Characterizing dynamic heterogeneities during nanogel degradation†

Understanding photodegradation of nanogels is critical for dynamic control of their properties and functionalities. We focus on nanogels formed by end-linking of four-arm polyethylene glycol precursors with photolabile groups and characterize dynamic heterogeneities in these systems during degradation. We use our recently developed dissipative particle dynamics framework that captures the controlled scission of bonds between the precursors and diffusion of degraded fragments at the mesoscale. To quantify spatiotemporal fluctuations in the local dynamic behavior, we calculate the self-part of the van-Hove correlation function for the reactive beads for nanogels degrading in various environments. We demonstrate strong deviations from the Gaussian behavior during the degradation and quantify variations in the non-Gaussian parameter as a function of the relative extent of degradation. We show that for the nanogels degrading in a good solvent, the peak values in the non-Gaussian parameter are observed significantly earlier than the reverse gel point, and earlier than the peak values in the dispersity of the broken off fragments. Further, our study shows that a systematic decrease in solvent quality significantly affects the behavior of the non-Gaussian parameter as a function of the relative extent of degradation. The findings of this study allow one to quantify the dynamic heterogeneities during degradation in various environments and can potentially provide guidelines for designing controllably degrading nanocarriers.