Solvent-Induced Assembly of One-Patch Silica Nanoparticles into Robust Clusters, Wormlike Chains and Bilayers

We report the synthesis and solvent-induced assembly of one-patch silica nanoparticles in the size range of 100-150 nm. They consisted, as a first approximation, of silica half-spheres of which the truncated face was itself concave and carried in its center a polymeric patch made of grafted polystyrene chains. The multistage synthesis led to 98% pure batches and allowed a fine control of the patch-to-particle size ratio from 0.69 to 1.54. The self-assembly was performed in equivolume mixtures of tetrahydrofuran and ethanol, making the polymeric patches sticky and ready to coalesce together. The assembly kinetics was monitored by collecting samples over time and analyzing statistically their TEM images. Small clusters, such as dimers, trimers, and tetramers, were formed initially and then evolved in part into micelles. Accordingly to previous simulation studies, more or less branched wormlike chains and planar bilayers were observed in the long term, when the patch-to-particle size ratio was high enough. We focused also on the experimental conditions that could allow preparing small clusters in a good morphology yield.