A Light-Induced Nonequilibrium Peptide Assembly Enables Programmable Catalysis

The dynamic regulation of self-assembled structures in nonequilibrium states is critical for mimicking biological functions, where energy-driven processes underpin spatiotemporal control of molecular activities. Herein, we report a light-responsive peptide assembly system that switches between thermodynamically stable equilibrium nanofibers and energy-dependent nonequilibrium nanoparticles. This dual-state behavior is enabled by spiropyran's (SPs) photoisomerization, which switches between the closed-ring SP and open-ring merocyanine (MC) forms. Crucially, this morphological transition enables programmable control of catalytic activity in Michael addition reactions. In the dark-stable equilibrium state, the nanofiber formed by peptide 1 exhibited robust catalysis, achieving over 95% yield. Under blue light, the nonequilibrium nanoparticle assembly of 1 completely abolished catalytic activity. Intermittent light exposure further demonstrates programmable regulation of reaction progression. The system's ability to couple structural dynamics with functional modulation offers a new avenue for designing programmable catalysts and adaptive materials.