Internal nanocrystalline structure and stiffness alterations of electrospun polycaprolactone-based mats after six months of in vitro degradation. An atomic force microscopy assay

Biodegradable electrospun nanofibrous scaffolds for bone tissue engineering applications have been extensively studied as they can provide attractive open-worked architecture resembling natural extracellular matrix, with tunable physical and mechanical properties enhancing positive cellular response. For this purpose, electrospun mats were tested in terms of morphology, mechanical and physical properties, degradation kinetics and related phenomena occurring in micro- and nanoscale. However, detailed description of internal nanostructures of electrospun mats and their changes related to in vitro degradation is still missing. In this manuscript, we report qualitative and quantitative evaluation of internal lamellar nanostructure of electrospun fibrous scaffolds made of pristine polycaprolactone and composite with polymeric matrix and nanoceramic (hydroxyapatite) filler during in vitro degradation. Morphological and mechanical studies performed with an atomic force microscope were followed by scanning electron microscope imaging and X-Ray diffraction. The results suggest degradation-dependent alteration of both organization and thickness of nano-scaled lamellas recorded with atomic force microscope. Moreover, changes of the material's internal structure were followed by enhanced stiffness and higher crystallinity of electrospun fibers.