Control and Preparation of Quaternized Chitosan and Carboxymethyl Chitosan Nanoscale Polyelectrolyte Complexes Based on Reactive Flash Nanoprecipitation.

Nanoscale polyelectrolyte complex materials have been extensively investigated for their promising application in protocell, drug carriers, imaging, and catalysis. However, the conventional preparation approach involving positive and negative polyelectrolytes leads to large size, wide size distribution, instability, and aggregation due to the nonhomogeneous mixing process. Herein, we employ reactive flash nanoprecipitation (RFNP) to control the mixing and preparation of the nanoscale polyelectrolyte complex. With RFNP, homogeneous mixing complexation between oppositely charged chitosan derivatives could be achieved, resulting in stable nanoscale complexes (NCs) with controllable size and narrow size distribution. The smallest size of NCs is found at specific pH due to the maximum attraction of positive and negative molecules of chitosan. The size can be modulated by altering the volumetric flow rates of inlet streams, concentration, and charge molar ratio of two oppositely charged chitosan derivatives. The charge molar ratio is also tuned to create NCs with positive and negative shells. There is no significant variation in the size of NCs produced at different intervals of time. This method allows continuous and tunable NC production and could have the potential for fast, practical translation.

Pickering Emulsions Based on the pH-Responsive Assembly of Food-Grade Chitosan.

Few natural, biocompatible, and inexpensive emulsifiers are available because such emulsifiers must satisfy severe requirements, be produced synthetically rather than naturally, be nontoxic, and require minimal effort to produce. Therefore, the synthesis of food-grade and biocompatible nanoparticles as an alternative to surfactants has recently received attention in the industry. However, many previous efforts involved chemical modification of materials or the introduction of secondary cocomponents for emulsion formation. To achieve the goal of simple preparation, we consider here chitosan nanoparticles to prepare Pickering emulsions of food-grade oil through the control of pH, without further chemical modification or extra additives. A mild process can prepare nanoparticles from chitosan by simply increasing the pH from 3.0 to 6.0. The results showed that the average radius of chitosan at pH 6.0 was 170 nm, while large aggregates were formed at pH 6.5. These nanoparticles were utilized to prepare the Pickering emulsion. The average size of emulsion droplets decreased upon increasing the pH from 3.0 to 6.0. Moreover, Pickering emulsions at different oil fractions and nanoparticle concentrations were stable and showed a low creaming index for 45 days. The emulsions were stable against coalescence and flocculation and behaved rheologically as gel-like, shear-thinning fluids (G' > G″). Pickering emulsion prevents the growth of the microorganism (Staphylococcus aureus) at different pH values and chitosan concentrations. These results demonstrate that chitosan nanoparticles could be a cost-effective and biocompatible emulsifier for the food or pharmaceutical industry for encapsulation and bioactive compounds, and Pickering emulsions have promising antibacterial effects for further applications.