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J Am Chem Soc. 2013 Mar 27;135(12):4765-70. doi: 10.1021/ja3122608. Epub 2013 Mar 13.

A supramolecular Janus hyperbranched polymer and its photoresponsive self-assembly of vesicles with narrow size distribution.

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School of Chemistry and Chemical Engineering, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, PR China.


Herein, we report a novel Janus particle and supramolecular block copolymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer. It is constructed by the noncovalent coupling between a hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of an azobenzene (AZO) group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin (CD) group through the specific AZO/CD host-guest interactions. Such an amphiphilic supramolecular polymer resembles a tree together with its root very well in the architecture and can further self-assemble into unilamellar bilayer vesicles with narrow size distribution, which disassembles reversibly under the irradiation of UV light due to the trans-to-cis isomerization of the AZO groups. In addition, the obtained vesicles could further aggregate into colloidal crystal-like close-packed arrays under freeze-drying conditions. The dynamics and mechanism for the self-assembly of vesicles as well as the bilayer structure have been disclosed by a dissipative particle dynamics simulation.


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