Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated Trichoderma

Abstract Terpene cyclases catalyze exquisite and complicated cyclization reactions to generate diverse terpenoid skeletons. Trichoderma fungi are important biocontrol agents, characteristic of producing complex bioactive tetracyclic diterpenoids named harzianes and trichodermanins, but their biosynt...

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Main Authors: Min-Jie Yang, De-Sen Li, Hua-Qin Deng, Wen-Yuan Li, Xin-Yu Zheng, Jonathan Gershenzon, Xue-Mei Niu, Yan Liu, Sheng-Hong Li
Format: Article
Language:English
Published: Nature Portfolio 2025-08-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-63055-4
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author Min-Jie Yang
De-Sen Li
Hua-Qin Deng
Wen-Yuan Li
Xin-Yu Zheng
Jonathan Gershenzon
Xue-Mei Niu
Yan Liu
Sheng-Hong Li
author_facet Min-Jie Yang
De-Sen Li
Hua-Qin Deng
Wen-Yuan Li
Xin-Yu Zheng
Jonathan Gershenzon
Xue-Mei Niu
Yan Liu
Sheng-Hong Li
author_sort Min-Jie Yang
collection DOAJ
description Abstract Terpene cyclases catalyze exquisite and complicated cyclization reactions to generate diverse terpenoid skeletons. Trichoderma fungi are important biocontrol agents, characteristic of producing complex bioactive tetracyclic diterpenoids named harzianes and trichodermanins, but their biosynthesis and biological functions have long been enigmatic. Here we identify TriDTCs, an unprecedented family of terpene cyclases in Trichoderma, responsible for cyclizing geranylgeranyl diphosphate (GGPP) into major diterpenes harzianol I and wickerol A, via heterologous expressions, gene deletion, and in vitro assays. TriDTCs represent a brand new class of terpene cyclases, lacking known motifs and diverging from all known enzymes. Mechanistically, TriDTCs likely employ a unique DxxDxxxD aspartate triad for cyclization initiation, a critical valine residue modulating product specificity, and “gatekeeper” residues for activity. Phylogenetic analysis shows TriDTCs have a narrow distribution in three fungal genera and are highly functionally specific within Trichoderma, suggesting a genus-specific acquisition and independent evolution. Functional studies implicated TriDTCs in fungal survival strategies by regulating formation of resistant propagules (chlamydospore in Trichoderma, sclerotia in Aspergillus oryzae). These findings expand the knowledge of terpene cyclase diversity and biological significance, herald a strategy to enhance Trichoderma’s biocontrol efficacy, and open avenues for pharmacological investigation of these diterpenoids.
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spelling doaj-art-e6a3f90ddc744969ae15bc3cac0ba1822025-08-24T11:38:35ZengNature PortfolioNature Communications2041-17232025-08-0116111210.1038/s41467-025-63055-4Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated TrichodermaMin-Jie Yang0De-Sen Li1Hua-Qin Deng2Wen-Yuan Li3Xin-Yu Zheng4Jonathan Gershenzon5Xue-Mei Niu6Yan Liu7Sheng-Hong Li8State Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of SciencesState Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of SciencesState Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of SciencesState Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of SciencesState Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of SciencesDepartment of Biochemistry, Max Planck Institute for Chemical EcologySchool of Life Sciences, State Key Laboratory for Conservation and Utilization of Bio-Resources & Key Laboratory for Microbial Resources of the Ministry of Education, Yunnan UniversityState Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of SciencesState Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of SciencesAbstract Terpene cyclases catalyze exquisite and complicated cyclization reactions to generate diverse terpenoid skeletons. Trichoderma fungi are important biocontrol agents, characteristic of producing complex bioactive tetracyclic diterpenoids named harzianes and trichodermanins, but their biosynthesis and biological functions have long been enigmatic. Here we identify TriDTCs, an unprecedented family of terpene cyclases in Trichoderma, responsible for cyclizing geranylgeranyl diphosphate (GGPP) into major diterpenes harzianol I and wickerol A, via heterologous expressions, gene deletion, and in vitro assays. TriDTCs represent a brand new class of terpene cyclases, lacking known motifs and diverging from all known enzymes. Mechanistically, TriDTCs likely employ a unique DxxDxxxD aspartate triad for cyclization initiation, a critical valine residue modulating product specificity, and “gatekeeper” residues for activity. Phylogenetic analysis shows TriDTCs have a narrow distribution in three fungal genera and are highly functionally specific within Trichoderma, suggesting a genus-specific acquisition and independent evolution. Functional studies implicated TriDTCs in fungal survival strategies by regulating formation of resistant propagules (chlamydospore in Trichoderma, sclerotia in Aspergillus oryzae). These findings expand the knowledge of terpene cyclase diversity and biological significance, herald a strategy to enhance Trichoderma’s biocontrol efficacy, and open avenues for pharmacological investigation of these diterpenoids.https://doi.org/10.1038/s41467-025-63055-4
spellingShingle Min-Jie Yang
De-Sen Li
Hua-Qin Deng
Wen-Yuan Li
Xin-Yu Zheng
Jonathan Gershenzon
Xue-Mei Niu
Yan Liu
Sheng-Hong Li
Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated Trichoderma
Nature Communications
title Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated Trichoderma
title_full Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated Trichoderma
title_fullStr Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated Trichoderma
title_full_unstemmed Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated Trichoderma
title_short Noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant-associated Trichoderma
title_sort noncanonical terpene cyclases for the biosynthesis of diterpenoids regulating chlamydospore formation in plant associated trichoderma
url https://doi.org/10.1038/s41467-025-63055-4
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