All-Natural Food-Grade Hydrophilic–Hydrophobic Core–Shell Microparticles: Facile Fabrication Based on Gel-Network-Restricted Antisolvent Method

Hydrophilic-hydrophobic core-shell microparticles are highly appealing for a variety of industrial applications (foods, pharmaceutics, cosmetics, biomedicines, etc.) owing to their unique properties of moisture resistance and controlled release. However, the fabrication of such structured microparticles proves to be nontrivial due to the difficulty in assembling two materials of distinctly different hydrophilicities and hydrophobicities. This paper reports a facile method to fabricate hydrophilic-hydrophobic core-shell microparticles using all-natural food-grade polysaccharides and proteins, based on a novel principle of gel-network-restricted antisolvent precipitation. Immersion of microgel beads prepared from hydrophilic polysaccharides (i.e., alginates, κ-carrageenan, agarose) into a hydrophobic protein solution (i.e., zein in 70% aqueous ethanol) enables slow and controllable antisolvent precipitation of a protein layer around the microbead surface, leading to the formation of a hydrophilic-hydrophobic core-shell structure. The method applies to various gelling systems and can easily tailor the particle size and shell thickness. The resulting freeze-dried microparticles demonstrate restricted swelling in water, improved moisture resistance, and sustained release of encapsulants, with great potential in applications such as protection of unstable and/or hygroscopic compounds and delivery and controlled release of drugs, bioactives, flavors, etc. The method is rather universal and can be extended to prepare more versatile core-shell structures using a large variety of hydrophilic and hydrophobic materials.