Amphiphilic building blocks for self-assembly: from amphiphiles to supra-amphiphiles.

The process of self-assembly spontaneously creates well-defined structures from various chemical building blocks. Self-assembly can include different levels of complexity: it can be as simple as the dimerization of two small building blocks driven by hydrogen bonding or as complicated as a cell membrane, a remarkable supramolecular architecture created by a bilayer of phospholipids embedded with functional proteins. The study of self-assembly in simple systems provides a fundamental understanding of the driving forces and cooperativity behind these processes. Once the rules are understood, these guidelines can facilitate the research of highly complex self-assembly processes. Among the various components for self-assembly, an amphiphilic molecule, which contains both hydrophilic and hydrophobic parts, forms one of the most powerful building blocks. When amphiphiles are dispersed in water, the hydrophilic component of the amphiphile preferentially interacts with the aqueous phase while the hydrophobic portion tends to reside in the air or in the nonpolar solvent. Therefore, the amphiphiles aggregate to form different molecular assemblies based on the repelling and coordinating forces between the hydrophilic and hydrophobic parts of the component molecules and the surrounding medium. In contrast to conventional amphiphiles, supra-amphiphiles are constructed on the basis of noncovalent interactions or dynamic covalent bonds. In supra-amphiphiles, the functional groups can be attached to the amphiphiles by noncovalent synthesis, greatly speeding their construction. The building blocks for supra-amphiphiles can be either small organic molecules or polymers. Advances in the development of supra-amphiphiles will not only enrich the family of conventional amphiphiles that are based on covalent bonds but will also provide a new kind of building block for the preparation of complex self-assemblies. When polymers are used to construct supra-amphiphiles, the resulting molecules are known as superamphiphiles. This Account will focus on the use of amphiphiles and supra-amphiphiles for self-assembly at different levels of complexity. We introduce strategies for the fabrication of robust assemblies through self-assembly of amphiphiles. We describe the supramolecular approach for the molecular design of amphiphiles through the enhancement of intermolecular interaction among the amphiphiles. In addition, we describe polymerization under mild conditions to stabilize the assemblies formed by self-assembly of amphiphiles. Finally, we highlight self-assembly methods driven by noncovalent interactions or dynamic covalent bonds for the fabrication of supra-amphiphiles with various topologies. Further self-assembly of supra-amphiphiles provides new building blocks for complex structures, and the dynamic nature of the supra-amphiphiles endows the assemblies with stimuli-responsive functions.