Aug 2026· Current Opinion in Chemical Biology· Vol 94, pp.
102756
· 0 citations· 84 references
Medicine
Abstract
Photobiocatalysis integrates enzymatic catalysis with photochemistry, enabling challenging radical transformations with high selectivity under mild conditions. Early developments in this field were largely driven by the discovery that enzyme-bound cofactors can form photoactive charge-transfer complexes with substrates, thereby initiating radical chemistry upon light irradiation. Recent advances, however, have substantially expanded the mechanistic landscape of photobiocatalysis through diverse mechanisms. This review summarizes major developments in photobiocatalysis reported since 2024. Rather than cataloging individual reactions, we focus on the fundamental mechanisms of radical generation and interception within enzyme active sites, and discuss how these mechanistic principles guide the discovery, engineering, and design of enzymes for new-to-nature photobiocatalysis.
This review centers on enzyme classes, covering nine key families: fatty acid photodecarboxylases, nicotinamide-dependent reductases, flavin-dependent "ene"-reductases, flavin-dependent "ene"-reductases, and others like artificial photoenzymes, and others like artificial photoenzymes.
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