A twist on amphiphilicity yields sticky supramolecular cones

Abstract

Amphiphilicity defines one of the most fundamental chemical self-assembly principles in constructing mesostructures that have long found use in nanotechnology and biomedical applications. Traditional amphiphiles are composed of two distinct parts – a hydrophobic segment covalently connected to a hydrophilic segment, and the geometry of amphiphile self-assembly is generally limited to highly symmetric spherical micelles and vesicles, as well as cylinders. In this study, we present a new twist to the basic hydrophobic–hydrophilic two-part amphiphile design by “mandatory” linking a few disturbing ionic peptides along the hydrophobic segment of an amphiphilic block copolymer. We report that such a twist on amphiphilicity yields unusual supramolecular cones. These cones demonstrate a surprising stickiness property at the base, which fosters spontaneous higher-order self-assembly. The apex angle, length, as well as the stickiness of the cones can all be tuned by chemical manipulations. Moreover, we reveal the delicate balance of forces that governs the unusual sticky supramolecular cone formation.