Water-based lubricants provide lubrication of rubbing surfaces in many technical, biological, and physiological applications. The structure of hydrated ion layers adsorbed on solid surfaces that determine the lubricating properties of aqueous lubricants is thought to be invariable in hydration lubrication. However, we prove that the ion surface coverage dictates the roughness of the hydration layer and its lubricating properties, especially under subnanometer confinement. We characterize different hydration layer structures on surfaces lubricated by aqueous trivalent electrolytes. Two superlubrication regimes are observed with friction coefficients of 10 ⁻⁴ and 10 ⁻³ , depending on the structure and thickness of the hydration layer. Each regime exhibits a distinct energy dissipation pathway and a different dependence to the hydration layer structure. Our analysis supports the idea of an intimate relationship between the dynamic structure of a boundary lubricant film and its tribological properties and offers a framework to study such relationship at the molecular level.

Improving nanoparticles (NPs) transport across biological barriers is a significant challenge that could be addressed through understanding NPs diffusion in dense and confined media. Here, we report the ability of soft NPs to shrink in confined environments, therefore boosting their diffusion compared to hard, non-deformable particles. We demonstrate this behavior by embedding microgel NPs in agarose gels. The origin of the shrinking appears to be related to the overlap of the electrostatic double layers (EDL) surrounding the NPs and the agarose fibres. Indeed, it is shown that screening the EDL interactions, by increasing the ionic strength of the medium, prevents the soft particle shrinkage. The shrunken NPs diffuse up to 2 orders of magnitude faster in agarose gel than their hard NP counterparts. These findings provide valuable insights on the role of long range interactions on soft NPs dynamics in crowded environments, and help rationalize the design of more efficient NP-based transport systems.