Self-Assembly of Single-Polymer-Tethered Nanoparticle Amphiphiles upon Varying Tail Length

We systematically investigated the roles of tail length on the self-assembly of shape amphiphiles composed of a hydrophobic polymer chain (tail) and a hydrophilic nanoparticle in selective solvent using Brownian dynamics simulations. The shape amphiphiles exhibited a variety of self-assembled aggregate morphologies which can be tuned by changing tail length (n) in combination with amphiphile concentration (φ) and system temperature (T*). Specifically, at high φ with T*=1.4, the morphology varied following the sequence "spheres → cylinders → vesicles" upon increasing n, agreeing well with experimental observations. At low φ with T*=1.4 or at high φ with T*=1.2, the morphology sequence becomes "spheres or spheres and cylinders mixture → cylinders → vesicles → spheres" upon increasing n, which has not been found experimentally. Two morphological phase diagrams depending on n and φ were constructed for T*=1.4 and 1.2, respectively. The rich phase behaviors on varying tail length could provide the feasible routes to fabricate target aggregate morphologies in various applications, especially for the vesicles with tunable thickness of membranes that are crucial in drug and gene delivery.