Self-assembly and elasticity of hierarchical proteoglycan–hyaluronan brushes

Spatially confined yet strongly hydrated assemblies made from the proteoglycan aggrecan and the polysaccharide hyaluronan (HA) are major, functionally important components of the pericellular space around chondrocytes, and in cartilage. To better understand, how mechanical properties arise from the supramolecular structure and dynamics of such assemblies, we have studied the effect of aggrecan on the physico-chemical properties of well-defined, planar HA brushes. From interaction studies by quartz crystal microbalance with dissipation monitoring and spectroscopic ellipsometry, and compression studies by combined colloidal probe atomic force/reflection interference contrast microscopy, we find that aggrecan readily intercalates into HA brushes in a reversible manner. Aggrecan induces a drastic swelling of HA brushes, generating self-assembled films of several micrometers in thickness that are highly hydrated (>99%), elastic and very soft. The Young modulus in the linear compression regime is well below 100 Pa, and reaches several kPa at strong compression. The implications of these findings for biological function are discussed.