Fully Aqueous Electrospinning of Binary PVP/Sodium-Alginate and PVP/Riboflavin Nanofibres: Additive Effects and UV-Assisted Processing

Electrospinning (ES) can produce nonwoven fibrous mats with high surface area and interconnected porosity, making them attractive for biomedical and functional material applications. However, conventional ES often relies on volatile organic solvents, raising safety, environmental, and translational concerns. Fully aqueous (“green”) ES offers an appealing alternative, although many water-soluble polymers remain difficult to spin and may show limited stability under hydrated conditions. In this study, two fully aqueous binary systems, poly(vinylpyrrolidone)–sodium alginate (PVP–SA) and poly(vinylpyrrolidone)–riboflavin (PVP–RF), were investigated to decouple the roles of sodium alginate (SA) and riboflavin (RF) on solution behaviour, fibre formation, morphology, dry-state mechanical properties, and surface chemistry. Aqueous PVP solutions (20% w/v; molecular weight 1.3 MDa) were blended with SA (1–5 wt% relative to PVP) or RF (1–10 wt% relative to PVP). Electrical conductivity and rheological properties were evaluated prior to ES under controlled conditions, with simultaneous ultraviolet (UV) exposure at 344 nm during fibre collection. RF did not significantly alter conductivity (~0.74–0.75 µS·cm−1), whereas SA increased conductivity up to 2.75 ± 0.03 µS·cm−1 at 5 wt%. All formulations exhibited shear-thinning behaviour, while 10 wt% RF increased the zero-shear viscosity relative to neat PVP. Morphological analysis showed that low SA contents produced uniform fibres, whereas higher SA levels (4–5 wt%) led to bead defects and reduced fibre diameter (down to 85 ± 25 nm). Dry-state mechanical performance decreased with increasing SA content, while 10 wt% RF improved tensile strength and toughness, reaching an ultimate tensile strength of 5.21 ± 0.15 MPa and toughness of 40.51 ± 1.53 MJ·m−3. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) indicated subtle UV-driven redistribution of surface chemical states, consistent with mild photo-oxidative microstructural modification rather than extensive covalent network formation. Because the UV irradiance was not directly measured and wet-state stability was not assessed, the UV-related findings are interpreted as preliminary chemical evidence rather than confirmation of stabilized fibre mats. Overall, this work establishes a solvent-free aqueous ES platform in which ionic and photoactive additives can be used to tailor fibre morphology, dry-state mechanical behaviour, and surface characteristics without toxic reagents.