Nanoscale Spatial Control over the Self-Assembly of Small Molecule Hydrogelators

Spatial control over molecular self-assembly at the nano scale offers great potential for many high-tech applications, yet remains a challenging task. Here, we report a polymer brush-mediated strategy to confine the self-assembly of hydrazone-based hydrogelators exclusively at nanoparticle surfaces. The surfaces of these nanoparticles are grafted with negatively charged polyacrylic acid, which enrich protons that can catalyze the in situ formation and self-assembly of hydrazone-based gelators. We found that, with respect to the polymer lengths, the concentration of the nanoparticles presents more significant effects on the self-assembly process and the properties of the resultant hydrogels, including gelation time, stiffness, and network morphology. More interestingly, the hydrogel fibers are found to be formed specifically around the nanoparticles, demonstrating the directed nanoscale molecular self-assembly. This work demonstrates that triggering molecular self-assembly using catalysis can serve as an effective way to realize directed molecular self-assembly at the nano scale, which may serve as a powerful approach to improve many material properties, such as the mechanical properties of supramolecular materials as we found in this work.