Supramolecular self-organization in PEO-modified C60 fullerene/water solutions:: Influence of polymer Molecular weight and nanoparticle concentration

Utilizing a first-principles-based coarse-grained implicit solvent model, we have investigated the self-association of C-60 fullerenes that have been symmetrically modified with six grafted poly(ethylene oxide) (PEO) chains in aqueous solution. Despite the highly symmetric nature of the pair interactions between PEO-grafted fullerenes, their supramolecular assemblies are highly anisotropic and resemble the linear clusters formed in Stockmayer fluids. The dipole-like interaction between these symmetrically modified fullerenes results from the shielding of the C60 fullerenes by PEO, favoring the addition of more PEO-grafted fullerenes to the linear clusters at the relatively unprotected ends. At low nanoparticle concentrations, self-association is dominated by the formation of stable dimers and trimers resulting from fullerene-fullerene contact and favorable PEO - fullerene interactions. With increasing nanoparticle concentration, larger clusters become increasingly probable. The molecular weight of the PEO tethers can be treated as a temperature-like analogue, with a reduction in average cluster size with increasing chain length due to increased steric repulsion, which is qualitatively similar to effects observed in Stockmayer fluids with increasing temperature. The role of PEO in supramolecular self-organization in PEO-modified C-60 fullerene/water solutions is complex, contributing not only to steric stabilization but also to favorable energetic interactions, nanoparticle shielding, and depletion-driven aggregation.