Cross-Linked Polystyrene Shells Grown on Iron Oxide Nanoparticles via Surface-Grafted AGET-ATRP in Microemulsion

Most applications of nanoparticles require robust stabilization, for example, by surface-bound ligands or the encapsulation within polymer shells. Furthermore, for biomedical applications, the particles must be dispersible in a complex biological environment. Thus, high-quality nanoparticles synthesized in organic solvents must be transferred into aqueous media. Here, we present a novel scalable method enabling the robust hydrophilic encapsulation of non-agglomerated nanoparticles by growing polystyrene shells via AGET-ATRP in microemulsion. To demonstrate this approach, we encapsulate iron oxide nanoparticles (diameter: 13.7 ± 0.6 nm). Because the ATRP initiator is grafted onto the nanoparticles' surface, the shells are covalently attached to the iron oxide cores. By varying the amount of monomers, the shell thickness can be adjusted precisely, as indicated by the increasing hydrodynamic size from ∼22 to 26 nm (DLS, number mean) with an increasing amount of added monomers. Moreover, the degree of cross-linking can be controlled by the amount of added divinylbenzene (DVB). To evaluate the robustness of the polymer shells against ion infusion, we introduce a novel colorimetric method, which is based on the formation of the red iron thiocyanate complex. After addition of HCl, the increase in absorbance at 468 nm indicates leaching of iron ions from the polymer-encapsulated core particles. These measurements confirm that with increasing shell thickness, significantly improved shielding is achieved. Furthermore, high concentrations of added DVB [33-50% (v/v) in a monomer mixture] improve the shielding effect. However, when smaller amounts of DVB were added [10-25% (v/v)], the shielding effect was diminished, even in comparison to non-cross-linked polymer shells. This finding suggests a higher porosity of shells with a low degree of cross-linking.