Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesis

Conventional heme enzymes utilize iron–oxygen intermediates to activate substrates and drive reactions. Recently, Chen et al. discovered a novel NADPH-independent superoxide mechanism of heme catalase EasC, which facilitates an O2-dependent radical oxidative cyclization reaction during ergot alkaloi...

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Main Authors: Yuanyuan Jiang, Zhong Li, Shengying Li
Format: Article
Language:English
Published: Elsevier 2025-06-01
Series:Engineering Microbiology
Subjects:
Online Access:http://www.sciencedirect.com/science/article/pii/S2667370325000219
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author Yuanyuan Jiang
Zhong Li
Shengying Li
author_facet Yuanyuan Jiang
Zhong Li
Shengying Li
author_sort Yuanyuan Jiang
collection DOAJ
description Conventional heme enzymes utilize iron–oxygen intermediates to activate substrates and drive reactions. Recently, Chen et al. discovered a novel NADPH-independent superoxide mechanism of heme catalase EasC, which facilitates an O2-dependent radical oxidative cyclization reaction during ergot alkaloid biosynthesis. This enzyme coordinates superoxide-mediated catalysis by connecting spatially distinct NADPH-binding pocket and heme pocket via a slender tunnel, offering a novel perspective on the catalytic mechanisms of heme enzymes in nature.
format Article
id doaj-art-0b8e25cb1ddd4c078dffc8bf92926a8a
institution Kabale University
issn 2667-3703
language English
publishDate 2025-06-01
publisher Elsevier
record_format Article
series Engineering Microbiology
spelling doaj-art-0b8e25cb1ddd4c078dffc8bf92926a8a2025-08-20T03:31:53ZengElsevierEngineering Microbiology2667-37032025-06-015210020710.1016/j.engmic.2025.100207Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesisYuanyuan Jiang0Zhong Li1Shengying Li2State Key Laboratory of Microbial Technology, Shandong University, Qingdao 266237, ChinaDepartment of Chemistry, University of Basel, Basel 4002, SwitzerlandState Key Laboratory of Microbial Technology, Shandong University, Qingdao 266237, China; Corresponding author.Conventional heme enzymes utilize iron–oxygen intermediates to activate substrates and drive reactions. Recently, Chen et al. discovered a novel NADPH-independent superoxide mechanism of heme catalase EasC, which facilitates an O2-dependent radical oxidative cyclization reaction during ergot alkaloid biosynthesis. This enzyme coordinates superoxide-mediated catalysis by connecting spatially distinct NADPH-binding pocket and heme pocket via a slender tunnel, offering a novel perspective on the catalytic mechanisms of heme enzymes in nature.http://www.sciencedirect.com/science/article/pii/S2667370325000219Ergot alkaloidsHeme catalaseSuperoxideCooperative catalysisRadical oxidative cyclization
spellingShingle Yuanyuan Jiang
Zhong Li
Shengying Li
Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesis
Engineering Microbiology
Ergot alkaloids
Heme catalase
Superoxide
Cooperative catalysis
Radical oxidative cyclization
title Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesis
title_full Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesis
title_fullStr Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesis
title_full_unstemmed Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesis
title_short Superoxide-mediated O2 activation drives radical cyclization in ergot alkaloid biosynthesis
title_sort superoxide mediated o2 activation drives radical cyclization in ergot alkaloid biosynthesis
topic Ergot alkaloids
Heme catalase
Superoxide
Cooperative catalysis
Radical oxidative cyclization
url http://www.sciencedirect.com/science/article/pii/S2667370325000219
work_keys_str_mv AT yuanyuanjiang superoxidemediatedo2activationdrivesradicalcyclizationinergotalkaloidbiosynthesis
AT zhongli superoxidemediatedo2activationdrivesradicalcyclizationinergotalkaloidbiosynthesis
AT shengyingli superoxidemediatedo2activationdrivesradicalcyclizationinergotalkaloidbiosynthesis