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 structure of the star-shaped particles, focusing on the intramolecular packing and the spatial arrangement of the arms. The results of our study can be used to design heterogeneous, internally nanostructured particles with two phases of distinct static properties for challenging specific applications of next-generation materials.
Keywords: atomistic simulations; intramolecular nanosegregation; mikto-arm copolymer stars; particle design; polymeric nanoparticles.