Nature has developed clever and intricate strategies to assemble simple building blocks into complex architectures, ranging from stacking in tubulin to complex twisting and folding in DNA. Drawing inspiration, much research has been done to mimic this molecular programming to develop well-defined nanoscale structures via nanoparticle (NP) self-assembly. However, architectures remain largely simplistic due to the isotropic nature of established assembly protocols. Consequently, we have developed a new self-assembly technique that utilizes favorable Lewis acid/base interactions, Cu(I)-catalyzed azide-alkyne cycloaddition, or host-guest interactions between block-co-polymers (BCPs) tethered to the surface of AuNPs. AuNPs are synthesized via reduction of a gold precursor, using sodium citrate as both a reducing and capping agent. Concurrently, thiol-terminated BCPs are synthesized via Reversible Addition-Fragmentation Chain-Transfer (RAFT) polymerization, with desired functionalities incorporated into the polymer backbone. Subsequently, these BCPs are tethered to the NP surface through ligand exchange, achieving hairy inorganic NPs (HINPs). We demonstrate, that through careful tuning of the BCP length and particle concentrations, we can control the interactions between particles, yielding structures (ie. dimers, trimers, tetramers, etc.) with high yields. Particularly intriguing is the ability to then transfer these structures into aqueous media without loss of structural integrity. Additionally, the use of reversible interactions yields structures that can be controllably assembled and disassembled using various stimuli.

Controlled self-assembly of water-soluble, “hairy”, inorganic nanoparticles (HINPs) into supracolloids with defined valence

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.