Supramolecular interaction based on metal-ligand coordination is of particular interest to design next-generation block copolymers with high tunability in terms of their composition and volume fraction. Metal nanoparticles grafted by supramolecular amphiphilic block copolymers can self-assemble to a number of nanostructures while retaining the dynamic properties of supramolecular polymers. In this talk, we show a new strategy to prepare amphiphilic colloid molecules using gold nanoparticles modified by thiol-terminated “V-shaped” metal-ligand block copolymers (VBCPs). Thiol-terminated “VBCPs are designed using the coordination of copper (Cu) with dipicolyamine (DPA) terminated polystyrene (PS-DPA) and pyridine (Py) terminated poly(<i>N,N</i><i>′</i>-dimethylacrylamide) (PDMA-Py). Driven by hydrophobicity of VBCPs, those gold nanoparticles with supramolecular polymers can form hollow vesicles and two-dimensional nanoplates in a selective solvent. The morphologies of assemblies are dominated by chemical composition of supramolecular polymers. Those assembled nanostructures preserve the dynamic properties of metal-ligand coordination. Upon the dissociation of metal-ligand coordination in supramolecular polymers, assembled nanostructures could be disrupted. We demonstrated that the assemblies from VBCPs could be respond to hydrochloride acid or other metal ions that compete the coordination with Cu.

Self-Assembly of plasmonic nanoparticle grafted with “V-shape” supramolecular block copolymers

ACS Fall 2021

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