Tunable Assembly of Organic-Inorganic Molecules into Hierarchical Superstructures as Ligase Mimics for Enhancing Tumor Photothermal Therapy.

The assembly of molecules into hierarchical superstructures is ubiquitous in the construction of novel geometrically complex hierarchical superstructures, attracting great attention. Herein, a metal-ligand cross-linking strategy is developed for the fabrication of ferric ion-dopamine coordination hierarchical superstructures. A range of superstructures with highly complex morphologies, such as flower-like, octopus-like, and hedgehog-like superstructures, are synthesized. The mechanism for formation of hierarchical superstructures involves the pre-cross-linking of ferric ion with dopamine molecules, the fabrication of iron-dopamine precursors aggregated into the spherical aggregates, the nanoscale aggregates sintering and ordering themselves upon equilibration, the nanodots polymerizing into nanorods, and finally the nanorods self-assembling into hierarchical superstructures. In-depth research illustrates that as the permittivity (ξ) of the reaction system increases, the resulting hierarchical superstructures tend to converge into spherical shape. As a proof of concept, the 0D nanospheres, 1D nanorods, and 3D hierarchical superstructures are fabricated through adjusting system permittivity. The hierarchical superstructure is utilized as peroxidase-like ligase mimics to enhance the effect of tumor photothermal treatment. Further in vitro and in vivo assays demonstrate that the hierarchical superstructure can effectively ablate tumor cells. This work opens new horizons in hierarchical superstructures with complex architectures, and has great potential in nanozymology, biomedical science, and catalysis.