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Main Authors: Fan, Baoqiang, Liu, Yinuo, Chi, Lu-Ping, Yang, Chaofan, Li, Shengying, Zhang, Wei
Format: Artículo científico
Language:en
Published: Advanced science (Weinheim, Baden-Wurttemberg, Germany) 2025
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Online Access:https://pubmed.ncbi.nlm.nih.gov/40788096/
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author Fan, Baoqiang
Liu, Yinuo
Chi, Lu-Ping
Yang, Chaofan
Li, Shengying
Zhang, Wei
author_facet Fan, Baoqiang
Liu, Yinuo
Chi, Lu-Ping
Yang, Chaofan
Li, Shengying
Zhang, Wei
Fan, Baoqiang
Liu, Yinuo
Chi, Lu-Ping
Yang, Chaofan
Li, Shengying
Zhang, Wei
collection PubMed - marine biology
contents Enhancing the β-Oxidation-Like Pathway for the Optimal Production of the Immunosuppressant Mycophenolic Acid. Fan, Baoqiang Liu, Yinuo Chi, Lu-Ping Yang, Chaofan Li, Shengying Zhang, Wei Mycophenolic Acid Oxidation-Reduction Penicillium Immunosuppressive Agents Peroxisomes Metabolic Engineering The recruitment of catabolic β-oxidation enzyme cascades and their reaction logic for natural product biosynthesis remains underexplored, representing a significant opportunity for synthetic biology to engineer novel pathways for structurally unique metabolites. In this study, the first functional reconstitution of the fungal β-oxidative cascade responsible for assembling the immunosuppressant mycophenolic acid (MPA) is reported. Through in vitro enzyme assays, five peroxisomal enzymes are identified that cooperatively mediate two iterative rounds of side-chain cleavage of the biosynthetic precursor MFDHMP-3C and revealed a key oxidative strategy for pharmacophore formation of MPA. These enzymes catalyzed sequential oxidation, dehydrogenation, hydration, reduction, isomerization, and reverse Claisen condensation reactions, mirroring canonical β-oxidation while adapting it for biosynthetic purposes. Furthermore, integrated overexpression of the rate-limiting peroxisomal acyl-CoA oxidase PbACOX323, peroxisomal biogenesis factor PbPex337, and endoplasmic reticulum (ER)-localized oxygenase MpaB' in Penicillium brevicompactum NRRL864 increased MPA production by 50% (from 0.77 to 1.15 g L), demonstrating the biotechnological efficacy of pathway optimization. This work establishes the first example of a full β-oxidation-like enzyme cascade in fungal natural product biosynthesis, providing a paradigm for the evolutionary repurposing of catabolic modules to drive synthetic innovation.
format Artículo científico
id pubmed_40788096
institution PubMed
language en
publishDate 2025
publisher Advanced science (Weinheim, Baden-Wurttemberg, Germany)
record_format pubmed
spellingShingle Enhancing the β-Oxidation-Like Pathway for the Optimal Production of the Immunosuppressant Mycophenolic Acid.
Fan, Baoqiang
Liu, Yinuo
Chi, Lu-Ping
Yang, Chaofan
Li, Shengying
Zhang, Wei
Mycophenolic Acid
Oxidation-Reduction
Penicillium
Immunosuppressive Agents
Peroxisomes
Metabolic Engineering
Enhancing the β-Oxidation-Like Pathway for the Optimal Production of the Immunosuppressant Mycophenolic Acid. Fan, Baoqiang Liu, Yinuo Chi, Lu-Ping Yang, Chaofan Li, Shengying Zhang, Wei Mycophenolic Acid Oxidation-Reduction Penicillium Immunosuppressive Agents Peroxisomes Metabolic Engineering The recruitment of catabolic β-oxidation enzyme cascades and their reaction logic for natural product biosynthesis remains underexplored, representing a significant opportunity for synthetic biology to engineer novel pathways for structurally unique metabolites. In this study, the first functional reconstitution of the fungal β-oxidative cascade responsible for assembling the immunosuppressant mycophenolic acid (MPA) is reported. Through in vitro enzyme assays, five peroxisomal enzymes are identified that cooperatively mediate two iterative rounds of side-chain cleavage of the biosynthetic precursor MFDHMP-3C and revealed a key oxidative strategy for pharmacophore formation of MPA. These enzymes catalyzed sequential oxidation, dehydrogenation, hydration, reduction, isomerization, and reverse Claisen condensation reactions, mirroring canonical β-oxidation while adapting it for biosynthetic purposes. Furthermore, integrated overexpression of the rate-limiting peroxisomal acyl-CoA oxidase PbACOX323, peroxisomal biogenesis factor PbPex337, and endoplasmic reticulum (ER)-localized oxygenase MpaB' in Penicillium brevicompactum NRRL864 increased MPA production by 50% (from 0.77 to 1.15 g L), demonstrating the biotechnological efficacy of pathway optimization. This work establishes the first example of a full β-oxidation-like enzyme cascade in fungal natural product biosynthesis, providing a paradigm for the evolutionary repurposing of catabolic modules to drive synthetic innovation.
title Enhancing the β-Oxidation-Like Pathway for the Optimal Production of the Immunosuppressant Mycophenolic Acid.
topic Mycophenolic Acid
Oxidation-Reduction
Penicillium
Immunosuppressive Agents
Peroxisomes
Metabolic Engineering
url https://pubmed.ncbi.nlm.nih.gov/40788096/