Insights into the Self-Assembly of a Heterocluster Janus Molecule into Colloidal Onions

Diverse nanostructures and nano-objects for advanced applications are created by the self-assembly of lipids, surfactants, and block copolymers. Understanding this process is critical for improving their functions and expanding their applications. Accordingly, we pioneered the synthesis and application of heterocluster Janus molecules (HCJMs), which resemble conventional amphiphiles. Their self-assembly into nanostructures and nano-objects can be directly characterized by transmission electron microscopy (TEM), allowing the process to be unraveled through the monitoring of the intermediates. In this study, we focused on the TEM characterization of HCJM-based colloidal onions, which have an onion-like inner structure, to gain insight into the self-assembly process from molecules to perfect onions. Multiple mechanisms, including molecular aggregation, structural ordering within aggregates into colloidal onions, and layer-by-layer growth caused by particle coarsening, contributed to the overall self-assembly process. The analysis also indicated that the reduction in the Gibbs free energy and bending free energy of curved layers are the driving forces for structural ordering and onion growth. Finally, this work provided a useful method for preparing colloidal onions for attractive applications in nanomedicine and other areas.