Enzymes
UniProtKB help_outline | 1 proteins |
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- Name help_outline (2E,6E)-farnesyl diphosphate Identifier CHEBI:175763 Charge -3 Formula C15H25O7P2 InChIKeyhelp_outline VWFJDQUYCIWHTN-YFVJMOTDSA-K SMILEShelp_outline CC(C)=CCC\C(C)=C\CC\C(C)=C\COP([O-])(=O)OP([O-])([O-])=O 2D coordinates Mol file for the small molecule Search links Involved in 170 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
- Name help_outline diphosphate Identifier CHEBI:33019 (Beilstein: 185088) help_outline Charge -3 Formula HO7P2 InChIKeyhelp_outline XPPKVPWEQAFLFU-UHFFFAOYSA-K SMILEShelp_outline OP([O-])(=O)OP([O-])([O-])=O 2D coordinates Mol file for the small molecule Search links Involved in 1,085 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
- Name help_outline sesquisabinene B Identifier CHEBI:143550 Charge 0 Formula C15H24 InChIKeyhelp_outline DYUSFBWNOCHOFP-RRFJBIMHSA-N SMILEShelp_outline C1[C@@]2(C[C@@H]2C(C1)=C)[C@H](CCC=C(C)C)C 2D coordinates Mol file for the small molecule Search links Involved in 1 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
Cross-references
RHEA:60016 | RHEA:60017 | RHEA:60018 | RHEA:60019 | |
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Reaction direction help_outline | undefined | left-to-right | right-to-left | bidirectional |
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Publications
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Substrate geometry controls the cyclization cascade in multiproduct terpene synthases from Zea mays.
Vattekkatte A., Gatto N., Koellner T.G., Degenhardt J., Gershenzon J., Boland W.
Multiproduct terpene synthases TPS4-B73 and TPS5-Delprim from maize (Zea mays) catalyze the conversion of farnesyl diphosphate (FDP) and geranyl diphosphate (GDP) into a complex mixture of sesquiterpenes and monoterpenes, respectively. Various isotopic and geometric isomers of natural substrates l ... >> More
Multiproduct terpene synthases TPS4-B73 and TPS5-Delprim from maize (Zea mays) catalyze the conversion of farnesyl diphosphate (FDP) and geranyl diphosphate (GDP) into a complex mixture of sesquiterpenes and monoterpenes, respectively. Various isotopic and geometric isomers of natural substrates like (2Z)-[2-(2)H]- and [2,4,4,9,9,9-(2)H6]-(GDP) and (2Z,6E)-[2-(2)H]- and [2,4,4,13,13,13-(2)H6]-(FDP) were synthesized analogous to presumptive reaction intermediates. On incubation with labeled (2Z) substrates, TPS4 and TPS5 showed much lower kinetic isotope effects than the labeled (2E) substrates. Interestingly, the products arising from the deuterated (2Z)-precursors revealed a distinct preference for cyclic products and exhibited an enhanced turnover on comparison with natural (2E)-substrates. This increase in the efficiency due to (2Z) configuration emphasizes the rate limiting effect of the initial (2E) → (2Z) isomerization step in the reaction cascade of the multiproduct terpene synthases. Apart from turnover advantages, these results suggest that substrate geometry can be used as a tool to optimize the biosynthetic reaction cascade towards valuable cyclic terpenoids. << Less
Org. Biomol. Chem. 13:6021-6030(2015) [PubMed] [EuropePMC]
This publication is cited by 1 other entry.
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The variability of sesquiterpenes emitted from two Zea mays cultivars is controlled by allelic variation of two terpene synthase genes encoding stereoselective multiple product enzymes.
Koellner T.G., Schnee C., Gershenzon J., Degenhardt J.
The mature leaves and husks of Zea mays release a complex blend of terpene volatiles after anthesis consisting predominantly of bisabolane-, sesquithujane-, and bergamotane-type sesquiterpenes. The varieties B73 and Delprim release the same volatile constituents but in significantly different prop ... >> More
The mature leaves and husks of Zea mays release a complex blend of terpene volatiles after anthesis consisting predominantly of bisabolane-, sesquithujane-, and bergamotane-type sesquiterpenes. The varieties B73 and Delprim release the same volatile constituents but in significantly different proportions. To study the molecular genetic and biochemical mechanisms controlling terpene diversity and distribution in these varieties, we isolated the closely related terpene synthase genes terpene synthase4 (tps4) and tps5 from both varieties. The encoded enzymes, TPS4 and TPS5, each formed the same complex mixture of sesquiterpenes from the precursor farnesyl diphosphate but with different proportions of products. These mixtures correspond to the sesquiterpene blends observed in the varieties B73 and Delprim, respectively. The differences in the stereoselectivity of TPS4 and TPS5 are determined by four amino acid substitutions with the most important being a Gly instead of an Ala residue at position 409 at the catalytic site of the enzyme. Although both varieties contain tps4 and tps5 alleles, their differences in terpene composition result from the fact that B73 has only a single functional allele of tps4 and no functional alleles of tps5, whereas Delprim has only a functional allele of tps5 and no functional alleles of tps4. Lack of functionality was shown to be attributable to frame-shift mutations or amino acid substitutions that greatly reduce the activity of their encoded proteins. Therefore, the diversity of sesquiterpenes in these two maize cultivars is strongly influenced by single nucleotide changes in the alleles of two terpene synthase genes. << Less
Plant Cell 16:1115-1131(2004) [PubMed] [EuropePMC]
This publication is cited by 3 other entries.
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The products of a single maize sesquiterpene synthase form a volatile defense signal that attracts natural enemies of maize herbivores.
Schnee C., Koellner T.G., Held M., Turlings T.C., Gershenzon J., Degenhardt J.
Plants can defend themselves against herbivores by attracting natural enemies of the herbivores. The cues for attraction are often complex mixtures of herbivore-induced plant volatiles, making it difficult to demonstrate the role of specific compounds. After herbivory by lepidopteran larvae, maize ... >> More
Plants can defend themselves against herbivores by attracting natural enemies of the herbivores. The cues for attraction are often complex mixtures of herbivore-induced plant volatiles, making it difficult to demonstrate the role of specific compounds. After herbivory by lepidopteran larvae, maize releases a mixture of volatiles that is highly attractive to females of various parasitic wasp species. We identified the terpene synthase TPS10 that forms (E)-beta-farnesene, (E)-alpha-bergamotene, and other herbivory-induced sesquiterpene hydrocarbons from the substrate farnesyl diphosphate. The corresponding gene is expressed in response to herbivore attack and is regulated at the transcript level. Overexpression of tps10 in Arabidopsis thaliana resulted in plants emitting high quantities of TPS10 sesquiterpene products identical to those released by maize. Using these transgenic Arabidopsis plants as odor sources in olfactometer assays showed that females of the parasitoid Cotesia marginiventris learn to exploit the TPS10 sesquiterpenes to locate their lepidopteran hosts after prior exposure to these volatiles in association with hosts. This dissection of the herbivore-induced volatile blend demonstrates that a single gene such as tps10 can be sufficient to mediate the indirect defense of maize against herbivore attack. << Less
Proc. Natl. Acad. Sci. U.S.A. 103:1129-1134(2006) [PubMed] [EuropePMC]
This publication is cited by 1 other entry.
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Molecular and biochemical evolution of maize terpene synthase 10, an enzyme of indirect defense.
Koellner T.G., Gershenzon J., Degenhardt J.
Maize plants attacked by lepidopteran larvae emit a volatile mixture that consists mostly of the sesquiterpene olefins, (E)-alpha-bergamotene and (E)-beta-farnesene. These volatiles are produced by the herbivore-induced terpene synthase TPS10 and attract natural enemies to the damaged plants. A su ... >> More
Maize plants attacked by lepidopteran larvae emit a volatile mixture that consists mostly of the sesquiterpene olefins, (E)-alpha-bergamotene and (E)-beta-farnesene. These volatiles are produced by the herbivore-induced terpene synthase TPS10 and attract natural enemies to the damaged plants. A survey of volatiles in maize lines and species of teosinte showed that the TPS10 products (E)-alpha-bergamotene and (E)-beta-farnesene are consistently induced by herbivory, indicating that release of TPS10 volatiles is a defense trait conserved among maize and its wild relatives. Sequence comparison of TPS10 from maize and its apparent orthologs from four teosinte species demonstrated stabilizing selection on this defense trait. The teosinte volatiles and the enzymatic activity of the apparent TPS10 orthologs were not completely uniform but varied in the ratio of (E)-alpha-bergamotene to (E)-beta-farnesene products formed. We identified a single amino acid in the active center which determines the ratio of (E)-alpha-bergamotene to (E)-beta-farnesene and has changed during the evolution of maize and teosinte species. Feeding experiments with the substrate (Z,E)-farnesyl diphosphate revealed that this amino acid controls the rate of isomerization of the (E,E)-farnesyl carbocation intermediate to the (Z,E)-configuration. << Less
Comments
The structure of sesquisabinene B does not correspond to the structure shown in K