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<p>Nitro compounds are indispensable in pharmaceuticals, agrochemicals, and energetic materials; however, their traditional synthesis is often constrained by environmental concerns and high energy demands. Biocatalytic nitration offers a more sustainable alternative, with horseradish peroxidase (HRP) and engineered P450BM3 emerging as two representative and extensively studied catalytic systems. HRP, a classic natural biocatalyst, inherently catalyzes the radical-mediated nitration of aromatic substrates. In contrast, P450BM3 exemplifies the power of enzyme engineering: its scaffold can be repurposed through rational design and the use of double-function small molecules (DFSMs) to enable non-natural transformations, such as alkene nitration. This review provides a comparative analysis of these two systems, examining their catalytic mechanisms, structural features, and performance metrics. By comparing HRP with P450BM3, this work aims to delineate their respective advantages and provide insights to guide the development of more efficient enzymatic nitration strategies.</p>

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Horseradish peroxidase and engineered P450BM3: progress and perspectives in biocatalytic nitration

  • 期刊论文

  • 发表日期：

    2026年5月29日

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  • You-chen Lin,
  • Qing-nan Jia,
  • Fang-fei Qin,
  • Yun-ting Liu,
  • Chao Xu,
  • Jian Zha,
  • Ying-jin Yuan

摘要

Nitro compounds are indispensable in pharmaceuticals, agrochemicals, and energetic materials; however, their traditional synthesis is often constrained by environmental concerns and high energy demands. Biocatalytic nitration offers a more sustainable alternative, with horseradish peroxidase (HRP) and engineered P450BM3 emerging as two representative and extensively studied catalytic systems. HRP, a classic natural biocatalyst, inherently catalyzes the radical-mediated nitration of aromatic substrates. In contrast, P450BM3 exemplifies the power of enzyme engineering: its scaffold can be repurposed through rational design and the use of double-function small molecules (DFSMs) to enable non-natural transformations, such as alkene nitration. This review provides a comparative analysis of these two systems, examining their catalytic mechanisms, structural features, and performance metrics. By comparing HRP with P450BM3, this work aims to delineate their respective advantages and provide insights to guide the development of more efficient enzymatic nitration strategies.