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A Versatile Strategy for Unimolecular Micelles Derived Hollow Polymer Nanoparticles as General Nanoreactors.

We reported the synthesis of well-defined hollow polymer nanoparticle derived from star-shaped unimolecular micelles. β-Cyclodextrin was first applied as an efficient macroinitiator to prepare star-shaped PCL via ring-opening polymerization (ROP). Then the star-shaped PCL was modified to be macro-RAFT agent for photo-induced electron/energy transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of S-Cl monomers. The prepared unimolecular micelles can be photo-crosslinked under UV irradiation after a simple nucleophilic substitution reaction which made -Cl groups to be -N3 groups. After the selective removal of PCL core, hollow polymer nanoparticles were achieved and exhibited to be a general nanoreactor strategy for the fabrication of nanocrystals with well-controlled architectures. In compared with unimolecular micelles templates, the nanocrystals prepared by hollow templates are absolutely pure as no polymer chains are embedded in the inorganic nanocrystals. In addition, by changing the concentration of the precursor, the structure of the nanocrystal can be changed from a normal spherical structure to a hollow structure.