Emergence of complexity inhierarchically organized chiral particles

The structural complexity of composite biomaterials and biomineralized particles arises from the hierarchical ordering of inorganic building blocks over multiple scales. While empirical observations of complex nanoassemblies are abundant, physicochemical mechanisms leading to their geometrical complexity are still puzzling, especially for non-uniformly sized components. Here we report the assembly of hierarchically organized particles (HOPs) with twisted spikes and other morphologies from polydisperse Au-Cys nanoplatelets. The complexity of Au-Cys HOPs is higher than biological counterparts or other complex particles as enumerated by graph theory methods. Their intricate organization emerges from competing chirality-dependent assembly restrictions that render assembly pathways primarily dependent on nanoparticle symmetry rather than size. These findings and HOPs phase diagrams open a pathway to a large family of colloids with complex architectures and unusual chiroptical and chemical properties.