Title: Nanoscopic Interfacial Hydrogel Viscoelasticity Revealed from Comparison of Macroscopic and Microscopic Rheology

Abstract: Deviations between macrorheological and particle-based microrheological measurements are often considered a nuisance and neglected. We study aqueous poly(ethylene oxide) (PEO) hydrogels for varying PEO concentrations and chain lengths that contain microscopic tracer particles and show that these deviations in fact reveal the nanoscopic viscoelastic properties of the particle-hydrogel interface. Based on the transient Stokes equation, we first demonstrate that the deviations are not due to finite particle radius, compressibility or surface-slip effects. Small-angle neutron scattering rules out hydrogel heterogeneities. Instead, we show that a generalized Stokes-Einstein relation, accounting for a nanoscopic interfacial shell around tracers with viscoelastic properties that significantly deviate from bulk, consistently explains our macrorheological and microrheological measurements. The extracted shell diameter is comparable with the PEO end-to-end distance, indicating the importance of dangling chain ends. Our methodology reveals the nanoscopic interfacial rheology of hydrogels and is generally applicable to different kinds of viscoelastic fluids and particles.