Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (6): 528-533.DOI: 10.6023/A20040121 Previous Articles     Next Articles

Article

Janus超支化超分子聚合物的构筑及电化学响应性自组装行为研究

戚美微, 刘勇, 周永丰   

  1. 上海交通大学 化学化工学院 上海 200240
  • 收稿日期:2020-04-24 发布日期:2020-06-03
  • 通讯作者: 周永丰 E-mail:yfzhou@sjtu.edu.cn
  • 基金资助:
    项目受国家自然科学基金重大项目(Nos.21890730,21890733)资助.

A Supramolecular Janus Hyperbranched Polymer and Its Electrochemically Responsive Self-Assembly Behavior

Qi Meiwei, Liu Yong, Zhou Yongfeng   

  1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240
  • Received:2020-04-24 Published:2020-06-03
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 21890730, 21890733).

Herein, we report a Janus supramolecular polymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer (JHBP). Firstly, hydrophilic hyperbranched polyglycerol with an apex of β-cyclodextrin (CD-g-HPG) and hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of a ferrocene (Fc-g-HBPO) were synthesized according to the anionic ring-opening multi-branching polymerization and cationic ring-opening polymerization, respectively. Then, amphiphilic supramolecular JHBP HBPO-b-HPG was constructed by adding H2O to cosolvent DMF through the special Fc/CD host-guest interactions and such an amphiphilic supramolecular polymer can further aggregated into assemblies. The formation and self-assembly process of supramolecular JHBP HBPO-b-HPG was tracked by dynamic light scattering (DLS). The results showed that when the volume percentage ratio of H2O/DMF was increased to 16%, the HBPO-b-HPG was formed with Dh of 5.6 nm, which is close to the size of the 1:1 complex of CD-g-HPG and Fc-g-HBPO, then, with H2O/DMF ratio continuing to increase, HBPO-b-HPG rapidly aggregated into assemblies. The 2D NOESY and cyclic voltammetry (CV) curves were also used to verify the Fc/CD host-guest complexation ability. The scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to characterize the morphology of the assemblies. The results showed that the HBPO-b-HPG self-assembled into unilamellar bilayer vesicles of around 260 nm. When NaCl was added after electrochemical oxidation, such vesicles could disassemble due to the cooperation of the transformation of Fc to oxidation state Fc+ and equal potential destruction. Finally, DLS tracking proved that such vesicles showed excellent stability under the conditions of heating and adding host and guest competition molecules.

Key words: Janus particle, hyperbranched polymer, host-guest interaction, vesicle, electrochemically responsive