The structural complexity of composite biomaterials and biomineralized particles arises from the hierarchical ordering of inorganic building blocks over multiple scales. Although empirical observations of complex nanoassemblies are abundant, the physicochemical mechanisms leading to their geometrical complexity are still puzzling, especially for nonuniformly sized components. We report the self-assembly of hierarchically organized particles (HOPs) from polydisperse gold thiolate nanoplatelets with cysteine surface ligands. Graph theory methods indicate that these HOPs, which feature twisted spikes and other morphologies, display higher complexity than their biological counterparts. 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 HOP phase diagrams open a pathway to a large family of colloids with complex architectures and unusual chiroptical and chemical properties.

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Chiral nanostructures have been extensively studied for bioanalysis and optoelectronics because of their high rotatory optical activity but not for enantioselective catalysis because of the chirality mismatch of geometric scales. Here, we investigate whether the catalytic activity of supraparticles (SPs) made from ZnS NPs could provide a general pathway to reconcile the difficulties. SPs synthesized by two different pathways could enantioselectively oxidize tyrosine (Tyr). Upon illumination with 300–450 nm photons, SPs could convert Tyr into the catechol derivative dihydroxyphenylalanine (DOPA) and Tyr–Tyr dimers coupled via a C–C bond. The enantiomeric preference of substrate conversion is 23–26%, which is an order of magnitude greater than that with metalorganic compounds for the comparable catalytic process in organic solvents. Chiral catalysis substantiated by a photocatalytic oxidation of tryptophan (Trp) could predominantly lead to catechol derivatives with similar enantiomeric preference of 21–25%. This study opens the door to enantioselective catalysts for aqueous mediums taking advantage of the catalytic, photonic, and self-assembly properties of chiral NPs.

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