Binding, unbinding and aggregation of crescent-shaped nanoparticles on nanoscale tubular membranes.

Using molecular dynamics simulations of a coarse-grained implicit solvent model, we investigate the binding of crescent-shaped nanoparticles (NPs) on tubular lipid membranes. The NPs adhere to the membrane through their concave side. We found that the binding/unbinding transition is first-order, with the threshold binding energy being higher than the unbinding threshold, and the energy barrier between the bound and unbound states at the transition that increases with increasing the NP's arclength Lnp or curvature mismatch µ = Rc/Rnp, where Rc and Rnp are the radii of curvature of the tubular membrane and the NP, respectively. Furthermore, we found that the threshold binding energy increases with increasing either Lnp or µ. NPs with curvature larger than that of the tubule (µ > 1) lie perpendicularly to the tubule's axis. However, for µ smaller than a specific arclength-dependent mismatch µ*, the NPs are tilted with respect to the tubule's axis, with the tilt angle that increases with decreasing µ. We also investigated the self-assembly of the NPs on the tubule at relatively weak adhesion strength and found that for µ > 1 and high values of Lnp, the NPs self-assemble into linear chains, and lie side-by-side. For µ < µ* and high Lnp, the NPs also self-assemble into chains, while being tilted with respect to the tubule's axis.

Membrane-mediated aggregation of anisotropically curved nanoparticles.

Using systematic numerical simulations, we study the self-assembly of elongated curved nanoparticles on lipid vesicles. Our simulations are based on molecular dynamics of a coarse-grained implicit-solvent model of self-assembled lipid membranes with a Langevin thermostat. Here we consider only the case wherein the nanoparticle-nanoparticle interaction is repulsive, only the concave surface of the nanoparticle interacts attractively with the lipid head groups and only the outer surface of the vesicle is exposed to the nanoparticles. Upon their adhesion on the vesicle, the curved nanoparticles generate local curvature on the membrane. The resulting nanoparticle-generated membrane curvature leads in turn to nanoparticle self-assembly into two main types of aggregates corresponding to chain aggregates at low adhesion strengths and aster aggregates at high adhesion strength. The chain-like aggregates are due to the fact that at low values of adhesion strength, the nanoparticles prefer to lie parallel to each other. As the adhesion strength is increased, a splay angle between the nanoparticles is induced with a magnitude that increases with increasing adhesion strength. The origin of the splay angles between the nanoparticles is shown to be saddle-like membrane deformations induced by a tilt of the lipids around the nanoparticles. This phenomenon of membrane mediated self-assembly of anisotropically curved nanoparticles is explored for systems with varying nanoparticle number densities, adhesion strength, and nanoparticle intrinsic curvature.