Hybrid Cyclopeptide‐Based Chemical Models for Allosteric Disulfide and Amyloid Self‐Assembly

We present here a series of isomeric disulfide-based hybrid cyclic peptides with different ring sizes. The water soluble pseudopeptidic macrocycles display a high intrinsic tendency to self-assemble. Microscopic investigations revealed amyloid like fibrillar morphology with autofluorescence. X-ray crystal structure of 23-membered macrocycle showed the presence of intramolecular hydrogen bonding and a unique S···O interaction. We delineate that the macrocyclic framework is an ideal platform to generate various classes of disulfide conformations. X-ray structure of the macrocycle further revealed the presence of an allosteric disulfide bond with -LHHook geometry.