Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase

IntroductionCannabinoids possess significant therapeutic potential, but their natural chemical diversity derived from plant biosynthesis is limited. Efficient biotransformation processes are required to expand the range of accessible cannabinoids. This study aimed to enhance the selective biosynthes...

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Main Authors: Hoe-Suk Lee, Jisu Park, Taejung Kim, Huitae Min, Seongsu Na, Soon Young Park, Young-Tae Park, Young Joo Yeon, Jungyeob Ham
Format: Article
Language:English
Published: Frontiers Media S.A. 2025-04-01
Series:Frontiers in Bioengineering and Biotechnology
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Online Access:https://www.frontiersin.org/articles/10.3389/fbioe.2025.1563708/full
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author Hoe-Suk Lee
Jisu Park
Jisu Park
Taejung Kim
Taejung Kim
Huitae Min
Seongsu Na
Seongsu Na
Soon Young Park
Young-Tae Park
Young-Tae Park
Young Joo Yeon
Jungyeob Ham
Jungyeob Ham
Jungyeob Ham
author_facet Hoe-Suk Lee
Jisu Park
Jisu Park
Taejung Kim
Taejung Kim
Huitae Min
Seongsu Na
Seongsu Na
Soon Young Park
Young-Tae Park
Young-Tae Park
Young Joo Yeon
Jungyeob Ham
Jungyeob Ham
Jungyeob Ham
author_sort Hoe-Suk Lee
collection DOAJ
description IntroductionCannabinoids possess significant therapeutic potential, but their natural chemical diversity derived from plant biosynthesis is limited. Efficient biotransformation processes are required to expand the range of accessible cannabinoids. This study aimed to enhance the selective biosynthesis of cannabigerolic acid (CBGA) and its derivatives with varying aliphatic chain lengths, which serve as key precursors to various cannabinoids.MethodsWe employed computational modeling and structure-guided mutagenesis to engineer the aromatic prenyltransferase NphB. Mutants were designed via in silico docking analyses to optimize substrate orientation and catalytic distance. The variants were expressed in E. coli, and their catalytic efficiencies were evaluated through in vivo whole-cell and in vitro enzymatic assays. Products were identified and quantified by UHPLC-MS.ResultsEngineered NphB variants exhibited significant improvements, with triple mutants achieving a 7-fold increase in CBGA production and a 4-fold increase in cannabigerovarinic acid production. Additionally, a single mutant also enhanced the synthesis of 3-geranyl orsellinic acid by 1.3-fold. Notably, novel enzymatic activity was identified that enabled the biosynthesis of 3-geranyl-2,4-dihydroxybenzoic acid. Structural analyses revealed that the mutations improved the spatial positioning of aromatic substrates relative to the co-substrate geranyl pyrophosphate.DiscussionThis study demonstrates the feasibility of enzyme design to tailor prenyltransferase specificity for the production of diverse CBGA derivatives. These findings lay the groundwork for the microbial production of novel cannabinoids and offer promising potential for the development of scalable biocatalytic systems for therapeutic and industrial applications.
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spelling doaj-art-e4805264ae544000a8b2bf0a290d40862025-08-20T02:16:50ZengFrontiers Media S.A.Frontiers in Bioengineering and Biotechnology2296-41852025-04-011310.3389/fbioe.2025.15637081563708Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferaseHoe-Suk Lee0Jisu Park1Jisu Park2Taejung Kim3Taejung Kim4Huitae Min5Seongsu Na6Seongsu Na7Soon Young Park8Young-Tae Park9Young-Tae Park10Young Joo Yeon11Jungyeob Ham12Jungyeob Ham13Jungyeob Ham14Department of Biochemical Engineering, Gangneung-Wonju National University, Gangneung, Republic of KoreaDepartment of Biochemical Engineering, Gangneung-Wonju National University, Gangneung, Republic of KoreaNatural Product Research Center, Korea Institute of Science and Technology (KIST), Gangneung, Republic of KoreaNatural Product Research Center, Korea Institute of Science and Technology (KIST), Gangneung, Republic of KoreaDivision of Natural Product Applied Science, University of Science and Technology (UST), Daejeon, Republic of KoreaNatural Product Research Center, Korea Institute of Science and Technology (KIST), Gangneung, Republic of KoreaDepartment of Biochemical Engineering, Gangneung-Wonju National University, Gangneung, Republic of KoreaNatural Product Research Center, Korea Institute of Science and Technology (KIST), Gangneung, Republic of KoreaNeoCannBio Co., Ltd., Seoul, Republic of KoreaNatural Product Research Center, Korea Institute of Science and Technology (KIST), Gangneung, Republic of KoreaDivision of Natural Product Applied Science, University of Science and Technology (UST), Daejeon, Republic of KoreaDepartment of Biochemical Engineering, Gangneung-Wonju National University, Gangneung, Republic of KoreaNatural Product Research Center, Korea Institute of Science and Technology (KIST), Gangneung, Republic of KoreaDivision of Natural Product Applied Science, University of Science and Technology (UST), Daejeon, Republic of KoreaNeoCannBio Co., Ltd., Seoul, Republic of KoreaIntroductionCannabinoids possess significant therapeutic potential, but their natural chemical diversity derived from plant biosynthesis is limited. Efficient biotransformation processes are required to expand the range of accessible cannabinoids. This study aimed to enhance the selective biosynthesis of cannabigerolic acid (CBGA) and its derivatives with varying aliphatic chain lengths, which serve as key precursors to various cannabinoids.MethodsWe employed computational modeling and structure-guided mutagenesis to engineer the aromatic prenyltransferase NphB. Mutants were designed via in silico docking analyses to optimize substrate orientation and catalytic distance. The variants were expressed in E. coli, and their catalytic efficiencies were evaluated through in vivo whole-cell and in vitro enzymatic assays. Products were identified and quantified by UHPLC-MS.ResultsEngineered NphB variants exhibited significant improvements, with triple mutants achieving a 7-fold increase in CBGA production and a 4-fold increase in cannabigerovarinic acid production. Additionally, a single mutant also enhanced the synthesis of 3-geranyl orsellinic acid by 1.3-fold. Notably, novel enzymatic activity was identified that enabled the biosynthesis of 3-geranyl-2,4-dihydroxybenzoic acid. Structural analyses revealed that the mutations improved the spatial positioning of aromatic substrates relative to the co-substrate geranyl pyrophosphate.DiscussionThis study demonstrates the feasibility of enzyme design to tailor prenyltransferase specificity for the production of diverse CBGA derivatives. These findings lay the groundwork for the microbial production of novel cannabinoids and offer promising potential for the development of scalable biocatalytic systems for therapeutic and industrial applications.https://www.frontiersin.org/articles/10.3389/fbioe.2025.1563708/fullcannabinoidcannabigerolic acid derivativearomatic prenyltransferase NphBcomputational enzyme designengineered E. coli whole cellbiocatalytic system
spellingShingle Hoe-Suk Lee
Jisu Park
Jisu Park
Taejung Kim
Taejung Kim
Huitae Min
Seongsu Na
Seongsu Na
Soon Young Park
Young-Tae Park
Young-Tae Park
Young Joo Yeon
Jungyeob Ham
Jungyeob Ham
Jungyeob Ham
Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase
Frontiers in Bioengineering and Biotechnology
cannabinoid
cannabigerolic acid derivative
aromatic prenyltransferase NphB
computational enzyme design
engineered E. coli whole cell
biocatalytic system
title Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase
title_full Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase
title_fullStr Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase
title_full_unstemmed Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase
title_short Biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase
title_sort biosynthesis of novel cannabigerolic acid derivatives by engineering the substrate specificity of aromatic prenyltransferase
topic cannabinoid
cannabigerolic acid derivative
aromatic prenyltransferase NphB
computational enzyme design
engineered E. coli whole cell
biocatalytic system
url https://www.frontiersin.org/articles/10.3389/fbioe.2025.1563708/full
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