Nanostructuring Single-Molecule Polymeric Nanoparticles via Macromolecular Architecture

Heterogeneous polymer-based nanoparticles comprise a very promising family of materials for a broad range of applications. Here, we present a detailed study of structural heterogeneities in nanostructured single-molecule nanoparticles in various environments by means of atomistic molecular dynamics simulations. The nanoparticles consist of mikto-arm star copolymers with two types of chemically incompatible arms, namely poly(ethylene oxide) (PEO) and polystyrene (PS), (PS)n,(PEO)n, where n is the number of arms. The immiscibility between the two components gives rise to intramolecularly nanostructured particles. The nanostructured objects resemble either “Janus-like” or “patchy-like” particles, depending on the number or the length of the arms (or both) as well as the interaction with the surrounding medium. The degree of intramolecular heterogeneity increases with increasing number of arms and with decreasing affinity of star components to the polymer host. We provide a detailed analysis of the internal s...