Diffusion-Controlled Drug Release from Electrospun Poly(3-hydroxybutyrate) Fibers with Beaded Architecture: An Experimental and Modeling Study.

The global transition from petrochemical to sustainable bio-based plastics has been strongly supported by electrospinning (ES), a versatile nanotechnology enabling the fabrication of ultrathin fibers with multifunctional properties. The solution ES process alongside the uniform fibers, a characteristic "beads-on-string" morphology, consisting of alternating cylindrical and spindle-like segments, is frequently observed. Once considered undesirable, these structures are now recognized as functional fibrous architectures with enhanced properties. This work explores the valorization of beaded fibers through combined experimental characterization and modeling, aiming to evaluate the impact of beading on drug diffusion and delivery performance. Poly(3-hydroxybutyrate) (PHB) was selected as the model biopolyester and dipyridamole (DPD) as the model drug. Ultrathin fibers were fabricated using the laboratory electrospinning device, EFV-1 (ICP, Moscow, Russia). The distance between the capillary nozzle and the anodic collector was set to 180 mm, with the capillary tip radius equal to 0.35 mm, and applied voltage between the electrodes was kept constant at 18 kV. Drug release profiles were obtained by simulating DPD diffusion in ellipsoidal (beads) and cylindrical fiber domains. Ultrathin fibers were fabricated by solution electrospinning under environmental conditions (at ambient temperature, 50% relative humidity). Morphology was analyzed via SEM, thermal properties via DSC, and structure via FTIR spectroscopy at different temperatures, including the melting point (~170 °C). Drug release kinetics were monitored using a UV-Vis spectroscopy. The impact of DPD diffusion within the ellipsoidal and cylindrical constituents of polymer filaments was considered to modulate release profiles for the development of innovative pharmaceutical platforms. Diffusion controlled drug release was computationally modeled using a specially designed simulation program, in good agreement with experimental data. The results demonstrate that morphological parameters significantly affect diffusion and release kinetics. The controlled exploitation of bead-on-string architectures may enable the design of electrospun materials with tunable absorption of pollutant filtration, mechanical performance, and flexibility in drug release profiles, for sustainable biopolymers like PHB.