Colloidal Particles with Triangular Patches.

Self-assembling colloidal particles into clathrate hydrates requires the particles to have tetrahedral bonds in the eclipsed conformation. It has been suggested that colloidal particles with eclipsed triangular-shaped patches can form clusters in the eclipsed conformation that leads to colloidal clathrate hydrates. However, in experiments, patches have been limited to circular shapes due to surface energy minimization. Here, we extend the particle synthesis strategy and show that colloidal particles with triangular patches can be readily fabricated by controlling the viscosity of the liquid oil droplets during a colloidal fusion process. The position, orientation, curvature, shape, and size of the patches are all exclusively determined by the intrinsic symmetry of the colloidal clusters, resulting in dipatch particles with eclipsed patches and tetrahedral patchy particles with patch vertices pointing toward each other. Patch curvature can be controlled by tuning the viscosity of the oil droplets and using different surfactants. Using strain-promoted azide-alkyne cycloaddition, single-stranded DNA can be selectively functionalized on the patches. However, after annealing these particles, dipatch particles form chains because the patches are too small to form clathrate hydrates. Under certain conditions, tetrahedral triangular patchy particles should prefer the eclipsed conformation, as it maximizes DNA hybridization. However, we observe random aggregates, which result from having triangular patches that are too big. We estimate that tetrahedral patchy particles that can crystallize need to be less than 1 μm in diameter.