Self-assembled shell cross-linked poly(acrylic acid-b-isoprene) (PAA78-b-PI97) micelles or cross-linked PAA nanocages in aqueous solution were used as templates for the preparation of novel polymer-inorganic nanocapsules. The hybrid nanostructures were typically 50-70 nm in diameter and consisted of spherical polymer nanoparticles or nanocages enclosed within a continuous 10-20 nm thick surface layer of amorphous calcium phosphate. Nucleation of calcium phosphate specifically in association with the polymer nanoparticles was facilitated by low supersaturation levels and by sequestration of Ca2+ ions within the carboxylate-rich PAA domains prior to addition of HPO4(2-). Modifications in ionic concentrations were used to control the calcium phosphate surface layer thickness and prepare mineralized cross-linked PAA-b-PI micelles with variable shell permeability. The permeability of beta-carotene into the hydrophobic PI core of mineralized shell cross-linked PAA-b-PI micelles was reduced by approximately 50 or 100% respectively for hybrid nanostructures enclosed within 10 or 20 nm thick calcium phosphate layers. Our results suggest that calcium phosphate-polymer cross-linked nanocapsules could have potential applications as pH-responsive biocompatible hybrid nanostructures for use in applications such as drug delivery, bioimaging, and therapeutics.

Supramolecular organization of organic amphiphiles with rigid molecular architecture can lead to persistent nontrivial packing arrangements. Wormlike cylindrical micelles of a rigid T‐shaped dendro‐calixrene (see image) are shown to be effective not only in curtailing the growth and macroscopic aggregation of CdS nanoparticles but also in promoting the surface organization of 2‐nm‐sized quantum dots.