nanoparticles promising high potential for drug delivery applications. Hence, these results have sparked significant interest in various scientific, industrial and technological fields.
A series of samples of Mg/Zn/Al LDHs (layered double hydroxides) materials was prepared by the co-precipitation and urea hydrolysis methods. They were modified with organic surfactants (acrylate and oleate anions) and characterized by X-ray diffraction, which corroborated the intercalation of anionic species into the interlayer space. The hydrophobized materials were incorporated at low contents (10 and 15 wt.%) to polystyrene, which was synthesized by emulsion polymerization techniques. The polymeric composites were analyzed by thermogravimetry to determine the decomposition temperature. The results demonstrated that the materials with Zn presented the greatest increment in the degradation temperature (7 °C < T < 54 °C). Moreover, the Friedman, Flynn–Wall–Ozawa, and Coats–Redfern models were compared to obtain the kinetic parameters of degradation process. The obtained order of decomposition of the Coats–Redfern model showed that the decomposition process occurs in at least two stages. Finally, the addition of environmentally friendly modified Layered Double Hydroxides (LDH) nanomaterials to the polystyrene (PS) matrix allowed for obtaining polymeric composites with higher thermal stability, retarding the decomposition process of PS.
Background: Cancer therapeutics development has been a challenge in medical and scientific areas due to their toxicity, limited biocompatibility, and unfortunate side effects. However, despite advances in early detection and the study of novel treatments, the mortality rate for breast cancer remains high, making it a significant global health concern. Objectives: In this study, poly(methyl methacrylate) (PMMA) nanoparticles functionalized with acrylic acid (AA), fumaramide (FA), and curcumin (CUR) as chelating and inhibitor agents were synthesized by emulsion polymerization techniques. Methods and Results: Comprehensive physiochemical characterization studies based on gravimetry, dynamic light scattering (DLS), electrophoresis, Fourier transform infrared (FT-IR), ultraviolet–visible (UV–Vis) and photoluminescence (PL) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM) revealed a pH dependence of nanoparticles that exhibit structural changes upon interaction with calcium (Ca2+) and magnesium (Mg2+) ions. Calorimetric thermodynamic properties measured by isothermal titration calorimetry (ITC) confirmed chelating coordination and positive cooperativity between the nanoparticles and metal ions. In vitro studies showed the low cytotoxicity of nanoparticles by fibroblast proliferation, and their chelation process was observed by fluorescence microscopy, with the loss of interaction between cells. Conclusions: These results suggest that the functionalized nanoparticles have potential in drug delivery systems (DDS) for targeted breast cancer therapies, providing a promising polymer material for more efficient and less toxic treatments.
Two series of novel amphiphilic compounds were synthesized based on carbamates and ureas structures, using a modification of the synthesis methods reported by bibliography. The compounds were tested for organic solvent removal in a model wastewater. The lipophilic group of all compounds was a hexadecyl chain, while the hydrophilic substituent was changed with the same modifications in both series. The structures were confirmed by FT-IR, NMR, molecular dynamic simulation and HR-MS and their ability to gel organic solvents were compared. The SEM images showed the ureas had a greater ability to gel organic solvents than the carbamates and formed robust supramolecular networks, with surfaces of highly interwoven fibrillar spheres. The carbamates produced corrugated and smooth surfaces. The determination of the minimum gelation concentration demonstrated that a smaller quantity of the ureas (compared to the carbamates, measured as the weight percentage) was required to gel each solvent. This advantage of the ureas was attributed to their additional N-H bond, which is the only structural difference between the two types of compounds, and their structures were corroborated by molecular dynamic simulation. The formation of weak gels was demonstrated by rheological characterization, and they demonstrated to be good candidates for the removal organic solvents.