Biomimetic Supramolecular Assemblies With Programmable Structural and Chiroptical Dynamics

ABSTRACT The kinetic–thermodynamic synergy in protein folding has inspired out‑of‑equilibrium nanostructures; however, precise control and real‑time visualization of their time‑dependent structural evolution remain inaccessible, leaving the formation mechanisms of the final structure fundamentally constrained. Herein, a biomimetic non‐equilibrium supramolecular assembly was developed, capable of spontaneous transformation from a metastable state to a thermodynamically stable state via a mechanism analogous to amyloidogenesis. This morphological evolution was accompanied by a fluorescence shift from yellow (580 nm) to green (520 nm), which enabled real‐time visual monitoring, along with an amplification of the g lum value to 5.0×10 − 3 . The kinetics of transformation can be modulated by chirality, temperature, stirring, and seeding. Notably, a hydrogel matrix mimicking crowded intracellular environments was employed to investigate the assembly evolution, revealing accelerated transformation kinetics. The resulting fluorescence‐tunable hydrogel was further exploited for time‐dependent information encryption. This work offering new avenues for designing dynamic biomimetic materials with programmable chiroptical functions.