Self-Assembly and Photoinduced Spindle-Toroid Morphology Transition of Macromolecular Double-Brushes with Azobenzene Pendants
Binbin Xu, Hongyu Qian, Shaoliang Lin
Abstract
Asymmetric macromolecular double-brushes (MDBs) are composed of two different side chains grafted on a linear backbone, possessing distinct assembly behaviors in comparison with conventional amphiphiles, owing to the Janus architecture and combined effects of backbone and hetero double-brushes. Additionally, the introduction of unique functionalities and responsiveness into the self-assembly system of MDBs endows extra opportunities to pursue morphologic diversity and intriguing properties. Herein, we report the synthesis of Janus-like MDBs of polyacrylate-g-poly(6-(4-butyl-4′-oxyazobenzene) hexyl acrylate)/poly(ethylene oxide) (PA-g-PAzo/PEO), in which hydrophilic PEO and hydrophobic PAzo brushes were grafted using the combination of concurrent ATRP and click reaction. Due to the special Janus topology and inter/intramolecular association of pendant azobenzene groups, amphiphilic PA-g-PAzo/PEO self-assembled into multimolecular rod and spindle-like aggregates. It is interesting that a transition of spindle-toroid-spindle was observed upon the alternative irradiation between UV and visible light, which is ascribed to the trans-to-cis isomerization of azobenzene molecular brushes. To our best knowledge, this is the first time that azobenzene-containing MDBs enable the fabrication of distinctive self-assembled morphologies and photoinduced toroid formation. The controlled synthesis of MDBs with unique functionalities and subsequent development of their structure–property relationships would shed light on the design and optimization of bottlebrush-based nanomaterials.