Nanobowls with controlled openings and interior holes driven by the synergy of hydrogen bonding and π-π interaction

Asymmetric nanoparticles such as nanobowls have promising potential in many fields due to their interior asymmetric cavities and specific concave structure. However, the fabrication of nanobowls and control over their openings and interior holes are still challenging. Herein we demonstrate a versatile strategy for preparing nanobowls with precisely controlled openings and interior holes based on the synergy of hydrogen bonding and π-π interaction of homopolymers. We designed and synthesized a series of amphiphilic homopolymers with an amino alcohol moiety and azobenzene pendant (poly(2-hydroxy-3-((4-(phenyldiazenyl)phenyl)amino)propyl methacrylate) (PHAzoMA)). The homopolymers can self-assemble into nanobowls due to the heterogeneous shrinkage of the preformed spheres. Upon increasing the molecular weight of the homopolymers from 10.1 to 76.9 kg mol^-1, the sizes of the openings of nanobowls can be precisely controlled from 242 to 423 nm with a linear relationship as a result of the enhancement of the hydrogen bonding and π-π interaction between homopolymer chains. Overall, we have prepared finely controlled nanobowls by the synergy of non-covalent interactions such as hydrogen bonding and π-π interaction of polymers, which opens a new avenue for the preparation of asymmetric nanoparticles.