Supramolecular Microcapsules via Microfluidic Interfacial Host–Guest Assembly: A Novel Strategy for Actives Encapsulation and Stimuli‐Responsive Delivery

ABSTRACT The development of intelligent encapsulation systems that ensure both the stability and stimuli‐responsive release of sensitive actives remains a critical challenge for personal care and pharmaceutical applications. This work presents a supramolecular strategy to fabricate intelligent microcapsules by integrating droplet microfluidics with host–guest chemistry. Specifically, phenylalanine‐functionalized chitosan (CS‐Phe) is designed to function as the guest polymer. Within the microfluidic system, positively charged CS‐Phe is electrostatically anchored at the water–oil interface and dynamically crosslinked by cucurbit[8]uril (CB[8]), thereby forming monodisperse microcapsules with tunable sizes and shapes. These microcapsules exhibit high encapsulation stability and are dual‐responsive to pH variations and competitive guests. This combination of properties establishes the resulting supramolecular microcapsules as a versatile platform for the intelligent encapsulation and on‐demand release of active ingredients.