Patterning of Polymer-Functionalized Nanoparticles with Varied Surface Mobilities of Polymers

The polymers can be either dynamically tethered to or permanently grafted to the nanoparticle to produce polymer-functionalized nanoparticles. The surface mobility of polymer ligands with one end anchored to the nanoparticle can affect the surface pattern, but the effect remains unclear. Here, we addressed the influence of lateral polymer mobility on surface patterns by performing self-consistent field theory calculations on a modeled polymer-functionalized nanoparticle consisting of immobile and mobile brushes. The results show that except for the radius of nanoparticles and grafting density, the fraction of mobile brushes substantially influences the surface patterning of polymer-functionalized nanoparticles, including striped patterns and patchy patterns with various patches. The number of patches on a nanoparticle increases as the fraction of mobile brushes decreases, favored by the entropy of immobile brushes. Critically, we found that broken symmetry usually occurs in patchy nanoparticles, associated with the balance of enthalpic and entropic effects. The present work provides a fundamental understanding of the dependence of surface patterning on lateral polymer mobility. The work could also guide the preparation of diversified nanopatterns, especially for the asymmetric patchy nanoparticles, enabling the fundamental investigation of the interaction between polymer-functionalized nanoparticles.