Self-Assembly of Nanoparticle Amphiphiles with Adaptive Surface Chemistry
journal contributionposted on 28.10.2014, 00:00 by Hee-Young Lee, Sun Hae Ra Shin, Aaron M. Drews, Aaron M. Chirsan, Sean A. Lewis, Kyle J. M. Bishop
We investigate the self-assembly of amphiphilic nanoparticles (NPs) functionalized with mixed monolayers of hydrophobic and hydrophilic ligands in water. Unlike typical amphiphilic particles with “fixed” surface chemistries, the ligands used here are not bound irreversibly but can rearrange dynamically on the particles’ surface during their assembly from solution. Depending on the assembly conditions, these adaptive amphiphiles form compact micellar clusters or extended chain-like assemblies in aqueous solution. By controlling the amount of hydrophobic ligands on the particles’ surface, the average number of nearest neighborsthat is, the preferred coordination numbercan be varied systematically from ∼1 (dimers) to ∼2 (linear chains) to ∼3 (extended clusters). To explain these experimental findings, we present an assembly mechanism in which hydrophobic ligands organize dynamically to form discrete patches between proximal NPs to minimize contact with their aqueous surroundings. Monte Carlo simulations incorporating these adaptive hydrophobic interactions reproduce the three-dimensional assemblies observed in experiment. These results suggest a general strategy based on reconfigurable “sticky” patches that may allow for tunable control over particle coordination number within self-assembled structures.