Chitin nanocrystals-stabilized emulsion as template for fabricating injectable suspension containing polylactide hollow microspheres.

One of the promising applications of rod-like chitin nanocrystals (ChNCs) is the use as particle emulsifier to develop Pickering emulsions. We reported a ChNC-stabilized oil-in-water emulsion system, and developed a Pickering emulsion-templated method to prepare polylactide (PLA) hollow microspheres here. The results showed that both non-modified ChNCs and acetylated ChNCs could well emulsify the dichloromethane (DCM) solution of PLA-in-aqueous mannitol solution systems, forming very stable emulsions. At the same oil-to-water ratios and ChNC loadings, the emulsion stability was improved with increasing acetylation levels of ChNCs, accompanied by reduced size of droplets. Through the solvent evaporation, the PLA hollow microspheres were templated successfully, and the surface structure was also strongly dependent on the acetylation level of ChNCs. At a low level of acetylation, the single-hole or multi-hole surface structure formed, which was attributed to the out-diffusion of DCM caused by the solvent extraction and evaporation. These surface defects decreased with increased acetylation levels of ChNCs. Moreover, the aqueous suspension with as-obtained PLA microspheres revealed shear-thinning property and good biocompatibility, thereby had promising application as injectable fillers. This work can provide useful information around tuning surface structures of the Pickering emulsion-templated polymer hollow microspheres by regulating acetylation level of ChNCs.

Effect of surface acetylation of chitin nanocrystals on the preparation and viscoelasticity of sunflower seed oil-in-water Pickering emulsions.

Acetylated chitin nanocrystals (ChNCs) were used as stabilizer in this work to prepare sunflower seed oil-in-water emulsions for the morphological and rheological studies. The results revealed that the acetylation with moderate degree of substitution (0.38) reduced hydrophilicity and increased surface charge level of rod-like ChNCs, and as a result, significantly improved the emulsifying ability of ChNCs. At the same oil/water ratio and particle loading, the emulsions stabilized with the acetylated ChNCs had far smaller droplet size (∼3 µm) as compared to the emulsions stabilized with the pristine ChNCs (5-7 µm). The increased droplets numbers and improved surface coating level resulted in the enhanced viscous resistance and yield stress level, which improved the physical stability of the acetylated ChNC-stabilized emulsions as a result. In addition, the droplet clusters easily formed in this system, contributing to weak strain overshoot and decreased large-deformation sensitivity during dynamic shear flow. Therefore, the acetylated ChNC-stabilized system showed enhanced transient stress overshoot during startup flow and weakened thixotropy during cyclic ramp shear flow as compared to the pristine ChNC-stabilized system. The relationships between surface acetylation of ChNCs and flow behavior of emulsions were then established, which provide valuable information on the modulation of the ChNC-stabilized Pickering emulsions.

Water-in-water Pickering emulsions stabilized by the starch nanocrystals with various surface modifications.

HYPOTHESIS: Using the platelet-like starch nanocrystals (SNCs) to stabilize emulsions is attractive because as-prepared emulsions have promising applications in cosmetics and food fields. Limited studies mainly focus on the oil-in-water system, and another important system, the water-in-water emulsions stabilized by SNCs, has not yet been unveiled. EXPERIMENTS: Two surface modification strategies, crosslinking and acetylation, were applied to tune surface property and aggregation of SNCs, and a common all-aqueous system (dextran/poly(ethylene glycol)) was used here as template. The viscoelasticity and morphology of emulsions were studied in terms of the SNC loadings and polymer ratios. FINDINGS: Crosslinking results in aggregation of SNCs, and the particle size increases (from 110 nm to 370 nm) with increased levels of substitution. This favors improving emulsifying ability of particles. Acetylation decreases the particle size (∼90 nm) and weakens the affinity of SNCs to the two aqueous phases, improving the emulsifying efficiency of SNCs. More intriguingly, the two emulsion systems show different phase inversion behaviors. The depletion-stabilization mechanism for the cross-linked SNCs and the diffusion-controlled mechanism for the acetylated SNCs are proposed using the emulsion viscoelasticity as probe. This study makes a comprehensive insight into the regulation of water-in-water emulsion morphology and types with the platelet-like SNCs.