Novel Electrospun Pullulan Fibers Incorporating Hydroxypropyl-β-Cyclodextrin: Morphology and Relation with Rheological Properties

Fibers produced by electrospinning from biocompatible, biodegradable and naturally occurring polymers have potential advantages in drug delivery and biomedical applications because of their unique functionalities. Here, electrospun submicron fibers were produced from mixtures containing an exopolysaccharide (pullulan) and a small molecule with hosting abilities, hydroxypropyl-β-cyclodextrin (HP-β-CD), thus serving as multi-functional blend. The procedure used water as sole solvent and excluded synthetic polymers. Rheological characterization was performed to evaluate the impact of HP-β-CD on pullulan entanglement concentration (C_E); the relationship with electrospinnability and fiber morphology was investigated. Neat pullulan solutions required three times C_E (~20% w/v pullulan) for effective electrospinning and formation of bead-free nanofibers. HP-β-CD (30% w/v) facilitated electrospinning, leading to the production of continuous, beadless fibers (average diameters: 853-1019 nm) at lower polymer concentrations than those required in neat pullulan systems, without significantly shifting the polymer C_E. Rheological, Differential Scanning Calorimetry (DSC) and Dynamic Light Scattering (DLS) measurements suggested that electrospinnability improvement was due to HP-β-CD assisting in pullulan entanglement, probably acting as a crosslinker. Yet, the type of association was not clearly identified. This study shows that blending pullulan with HP-β-CD offers a platform to exploit the inherent properties and advantages of both components in encapsulation applications.