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Left: previously we developed a photoenzyme for [2 + 2] cycloadditions (EnT1.3) by genetically encoding a non-canonical amino acid containing a benzophenone side chain (BpA, violet) 25 . Structural analysis of product-bound EnT1.3 (PDB: 7ZP7 , product depicted in cyan) showed a sophisticated active site network, including -stacking and hydrogen-bonding interactions. This photosensitizer requires irradiation with UV light (365–395 nm) for excitation. Chemical scheme showing the targeted intramolecular [2 + 2] photocycloaddition of an oxygen-linked quinoline substrate.

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