Photo‐Responsive Glyco‐Microfibers: Design, Self‐Assembly, and Morphological Control of Aqueous Microdroplets

ABSTRACT The development of stimuli‐responsive supramolecular architectures composed of small synthetic molecules is of considerable importance for emulating and understanding the molecular self‐assembly processes occurring inside living cells. Fibrous architectures are particularly crucial as they serve as structural frameworks that reinforce artificial cells and regulate their morphology and internal viscosity, analogous to cytoskeletal components such as microtubules and actin filaments in living cells. We herein report the construction of supramolecular microfibers via aqueous self‐assembly of a glucosamine derivative functionalized with a 2‐nitrobenzyl group. This aromatic moiety promotes self‐assembly through π–π interactions and simultaneously imparts photo‐responsiveness to the supramolecular microfibers. Next, the photo‐responsive glyco‐microfibers are encapsulated within water‐in‐oil microdroplets serving as confined aqueous environments. The formation and subsequent photo‐triggered dis‐assembly of the glyco‐microfibers inside these microdroplets enabled spatiotemporally controlled morphological changes at the microscale. These findings offer a useful contribution toward the bottom‐up construction of artificial cells with dynamic and controllable internal supramolecular architectures.