Improved oxidative barrier properties of emulsions stabilized by silica–polymer microparticles for enhanced stability of encapsulants

• Electrostatic complexation of silica nanoparticles and ε-polylysine formed microparticles.
• Microparticle stabilized emulsions showed lower permeation of peroxyl radicals.
• Microparticles quenched peroxyl radicals more effectively than silica nanoparticles.
• Retinol was more stable in microparticle stabilized emulsions.

The materials encapsulated within oil-in-water emulsions are prone to oxidation due to the permeation of oxidative species across the oil–water interface and into the lipid phase. Thus, the oxidative barrier properties of the interfacial layer are pivotal in reducing oxidation within emulsified oils. To enhance these barrier properties, we explored an approach of stabilizing emulsions using ‘silica–polymer microparticles’. We hypothesize that these microparticles will enhance the barrier properties of emulsion interfaces by mechanisms such as higher interfacial thickness and quenching of oxidative species before they permeate into the emulsions. Silica–ε-polylysine (Si–EPL) microparticles were synthesized by electrostatic aggregation of anionic silica nanoparticles and cationic ε-polylysine in the aqueous phase. Formation of Si–EPL microparticles was validated using particle size, ζ-potential and scanning electron microscopy measurements. These microparticles were subsequently used for emulsion stabilization. Emulsions stabilized by silica nanoparticles alone were used as control. Oxidative barrier properties were determined by measuring the rate of permeation of peroxyl radicals from the aqueous to the oil phase of the emulsion using fluorescence based methods. The rate of permeation of peroxyl radicals was significantly lower in emulsions stabilized by Si–EPL microparticles compared to that stabilized by silica nanoparticles. One of the mechanisms responsible for the observed effect was enhanced quenching of peroxyl radical by Si–EPL microparticles before they can permeate inside the oil phase. To further validate the results, stability of a model bioactive compound, retinol, encapsulated in these emulsions was compared. Consistent with peroxyl radical permeation measurements, emulsion stabilized by Si–EPL microparticles significantly improved the oxidative stability of retinol compared to that stabilized by silica nanoparticles alone. Thus, by engineering the physical properties of the interfacial layers, the oxidation of the encapsulants in emulsions can be controlled.