Programming lipid oxidation pathways via electron transfer-tunable nanozymes.

Controlling selectivity within complex reaction networks remains a central challenge in catalysis. Here, we demonstrate that the electron transfer capacity (ETC) of functionalized iron-based nanozymes can serve as a programmable parameter to direct lipid oxidation pathways. By engineering Fe3O4@MOF composites doped with Cu, Pt, SiO2, or TiO2, we obtained a theoretical ETC gradient ranging from 1.83 to 0.27 e-, which dictated divergent product distributions: from aldehydes/ketones (Cu) to esters (Pt) and carboxylic acids (TiO2), or stabilization (SiO2). Integrated multi-omics analyses indicate that electron flux correlates with the selectivity of radical-mediated oxidative pathways. This work introduces a materials-based paradigm for predictable control over reaction selectivity, with implications extending from flavor science to programmable chemical synthesis.