Directing transformation pathways of hierarchical assemblies by recycling oxidative photolysis

Structure formation in living systems builds upon balancing kinetic and thermodynamic landscapes powered by recycling covalent bond chemistry. Although recent synthetic efforts have been able to achieve these processes in part, the combination is necessary to identify key mechanisms that confer nature’s structural precision within a complex environment. We design a photolytic peptide that dissipates downstream chemical energy to control the transience and interconversion between its two active supramolecular forms via disulfide formation. The thiol assembles with slow kinetics via an isodesmic mechanism whereas the disulfide form induces aromatic chirality that propagates into helical twists within the nanostructure. Multiple structural states found under the same global conditions show that the assembly network demonstrate similar biological plasticity and can be directed by the recycling pathway. The approach demonstrate the importance of reaction complexity in creating supramolecular architectures that are inaccessible via conventional means.