Spontaneous and Template-Directed Emergence of Low-Symmetry Foldamers from Dynamic Homomeric Sequences

Creating large objects from simple subunits rarely results in structures that are of low symmetry as well as of low polydispersity. We now report the spontaneous and uniquely selective oligomerization of simple monomer units into oligomers that are of uniform length, have complex low symmetry structures and are conformationally well-defined. The occurrence of such structures is both frequent and diverse. It is driven by the spontaneous folding into three-dimensional shapes akin to those exhibited by biopolymers. We also show that templates can direct the formation of new functional foldamers. The resulting structures carry imprints of the templates and are therefore capable of binding these. This behavior resembles that of molecularly imprinted polymers (MIPs), with the important distinction that the selected oligomers are uniform and conformationally well-defined, whereas MIPs suffer from heterogeneity in structure, shape and size.