Interfacial Chemistry of Conical Fullerene Amphiphiles in Water.

Abstract

Amphiphiles are used for a variety of applications in our daily life and in industrial processes. They typically possess hydrophobic and hydrophilic moieties within the molecule, thereby performing a myriad of functions through the formation of two- and three-dimensional assemblies in water, such as Gibbs monolayers and micelles. However, these functions are often inseparable because they emerge from the same structural feature of the molecule, and are difficult to control because the structural diversity is limited to either long-chain hydrocarbons bearing a polar end group(s) or polymers bearing polar groups exposed to the exterior surface. In this Account, we describe the chemistry of a new class of amphiphiles, conical fullerene amphiphiles (CFAs), utilizing a superhydrophobic [60]fullerene group as a nonpolar apex with added structural features to make it soluble in water. By selective functionalization of only one side of the fullerene molecule, the CFA molecules spontaneously assemble in water through strong hydrophobic interactions among the fullerene apexes and exhibit unusual supramolecular and interfacial behavior. They form unilamellar micelles and vesicles at a critical aggregation concentration as low as micromolar, not showing any air-water and oil-water interfacial activity. The strong preference for self-assembly in water over monolayer formation at an air-water interface makes CFAs unique among conventional nonpolymeric surfactants. The CFA assemblies are often so mechanically robust that they can be transferred to the surface of a solid substrate and analyzed by high-resolution microscopy. Because of this rigid conical structure of a few nanometers in size, CFA molecules aggregate readily in water to form a hierarchical assembly with biomolecules and nanomaterials while maintaining the structural integrity of the CFA aggregate to form multicomponent agglomerates of controllable structural features. For instance, tissue-selective in vivo transport of DNA and siRNA has been achieved. Hybridization of a CFA vesicle with a transition metal catalyst enables the construction of a structurally defined nanospace and an interface for precise control of the nanoscale morphology of polymers. Solubilization of hydrophobic nanocarbons and nanoparticles is also achieved through hemimicelle formation on solid surfaces. The examples reported here illustrate the potential of the conical fullerene motif for the design of amphiphiles as well as supramolecular structures at molecular and tens of nanometers scale.