Combining Precipitation and Vitrification to Control the Number of Surface Patches on Polymer Nanocolloids

In an effort to incorporate increasingly higher levels of functionality into soft nanoparticles, heterogeneously structured particles stand out as a simple means to enhance functionality by tailoring only particle architecture. Various means exist for the fabrication of particles with specific structural configurations; however, the tunability of particle morphology is still a challenging and often laborious task, especially in self-assembled systems where a single equilibrium configuration dominates. Improved strategies for multipatch particle assembly are therefore needed to allow for the tailoring of particle structure via a single, continuous assembly route. One means of accomplishing this is through kinetic trapping of particle morphologies along the path to the final equilibrium configuration in precipitation-induced, phase-separating polymer blends. Here, we demonstrate this capability by using rapid nanoprecipitation to control the overall size, composition, and patch distribution of soft colloids. In particular, we illustrate that polymer feed concentration, blend ratio, and polymer molecular weight can all serve as functional handles with which to consistently alter particle patch distributions in a self-assembling homopolymer system without redesigning the starting materials. We furthermore delineate the role of polymer vitrification in the determination of particle structure.