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The molecular design principles, characteristics and development of supramolecular amphiphiles are summarized. Supramolecular amphiphiles are designed by using multiple hydrogen bonding as an essential source of noncovalent interactions in aqueous self-assembly. The supramolecular amphiphiles considered here are composed of molecular pairs designed to acquire enhanced amphiphilicity, i.e., the ability to form stable and ordered molecular assemblies on the formation of multiple—and when more appropriate complementary—hydrogen bonds. These hydrogen bonding mediated amphiphiles further hierarchically self-assemble in a given environment. Their secondary and higher assembly architectures are greatly influenced by the dispersed media via solvophilic–solvophobic interactions.

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