Large amplitude oscillatory shear (LAOS) for nonlinear rheological behavior of heterogeneous emulsion gels made from natural supramolecular gelators.

The linear and nonlinear rheological behaviors of heterogeneous emulsions gels made from natural glycyrrhizic acid (GA) nanofibrils and sitosterol-oryzanol mixtures (sterols) were investigated using small amplitude oscillatory shear (SAOS) and large amplitude oscillatory shear (LAOS). The nonlinear rheological response was qualitatively analyzed using normalized Lissajous-Bowditch curves. The microstructure of the emulsion gels strongly depended on the concentration of sterols in the oil phase, and showed a percolated segregated network at 10-20 wt% sterols due to the partial coalescence of droplets, and a jamming transition without coalescence at higher sterols concentration of 30 wt%. The microstructure differences led to different linear and nonlinear viscoelastic behaviors of these emulsion gels. SAOS tests showed that the oil phase structuring by the sterols significantly enhance the viscoelasticity of GA nanofibril emulsion gels, and the percolating emulsion gels exhibited higher elasticity than the jammed emulsion gel, as evidenced by a lower damping factor and frequency power-law exponent. The data of crossover strain, phase angle, and the normalized Lissajous-Bowditch curves from LAOS tests further revealed that compared to the samples in a jammed state or without oil phase structuring, the emulsion gels with a percolating segregated network showed higher structural elasticity and thus were more resistant to large deformations, probably due to the slow relaxation of rigid, hydrodynamically interacting clusters of partially coalesced droplets. These findings could potentially aid in the design of novel emulsion gels, based on all-natural and sustainable building blocks, with specific textural and functional properties for foods, cosmetics, and pharmaceutical applications.

Highly stable and thermo-responsive gel foams by synergistically combining glycyrrhizic acid nanofibrils and cellulose nanocrystals.

HYPOTHESIS: Natural saponin glycyrrhizic acid (GA) and GA nanofibrils (GNFs) are effective foaming agents for formulation of aqueous food-grade foams. Through the synergistic combination of soft semiflexible GNFs with rigid nanofiller cellulose nanocrystals (CNCs), it should be possible to create advanced composite foams with a more complex structure and diverse properties including high stability and stimuli responsiveness. EXPERIMENTS: Foams containing mixtures of GNFs and CNCs were prepared, and their formation and stability were investigated. A range of microscopy techniques and small deformation oscillatory shear were adopted to examine the microstructure and viscoelasticity of foams, and a stabilization mechanism for highly stable foams was then established. Further, the temperature-responsive destabilization of foams was evaluated. FINDINGS: CNCs are homogeneously distributed in the architecture and mechanically reinforce the GNF fibrillar network, leading to a highly viscoelastic composite network in the continuous phase of foams, which is the key factor responsible for their high stability. Such ultra-stable gel foams display tunable thermo-responsive behavior and a rapid on-demand destabilization upon heating by inducing a phase transition of the bulk composite network. Our work opens up new scenarios on the use of a novel combination of all-natural, sustainable nanoscale building blocks to develop aqueous "superfoams" which are highly stable, stimulable and processable.

Self-Assembled Egg Yolk Peptide Micellar Nanoparticles as a Versatile Emulsifier for Food-Grade Oil-in-Water Pickering Nanoemulsions.

Pickering emulsions stabilized by food-grade particles have garnered increasing interest in recent years due to their promising applications in biorelated fields such as foods, cosmetics, and drug delivery. However, it remains a big challenge to formulate nanoscale Pickering emulsions from these edible particles. Herein we show that a new Pickering nanoemulsion that is stable, monodisperse, and controllable can be produced by employing the spherical micellar nanoparticles (EYPNs), self-assembled from the food-derived, amphiphilic egg yolk peptides, as an edible particulate emulsifier. As natural peptide-based nanoparticles, the EYPNs have a small particle size, intermediate wettability, high surface activity, and deformability at the interface, which enable the formation of stable Pickering nanodroplets with a mean dynamic light scattering diameter below 200 nm and a polydispersity index below 0.2. This nanoparticle system is versatile for different oil phases with various polarities and demonstrates the easy control of nanodroplet size through tuning the microfluidization conditions or the ratio of EYPNs to oil phase. These food-grade Pickering nanoemulsions, obtained when the internal phase is an edible vegetable oil, have superior stability during long-term storage and spray-drying based on the irreversible and compact adsorption of intact EYPNs at the nanodroplet surface. This is the first finding of a natural edible nano-Pickering emulsifier that can be used solely to make stable food Pickering nanoemulsions with the qualities of simplicity, versatility, low cost, and the possibility of controllable and mass production, which make them viable for many sustainable applications.