Biopolymers, which are biodegradable and inherently functional, have high potential for specialized applications (e.g., disposable and transient systems and biomedical treatment). For this, it is important to create composite materials with precisely defined chain interactions and tailored properties. This work shows that for a chitosan–gelatin material, both glycerol and isosorbide are effective plasticizers, but isosorbide could additionally disrupt the polyelectrolyte complexation (PEC) between the two biopolymers, which greatly impacts the glass transition temperature (Tg), mechanical properties, and water absorption. While glycerol-plasticized samples without nanofiller or with graphene oxide (GO) showed minimal water uptake, the addition of isosorbide and/or montmorillonite (MMT) made the materials hydrolytically unstable, likely due to disrupted PEC. However, these samples showed an opposite trend in surface hydrophilicity, which means surface chemistry is controlled differently from chain structure. This work highlights different mechanisms that control the different properties of dual-biopolymer systems and provides an updated definition of biopolymer plasticization, and thus could provide important knowledge for the future design of biopolymer composite materials with tailored surface hydrophilicity, overall hygroscopicity, and mechanical properties that meet specific application needs.

To improve the fresh-keeping of highly perishable fruits with high commercial value, a novel starch-based foam packaging material was developed in this study. The foam incorporated the antiseptic ingredient Na2S2O5, which chemically interacted with environmental moisture to release SO2 as an antifungal agent. Scanning electron microscopy (SEM), moisture absorption and mechanical measurements were used to characterize the unique sandwich-like inner structure of the foam which allowed for the modulable release of SO2. The starch-based foam exhibited sufficient resilience (~100%) to provide ideal cushioning to prevent physical damage to fresh fruits during transportation. When 25 g/m2 of Na2S2O5 was applied, the foam stably released over 100 ppm SO2 and demonstrated satisfactory antifungal performance (inhibition over 60%) in terms of maintaining the appearance and nutritional values (such as soluble solids 14 vs. 11%, total acidity 0.45 vs. 0.30%, and Vitamin C 3.4 vs. 2.5 mg/100 g) of fresh grapes during a 21 day storage period. Additionally, the residual SO2 (14 mg/kg) also meets the safety limits (<30 mg/kg). These research findings suggest great potential for the utilization of this novel foam in the food industry.