Electrospinning Preparation of High‐Starch‐Content Composite Micro/Nanofibers: Using Water as the Dispersion Medium

Starch‐based fibers possess remarkable advantages, including renewability, excellent biocompatibility, biodegradability, and environmental friendliness, offering broad potential in biomedical and food‐packaging applications. To overcome the poor spinnability and limited starch content of native starch—caused by high amylopectin content, short chain length, and insufficient molecular entanglement—this study employs isoamylase to debranch gelatinized starch, producing enzymatically treated starch (EGST, Enzymatically Gelatinized Starch Treated), in order to regulate the branching structure and chain‐length distribution of starch, and further investigate its rheological behavior and spinnability in aqueous systems. Using water as the dispersion medium, EGST is blended with polyvinyl alcohol (PVA) aqueous solution to prepare spinning dopes, and the effects and underlying mechanisms of enzymolysis degree, blend ratio, and electrospinning parameters on rheological behavior, spinnability, and fiber morphology are systematically investigated. By optimizing the rheology of the EGST/PVA system and the electrospinning conditions, continuous and bead‐free high‐starch‐content composite micro/nanofibers with a starch content of up to 60% and diameters of 200–400 nm are successfully fabricated. This work demonstrates the water‐based fabrication of high‐starch‐content composite micro/nanofibers using water as the dispersion medium and provides a feasible strategy for the fabrication of starch composite nanofibers with high starch content and good processability.