Programmable Chirality Transfer: Seeding-Directed Co-Assembly of Functional Molecules With Amyloid Frameworks

We report a highly effective and universal strategy for linking small achiral functional molecules with amyloid fibrils, enabling efficient transfer of chirality from the chiral amyloid network to supramolecularly co-assembled entities. This seeding-and-co-assembly approach, based on incorporating functional molecules (e.g., dyes) during ongoing seed-directed amyloid formation, facilitates their templating by the amyloid framework while constraining fibril morphological diversity through suppression of secondary nucleation. Chirality transfer is evidenced by pronounced induced electronic circular dichroism (IECD) with anisotropy factor (g) reaching up to 1.3 × 10^{- 2} (g_ECD) and anomalously high and previously unreported induced vibrational circular dichroism (IVCD) with g_VCD of 1.5 × 10^{- 3}. The acquired handedness arises either from supramolecular ordering of flexible molecules on the fibril surface or from incorporation of more rigid pigment molecules into the amyloid framework. Importantly, this process is tunable: dye concentration and solvent type act as programmable parameters that modulate hierarchical organization and chiroptical properties of the resulting assemblies. Overall, this strategy establishes amyloid fibrils as versatile chiral scaffolds for the rational design of hybrid nanomaterials exhibiting strong circular dichroism and/or circularly polarized luminescence (CPL).