Aggrecan, a large biological polyelectrolyte molecule with a bottlebrush shape, forms complexes with hyaluronic acid (HA) that provide compressive resistance in cartilage. In solutions of aggrecan alone, the concentration dependence of the osmotic pressure Π is marked by self-assembly of the molecules into aggregates. When HA is added to the solution at low aggrecan concentration c, the osmotic pressure is reduced, but in the physiological concentration range this trend is reversed. The osmotic modulus c∂Π∕∂c, which determines load bearing resistance, is enhanced in the HA-containing solutions. Dynamic light scattering (DLS) measurements show that the aggregates behave like microgels and that they become denser as the aggrecan concentration increases. The degree of densification is greatest at large distance scales in the microgels, but decreases at short distance scales. Measurements at higher resolution, involving small angle neutron scattering and small angle x-ray scattering (SAXS), confirm that at length scales shorter than 1000 Å, the density is independent of the concentration and that the individual bottlebrushes in the microgels retain their identity. The absence of collective diffusion modes in the relaxation spectrum, measured by DLS and neutron spin echo, corroborates the lack of interpenetration among the aggrecan subunits in the microgel. Complexation with HA modifies the long-range spatial organization of the microgels. Comparison of the scattering pattern of the individual aggrecan molecules obtained from SAXS measurements with that of the complexes measured by DLS shows that the aggrecan-HA structure is denser and is more uniform than the random microgels. This enhanced space-filling property allows higher packing densities to be attained, thus, optimizing resistance to osmotic compression
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