Electrospinning was used to obtain multifunctional fibrous composite materials with a matrix of poly-ɛ-caprolactone (PCL) and 2 wt.% addition of a nanofiller: montmorillonite (MMT), montmorillonite intercalated with gentamicin sulphate (MMTG) or gentamicin sulphate (G). In the first stage, the aluminosilicate gallery was modified by introducing gentamicin sulfate into it, and the effectiveness of the intercalation process was confirmed on the basis of changes in the clay particle size from 0.5 µm (for MMT) to 0.8 µm (for MMTG), an increase in the interplanar distance d001 from 12.3 Å (for MMT) to 13.9 Å (for MMTG) and altered clay grain morphology. In the second part of the experiment, the electrospinning process was carried out in which the polymer nonwovens with and without the modifier were prepared directly from dichloromethane (DCM) and N,N-dimethylformamide (DMF). The nanocomposite fibrous membranes containing montmorillonite were prepared from the same polymer solution but after homogenization with the modifier (13 wt.%). The degree of dispersion of the modifier was evaluated by average microarray analysis from observed area (EDS), which was also used to determine the intercalation of montmorillonite with gentamicin sulfate. An increase in the size of the fibers was found for the materials with the presence of the modifier, with the largest diameters measured for PCL_MMT (625 nm), and the smaller ones for PCL_MMTG (578 nm) and PCL_G (512 nm). The dispersion of MMT and MMTG in the PCL fibers was also confirmed by indirect studies such as change in mechanical properties of the nonwovens membrane, where the neat PCL nonwoven was used as a reference material. The addition of the modifier reduced the contact angle of PCL nonwovens (from 120° for PCL to 96° for PCL_G and 98° for PCL_MMTG). An approximately 10% increase in tensile strength of the nonwoven fabric with the addition of MMT compared to the neat PCL nonwoven fabric was also observed. The results of microbiological tests showed antibacterial activity of all obtained materials; however, the inhibition zones were the highest for the materials containing gentamicin sulphate, and the release time of the active substance was significantly extended for the materials with the addition of montmorillonite containing the antibiotic. The results clearly show that the electrospinning technique can be effectively used to obtain nanobiocomposite fibers with the addition of nonintercalated and intercalated montmorillonite with improved strength and increased stiffness compared to materials made only of the polymer fibers, provided that a high filler dispersion in the spinning solution is obtained.
Keywords: antibacterial properties; electrospinning; fibrous membrane; mechanical properties; montmorillonite; nanobiocomposites; nanocomposites.