|413. Gröschel, A.H.; Schacher, F.H.; Schmalz, H.; Borisov, O.V.; Zhulina, E.B.; Walther, A.; Müller, A.H.E.: Precise hierarchical self-assembly of multicompartment micelles, Nat. Commun. 3, published online on February 28 (2012) -- DOI: 10.1038/ncomms1707|
Hierarchical self-assembly offers elegant and energy-efficient bottom-up strategies for the structuring of future complex materials. For block copolymers, the last decade witnessed great progress in diversifying the structural complexity of solution-based assemblies into multicompartment micelles (MCMs). However, a general understanding of what governs MCM morphologies and polydispersity, and how to manipulate their hierarchical superstructures using straightforward concepts and readily accessible polymers remains unreached. We herein demonstrate how to create most homogeneous MCMs with unprecedented control of nanostructuration via the intermediate pre-assembly of subunits. This directed self-assembly leads to a step-wise reduction of the degree of conformational freedom and dynamics and avoids undesirable kinetic obstacles during the structure build-up. It yields a general concept for homogeneous populations of well-defined MCMs with precisely tunable patchiness, while using simplest linear ABC triblock terpolymers. We further demonstrate control over the hierarchical step-growth polymerization of MCMs into micron-scale segmented supracolloidal polymers as an example of programmable mesoscale colloidal hierarchies via well-defined patchy nanoobjects.