A molecular strategy for creating functional vesicles with balancing structural stability and stimuli-responsiveness

Vesicles, closed bilayer structures composed of amphiphiles, have attracted considerable attention as functional materials. Structural stability and stimulus responsiveness are required for next-generation functional vesicles. However, there is a dilemma between these properties because the desired membrane structure varies in terms of structural stability and stimulus sensitivity. Herein, we propose a new approach for the development of giant vesicles (GVs) through the molecular design and synthesis of amphiphiles with or without amide linkages, forming hydrogen bonding. From the ¹H NMR analysis and fluorescence spectra of environment-responsive probes, intermolecular hydrogen bonding between the amide linkages in the membrane contributed to the enhanced structural stability of the GVs. Moreover, by adding amphiphiles containing a photoresponsive azobenzene moiety to GVs composed of amphiphiles with or without amide linkages, a distinct mechanism of photoresponsive deformation was observed: the former exhibited large and irreversible deformation, while the latter showed a modest and reversible manner due to the photoisomerisation of azobenzene under ultraviolet and subsequent visible light illumination. This difference was also attributed to the membrane structure affected by intermolecular hydrogen bonding. Based on these results, the finding provides a molecular methodology for developing highly functional vesicles.