The hierarchical emergence of worm-like chain behaviour from globular domain polymer chains

Biological organisms make use of hierarchically organised structures to modulate mechanical behaviour across multiple lengthscales, allowing microscopic objects to generate macroscopic effects. Within these structural hierarchies, the resultant physical behaviour of the entire system is determined not only by the intrinsic mechanical properties of constituent subunits, but also by their organisation in three-dimensional space. When these subunits are polyproteins, colloidal chains or other globular domain polymers, the Kratky–Porod model is often assumed for the individual subunits. Hence, it is implicitly asserted that the polymeric object has an intrinsic parameter, the persistence length, that defines its flexibility. However, the persistence lengths extracted from experiment vary, and are often relatively small. Through a series of simulations on polymer chains formed of globular subunits, we show that the persistence length itself is a hierarchical structural property, related not only to the intrinsic mechanical properties of the underlying monomeric subunits, but emerging due to the organisation of inhomogenous geometry along the polymer contour.