Dynamics of Soft and Hairy Polymer Nanoparticles in a Suspension by NMR Relaxation

The design of surface-modified functional nanoparticles (NPs) is used to control the properties of the NPs and the NP/environment interactions. The efficient control of the final behavior of the NPs demands a comprehensive understanding of the resulting system. This is particularly challenging for systems with an architecture of the type polymer core-polymer canopy. In such systems, one of the key parameters influencing the behavior of the NPs is the local dynamics of the polymer canopy. However, because the grafting points of the canopy are experiencing their own local dynamics, predicting the final behavior of such systems is difficult. To get a deeper understanding of NPs made of a soft and swollen polymer core and a swollen polymer canopy, we prepared a library of hairy NPs made of a polystyrene (PS) core and a canopy of grafted poly(methyl acrylate) (PMA) chains. The softness of the PS core and the thickness of the PMA canopy were controlled, and the behavior and dynamics of the soft and hairy PS-PMA NPs in suspension were measured by ¹H NMR relaxation and dynamic light scattering. It was observed that the rigid PS core slowed down the subsegmental dynamics of the PMA chains, while thick PMA canopies accelerated the relaxation of the PS core. The dynamics of the NPs in suspension was the result of the interplay between the PS core and the PMA canopy.