Aggregation of a versatile triblock copolymer into pH-responsive cross-linkable nanostructures in both organic and aqueous media.

The self-assembly of linear poly(ethylene oxide)-b-poly(glycerol monomethacrylate)-b-poly[2-(diisopropylamino)ethyl methacrylate] (PEO-b-PG2MA-b-PDPA) triblock copolymer into pH-responsive cross-linkable nanostructures in both organic and aqueous media is reported. Light scattering (LS), electron transmission microscopy (TEM), and nuclear magnetic resonance spectroscopy (NMR) techniques revealed that spherical particles with a core-shell architecture originated upon direct copolymer dissolution in THF, with PG2MA middle blocks occupying the nucleus, and PEO + PDPA segments forming the external layer. The hydroxylated core could be conveniently reticulated to form core cross-linked (CCL) micelles, which swelled without dissociating in presence of water at pH < pK(a) of amino groups. In the absence of stabilizing mechanisms (cross-links), the aggregates first disassembled in response to changes in the solvent selectivity due to water addition and eventually self-assembled again into spherical particles with a three-layered core-shell-corona structure. While pH-responsive PDPA segments were located at the core, PG2MA and PEO blocks composed the inner shell and corona, respectively. The interactions that facilitate micelle existence were reinforced by covalent cross-links in the PG2MA inner shell. Thus, depending on both the solution pH and the presence of cross-links, micelles exhibiting either pH-triggered or diffusion-controlled release mechanisms could be prepared. The encapsulation of enough amounts of guest molecules that interact strongly with the core-forming block led to the formation of cylindrical micelles. These results demonstrate that at least five different types of aggregates can be prepared from this versatile triblock copolymer, thus emphasizing the great potential of combining macromolecular design and sample manipulation strategies to devise functional nanostructures.