Hyaluronan, lubricin and phospholipids, molecules ubiquitous in synovial joints, such as hips and knees, have separately been invoked as the lubricants responsible for the remarkable lubrication of articular cartilage; but alone, these molecules cannot explain the extremely low friction at the high pressures of such joints. We find that surface-anchored hyaluronan molecules complex synergistically with phosphatidylcholine lipids present in joints to form a boundary lubricating layer, which, with coefficient of friction μ≈0.001 at pressures to over 100 atm, has a frictional behaviour resembling that of articular cartilage in the major joints. Our findings point to a scenario where each of the molecules has a different role but must act together with the others: hyaluronan, anchored at the outer surface of articular cartilage by lubricin molecules, complexes with joint phosphatidylcholines to provide the extreme lubrication of synovial joints via the hydration–lubrication mechanism.

No abstract

The lubrication of hydrogels arises from fluid or solvated surface phases. By contrast, the lubricity of articular cartilage, a complex biohydrogel, has been at least partially attributed to nonfluid, lipid-exposing boundary layers. We emulated this behavior in synthetic hydrogels by incorporating trace lipid concentrations to create a molecularly thin, lipid-based boundary layer that renews continuously. We observed a 80% to 99.3% reduction in friction and wear relative to the lipid-free gel, over a wide range of conditions. This effect persists when the gels are dried and then rehydrated. Our approach may provide a method for sustained, extreme lubrication of hydrogels in applications from tissue engineering to clinical diagnostics.

Prompted by the recent discovery that water and aqueous monovalent Na+ solutions remain fluid-like when confined to films of a few molecular layers between mica surfaces,[Raviv et al., Nature, 2001, 413, 51-54; and Raviv and Klein, Science, 2002, 297, 1540-1543] we now extend the previous study by comparing the shear- and normal-force properties of 0.1 M Na+, Cs+ and Ni2+ salt solutions which demonstrate a diverse range of behaviours under confinement. In the case of hydrated Na+ we extend the previous study to higher pressures, up to approximately 10 atmospheres, and record similar fluidity of the hydration layers at these elevated pressures. Aqueous Cs+ films under confinement between mica sheets have been found to be unable to support an applied load--that is to say they do not demonstrate any hydration repulsion regime--as a result of their lower hydration energy [see Goldberg et al., Phys. Chem. Chem. Phys., 2008, 10, 4939-4945] which contrasts with the properties of Na+. We show that 0.1 M Ni2+ solution remains close to its bulk viscosity down to nanometre thin films, but does not demonstrate a hydration repulsion. By comparing the properties of this range of cations, with differing valency and hydration, we aim to examine the conditions under which ions serve as effective lubricants and what we call the 'hydration lubrication' mechanism.

Lubrication by hydration shells that surround, and are firmly attached to, charges in water, and yet are highly fluid, provide a new mode for the extreme reduction of friction in aqueous media. We report new measurements, using a mica surface-force balance, on several different systems which exhibit hydration lubrication, extending earlier studies significantly to shed new light on the nature and limits of this mechanism. These include lubrication by hydrated ions trapped between charged surfaces, and boundary lubrication by surfactants, by polyzwitterionic brushes and by close-packed layers of phosphatidylcholine vesicles. Sliding friction coefficients as low as 10(-4) or even lower, and mean contact pressures of up to 17 MPa or higher are indicated. This suggests that the hydration lubrication mechanism may underlie low-friction sliding in biological systems, in which such pressures are rarely exceeded.