Soft self-assembled nanoparticles with temperature-dependent properties

Abstract

The fabrication of versatile building blocks that are reliably self-assemble into desired ordered and disordered phases is amongst the hottest topics in contemporary material science. To this end, microscopic units of varying complexity, aimed at assembling the target phases, have been thought, designed, investigated and built. Such a path usually requires laborious fabrication techniques, especially when a specific funcionalisation of the building blocks is required. Telechelic star polymers, i.e., star polymers made of a number $f$ of di-block copolymers consisting of solvophobic and solvophilic monomers grafted on a central anchoring point, spontaneously self-assemble into soft patchy particles featuring attractive spots (patches) on the surface. Here we show that the tunability of such a system can be widely extended by controlling the physical and chemical parameters of the solution. Indeed, at fixed external conditions the self-assembly behaviour depends only on the number of arms and/or on the ratio of solvophobic to solvophilic monomers. However, changes in temperature and/or solvent quality makes it possible to reliably change the number and size of the attractive patches. This allows to steer the mesoscopic self-assembly behaviour without modifying the microscopic constituents. Interestingly, we also demonstrate that diverse combinations of the parameters can generate stars with the same number of patches but different radial and angular stiffness. This mechanism could provide a neat way of further fine-tuning the elastic properties of the supramolecular network without changing its topology.