Bowl-Shaped Polydopamine Nanocapsules: Control of Morphology via Template-Free Synthesis.

Synthesis of hollow polydopamine bowl-shaped nanoparticles (nanobowls), as small as 80 nm in diameter, via a one-pot template-free rapid method is reported. Addition of dopamine to a solution of 0.606 mg/mL tris(hydroxymethyl)aminomethane in an ethanol/water mixed solvent resulted in the formation of hollow spherical nanocapsules within 2 h. At longer reaction times, the formation of conventional solid nanospheres dominated the reaction. The wall thickness of the nanocapsules increased with increasing dopamine concentration in the reaction medium. Wall thickness was also influenced by oxygen availability during the reaction. Nanocapsules with thin walls were prone to collapse. When dried, over 90% of the nanocapsules with wall thickness on the order of 11 nm collapsed. Also, the degree of collapse of individual nanoparticles changed from complete to partial to no collapse as the wall thickness was increased. Varying the ethanol content affected the cavity size and overall dimension of the nanocapsules produced but did not result in a significant change to the wall thickness. A mechanism describing the formation of the nanocapsules and their subsequent collapse into nanobowls is presented. The shape-tunable nanobowls prepared through this green, rapid, and affordable method are expected to have applications in the biomedical, electrochemical, and catalytic fields.