Cholesterol-Functionalized Linear/Brush Block Copolymers for Metal-Incorporated Nanostructures with Modulated Core Density and Enhanced Self-Assembly Efficiency.

Metal-mediated self-assembly of chelating double-hydrophilic block copolymer has become a facile preparation strategy of great importance for the metal-chelated hybrid nanostructures. Herein, we present a delicate control over the morphology regulation of metal-chelated nanostructures by a terminal modification of polymer building blocks with mesogenic cholesterol. Such a molecular design motif at an end of chelating linear/brush-type block copolymer imparts not only additional hydrophobicity for enhanced cohesive force to facilitate the metal-mediated self-assembly, but also significant morphological alteration of a metal-chelated core that otherwise generally forms a spherical interior with cholesterol-free block copolymers. The presence of cholesterol entities localized at the central core further allows for the density modulation of the final Pt-chelated nanostructures while maintaining the colloidal stability, comparable to that of the cholesterol-free nanoparticles in physiological conditions. This metal-mediated assembly strategy with modified polymer building blocks can provide a potential platform for the delivery of inorganic agents.