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Bitter vetch protein films containing positively charged spermidine, alone or with low amounts of glycerol, showed high tensile strength that progressively decreased by increasing the plasticizer concentration. Accordingly, lower film elongation at break and higher Young's module values were detected in the presence of the polyamine without or with small amounts of glycerol. These data suggest that spermidine not only acts as a plasticizer itself by ionically interacting with proteins, but that it also facilitates glycerol-dependent reduction of the intermolecular forces along the protein chains, consequently improving the film flexibility and extensibility. Thus, spermidine may be considered not only as a primary, but also as a secondary plasticizer because of its ability to enhance glycerol plasticizing performance. Such double behavior of the polyamine was confirmed by the film permeability tests, since spermidine increased the barrier properties to gases and water vapor, while glycerol emphasized this effect at low concentrations but led to its marked reversal at high concentrations. Film microscopic images also substantiated these findings, showing more compact, cohesive, and homogeneous matrices in all spermidine-containing films.

Tuning the Functional Properties of Bitter Vetch (Vicia ervilia) Protein Films Grafted with Spermidine