A novel narrowly-distributed (ND) polymeric micelle obtained in combination with host–guest recognition and self-assembly is reported. First, the adamantyl-terminated hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO-AD) was synthesized by esterification of hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] (HBPO) with 1-adamantanecarbonyl chloride. Then the ND polymeric core-shell micelles, with the hydrophobic HBPO-AD cores and hydrophilic beta-cyclodextrin (β-CD) shells, were prepared via host–guest inclusion complexation of HBPO-AD and β-CD. The resultant polymer micelles were well characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Interestingly, after annealing at a temperature above the glass transition temperature (Tg) for a certain time, the polymeric micelles can further self-assemble and fuse into two-dimensional (2D) sheets. The TEM, SEM and atomic force microscopy (AFM) characterization validate that the sheets are formed through stacking and fusion of tightly packed nanoparticles. In addition, the formation mechanism of polymeric complex micelles and 2D sheets has also been discussed.
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