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Main Authors: Liao, Ge, Sun, Ruolan, Shen, Zilin, Luo, Zhiteng, Pang, Cuiping, Shen, Zhuanglin, Wei, Anfu, Mi, Chengneng, Wu, Gengfan, Li, Fengfang, Li, Yong-Xin, Hoi, Kin Kuan, Pan, Xiaojing, Tang, Xiaoyu
Format: Artículo científico
Language:en
Published: Nature communications 2026
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Online Access:https://pubmed.ncbi.nlm.nih.gov/41617701/
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author Liao, Ge
Sun, Ruolan
Shen, Zilin
Luo, Zhiteng
Pang, Cuiping
Shen, Zhuanglin
Wei, Anfu
Mi, Chengneng
Wu, Gengfan
Li, Fengfang
Li, Yong-Xin
Hoi, Kin Kuan
Pan, Xiaojing
Tang, Xiaoyu
author_facet Liao, Ge
Sun, Ruolan
Shen, Zilin
Luo, Zhiteng
Pang, Cuiping
Shen, Zhuanglin
Wei, Anfu
Mi, Chengneng
Wu, Gengfan
Li, Fengfang
Li, Yong-Xin
Hoi, Kin Kuan
Pan, Xiaojing
Tang, Xiaoyu
Liao, Ge
Sun, Ruolan
Shen, Zilin
Luo, Zhiteng
Pang, Cuiping
Shen, Zhuanglin
Wei, Anfu
Mi, Chengneng
Wu, Gengfan
Li, Fengfang
Li, Yong-Xin
Hoi, Kin Kuan
Pan, Xiaojing
Tang, Xiaoyu
collection PubMed - marine biology
contents Evolutionary repurposing of a metabolic thiolase complex enables antibiotic biosynthesis. Liao, Ge Sun, Ruolan Shen, Zilin Luo, Zhiteng Pang, Cuiping Shen, Zhuanglin Wei, Anfu Mi, Chengneng Wu, Gengfan Li, Fengfang Li, Yong-Xin Hoi, Kin Kuan Pan, Xiaojing Tang, Xiaoyu Anti-Bacterial Agents Hydroxymethylglutaryl-CoA Synthase Bacterial Proteins Acetyl-CoA C-Acetyltransferase Models, Molecular Cryoelectron Microscopy Substrate Specificity Evolution, Molecular Thiolester Hydrolases The functional diversification of biosynthetic enzymes underlies the chemical richness of natural products, yet how primary metabolic enzymes evolve to acquire specialized functions in secondary metabolism remains elusive. Here, we report a tripartite enzyme complex from oral Streptococcus species-comprising 3-hydroxy-3-methylglutaryl (HMG)-CoA synthase (HMGS), acetyl-CoA acetyltransferase (ACAT), and a DUF35 protein-that catalyzes an unusual Friedel-Crafts C-acetylation on a pyrrolidine-2,4-dione scaffold, completing the biosynthesis of the antibiotic reutericyclin A. Cryo-electron microscopy of the S. macacae-derived thiolase complex (SmaATase) reveals a conserved architecture resembling the archaeal HMGS/ACAT/DUF35 complex involved in the mevalonate pathway, yet with key catalytic residues rewired to reprogram substrate specificity. Biochemical characterization, molecular modeling, and evolutionary analysis confirmed that the ancestral activity of HMG-CoA synthesis has been lost, while the complex has been repurposed to mediate Friedel-Crafts C-acylation of small molecule acceptors. These findings reveal a rare example of thiolase complex neofunctionalization, shedding light on an underexplored trajectory in enzyme evolution and offering a template for engineering C-C bond-forming catalysts in synthetic biology.
format Artículo científico
id pubmed_41617701
institution PubMed
language en
publishDate 2026
publisher Nature communications
record_format pubmed
spellingShingle Evolutionary repurposing of a metabolic thiolase complex enables antibiotic biosynthesis.
Liao, Ge
Sun, Ruolan
Shen, Zilin
Luo, Zhiteng
Pang, Cuiping
Shen, Zhuanglin
Wei, Anfu
Mi, Chengneng
Wu, Gengfan
Li, Fengfang
Li, Yong-Xin
Hoi, Kin Kuan
Pan, Xiaojing
Tang, Xiaoyu
Anti-Bacterial Agents
Hydroxymethylglutaryl-CoA Synthase
Bacterial Proteins
Acetyl-CoA C-Acetyltransferase
Models, Molecular
Cryoelectron Microscopy
Substrate Specificity
Evolution, Molecular
Thiolester Hydrolases
Evolutionary repurposing of a metabolic thiolase complex enables antibiotic biosynthesis. Liao, Ge Sun, Ruolan Shen, Zilin Luo, Zhiteng Pang, Cuiping Shen, Zhuanglin Wei, Anfu Mi, Chengneng Wu, Gengfan Li, Fengfang Li, Yong-Xin Hoi, Kin Kuan Pan, Xiaojing Tang, Xiaoyu Anti-Bacterial Agents Hydroxymethylglutaryl-CoA Synthase Bacterial Proteins Acetyl-CoA C-Acetyltransferase Models, Molecular Cryoelectron Microscopy Substrate Specificity Evolution, Molecular Thiolester Hydrolases The functional diversification of biosynthetic enzymes underlies the chemical richness of natural products, yet how primary metabolic enzymes evolve to acquire specialized functions in secondary metabolism remains elusive. Here, we report a tripartite enzyme complex from oral Streptococcus species-comprising 3-hydroxy-3-methylglutaryl (HMG)-CoA synthase (HMGS), acetyl-CoA acetyltransferase (ACAT), and a DUF35 protein-that catalyzes an unusual Friedel-Crafts C-acetylation on a pyrrolidine-2,4-dione scaffold, completing the biosynthesis of the antibiotic reutericyclin A. Cryo-electron microscopy of the S. macacae-derived thiolase complex (SmaATase) reveals a conserved architecture resembling the archaeal HMGS/ACAT/DUF35 complex involved in the mevalonate pathway, yet with key catalytic residues rewired to reprogram substrate specificity. Biochemical characterization, molecular modeling, and evolutionary analysis confirmed that the ancestral activity of HMG-CoA synthesis has been lost, while the complex has been repurposed to mediate Friedel-Crafts C-acylation of small molecule acceptors. These findings reveal a rare example of thiolase complex neofunctionalization, shedding light on an underexplored trajectory in enzyme evolution and offering a template for engineering C-C bond-forming catalysts in synthetic biology.
title Evolutionary repurposing of a metabolic thiolase complex enables antibiotic biosynthesis.
topic Anti-Bacterial Agents
Hydroxymethylglutaryl-CoA Synthase
Bacterial Proteins
Acetyl-CoA C-Acetyltransferase
Models, Molecular
Cryoelectron Microscopy
Substrate Specificity
Evolution, Molecular
Thiolester Hydrolases
url https://pubmed.ncbi.nlm.nih.gov/41617701/