Yuanyuan Jiang, Junjie Zhang, Zhong Li, Lingyan Wang, Yuyu Guo, Yuxuan Li, Xisong Feng, Wen Gao, Yong Li, Zijia Li, Jieke Du, Guoqiang Zhang, Piqian Gong, Wenhan Fang, Xiang Gao, Mingyi Bai, Frank Hollmann, Mei Zhang, He Huang, Binju Wang, Sudong Mo, Huarong Li, Wei Peng, Shengying Li
Herbicides in combination with genetically modified herbicide-resistant crops have revolutionized modern weed management, increased crop yields, and facilitated farming practices. However, rapid evolution of herbicide-resistant weeds necessitates new resistance traits to sustain control efficacy. Here, we introduce a terminal carboxyl anchoring mechanism-inspired approach for precise discovery of P450 herbicide resistance genes, by which a number of bacterial P450 peroxygenases are predicted and confirmed to degrade auxin herbicides. Upon enzyme engineering, the optimal mutant P450BSβ-F46A can efficiently degrade diverse auxin herbicides and other carboxyl-containing herbicides. Mechanistic studies reveal that Compound I-mediated hydroxylation initiates the C‒O bond cleavage, followed by aromatic ring hydroxylation, thus forming a unique two-step degradation pathway. Transgenic rice expressing P450BSβ-F46A-CPR confers significant resistance to a recently commercialized auxin herbicide fluchloraminopyr. This work demonstrates the potential of the mechanism-driven strategy in directed discovery of broad-spectrum resistance genes for herbicide-resistant crop engineering.