Silent catalytic promiscuity in the high-fidelity terpene cyclase δ-cadinene synthase

Loizzi, Marianna; Miller, David J.; Allemann, Rudolf Konrad

doi:10.1039/c8ob02821d

Cited by 10 publications

(7 citation statements)

References 69 publications

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“…The predicted pathway is that FPP is catalyzed by NES1 to produce ( S , E )-nerolidol and then catalyzed by TPS1 to produce δ-cadinene, which in turn is catalyzed by a series of P450 enzymes to produce HHO. 42 Genes in the predicted steps ( NES1 , TPS1 , P4501 , and P502 ) were also identified in the biosynthetic pathway of KEGG sesquiterpenes and triterpenes. Among them, NES1 , TPS1 , and P4501 have a positive correlation with HHO and all have a high accumulation in blades.…”

Section: Resultsmentioning

confidence: 99%

“…The HHO prediction steps are speculated on according to the literature. The predicted pathway is that FPP is catalyzed by NES1 to produce ( S , E )-nerolidol and then catalyzed by TPS1 to produce δ-cadinene, which in turn is catalyzed by a series of P450 enzymes to produce HHO . Genes in the predicted steps ( NES1 , TPS1 , P4501 , and P502 ) were also identified in the biosynthetic pathway of KEGG sesquiterpenes and triterpenes.…”

Section: Resultsmentioning

confidence: 99%

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Transcriptome and Metabolome Analysis of the Synthesis Pathways of Allelochemicals in Eupatorium adenophorum

et al. 2022

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Eupatorium adenophorum (Crofton weed) is an invasive weed in more than 30 countries. It inhibits the growth of surrounding plants by releasing allelochemicals during its invasion. However, the synthetic pathways and molecular mechanisms of its allelochemicals have been rarely reported. In this study, the related genes and pathways of allelochemicals in E. adenophorum were analyzed. Transcriptome analysis showed that differentially expressed genes (DEGs) were mainly enriched in the phenylpropanoid biosynthetic pathway and flavonoid biosynthetic pathway. Thirty-three DEGs involved in the synthesis of allelochemicals were identified, and 30 DEGs showed significant differences in blades and stems. Six allelochemicals were identified from blades and stems by ultraperformance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Correlation analysis of genes and metabolites showed a strong correlation between the five genes and allelochemicals. In addition, this study supplemented the biosynthetic pathway of Eupatorium adenophorum B (HHO). It was found that acyclic sesquiterpene synthase (NES), δ-cadinene synthase (TPS), and cytochrome P450 (P450) were involved in the synthesis of HHO. These findings provide a dynamic spectrum consisting of allelochemical metabolism and a coexpression network of allelochemical synthesis genes in E. adenophorum .

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Transcriptome and Metabolome Analysis of the Synthesis Pathways of Allelochemicals in Eupatorium adenophorum

et al. 2022

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“…Cadinene and muurolene skeletons may also result from an earlier rearrangement from farnesyl to the nerolidyl cation [40,[101][102][103][104]. Germacradienyl cation forming by 1.10-cyclization.…”

Section: Cadalane Skeletonmentioning

confidence: 99%

“…were reported in the species of laurel (Leonurus sibiricus), fig (Ficus carica), cotton (Gossypium hirsutum), not showing any germacrene D in the products [76,99,100], as well as V. megapotamica and V. capitata [25,67], which have δ-cadinene in larger amounts. Cadinene and muurolene skeletons may also result from an earlier rearrangement from farnesyl to the nerolidyl cation [40,[101][102][103][104]. Germacradienyl cation forming by 1.10-cyclization.…”

Section: Cadalane Skeletonmentioning

confidence: 99%

Taxonomic Insights and Its Type Cyclization Correlation of Volatile Sesquiterpenes in Vitex Species and Potential Source Insecticidal Compounds: A Review

2021

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Sesquiterpenes (SS) are secondary metabolites formed by the bonding of 3 isoprene (C5) units. They play an important role in the defense and signaling of plants to adapt to the environment, face stress, and communicate with the outside world, and their evolutionary history is closely related to their physiological functions. This review considers their presence and extensively summarizes the 156 sesquiterpenes identified in Vitex taxa, emphasizing those with higher concentrations and frequency among species and correlating with the insecticidal activities and defensive responses reported in the literature. In addition, we classify the SS based on their chemical structures and addresses cyclization in biosynthetic origin. Most relevant sesquiterpenes of the Vitex genus are derived from the germacredienyl cation mainly via bicyclogermacrene and germacrene C, giving rise to aromadrendanes, a skeleton with the highest number of representative compounds in this genus, and 6,9-guaiadiene, respectively, indicating the production of 1.10-cyclizing sesquiterpene synthases. These enzymes can play an important role in the chemosystematics of the genus from their corresponding routes and cyclizations, constituting a new approach to chemotaxonomy. In conclusion, this review is a compilation of detailed information on the profile of sesquiterpene in the Vitex genus and, thus, points to new unexplored horizons for future research.

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“…In recent years, efforts have been pursued to validate the substrate specificity of TCs, in particular mono- and sesquiterpene cyclases. − The introduction of oxygen, sulfur, and halogen atoms into the backbone of FPP 1 represents one type of unnatural FPP derivative of which “FPP-ether” 5 is a noteworthy example (Scheme ). When this derivative was reacted with presilphiperfolan-8β-ol synthase (BcBOT2), a fungal sesquiterpene cyclase from Botrytis cinerea , tricyclic terpenoid 6 was isolated that reveals a significantly altered backbone compared to that of the natural cyclization product presilphiperfolan-8β-ol ( 2 )…”

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confidence: 99%

Mechanistic Similarities of Sesquiterpene Cyclases PenA, Omp6/7, and BcBOT2 Are Unraveled by an Unnatural “FPP-Ether” Derivative

2021

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The sesquiterpene cyclases pentalenene synthase (PenA) and two Δ6-protoilludene synthases Omp6 and Omp7 convert a FPP ether into several new tetrahydrofurano terpenoids, one of which is also formed as the main product by the sesquiterpene cyclase BcBOT2. Thus, PenA, Omp6/7, and BcBOT2 follow closely related catalytic pathways and induce similar folding of their diphosphate substrates despite low levels of amino acid sequence similarity. Some of the new terpenoids show pronounced olfactoric properties.

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Silent catalytic promiscuity in the high-fidelity terpene cyclase δ-cadinene synthase

Abstract: Aza-analogues of carbocations inhibit δ-cadinene synthase: 1,6-cyclisation.

Cited by 10 publications

References 69 publications

Transcriptome and Metabolome Analysis of the Synthesis Pathways of Allelochemicals in Eupatorium adenophorum

Transcriptome and Metabolome Analysis of the Synthesis Pathways of Allelochemicals in Eupatorium adenophorum

Taxonomic Insights and Its Type Cyclization Correlation of Volatile Sesquiterpenes in Vitex Species and Potential Source Insecticidal Compounds: A Review

Mechanistic Similarities of Sesquiterpene Cyclases PenA, Omp6/7, and BcBOT2 Are Unraveled by an Unnatural “FPP-Ether” Derivative

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