Infection with pathogenic microorganisms is of great concern in many areas, especially in healthcare, but also in food packaging and storage, or in water purification systems. Antimicrobial polymer nanocomposites have gained great popularity in these areas. Therefore, this study focused on new approaches to develop thin antimicrobial films based on biodegradable polycaprolactone (PCL) with clay mineral natural vermiculite as a carrier for antimicrobial compounds, where the active organic antimicrobial component is antifungal ciclopirox olamine (CPX). For possible synergistic effects, a sample in combination with the inorganic antimicrobial active ingredient zinc oxide was also prepared. The structures of all the prepared samples were studied by X-ray diffraction, FTIR analysis and, predominantly, by SEM. The very different structure properties of the prepared nanofillers had a fundamental influence on the final structural arrangement of thin PCL nanocomposite films as well as on their mechanical, thermal, and surface properties. As sample PCL/ZnOVER_CPX possessed the best results for antimicrobial activity against examined microbial strains, the synergic effect of CPX and ZnO combination on antimicrobial activity was proved, but on the other hand, its mechanical resistance was the lowest.

Microbial infection and biofilm formation are both problems associated with medical implants and devices. In recent years, hybrid organic-inorganic nanocomposites based on clay minerals have attracted significant attention due to their application potential in the field of antimicrobial materials. Organic drug/metal oxide hybrids exhibit improved antimicrobial activity, and intercalating the above materials into the interlayer of clay endows a long-term and controlled-release behavior. Since antimicrobial activity is strongly related to the structure of the material, ultrasonic treatment appears to be a suitable method for the synthesis of these materials as it can well control particle size distribution and morphology. This study aims to prepare novel, structurally stable, and highly antimicrobial nanocomposites based on zinc oxide/vermiculite/chlorhexidine. The influence of ultrasonic treatment at different time intervals and under different intercalation conditions (ultrasonic action in a breaker or in a Roset’s vessel) on the structure, morphology, and particle size of prepared hybrid nanocomposite materials was evaluated by the following methods: scanning electron microscopy, X-ray diffraction, energy dispersive X-ray fluorescence spectroscopy, carbon phase analysis, Fourier transforms infrared spectroscopy, specific surface area measurement, particle size analysis, and Zeta potential analysis. Particle size analyses confirmed that the ultrasonic method contributes to the reduction of particle size, and to their homogenization/arrangement. Further, X-ray diffraction analysis confirmed that ultrasound intercalation in a beaker helps to more efficiently intercalate chlorhexidine dihydrochloride (CH) into the vermiculite interlayer space, while a Roset’s vessel contributed to the attachment of the CH molecules to the vermiculite surface. The antibacterial activity of hybrid nanocomposite materials was investigated on Gram negative (Escherichia coli, Pseudomonas aeruginosa) and Gram positive (Staphylococcus aureus, Enterococcus faecalis) bacterial strains by finding the minimum inhibitory concentration. All hybrid nanocomposite materials prepared by ultrasound methods showed high antimicrobial activity after 30 min, with a long-lasting effect and without being affected by the concentration of the antibacterial components zinc oxide (ZnO) and CH. The benefits of the samples prepared by ultrasonic methods are the rapid onset of an antimicrobial effect and its long-term duration.