pH-switchable pickering emulsions stabilized by polyelectrolyte-biosurfactant complex coacervate colloids

Abstract

Hypothesis: Polyelectrolyte-surfactant complexes (PESCs) have long been employed as oil-in-water (o/w) emulsions stabilizers, but never in the structure of colloidal complex coacervates providing a Pickering effect. The complexed state of PESCs could make them unsuitable o/w Pickering emulsifiers, which instead require a balance between colloidal structure and stability, amphiphilicity and wettability. Here we hypothesize that PESCs coacervates are efficient Pickering stabilizers. Instead of classical surfactants, we employ sophorolipid (SL) biosurfactants, atypical anionic/neutral stimuli-responsive biosurfactants. Despite their tunable charge and mild amphiphilic character, they can be used in combination with cationic/neutral polyelectrolytes (chitosan, CHL, or poly-l-lysine, PLL) to form PESC coacervates for the development of biobased, but also pH-switchable, Pickering emulsions.

Experiments: Aqueous solutions of SL-CHL (or SL-PLL) complex coacervates are emulsified with dodecane. Confocal laser scanning microscopy (CLSM) and scanning electron microscopy under cryogenic conditions (cryo-SEM) demonstrate the Pickering effect, while optical microscopy and oscillatory rheology respectively assess the emulsion formation and relative viscoelastic properties.

Findings: Both SL-CHL and SL-PLL PESCs stabilize o/w emulsions up to Φ_oil of 0.7 only in the pH region of complex coacervation (6 < pH < 9): outside this range, phase separation occurs. Rheology shows a typical solid-like response and mechanical recovery upon applying large deformations. CLSM and cryo-SEM highlight a colloidal structure, associated to the complex coacervates, of the oil/water interface and suggest a Pickering effect. These findings demonstrate the Pickering effect from PESC coacervates and the possibility to use biobased and biocompatible components, with application potential in cosmetics, food science, or oil recovery.

Keywords: Bolaamphiphiles; Complex coacervates; Pickering emulsion; Polyelectrolyte Surfactant Complex (PESC); Polyelectrolytes; Sophorolipids; Surfactants; pH-responsive.