In this study, the effect of the ionic cross-linking mode on the ability to control physical properties and in vitro release behavior of the dexamethasone (DEX) drug from chitosan (CS) and chitosan/hydroxyapatite (CS/HA) beads was investigated. CS solutions without and with HA and DEX were dripped into two coagulation solutions, prepared with a non-toxic ionic crosslinker (sodium tripolyphosphate, TPP) and distilled water, one at pH = 9.0 and other at pH = 6.0. Optical microscopy (OM) and scanning electron microscopy (SEM) results showed changes on the surface topology of the beads, with a reduction of roughness for beads prepared at pH = 6.0 and an increase for the one prepared at pH = 9.0. The diameter and sphericity of the beads prepared at pH = 6.0 proved more uniform and had a larger pore size with a good interconnectivity framework. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) suggested a higher crosslinking degree for beads prepared at pH = 6.0, corroborated by X-ray diffraction profiles (XRD) analysis that indicated a decrease in the crystalline structure for such beads. In in vitro drug release data, all beads presented a sustained release during the studied period (24 h). The drug release rate was affected by the pH of the coagulation solution used in the preparation of the beads. The in vitro kinetics of the release process was of the Peppas–Sahlin model, controlled by both diffusion and relaxation of polymer chains or swelling (anomalous transport mechanism). Our results suggest that DEX-loaded CS/HA beads, crosslinked in TPP coagulation solution at pH = 9.0, led to a decrease in the DEX release rate and prolonged the release period. Thus, this composition might have prospective as a functional material for bone and cartilage tissue engineering.

This work aimed to prepare chitosan/clay microspheres, by the precipitation method, for use in drug carrier systems. The influence of the process parameters, particularly two airflows of the drag system (2.5 and 10 L·min⁻¹) on the microspheres physical dimensions and properties, such as microstructure, degree of swelling and porosity were evaluated. The samples were characterized by optical microscopy (OM), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Water absorption and porosity tests were also performed. The results showed that the process parameters affected the size of the microspheres. The diameter, volume and surface area of the chitosan/clay microspheres decreased when they were prepared with the higher airflow of the drag system. The microspheres presented a porous microstructure, being the pore size, percentage of porosity and degree of swelling affected not only by the process parameters but also by the type of clay. Hybrids (chitosan/clay) with intercalated morphology were obtained and the hybrid prepared with montmorillonite clay at higher airflows of the drag system presented the greatest interlayer spacing and a more disordered morphology. Thus, it is certain that the chitosan/clay nanocomposite microspheres prepared with montmorillonite (CL clay) at higher airflows of the drag system can have good drug-controlled release properties.