<i>α</i>‐Helix‐Driven Regulation of Aqueous Circularly Polarized Luminescence in Homopolypeptide Self‐Assembly

ABSTRACT Biopolymer‐driven supramolecular chirality in aqueous media has gained significant advancements in hierarchical chiral nanostructures. However, researches on the aqueous circularly polarized luminescence (CPL) induced by supramolecular self‐assembly and its mechanism have been rarely reported. Herein, we explore the hierarchical chirality transfer in self‐assembled fluorescent homopolypeptide systems showing aqueous CPL, and unveil an α ‐helix‐dominated CPL regulation mechanism. A relationship is established between molecular structure (degree of polymerization, DP), supramolecular assembly (self‐assembly temperature, T SA ), and resulting CPL properties. The stabilization for the homopolypeptide α ‐helix by increasing DP and decreasing T SA enables efficient chirality transfer from the polypeptide backbone to its terminal chromophore, thereby improving CPL properties. Our work elucidates the critical role of α ‐helix control in aqueous CPL systems, providing insights for designing biocompatible and tunable CPL‐active nanomaterials.