Self-Assembly of Nanoparticle–Surfactant Complexes with Rodlike Micelles: A Molecular Dynamics Study

The self-assembly of nanoparticles (NPs) with cationic micelles of cetyltrimethylammonium chloride (CTAC) is known to produce stable nanogels with rich rheological and optical properties. Coarse-grained molecular dynamics (MD) simulations are performed to explore the molecular mechanisms underlying this self-assembly process. In an aqueous solution of CTAC surfactants, a negatively charged NP with a zeta potential of less than −45 mV is observed to form a stable vesicular structure in which the particle surface is almost entirely covered with a double layer of surfactants. In comparison, surfactants form a monolayer, or a corona, around an uncharged hydrophobic NP with the tailgroups physically adsorbed onto the particle. In the presence of sodium salicylate salt, such NP–surfactant complexes (NPSCs) interact with rodlike CTAC micelles, resulting in the formation of stable junctions through the opening up of the micelle end-cap followed by surfactant exchange, which is diffusion-limited. The diffusive regime spans several hundred nanoseconds, thereby necessitating MD simulations over microsecond time scales. The energetics of NPSC–micelle complexation is analyzed from the variation in the total pair-potential energy of the structures