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.

受小生物分子协调自组装启发，Mn ²⁺自组装诱导l-胱氨酸生成的金属基质复合材料用于固定酶，以满足高级酶工程的需要。牛血清白蛋白（BSA）定向自组装系统的形态表明蛋白质分子可以直接参与协调的自组装过程。类似地，使用脂肪酶和大豆脂氧化酶（I 型）代替 BSA 构建双酶定向自组装系统，以进行级联反应，将大豆油快速转化为脂肪酸氢过氧化物 (HPO)，这是具有潜在用途的有价值的中间体在抗癌医学中。通过优化操作条件，生物转化可在3 h内产生1527.0 μmol·HPOs/mL·油。同时，HPOs的主要成分是由大豆脂氧合酶的pH依赖性机制引起的亚油酸的13-氢过氧化物。此外，回收的生物催化剂在9批次中的相对收率仍为84.7%，表明其运行稳定性良好，可进一步降低工业成本。因此，新设计的策略为将自组装引入酶工程拓宽了视野，特别适合与更多新的催化单元集成。