Surfactant-Free d‑Limonene Encapsulation in Spray-Dried Alginate Microcapsules Cross-Linked by In Situ Internal Gelation

Microencapsulation facilitates incorporating bioactive volatile compounds into products throughout the food, health, and cosmetics industries. To minimize the number of ingredients when microencapsulating volatile oils, we examined surfactant-free encapsulation of d-limonene in cross-linked alginate microcapsules (CLAMs) via in situ cross-linking during spray drying. Surfactant-free CLAMs (SF-CLAMs) were prepared by forming a Pickering d-limonene emulsion stabilized by calcium carbonate nanoparticles (CaCO3-NPs), combining with alginates, and then spray drying. CaCO3-NPs served as both the emulsifier and the reservoir of alginate cross-linking agent. SF-CLAMs, with a volatile retention of 73.1 ± 4.7% and total limonene content of 13.6 ± 8.6% (w/w, d.b.), exhibited core–shell morphology where CaCO3-NPs surrounded large emulsion cores (∼5 μm) encased in densely cross-linked alginate shells. Limonene was fully retained for up to 4 h in SF-CLAMs in water at 37 °C. Moreover, microencapsulation in SF-CLAMs minimized release in simulated gastric fluid (2.2 ± 0.3% in 2 h) while fully releasing in simulated gastric fluid at 37 °C.