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<p>Cleavage of hexopyranose to short-chain carbohydrates plays crucial roles in carbon metabolism and energy supply. Currently, the carbon–carbon bond scission of hexopyranose involves two types of reaction: the widely distributed retro-aldol reaction and the transketo-like reaction observed in <i>Bifidobacteria</i>. Here we report the discovery and characterization of metalloenzyme Art22, which is involved in the sugar moiety modification of aurantinin B (ART B), an antibacterial agent from <i>Bacillus</i>. Art22 adopts a TIM-barrel fold, enabling the activation of 4-keto ART B into potent antibiotic ART B via rapid isomerization. In addition, it protects the ART-producing <i>Bacillus</i> by detoxifying cellular ART B to ART B1–B3 via slow oxidative cleavage of the 3-keto hexopyranose to short-chain carbohydrates and CO<sub>2</sub>. Guided by structural, mutagenic and computational studies, we reveal an anhydride-mediated mechanism for Art22-catalysed oxygenation reactions, which expands the catalytic repertoire of TIM-barrel enzymes and adds an oxidative path for hexopyranose cleavage.</p><p></p>

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Oxidative cleavage of hexopyranose by a TIM-barrel isomerase

  • 期刊论文

  • 发表日期：

    2025年9月24日

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  • Pengwei Li,
  • Dacheng Wang,
  • Lu Guo,
  • Yanru Chen,
  • Huijin Mao,
  • Zelian Zhao,
  • Min Wang,
  • Meng Chen,
  • Zhengren Xu,
  • Binju Wang,
  • Defeng Li,
  • Yihua Chen

摘要

Cleavage of hexopyranose to short-chain carbohydrates plays crucial roles in carbon metabolism and energy supply. Currently, the carbon–carbon bond scission of hexopyranose involves two types of reaction: the widely distributed retro-aldol reaction and the transketo-like reaction observed in Bifidobacteria. Here we report the discovery and characterization of metalloenzyme Art22, which is involved in the sugar moiety modification of aurantinin B (ART B), an antibacterial agent from Bacillus. Art22 adopts a TIM-barrel fold, enabling the activation of 4-keto ART B into potent antibiotic ART B via rapid isomerization. In addition, it protects the ART-producing Bacillus by detoxifying cellular ART B to ART B1–B3 via slow oxidative cleavage of the 3-keto hexopyranose to short-chain carbohydrates and CO2. Guided by structural, mutagenic and computational studies, we reveal an anhydride-mediated mechanism for Art22-catalysed oxygenation reactions, which expands the catalytic repertoire of TIM-barrel enzymes and adds an oxidative path for hexopyranose cleavage.