Multipoint Lock-and-Key Assembly of Particles with Anisotropic Dents toward Modeling Rigid Macromolecules in a Colloidal Scale.

Multipoint lock-and-key particle assembly, consisting of lock particles with multiple anisotropic dents and rod-shaped particles as key particles, is developed for colloidal modeling application. The lock particles were connected with each other at a key particle as their joint in the presence of depletants, forming rigid colloidal molecules imitating rigid polymers (e.g., polymers containing aromatic rings and intramolecular hydrogen bonds). A single-particle level observation was conducted to visualize the colloidal polymerization of the particle assembly. Motion trajectories of the lock particles observed by optical microscopy indicated that the particle diffusivity was dramatically lowered when the lock particle connected with another one, suggesting that particle diffusion was suppressed by particle assembly formation. Because the kinetic and regioselectivity of colloidal polymerization are assumed to be analogous to those at the atomic scale, the proposed lock-and-key assembly can be a promising colloidal model for atomic-scale polymers associated with their micro-Brownian motion.