Artificial Light‐Harvesting Complexes Enable Rieske Oxygenase Catalyzed Hydroxylations in Non‐Photosynthetic cells

In this study, we coupled a well‐established whole‐cell system based on E. coli via light‐harvesting complexes to Rieske oxygenase (RO)‐catalyzed hydroxylations in vivo. Although these enzymes represent very promising biocatalysts, their practical applicability is hampered by their dependency on NAD(P)H as well as their multicomponent nature and intrinsic instability in cell‐free systems. In order to explore the boundaries of E. coli as chassis for artificial photosynthesis, and due to the reported instability of ROs, we used these challenging enzymes as a model system. The light‐driven approach relies on light‐harvesting complexes such as eosin Y, 5(6)‐carboxyeosin, and rose bengal and sacrificial electron donors (EDTA, MOPS, and MES) that were easily taken up by the cells. The obtained product formations of up to 1.3 g L−1 and rates of up to 1.6 mm h−1 demonstrate that this is a comparable approach to typical whole‐cell transformations in E. coli. The applicability of this photocatalytic synthesis has been demonstrated and represents the first example of a photoinduced RO system. Illuminate me! The photoactivation of Rieske dioxygenases in the absence of glucose or any cofactor was successfully conducted using several photosensitizers for the bioconversion of three different substrates, which represents the first example of a photoinduced Rieske system.