Bi-enzyme directed self-assembled system toward biomimetic synthesis of fatty acid hydroperoxides like soybean

Abstract Inspired by coordinated self-assembly of small biomolecules, self-assembly of Mn2+ induced l -cystine generated metal-matrix composites is constructed to immobilize enzymes to meet the need of advanced enzyme engineering. Morphology of bovine serum albumin (BSA) directed self-assembled system suggests that protein molecules can directly get involved in coordinated self-assembling process. Similarly, construction of a two-enzyme directed self-assembled system with lipase and soybean lipoxygenase (I type) instead of BSA is employed to perform the cascade reaction in fast transforming soybean oil into fatty acid hydroperoxides (HPOs), valuable intermediates with potential use in anti-cancer medicine. The bioconversion can yield 1527.0 μmol·HPOs/mL·oil within 3 h upon optimizing the operating conditions. Meanwhile, the major component of HPOs is 13-hydroperoxides of linoleic acid caused by pH-dependent mechanism of soybean lipoxygenase. Moreover, a relative yield of 84.7% can be retained at 9 batches of the recycled biocatalyst, indicating a good operating stability, which can further reduce industrial cost. Therefore, the newly designed strategy broadens horizon for the incorporation of self-assembly into enzyme engineering, and specially adapts to be integrated with more new catalytic units.