Temperature-Directed Formation of Anisotropic Kettlebell and Tadpole Nanostructures in the Absence of a Swelling-Induced Solvent

Anisotropic Janus (“snowman”) nanoparticles with a single protrusion are currently made via the solvent swelling-induced method. Here, we demonstrate without the aid of toxic solvents a generally applicable method for the formation of anisotropic polymer nanoparticles directly in water by controlling polymer mobility through tuning its glass transition temperature (T_g). Spherical structures, formed immediately after the emulsion polymerization, transformed into uniform tadpoles (with head diameter ≈60 nm and tail length ≈130 nm) through the protrusion of a single cylindrical tail when cooled to a temperature above the T_g of the polymer. Cooling the spheres to below the T_g produced kinetically trapped kettlebell structures that could be freeze-dried and rehydrated without any structural change. These unique kettlebells could transform into uniform tadpoles by heating above the T_g, representing a triggered and on-demand structural reorganization.