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Kazuhiko Matsuda - One of the best experts on this subject based on the ideXlab platform.
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Jasmonic acid is not a biosynthetic intermediate to produce the pyrethrolone moiety in Pyrethrin II.
Scientific reports, 2020Co-Authors: Ryo Matsui, Kazuhiko Matsuda, Kisumi Takiguchi, Naoshige Kuwata, Katsunari Oki, Kosaku Takahashi, Hideyuki MatsuuraAbstract:Pyrethrum (Tanacetum cinerariifolium) produces insecticidal compounds known as Pyrethrins. Pyrethrins are esters; the acid moiety is either trans-chrysanthemic acid or pyrethric acid and the alcohol moiety of Pyrethrins is either pyrethrolone, cinerolone, or jasmolone. It was generally accepted that cis-jasmone was biosynthetic intermediate to produce the alcohol moieties of Pyrethrin, and the biosynthetic origin of the cis-jasmone was postulated to be jasmonic acid. However, there was no direct evidence to prove this hypothesis. In order to uncover the origin of pyrethrolone moiety in Pyrethrin II, feeding experiments were performed employing deuterium- and 13C-labeled compounds as substrates, and the expected labeled compounds were analyzed using UPLC MS/MS system. It was found that the pyrethrolone moiety in Pyrethrin II was derived from 12-oxo-phytodienoic acid (OPDA), iso-OPDA and cis-jasmone but not from methyl jasmonate and 3-oxo-2-(2'-[Z]-pentenyl)-cyclopentane-1-hexanoic acid. The results supported that the biosynthesis of the pyrethrolone moiety in Pyrethrin II partially used part of the jasmonic acid biosynthetic pathway, but not whole.
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selective regulation of Pyrethrin biosynthesis by the specific blend of wound induced volatiles in tanacetum cinerariifolium
Plant Signaling & Behavior, 2016Co-Authors: Koji Sakamori, Hideyuki Matsuura, Naoaki Ono, Makoto Ihara, Hideyuki Suzuki, Ken Tanaka, Daisaku Ohta, Shigehiko Kanaya, Kazuhiko MatsudaAbstract:Natural Pyrethrins are used to control household and agricultural pests, and it is of value to understand biosynthesis in Tanacetum cinerariifolium for enhanced production. We previously found that a blend of four green leaf volatiles (GLVs) and (E)-β-farnesene emitted by T. cinerariifolium seedlings enhanced gene expressions of certain biosynthetic enzymes in unwounded seedlings; however, the extent to which such a regulation facilitates Pyrethrin biosynthesis remains unknown. Here we have investigated the effects of the blend of the volatile organic compounds (VOCs) on gene expressions of seven biosynthetic enzymes. VOC treatment resulted in enhanced chrysanthemyl diphosphate synthase (CDS), chrysanthemic acid synthase (CAS), Tanacetum cinerariifolium GDSL lipase (TcGLIP) and acyl-Coenzyme A oxidase 1 (ACX1) gene expressions that reached a peak at a 12 h VOC treatment, whereas the treatment minimally influenced the expressions of other biosynthetic genes. In undifferentiated Tanacetum tissues, such VOC-induced amplification of CDS, CAS, TcGLIP and ACX1 gene expressions were markedly reduced, suggesting that a high-resolution, VOC-mediated communication is an event selective to differentiated plants.
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Requirement of Catalytic-Triad and Related Amino Acids for the Acyltransferase Activity of Tanacetum cinerariifolium GDSL Lipase/Esterase TcGLIP for Ester-Bond Formation in Pyrethrin Biosynthesis
Bioscience biotechnology and biochemistry, 2013Co-Authors: Yukio Kikuta, Yamada, Tomonori Mitsumori, Takayuki Takeuchi, Nakayama Koji, Yoshio Katsuda, Akikazu Hatanaka, Kazuhiko MatsudaAbstract:We have recently discovered that a GDSL lipase/esterase (TcGLIP) in Tanacetum cinerariifolium catalyzed acyltransferase activity to form an ester bond in the natural insecticide, Pyrethrin. TcGLIP contained Ser40 in Block I, Gly64 in Block II, Asn168 in Block III and Asp318 and His321 in Block V, suggesting underlying hydrolase activity, although little is known about their role in acyltransferase activity. We expressed TcGLIP here in Esherichia coli as a fusion with maltose-binding protein (MBP), part of the fusion being cleaved with a protease to obtain MBP-free TcGLIP. A kinetic analysis revealed that the MBP moiety scarcely influenced the kinetic parameters. The effects on acyltransferase activity of mutations of Gly64, Asn168, Asp318 and His321 were investigated by using MBP-fused TcGLIP. Mutations of these amino acids markedly reduced the acyltransferase activity, suggesting their critical role in the production of Pyrethrins.
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requirement of catalytic triad and related amino acids for the acyltransferase activity of tanacetum cinerariifolium gdsl lipase esterase tcglip for ester bond formation in Pyrethrin biosynthesis
Bioscience Biotechnology and Biochemistry, 2013Co-Authors: Yukio Kikuta, Tomonori Mitsumori, Takayuki Takeuchi, Yoshio Katsuda, Akikazu Hatanaka, Gen Yamada, Koji Nakayama, Kazuhiko MatsudaAbstract:We have recently discovered that a GDSL lipase/esterase (TcGLIP) in Tanacetum cinerariifolium catalyzed acyltransferase activity to form an ester bond in the natural insecticide, Pyrethrin. TcGLIP contained Ser40 in Block I, Gly64 in Block II, Asn168 in Block III and Asp318 and His321 in Block V, suggesting underlying hydrolase activity, although little is known about their role in acyltransferase activity. We expressed TcGLIP here in Esherichia coli as a fusion with maltose-binding protein (MBP), part of the fusion being cleaved with a protease to obtain MBP-free TcGLIP. A kinetic analysis revealed that the MBP moiety scarcely influenced the kinetic parameters. The effects on acyltransferase activity of mutations of Gly64, Asn168, Asp318 and His321 were investigated by using MBP-fused TcGLIP. Mutations of these amino acids markedly reduced the acyltransferase activity, suggesting their critical role in the production of Pyrethrins.
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Pyrethrin Biosynthesis and Its Regulation in Chrysanthemum cinerariaefolium
Topics in current chemistry, 2011Co-Authors: Kazuhiko MatsudaAbstract:Pyrethrins are a natural insecticide biosynthesized by the plant pyrethrum [Chrysanthemum cinerariaefolium (Current species name: Tanacetum cinerariifolium)] of the family Asteraceae. Although Pyrethrins have been used to control household pests for the past century, little is known about the mechanism of biosynthesis, contrasting with intensive research on their synthetic analogs, pyrethroids. The author studied Pyrethrin biosynthesis in young seedlings of C. cinerariaefolium. The results of experiments using 13C-labeled glucose as the biosynthesis precursor indicated that the acid and alcohol moieties are biosynthesized via the 2-C-methyl-d-erythritol 4-phosphate (MEP) and oxylipin pathways, respectively. Further study on the effects of wound-induced signals in leaves showed that biosynthesis is enhanced in response to both volatile and nonvolatile signals.
Nina Jeran - One of the best experts on this subject based on the ideXlab platform.
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Pyrethrin from Dalmatian pyrethrum (Tanacetum cinerariifolium/Trevir./Sch. Bip.): biosynthesis, biological activity, methods of extraction and determination
Phytochemistry Reviews, 2020Co-Authors: Nina Jeran, Martina Grdiša, Filip Varga, Zlatko Šatović, Zlatko Liber, Dario Dabić, Martina BiošićAbstract:Pyrethrin is a potent biopesticide, a natural mixture of six compounds (Pyrethrin I and II, cinerin I and II, and jasmolin I and II), biosynthesized in plants of Dalmatian pyrethrum ( Tanacetum cinerariifolium /Trevir./Sch. Bip.), a species endemic to the eastern Adriatic coast, but grown worldwide. Not many known natural insecticides encompass such superior qualities as Pyrethrin—very high efficacy against a broad spectrum of pests in combination with minor adverse effects on human health and the environment. In previous decades, Pyrethrin was largely replaced by its synthetic derivatives, pyrethroids. However, due to their harmful effects on various species and ecosystems, the use of Pyrethrin should again take the lead. This review summarizes one century (1920–2020) of research on the properties and use of pyrethrum as a source of Pyrethrins. The primary focus is on presenting its current advantages and disadvantages, toxicity on target and non-target species, biosynthesis, factors that influence the Pyrethrins content in pyrethrum, comparison of different methods of their extraction and determination; as well as its production potential and development of new products. The final goal is to present possible approaches to improve and enhance the use of this highly effective but still underused phytochemical insecticide with unique properties.
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Pyrethrin from dalmatian pyrethrum tanacetum cinerariifolium trevir sch bip biosynthesis biological activity methods of extraction and determination
Phytochemistry Reviews, 2020Co-Authors: Nina Jeran, Martina Grdiša, Filip Varga, Zlatko Liber, Zlatko Satovic, Dario Dabic, Martina BiosicAbstract:Pyrethrin is a potent biopesticide, a natural mixture of six compounds (Pyrethrin I and II, cinerin I and II, and jasmolin I and II), biosynthesized in plants of Dalmatian pyrethrum (Tanacetum cinerariifolium/Trevir./Sch. Bip.), a species endemic to the eastern Adriatic coast, but grown worldwide. Not many known natural insecticides encompass such superior qualities as Pyrethrin—very high efficacy against a broad spectrum of pests in combination with minor adverse effects on human health and the environment. In previous decades, Pyrethrin was largely replaced by its synthetic derivatives, pyrethroids. However, due to their harmful effects on various species and ecosystems, the use of Pyrethrin should again take the lead. This review summarizes one century (1920–2020) of research on the properties and use of pyrethrum as a source of Pyrethrins. The primary focus is on presenting its current advantages and disadvantages, toxicity on target and non-target species, biosynthesis, factors that influence the Pyrethrins content in pyrethrum, comparison of different methods of their extraction and determination; as well as its production potential and development of new products. The final goal is to present possible approaches to improve and enhance the use of this highly effective but still underused phytochemical insecticide with unique properties.
Eran Pichersky - One of the best experts on this subject based on the ideXlab platform.
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How Plants Synthesize Pyrethrins: Safe and Biodegradable Insecticides
Trends in plant science, 2020Co-Authors: Daniel B. Lybrand, Eran PicherskyAbstract:Natural Pyrethrin insecticides produced by Dalmatian pyrethrum (Tanacetum cinerariifolium) have low mammalian toxicity and short environmental persistence, providing an alternative to widely used synthetic agricultural insecticides that pose a threat to human health and the environment. A recent surge of interest in the use of Pyrethrins as agricultural insecticides coincides with the discovery of several new genes in the Pyrethrin biosynthetic pathway. Elucidation of this pathway facilitates efforts to breed improved pyrethrum varieties and to engineer plants with improved endogenous defenses or hosts for heterologous Pyrethrin production. We describe the current state of knowledge related to global pyrethrum production, the Pyrethrin biosynthetic pathway and its regulation, and recent efforts to engineer the Pyrethrin pathway in diverse plant hosts.
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Pyrethrin biosynthesis the cytochrome p450 oxidoreductase cyp82q3 converts jasmolone to pyrethrolone
Plant Physiology, 2019Co-Authors: Daniel B. Lybrand, Fei Zhou, Eran PicherskyAbstract:The plant pyrethrum (Tanacetum cinerariifolium) synthesizes highly effective natural pesticides known as Pyrethrins. Pyrethrins are esters consisting of an irregular monoterpenoid acid and an alcohol derived from jasmonic acid (JA). These alcohols, referred to as rethrolones, can be jasmolone, pyrethrolone, or cinerolone. We recently showed that jasmolone is synthesized from jasmone, a degradation product of JA, in a single hydroxylation step catalyzed by jasmone hydroxylase (TcJMH). TcJMH belongs to the CYP71 clade of the cytochrome P450 oxidoreductase family. Here, we used coexpression analysis, heterologous gene expression, and in vitro biochemical assays to identify the enzyme responsible for conversion of jasmolone to pyrethrolone. A further T. cinerariifolium cytochrome P450 family member, CYP82Q3 (designated Pyrethrolone Synthase; TcPYS), appeared to catalyze the direct desaturation of the C1–C2 bond in the pentyl side chain of jasmolone to produce pyrethrolone. TcPYS is highly expressed in the trichomes of the ovaries in pyrethrum flowers, similar to TcJMH and other T. cinerariifolium genes involved in JA biosynthesis. Thus, as previously shown for biosynthesis of the monoterpenoid acid moiety of Pyrethrins, rethrolones are synthesized in the trichomes. However, the final assembly of Pyrethrins occurs in the developing achenes. Our data provide further insight into Pyrethrin biosynthesis, which could ultimately be harnessed to produce this natural pesticide in a heterologous system.
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pyrethric acid of natural Pyrethrin insecticide complete pathway elucidation and reconstitution in nicotiana benthamiana
New Phytologist, 2019Co-Authors: Anthony L Schilmiller, Maarten A Jongsma, Henriette D L M Van Eekelen, Ric C H De Vos, Eran PicherskyAbstract:In the natural pesticides known as Pyrethrins, which are esters produced in flowers of Tanacetum cinerariifolium (Asteraceae), the monoterpenoid acyl moiety is pyrethric acid or chrysanthemic acid. We show here that pyrethric acid is produced from chrysanthemol in six steps catalyzed by four enzymes, the first five steps occurring in the trichomes covering the ovaries and the last one occurring inside the ovary tissues. Three steps involve the successive oxidation of carbon 10 (C10) to a carboxylic group by TcCHH, a cytochrome P450 oxidoreductase. Two other steps involve the successive oxidation of the hydroxylated carbon 1 to give a carboxylic group by TcADH2 and TcALDH1, the same enzymes that catalyze these reactions in the formation of chrysanthemic acid. The ultimate result of the actions of these three enzymes is the formation of 10‐carboxychrysanthemic acid in the trichomes. Finally, the carboxyl group at C10 is methylated by TcCCMT, a member of the SABATH methyltransferase family, to give pyrethric acid. This reaction occurs mostly in the ovaries. Expression in N. benthamiana plants of all four genes encoding aforementioned enzymes, together with TcCDS, a gene that encodes an enzyme that catalyzes the formation of chrysanthemol, led to the production of pyrethric acid.
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jasmone hydroxylase a key enzyme in the synthesis of the alcohol moiety of Pyrethrin insecticides
Plant Physiology, 2018Co-Authors: Fei Zhou, Eran PicherskyAbstract:Pyrethrins are synthesized by the plant pyrethrum (Tanacetum cinerariifolium), a chrysanthemum relative. These compounds possess efficient insecticidal properties and are not toxic to humans and most vertebrates. Pyrethrum flowers, and to a smaller extent leaves, synthesize six main types of Pyrethrins, which are all esters of a monoterpenoid acid moiety and an alcohol moiety derived from jasmonic acid. Here, we identified and characterized the enzyme responsible for the conversion of jasmone, a derivative of jasmonic acid, to jasmolone. Feeding pyrethrum flowers with jasmone resulted in a 4-fold increase in the concentration of free jasmolone as well as smaller but significant proportional increases in free pyrethrolone and all three type I Pyrethrins. We used floral transcriptomic data to identify cytochrome P450 genes whose expression patterns were most highly correlated with that of a key gene in Pyrethrin biosynthesis, T. cinerariifolium chrysanthemyl diphosphate synthase. The candidate genes were screened for jasmone hydroxylase activity through transient expression in Nicotiana benthamiana leaves fed with jasmone. The expression of only one of these candidate genes produced jasmolone; therefore, this gene was named T. cinerariifolium jasmolone hydroxylase (TcJMH) and given the CYP designation CYP71AT148. The protein encoded by TcJMH localized to the endoplasmic reticulum, and microsomal preparations from N. benthamiana leaves expressing TcJMH were capable of catalyzing the hydroxylation of jasmone to jasmolone in vitro, with a Km value of 53.9 µm. TcJMH was expressed almost exclusively in trichomes of floral ovaries and was induced in leaves by jasmonate.
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coexpression analysis identifies two oxidoreductases involved in the biosynthesis of the monoterpene acid moiety of natural Pyrethrin insecticides in tanacetum cinerariifolium
Plant Physiology, 2018Co-Authors: Gaurav D Moghe, Krystle Wiegertrininger, Anthony L Schilmiller, Cornelius S Barry, Eran PicherskyAbstract:Flowers of Tanacetum cinerariifolium produce a set of compounds known collectively as Pyrethrins, which are commercially important pesticides that are strongly toxic to flying insects but not to most vertebrates. A Pyrethrin molecule is an ester consisting of either trans-chrysanthemic acid or its modified form, pyrethric acid, and one of three alcohols, jasmolone, pyrethrolone, and cinerolone, that appear to be derived from jasmonic acid. Chrysanthemyl diphosphate synthase (CDS), the first enzyme involved in the synthesis of trans-chrysanthemic acid, was characterized previously and its gene isolated. TcCDS produces free trans-chrysanthemol in addition to trans-chrysanthemyl diphosphate, but the enzymes responsible for the conversion of trans-chrysanthemol to the corresponding aldehyde and then to the acid have not been reported. We used an RNA sequencing-based approach and coexpression correlation analysis to identify several candidate genes encoding putative trans-chrysanthemol and trans-chrysanthemal dehydrogenases. We functionally characterized the proteins encoded by these genes using a combination of in vitro biochemical assays and heterologous expression in planta to demonstrate that TcADH2 encodes an enzyme that oxidizes trans-chrysanthemol to trans-chrysanthemal, while TcALDH1 encodes an enzyme that oxidizes trans-chrysanthemal into trans-chrysanthemic acid. Transient coexpression of TcADH2 and TcALDH1 together with TcCDS in Nicotiana benthamiana leaves results in the production of trans-chrysanthemic acid as well as several other side products. The majority (58%) of trans-chrysanthemic acid was glycosylated or otherwise modified. Overall, these data identify key steps in the biosynthesis of Pyrethrins and demonstrate the feasibility of metabolic engineering to produce components of these defense compounds in a heterologous host.
Martina Biošić - One of the best experts on this subject based on the ideXlab platform.
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Pyrethrin from Dalmatian pyrethrum (Tanacetum cinerariifolium/Trevir./Sch. Bip.): biosynthesis, biological activity, methods of extraction and determination
Phytochemistry Reviews, 2020Co-Authors: Nina Jeran, Martina Grdiša, Filip Varga, Zlatko Šatović, Zlatko Liber, Dario Dabić, Martina BiošićAbstract:Pyrethrin is a potent biopesticide, a natural mixture of six compounds (Pyrethrin I and II, cinerin I and II, and jasmolin I and II), biosynthesized in plants of Dalmatian pyrethrum ( Tanacetum cinerariifolium /Trevir./Sch. Bip.), a species endemic to the eastern Adriatic coast, but grown worldwide. Not many known natural insecticides encompass such superior qualities as Pyrethrin—very high efficacy against a broad spectrum of pests in combination with minor adverse effects on human health and the environment. In previous decades, Pyrethrin was largely replaced by its synthetic derivatives, pyrethroids. However, due to their harmful effects on various species and ecosystems, the use of Pyrethrin should again take the lead. This review summarizes one century (1920–2020) of research on the properties and use of pyrethrum as a source of Pyrethrins. The primary focus is on presenting its current advantages and disadvantages, toxicity on target and non-target species, biosynthesis, factors that influence the Pyrethrins content in pyrethrum, comparison of different methods of their extraction and determination; as well as its production potential and development of new products. The final goal is to present possible approaches to improve and enhance the use of this highly effective but still underused phytochemical insecticide with unique properties.
Martina Biosic - One of the best experts on this subject based on the ideXlab platform.
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Pyrethrin from dalmatian pyrethrum tanacetum cinerariifolium trevir sch bip biosynthesis biological activity methods of extraction and determination
Phytochemistry Reviews, 2020Co-Authors: Nina Jeran, Martina Grdiša, Filip Varga, Zlatko Liber, Zlatko Satovic, Dario Dabic, Martina BiosicAbstract:Pyrethrin is a potent biopesticide, a natural mixture of six compounds (Pyrethrin I and II, cinerin I and II, and jasmolin I and II), biosynthesized in plants of Dalmatian pyrethrum (Tanacetum cinerariifolium/Trevir./Sch. Bip.), a species endemic to the eastern Adriatic coast, but grown worldwide. Not many known natural insecticides encompass such superior qualities as Pyrethrin—very high efficacy against a broad spectrum of pests in combination with minor adverse effects on human health and the environment. In previous decades, Pyrethrin was largely replaced by its synthetic derivatives, pyrethroids. However, due to their harmful effects on various species and ecosystems, the use of Pyrethrin should again take the lead. This review summarizes one century (1920–2020) of research on the properties and use of pyrethrum as a source of Pyrethrins. The primary focus is on presenting its current advantages and disadvantages, toxicity on target and non-target species, biosynthesis, factors that influence the Pyrethrins content in pyrethrum, comparison of different methods of their extraction and determination; as well as its production potential and development of new products. The final goal is to present possible approaches to improve and enhance the use of this highly effective but still underused phytochemical insecticide with unique properties.
