Braiding, branching and chiral amplification of nanofibres in supramolecular gels [dataset]

Helical nanofibres play key roles in many biological processes. Entanglements between helices can aid gelation by producing thick, interconnected fibres — for example the strain-stiffening of fibrin, actin and collagen under tension — but the details of this process are poorly understood. Herein we describe the assembly of an achiral oligo(urea) peptidomimetic compound into supramolecular helices. Aggregation of adjacent helices leads to the formation of fibrils, which further intertwine to produce high-fidelity braids with periodic crossing patterns. A braid-theory analysis suggests that braiding is governed by rigid topological constraints, and that branching occurs due to crossing defects in the developing braids. Mixed-chirality helices assemble into relatively complex, odd-stranded braids, but can also form helical bundles by undergoing inversions of chirality. The oligo(urea) assemblies are also highly sensitive to chiral amplification, proposed to occur through a majority rules mechanism — trace chiral materials can promote the formation of gels containing only homochiral helices.