Ternary Interactions of Starch, Protein, and Polyphenols in Constructing Composite Thermoplastic Starch-Based Edible Packaging: Optimization of Preparation Techniques and Investigation of Film-Formation Mechanisms

Biodegradable starch-based films often suffer from insufficient mechanical strength, which limits their practical applications. To enhance film performance, this study optimized the preparation of composite thermoplastic starch (CTPS) films composed of corn starch, sorbitol, whey protein isolate (WPI), and gallic acid (GA). The optimized formulation—0.074 g/mL corn starch, 47.5% sorbitol, 5.6% WPI, and 2.0 mg/mL GA—yielded films with a tensile strength of 3.11 ± 0.31 MPa and an elongation at break of 43.35 ± 0.69%, achieving a desirable balance between flexibility and strength. Mechanistic investigations using in situ Fourier-transform infrared spectroscopy (FTIR), low-field nuclear magnetic resonance (LF-NMR), confocal laser scanning microscopy (CLSM), and molecular docking revealed a ternary interaction system among starch, WPI, and GA. These components primarily interacted through hydrogen bonding and van der Waals forces. Such non-covalent interactions enhanced the short-range molecular ordering of the starch matrix, stabilized the secondary structure of WPI, and facilitated water redistribution during film formation. The resulting interaction network among starch, proteins, and polyphenols significantly improved the mechanical properties and antioxidant capacity of the CTPS films.