Molecular complexes based on proteins and ionic polysaccharides have considerable potential for encapsulation of functional food components, but their widespread utilization is limited because their structure is highly sensitive to pH and ionic strength. We have investigated the possibility of creating stable hydrogel particles by thermal treatment of protein (beta-lactoglobulin) and cationic polysaccharide (chitosan) mixtures. Mixed solutions of beta-lactoglobulin (0.5 wt %) and chitosan (0.1 wt %) were prepared at various pH's (3-8) and were heated (80 degrees C for 20 min). Prior to heating, the biopolymer mixtures formed molecular complexes at pH values where there was an electrostatic attraction between the protein and the polysaccharide: soluble complexes at pH 4.5; complex coacervates at pH 5.0 and 5.5; precipitates at pH>5.5. After heating, relatively small (d approximately 140 nm) and cationic (zeta>+20 mV) hydrogel particles were formed at pH 4.5, but much larger aggregates were formed at pH 5.0 and higher (d>1000 nm). The thermally treated hydrogel particles formed at pH 4.5 maintained their initial particle size when the pH was subsequently adjusted within the range pH 3-5, but they aggregated when the pH was adjusted to >pH 5 because of a reduction in the magnitude of their electrical charge. This study suggests that hydrogel particles can be formed by heating mixed protein-polysaccharide systems under controlled conditions. These hydrogel particles may be useful for encapsulation of functional food components.
The impact of a cationic polyelectrolyte on the pH sensitivity of the electrical charge and aggregation stability of protein-coated lipid droplets was examined. One percent (w/w) corn oil-in-water emulsions containing lipid droplets coated by β-lactoglobulin [0.05% (w/w) β-Lg, 10 mM acetate buffer, pH 3] were prepared in the absence ("primary" emulsions) and presence ("secondary" emulsions) of chitosan (0 to 0.05 wt%). The pH (3 to 8) of these emulsions was adjusted, and the particle charge, particle size, creaming stability, and microstructure were measured. Chitosan adsorbed to the β-Lg-coated droplets from pH 4.5 to 7.5, which was attributed to electrostatic attraction between the cationic polyelectrolyte and anionic patches on the droplet surfaces. Droplets coated by β-Lg-chitosan had better stability to flocculation than those coated by β-Lg alone around the isoelectric point of the adsorbed proteins (pH 4.5 to 5.5), which was attributed to increased electrostatic and steric repulsion between the droplets. We have shown that chitosan may be used to modulate the electrical characteristics and stability of protein-coated lipid droplets, which may be useful in the design and formation of delivery systems for use in the food, pharmaceutical, and other industries.
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