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Abstract Cooperative catalysis with an enzyme and a small‐molecule photocatalyst has recently emerged as a potentially general activation mode to advance novel biocatalytic reactions with synthetic utility. Herein, we report cooperative photobiocatalysis involving an engineered nonheme Fe enzyme and a tailored photoredox catalyst to achieve enantioconvergent decarboxylative azidation, thiocyanation, and isocyanation of redox‐active esters via a radical mechanism. We repurposed and further evolved metapyrocatechase (MPC), a nonheme Fe extradiol dioxygenase not previously studied in new‐to‐nature biocatalysis, for the enantioselective C─N₃, C─SCN, and C─NCO bond formation via an enzymatic Fe─X intermediate (X═N₃, NCS, and NCO). A range of primary, secondary, and tertiary alkyl radical precursors were effectively converted by our engineered MPC, allowing the syntheses of organic azides, thiocyanates, and isocyanates with good to excellent enantiocontrol. Further derivatization of these products furnished valuable compounds including enantioenriched amines, triazoles, ureas, and SCF₃‐containing products. DFT and MD simulations shed light on the mechanism as well as the binding poses of the alkyl radical intermediate in the enzyme active site and the π‐facial selectivity in the enantiodetermining radical rebound. Overall, cooperative photometallobiocatalysis with nonheme Fe enzymes provides a means to develop challenging asymmetric radical transformations eluding small‐molecule catalysis. 

The capability of stiffness manipulation for materials and structures is essential for tuning motion, saving energy, and delivering high power. However, high-efficiency in situ stiffness manipulation has not yet been successfully achieved despite many studies from different perspectives. Here, curved origami patterns were designed to accomplish in situ stiffness manipulation covering positive, zero, and negative stiffness by activating predefined creases on one curved origami pattern. This elegant design enables in situ stiffness switching in lightweight and space-saving applications, as demonstrated through three robotic-related components. Under a uniform load, the curved origami can provide universal gripping, controlled force transmissibility, and multistage stiffness response. This work illustrates an unexplored and unprecedented capability of curved origami, which opens new applications in robotics for this particular family of origami patterns.