Electrospun polycaprolactone (PCL) membranes have been widely explored in the literature as a solution for several applications in tissue engineering and regenerative medicine. PCL hydrophobicity and its lack of bioactivity drastically limit its use in the medical field. To overcome these drawbacks, many promising strategies have been developed and proposed in the literature. In order to increase the bioactivity of electrospun PCL membranes designed for guided bone and tissue regeneration purposes, in the present work, the membranes were functionalized with a coating of bioactive lactose-modified chitosan (CTL). Since CTL can be used for the synthesis and stabilization of silver nanoparticles, a coating of this compound was employed here to provide antibacterial properties to the membranes. Scanning electron microscopy imaging revealed that the electrospinning process adopted here allowed us to obtain membranes with homogeneous fibers and without defects. Also, PCL membranes retained their mechanical properties after several weeks of aging in simulated body fluid, representing a valid support for cell growth and tissue development. CTL adsorption on membranes was investigated by fluorescence microscopy using fluorescein-labeled CTL, resulting in a homogeneous and slow release over time. Inductively coupled plasma–mass spectrometry was used to analyze the release of silver, which was shown to be stably bonded to the CTL coating and to be slowly released over time. The CTL coating improved MG63 osteoblast adhesion and proliferation on membranes. On the other hand, the presence of silver nanoparticles discouraged biofilm formation by Pseudomonas aeruginosa and Staphylococcus aureus without being cytotoxic. Overall, the stability and the biological and antibacterial properties make these membranes a valid and versatile material for applications in guided tissue regeneration and in other biomedical fields like wound healing.

The employment of coaxial fibers for guided tissue regeneration can be extremely advantageous since they allow the functionalization with bioactive compounds to be preserved and released with a long-term efficacy. Antibacterial coaxial membranes based on poly-ε-caprolactone (PCL) and rifampicin (Rif) were synthesized here, by analyzing the effects of loading the drug within the core or on the shell layer with respect to non-coaxial matrices. The membranes were, therefore, characterized for their surface properties in addition to analyzing drug release, antibacterial efficacy, and biocompatibility. The results showed that the lower drug surface density in coaxial fibers hinders the interaction with serum proteins, resulting in a hydrophobic behavior compared to non-coaxial mats. The air-plasma treatment increased their hydrophilicity, although it induced rifampicin degradation. Moreover, the substantially lower release of coaxial fibers influenced the antibacterial efficacy, tested against Escherichia coli, Staphylococcus aureus, and Pseudomonas aeruginosa. Indeed, the coaxial matrices were inhibitory and bactericidal only against S. aureus, while the higher release from non-coaxial mats rendered them active even against E. coli. The biocompatibility of the released rifampicin was assessed too on murine fibroblasts, revealing no cytotoxic effects. Hence, the presented coaxial system should be further optimized to tune the drug release according to the antibacterial effectiveness.

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