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Colloidal gels assembled from nanoparticles (NPs) are a versatile class of soft network-based materials capable of rich dynamic, mechanical, and even optical or magnetic responses to stimuli. Their behaviors are governed by dynamics of heterogeneous structures coupled across multiple length and timescales. Observable dynamics range from nanoparticle diffusion and clustering to mesoscopic cluster dynamics and interactions to localized or collective network relaxations. Understanding how these hierarchically organized processes relate to macroscopic network properties remains a broad and unresolved problem in soft matter physics. The mechanisms of gel formation can depend sensitively on the pathway and the nature of NP interactions, thus far preventing a unified theoretical bridge between nanoscopic interactions, structural evolution, and network dynamics. Indirect measurement of dynamics using light-scattering techniques provides an experimental means to quantify underlying particle and network motion. The rich dynamic behavior of NP gels warrants consideration of a broad range of models to help interpret nonlinear relaxation phenomena such as anomalous diffusion, nonergodicity, and intrinsically nonequilibrium or mechanically driven dynamics. X-ray photon correlation spectroscopy (XPCS) has emerged as a powerful tool for probing nanoscopic motion in nanoparticle gels but alone cannot resolve the full spatiotemporal spectrum of dynamics that drive gelation, aging, and network mechanical properties. While rheo-XPCS enables simultaneous probing of nanoscale and bulk mechanical responses, complementary light scattering, microscopy, or simulations can extend spatiotemporal characterization and, consequently, understanding of NP gel network physics. Implementing a modular model platform with tunable primary nanoparticle features allows systematic variation of nanoscopic characteristics that drive emergent gel responses and inform the development of theoretical models for a wide range of soft, dynamic, nanostructured materials. Gels formed from particles with unique structural proxies, such as electromagnetic coupling in plasmonic NPs, provide additional metrics for model validation and offer opportunities to develop computational methods for the efficient and accurate replication of NP gel properties. The rapid expansion of XPCS capabilities at fourth-generation light sources, combined with complementary tools and robust model systems, positions the field to move beyond descriptive fundamental studies toward the design of nanoparticle gels with adaptive and programmable behaviors. 

Dynamic covalent cross-links impart hydrogels with viscoelastic and self-healing properties, motivating applications as biomimetic cell scaffolds and injectable materials. The long bond lifetime results in complex rheological behavior including shear thickening. We hypothesized that this behavior applies broadly across dynamic covalent hydrogels and can be engineered through reaction rate constants. Thus, we synthesized multiarm poly(ethylene glycol) (PEG) hydrogels with conjugate addition, boronate ester, or terpyridine-zinc cross-links, which tune bond dissociation kinetics and hydrogel relaxation times over four orders of magnitude. All formulations exhibited shear thickening, with the onset dictated by the relaxation time. Although multiple mechanisms may underlie this behavior, chain stretching is hypothesized to contribute to shear thickening, as the cross-linking concentration remained constant under shear and networks with more defects correlated with increased shear thickening. These molecular and structural drivers of shear thickening apply across dilute dynamic covalent tetra-PEG hydrogels, clarifying their suitability for applications under shear.