Formation of high-concentration alginate microgels via double emulsion Shell-mediated gelation and osmotic shrinkage.

We present a microfluidic strategy for fabricating high-concentration alginate microgels through a combination of shell-mediated gelation and osmotic shrinkage. Using a water-in-oil-in-water double emulsion platform, we introduce a thermally responsive oil shell that undergoes a phase transition upon cooling. This phase change allows spatial control over calcium ion diffusion into the alginate core by forming transient diffusion channels, resulting in localized and uniform ionic crosslinking. To overcome limitations associated with high-viscosity alginate formulations, we apply a hypertonic osmotic shrinkage step prior to gelation, which concentrates the alginate phase and enables the formation of microgels with final polymer concentrations up to 10 %. The resulting microgels exhibit well-defined morphology, high monodispersity, and tunable molecular permeability depending on the degree of concentration. Diffusion studies using fluorescent tracers confirm that permeability can be adjusted by modifying the initial alginate content and shrinkage conditions. This approach provides a controllable and chemically mild method for producing alginate microgels with tailored structural and transport properties, suitable for biomedical and pharmaceutical applications.