Programmable α-Helices Enable Multiple Shape Memory in Peptides

Multiple shape memory polymers (multi-SMPs) can store multiple temporary shapes in a single cycle, offering enhanced adaptability in complex environments. Yet, most multi-SMPs rely on sophisticated copolymer designs to create discrete transition domains, limiting their simplicity and scalability. Here, we report homopeptide films with either α-helical or random-coil conformations that display distinct shape memory behaviors. Remarkably, α-helical films encode at least six thermally actuated shapes enabled by their programmable helices. The rod-like helices confer superior thermal stability and drive ordered lattice formation, leading to two broad thermoresponsive transitions associated with the glass transition and lattice reorganization. In addition, the noncovalent nature of the peptide films affords efficient healing. This chemically straightforward yet functionally versatile strategy provides a scalable platform for the development of next-generation shape-morphing materials.