Giant surfactants based on molecular nanoparticles: Precise synthesis and solution self-assembly

ABSTRACT Giant surfactants are polymer‐tethered molecular nanoparticles (MNPs) and can be considered as a subclass of giant molecules. The MNPs serve as functionalized heads with persistent shape and volume, which may vary in size, symmetry, and surface chemistry. The covalent conjugation of MNPs and polymer tails affords giant surfactants with diverse composition and architecture. Synthetic strategies such as “grafting‐from” and “grafting‐onto” have been successfully applied to the precise synthesis of giant surfactants, which is further facilitated by the emergence of “click” chemistry reactions. In many aspects, giant surfactants capture the essential features of small‐molecule surfactants, yet they have much larger sizes. They bridge the gap between small‐molecule surfactants and traditional amphiphilic macromolecules. Their self‐assembly behaviors in solution are summarized in this Review. Micelle formation is affected not only by their primary chemical structures, but also by the experimental conditions. This new class of materials is expected to deliver general implications on the design of novel functional materials based on MNP building blocks in the bottom‐up fabrication of well‐defined nanostructures. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1309–1325 Giant surfactants have emerged as a new class of self‐assembling materials that capture the structural features of both small‐molecule surfactants and amphiphilic block copolymers. Comprised of polymer‐tethered molecular nanoparticles, they display unique self‐assembled nanostructures in solution. This review summarizes recent progress on the study of giant surfactants, focusing on the design and synthesis of prototype giant surfactants, as well as their rich self‐assembled morphologies in solution states.