Thermoresponsive Nanoparticles with Cyclic-Polymer-Grafted Shells Are More Stable than with Linear-Polymer-Grafted Shells: Effect of Polymer Topology, Molecular Weight, and Core Size.

Polymer brush-grafted superparamagnetic iron oxide nanoparticles can change their aggregation state in response to temperature and are potential smart materials for many applications. Recently, the shell morphology imposed by grafting to a nanoparticle core was shown to strongly influence the thermoresponsiveness through a coupling of intrashell solubility transitions and nanoparticle aggregation. We investigate how a change from linear to cyclic polymer topology affects the thermoresponsiveness of poly(2-isopropyl-2-oxazoline) brush-grafted superparamagnetic iron oxide nanoparticles. Linear and cyclic polymers with three different molecular weights (7, 18, and 24.5 kg mol(-1)) on two different core sizes (3.7 and 9.2 nm) and as free polymer were investigated. We observed the critical flocculation temperature (CFT) during temperature cycling dynamic light scattering experiments, the critical solution temperature (CST), and the transition enthalpy per monomer during differential scanning calorimetry measurements. When all conditions are identical, cyclic polymers increase the colloidal stability and the critical flocculation temperature compared to their linear counterparts. Furthermore, the cyclic polymer shows only one uniform transition, while we observe multiple transitions for the linear polymer shells. We link the single transition and higher colloidal stability to the absence in cyclic PiPrOx shells of a dilute outer part where the particle shells can interdigitate.