Hybrid Silica Cage-Type Nanostructures Made from Triply Hydrophilic Block Copolymers Single Micelles.

Controlling the structure and functionality of porous silica nanoparticles has been a continuous source of innovation with important potential for advanced biomedical applications. Their synthesis, however, usually involves passive surfactants or amphiphilic copolymers that do not add value to the material after synthesis. In contrast, polyion complex (PIC) micelles based on hydrophilic block copolymers allow for the direct synthesis of intrinsically functional hybrid materials. While most previous studies have focused on bulk materials made from double-hydrophilic block copolymers (DHBC), in this work we have synthesized a triple-hydrophilic block copolymer (THBC) and demonstrated both its PIC micellization and its potential for hybrid mesoporous silica nanomaterials. Introducing this THBC has allowed to direct the transition from bulk three-dimensional (3D) materials to zero-dimensional (0D) nanomaterials with cage-type structures. The stabilization and isolation of these nanostructures formed around discrete individual micelles has been made possible by the careful design of the three different blocks that each play a key role. These nanostructures could also be synthesized from hybrid PIC micelles based on THBC-multivalent metal ions complexes, offering a direct route to metal/silica composite nanoparticles. This class of THBC polymers therefore creates significant opportunities for the synthesis of nanostructures with complex and functional architectures.