In this study, negatively charged catanionic vesicles/hydrophobically modified hydroxyethylcellulose polymers thermo-responsive hydrogels have been fabricated. Vesicular aggregates were found to act as multifunctional junctions for networking of modified-cellulose water solutions. The contributions of the electrostatic and hydrophobic interactions were evaluated by changing either vesicles composition or the polymer hydrophobic substitution. Thermal-induced size and lamellarity of hydrogelenclosed vesicles were detected, with further polygonal shape changes induced by cellulose-based polymer addition. The thermal transition was also found to tune hydrogel mechanical behaviour. The network formation was further assessed through molecular insights, which allow to determine the arrangement of the polymer chains on the vesicles’ surface. The examined systems exhibited interesting thermo-responsive characteristics. Thus, vesicularly crosslinked hydrogels herein presented can offer a wide variety of applications, i.e. in biomedical field, as multi-drug delivery systems, thanks to their ability to provide for different environments to guest molecules, comprising bulk water, vesicles’ interior and bilayers, sites on polymeric chains.
