Assembly of responsive-shape coated nanoparticles at water surfaces

Nanoparticle (NP) assembly and aggregation can be controlled using a variety of organic coatings that bind to the nanoparticle surface and alter its affinity for solvent and other particles. We show that surprisingly simple short chain polymer coatings can be effectively used to selectively control the aggregation of very small nanoparticles by taking advantage of the environment-responsive shape produced by the coating's spontaneous asymmetry on high-curvature nanoparticles. Using extremely long molecular dynamics simulations of alkanethiol coated Au nanoparticles, we show that varying the terminal groups of a nanoparticle coating dramatically alters the coating shape at the water liquid-vapor interface, producing very different assembly morphologies. NPs with CH3-terminated coatings assemble into short linear groupings with a highly aligned structure at early time and then form more disordered clusters as these linear groupings further assemble. NPs with COOH-terminated coatings assemble into dimers and disordered clumps with no preferred alignment at short time and longer disordered chains of particles at longer times. We also find that the responsive shape of the coating continues to adapt to local environment during assembly. The orientations of chains within NP coatings are significantly different when the NPs are arranged in aggregates than when they are isolated.