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In Vitro Reconstitution of a Bacterial Ergothioneine Sulfonate Catabolic Pathway
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    In Vitro Reconstitution of a Bacterial Ergothioneine Sulfonate Catabolic Pathway
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    • Qiongxiang Yan
      Qiongxiang Yan
      Guangdong Provincial Key Laboratory of Biotechnology for Plant Development, Guangzhou Key Laboratory of Subtropical Biodiversity and Biomonitoring, Institute of Ecological Science, School of Life Sciences, South China Normal University, Guangzhou 510631, China
    • Hua Huang*
      Hua Huang
      Guangdong Provincial Key Laboratory of Biotechnology for Plant Development, Guangzhou Key Laboratory of Subtropical Biodiversity and Biomonitoring, Institute of Ecological Science, School of Life Sciences, South China Normal University, Guangzhou 510631, China
      *Email: [email protected]
      More by Hua Huang
    • Xinshuai Zhang*
      Xinshuai Zhang
      Guangdong Provincial Key Laboratory of Biotechnology for Plant Development, Guangzhou Key Laboratory of Subtropical Biodiversity and Biomonitoring, Institute of Ecological Science, School of Life Sciences, South China Normal University, Guangzhou 510631, China
      *Email: [email protected]
    Other Access OptionsSupporting Information (2)

    ACS Catalysis

    Cite this: ACS Catal. 2022, 12, 9, 4825–4832
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    https://doi.org/10.1021/acscatal.2c00169
    Published April 8, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Naturally occurring l-ergothioneine is a ubiquitous histidine-derived sulfur metabolite produced by bacteria and fungi. Plants acquire ergothioneine from their soil environment, whereas animals accumulate it through dietary intake. It is widely believed that ergothioneine functions as a protective antioxidant to eradicate reactive oxygen and nitrogen species. Ergothioneine oxidation leads to the metabolite ergothioneine sulfonate. Using a “genomic enzymology” strategy, we have determined the chemical steps for the ergothioneine sulfonate catabolic pathway, which involves a previously unknown reductive desulfonation reaction catalyzed by members of ornithine cyclodeaminase superfamily. In vitro reconstitution of the full pathway was demonstrated using the cloned and purified pathway enzymes fromAgrobacterium radiobacter K84. Through the identification of pathway gene homologues, the biological range of the ergothioneine sulfonate pathway was found to include α-,γ-proteobacterial, and actinobacterial species.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.2c00169.

    • Interpretation of SSN and GNN, experimental protocols (for enzyme preparation, enzymatic synthesis of sulfourocanate, enzyme kinetic assays, 1H NMR assays, detection of sulfite, detection of glutamate, and detection of ammonia), supplementary tables and figures (PDF)

    • Ergothioneine sulfonate lyase data (XLSX)

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    Cited By

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    Citation Statements
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    This article is cited by 8 publications.

    1. Chenxi Feng, Qiongxiang Yan, Xianyi Li, Hong Zhao, Hua Huang, Xinshuai Zhang. Discovery of a Gut Bacterial Pathway for Ergothioneine Catabolism. Journal of the American Chemical Society 2025, 147 (1) , 257-264. https://doi.org/10.1021/jacs.4c09350
    2. Zhe Zhou, Stavroula K. Hatzios. Microbial metabolism of host-derived antioxidants. Current Opinion in Chemical Biology 2025, 84 , 102565. https://doi.org/10.1016/j.cbpa.2024.102565
    3. Egor Y. Nalivaiko, Florian P. Seebeck. A Rhodanese‐Like Enzyme that Catalyzes Desulfination of Ergothioneine Sulfinic Acid. ChemBioChem 2024, 25 (9) https://doi.org/10.1002/cbic.202400131
    4. Egor Y. Nalivaiko, Camille M. Vasseur, Florian P. Seebeck. Enzyme‐Catalyzed Oxidative Degradation of Ergothioneine. Angewandte Chemie 2024, 136 (8) https://doi.org/10.1002/ange.202318445
    5. Egor Y. Nalivaiko, Camille M. Vasseur, Florian P. Seebeck. Enzyme‐Catalyzed Oxidative Degradation of Ergothioneine. Angewandte Chemie International Edition 2024, 63 (8) https://doi.org/10.1002/anie.202318445
    6. Yibo Guo, Ke Shen, Xinshuai Zhang, Hua Huang. In vitro characterization of alternative l-threonate and d-erythronate catabolic pathways. Biochemical and Biophysical Research Communications 2024, 695 , 149440. https://doi.org/10.1016/j.bbrc.2023.149440
    7. Hui-Min Liu, Wei Tang, Xiao-Yi Wang, Jing-Jing Jiang, Wei Zhang, Wei Wang. Safe and Effective Antioxidant: The Biological Mechanism and Potential Pathways of Ergothioneine in the Skin. Molecules 2023, 28 (4) , 1648. https://doi.org/10.3390/molecules28041648
    8. Huan Meng, Ming-Shang Liu, Wei Shu. Organothianthrenium salts: synthesis and utilization. Chemical Science 2022, 13 (46) , 13690-13707. https://doi.org/10.1039/D2SC04507A

    ACS Catalysis

    Cite this: ACS Catal. 2022, 12, 9, 4825–4832
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acscatal.2c00169
    Published April 8, 2022
    Copyright © 2022 American Chemical Society

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