Self-Consistent Field Modeling of Bottle-Brush with Aggrecan-like Side Chain

Bottle-brush polymers with aggrecan-like side chains represent a class of biomimetic macromolecules that replicate key structural and functional features of natural complexes of aggrecans with hyaluronic acid (HA) which are the major components of articular cartilage. In this study, we employ numerical self-consistent field (SCF) modeling combined with analytical theory to investigate the conformational properties of cylindrical molecular bottle-brushes composed of aggrecan-like double-comb side chains tethered to the main chain (the backbone of the bottle-brush). We demonstrate that the architecture of the brush-forming double-comb chains and, in particular, the distribution of polymer mass between the root and peripheral domains significantly influences the spatial distribution of primary side chain ends, leading to formation of a “dead” zone near the backbone of the bottle-brush and non-uniform density profiles. The axial stretching force imposed by grafted double-combs in the main chain, as well as normal force acting at the junction point between the bottle-brush backbone and the double-comb side chain are shown to depend strongly on the side-chain architecture. Furthermore, we analyze the induced bending rigidity and persistence length of the bottle-brush, revealing that while the overall scaling behavior follows established power laws, the internal structure can be finely tuned without altering the backbone stiffness. These theoretical findings provide valuable insights into relations between architecture and properties of bottle-brush-like supra-biomolecular structures, such as aggrecan-hyaluronan complexes.