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(2E,6E)-farnesyl diphosphate
(+)-5-epiaristolochene + diphosphate
(2E,6E)-farnesyl diphosphate
5-epi-aristolochene + diphosphate
-
-
-
?
(2E,6Z)-6-fluorofarnesyl diphosphate
(-)-1-fluorogermacrene A
-
the fluoro substitution at the C6 position of farnesyl diphosphate has negligible effects on enzyme binding, substrate orientation, diphosphate ionization, and the initial 1,10 ring closure catalyzed by TEAS
sole product, 58% yield
-
?
(2E,6E)-farnesyl diphosphate
(+)-5-epiaristolochene + diphosphate
-
single major sesquiterpene product
-
?
(2E,6E)-farnesyl diphosphate
(+)-5-epiaristolochene + diphosphate
-
-
-
-
?
(2E,6E)-farnesyl diphosphate
(+)-5-epiaristolochene + diphosphate
-
-
-
?
(2E,6E)-farnesyl diphosphate
(+)-5-epiaristolochene + diphosphate
-
-
(+)-5-epiaristolochene constitutes about 85% of hyxdrocarbon products
-
?
(2E,6E)-farnesyl diphosphate
(+)-5-epiaristolochene + diphosphate
-
-
about 79% of hydrocarbon product, plus about 6% of (-)-4-epi-eremophilene, 3.6% of (+)-germacrene A and 22 hydrocarbons contributing about 12% of TEAS sesquiterpene products. The pathway to the by-products starts with a 1,6 cyclization of the (Z,E)-farnesyl cation, followed by a 1,2 hydride shift leading to a syn-6,10 ring closure which generates an acoradilyl cation. Elimination of a proton from either C12 or C13 of the isopropylidene tail of the acoradilyl cation readily explains the formation of ?-acoradiene. Alternatively, a 2,11 ring closure followed by elimination of a proton at C2 is the likely pathway to (-)-alpha-cedrene. A 3,11 ring closure of the acoradilyl cation is the most common event, based on the relative abundance of isomerization products observed, and is followed by Wagner-Meerwein rearrangement and proton elimination from C15 to produce isoprezizaene, the dominant (Z,E)-farnesyl cation-derived product
-
?
(2E,6E)-farnesyl diphosphate
(+)-5-epiaristolochene + diphosphate
reaction proceeds via geracrene A as an intermediate. Proton donation by residue Y520 is responsible for the activation of germacrene A to a eudesmane cation
-
-
?
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0.0016 - 0.014
(2E,6E)-farnesyl diphosphate
0.0197
(2E,6Z)-6-fluorofarnesyl diphosphate
-
pH 7.0, 22°C
0.0016
(2E,6E)-farnesyl diphosphate
-
fusion construct epiaristolochene synthase/farnesyl diphosphate synthase, pH 8.0, 30°C
0.0017
(2E,6E)-farnesyl diphosphate
-
wild-type, pH 8.0, 30°C
0.0023
(2E,6E)-farnesyl diphosphate
wild-type, pH 7.5, 30°C
0.0026
(2E,6E)-farnesyl diphosphate
-
fusion construct farnesyl diphosphate synthase/epiaristolochene synthase, pH 8.0, 30°C
0.0081
(2E,6E)-farnesyl diphosphate
mutant Y520F, pH 7.5, 30°C
0.0084
(2E,6E)-farnesyl diphosphate
-
pH 7.0, 22°C
0.014
(2E,6E)-farnesyl diphosphate
-
pH 7.5, 22°C
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Y520F
3% of wild-type catalytic efficiency, reaction prooduct is germacrene A
additional information
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heterologous expression of EAS in transgenic rice does not interfere with the activities of endogenous squalene synthase or farnesyl diphosphatase. The induction of EAS enzyme activity is accompanied by an increase in EAS mRNA when challenged by the elicitor. The EAS ectopic expression in transgenic rice plants results in the synthesis of 5-epi-aristolochene in vivo upon elicitor treatment
additional information
-
construction of fusion proteins with farnesyl diphosphate synthase FPPS from Artemisia annua. The fusion enzymes produce epi-aristolochene from isopentenyl diphosphate through a coupled reaction. The Km values of FPPS and eAS for isopentenyl diphosphate and farnesyl diphosphate, respectively, are essentially the same for the single and fused enzymes. The bifunctional enzymes show a more efficient conversion of isopentenyl diphosphate to epi-aristolochene than the corresponding amount of single enzymes
additional information
engineering of a thermostable mutant by SCADS algorithm to suggest mutations based on side-chain interactions consistent with the nearby protein backbone, neighboring sidechains, and the local environment, and by replacement of solvent-exposed hydrophobic residues and the addition of salt bridges on the surface of the mutant enzyme. Contrary to wild-type, mutant is still active to 65°C but produces additional sesquiterpene products
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O'Maille, P.E.; Chappell, J.; Noel, J.P.
Biosynthetic potential of sesquiterpene synthase: alternative product of tobacco 5-epi-aristolochene synthase
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448
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315
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122
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Nicotiana tabacum (Q40577)
-
brenda
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60
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brenda
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