Nanoparticle Brushes: Macromolecular Ligands for Materials Synthesis.

ConspectusColloidal nanoparticles have unique attributes that can be used to synthesize materials with exotic properties, but leveraging these properties requires fine control over the particles' interactions with one another and their surrounding environment. Small molecules adsorbed on a nanoparticle's surface have traditionally served as ligands to govern these interactions, providing a means of ensuring colloidal stability and dictating the particles' assembly behavior. Alternatively, nanoscience is increasingly interested in instead using macromolecular ligands that form well-defined polymer brushes, as these brushes provide a much more tailorable surface ligand with significantly greater versatility in both composition and ligand size. While initial research in this area is promising, synthesizing macromolecules that can appropriately form brush architectures remains a barrier to their more widespread use and limits understanding of the fundamental chemical and physical principles that influence brush-grafted particles' ability to form functional materials. Therefore, enhancing the capabilities of polymer-grafted nanoparticles as tools for materials synthesis requires a multidisciplinary effort, with specific focus on both developing new synthetic routes to polymer-brush-coated nanoparticles and investigating the structure-property relationships the brush enables.In this Account, we describe our recent work in developing polymer brush coatings for nanoparticles, which we use to modulate particle behavior on demand, select specific nanoscopic architectures to form, and bolster traditional bulk polymers to form stronger materials by design. Distinguished by the polymer type and capabilities, three classes of nanoparticles are discussed here: nanocomposite tectons (NCTs), which use synthetic polymers end-functionalized with supramolecular recognition groups capable of directing their assembly; programmable atom equivalents (PAEs) containing brushes of synthetic DNA that employ Watson-Crick base pairing to encode particle binding interactions; and cross-linkable nanoparticles (XNPs) that can both stabilize nanoparticles in solution and polymer matrices and subsequently form multivalent cross-links to strengthen polymer composites. We describe the formation of these brushes through "grafting-from" and "grafting-to" strategies and illustrate aspects that are important for future advancement. We also examine the new capabilities brushes provide, looking closely at dynamic polymer processes that provide control over the assembly state of particles. Finally, we provide a brief overview of the technological applications of nanoparticles with polymer brushes, focusing on the integration of nanoparticles into traditional materials and the processing of nanoparticles into bulk solids.