Bacterial lipoxygenases for fatty acid oxyfunctionalization: advances and future directions

The shift to a biobased economy aims to reduce dependence on fossil fuels by converting biological materials, such as plant-derived and algae-derived fatty acids, into valuable compounds. The enzymatic oxyfunctionalization of fatty acids is of special interest because it enables the eco-friendly synthesis of a wide range of products with unique properties. Lipoxygenases (LOXs) are key oxyfunctionalization enzymes featuring broad substrate specificities and distinct regioselectivities. Among them, bacterial LOXs remain underexplored compared to their eukaryotic counterparts, representing an untapped resource with unique structural and functional traits. This review highlights recent advances in bacterial LOXs, emphasizing their versatile oxidative capabilities via dioxygenase and hydroperoxide isomerase activities. Key strategies, including protein engineering and oxygen level modulation, are discussed for modifying substrate specificity, regioselectivity, and preferred catalytic pathway. Multi-enzyme cascade reactions further expand the scope of LOX-derived products, unlocking new applications in biotechnological contexts. We address challenges in harnessing bacterial LOXs' biocatalytic potential and propose solutions to optimize their performance. This work enhances understanding of bacterial LOXs and highlights their potential for transformative biotechnological applications in fatty acid derivatization.