Plasticizing Effects of Polyamines in Protein-Based Films.

Zeta potential and nanoparticle size were determined on film forming solutions of native and heat-denatured proteins of bitter vetch as a function of pH and of different concentrations of the polyamines spermidine and spermine, both in the absence and presence of the plasticizer glycerol. Our results showed that both polyamines decreased the negative zeta potential of all samples under pH 8.0 as a consequence of their ionic interaction with proteins. At the same time, they enhanced the dimension of nanoparticles under pH 8.0 as a result of macromolecular aggregations. By using native protein solutions, handleable films were obtained only from samples containing either a minimum of 33 mM glycerol or 4 mM spermidine, or both compounds together at lower glycerol concentrations. However, 2 mM spermidine was sufficient to obtain handleable film by using heat-treated samples without glycerol. Conversely, brittle materials were obtained by spermine alone, thus indicating that only spermidine was able to act as an ionic plasticizer. Lastly, both polyamines, mainly spermine, were found able to act as "glycerol-like" plasticizers at concentrations higher than 5 mM under experimental conditions at which their amino groups are undissociated. Our findings open new perspectives in obtaining protein-based films by using aliphatic polycations as components.

Polyamines as new cationic plasticizers for pectin-based edible films.

Zeta potential and particle size were determined on pectin aqueous solutions as a function of pH and the effects of calcium ions, putrescine and spermidine on pectin film forming solutions and derived films were studied. Ca(2+) and polyamines were found to differently influence pectin zeta potential as well as thickness and mechanical and barrier properties of pectin films prepared at pH 7.5 either in the presence or absence of the plasticizer glycerol. In particular, Ca(2+) was found to increase film tensile strength and elongation at break only in the presence of glycerol and did not affect film thickness and permeability to both water vapor and CO2. Conversely, increasing polyamine concentrations progressively reduced film tensile strength and markedly enhanced film thickness, elongation at break and permeability to water vapor and CO2, both in the presence and absence of glycerol. Our findings indicate that polyamines give rise to a structural organization of the heteropolysaccharide different from that determined by calcium ions, previously described as "egg box" model, and suggest their possible application as plasticizers to produce pectin-based "bioplastics" with different features.