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First biosynthetic pathway of 1-hepten-3-one in Iporangaia pustulosa (Opiliones).

Rocha DF, Wouters FC, Machado G, Marsaioli AJ - Sci Rep (2013)

Bottom Line: Our analysis also indicates the presence of methylmalonyl-CoA mutase, converting acetate into propionyl-CoA via succinyl-CoA, together with other C₃ unit routes.This is the first biosynthetic study of alkyl vinyl ketones in arthropods.Our results shed light on the origin and diversification of chemical compounds in a major arthropod group.

View Article: PubMed Central - PubMed

Affiliation: Chemistry Institute, State University of Campinas, POB 6154, 13083-970 Campinas, SP, Brazil.

ABSTRACT
Arthropods produce a great variety of natural compounds, many of which have unexplored biosynthesis. Among the armored harvestmen (Arachnida: Opiliones) of the suborder Laniatores, the defensive gland exudates contain vinyl ketones and other constituents of supposed polyketide origin. We have studied the biosynthesis of 1-hepten-3-one in the Neotropical harvestman Iporangaia pustulosa by feeding individuals with ¹³C-labeled precursors, demonstrating its mixed acetate/propionate origin. ¹³C NMR spectroscopy showed an unusual labeling pattern suggesting different propionate sources for starting and extender units. Our analysis also indicates the presence of methylmalonyl-CoA mutase, converting acetate into propionyl-CoA via succinyl-CoA, together with other C₃ unit routes. This is the first biosynthetic study of alkyl vinyl ketones in arthropods. Our results shed light on the origin and diversification of chemical compounds in a major arthropod group.

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Results of the experiment in which Iporangaia pustulosa individuals were fed [13C3]propionate.(a) 13C NMR spectrum (125 MHz, CDCl3) of the exudate containing 1 as major compound. (b) Extended signals of 13C enriched positions showing 13C-13C coupling patterns.
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f2: Results of the experiment in which Iporangaia pustulosa individuals were fed [13C3]propionate.(a) 13C NMR spectrum (125 MHz, CDCl3) of the exudate containing 1 as major compound. (b) Extended signals of 13C enriched positions showing 13C-13C coupling patterns.

Mentions: The enrichment by [13C3]propionate is given by the integration ratio of the satellite lines by the sum of all carbon signals1112 (Fig. 2, Table 1). Positions C-1, C-2, C-5, C-6 and C-7 were labeled, and at C-1 and C-2 the enrichment was weaker. All labeled positions showed increased satellite lines.


First biosynthetic pathway of 1-hepten-3-one in Iporangaia pustulosa (Opiliones).

Rocha DF, Wouters FC, Machado G, Marsaioli AJ - Sci Rep (2013)

Results of the experiment in which Iporangaia pustulosa individuals were fed [13C3]propionate.(a) 13C NMR spectrum (125 MHz, CDCl3) of the exudate containing 1 as major compound. (b) Extended signals of 13C enriched positions showing 13C-13C coupling patterns.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC3818658&req=5

f2: Results of the experiment in which Iporangaia pustulosa individuals were fed [13C3]propionate.(a) 13C NMR spectrum (125 MHz, CDCl3) of the exudate containing 1 as major compound. (b) Extended signals of 13C enriched positions showing 13C-13C coupling patterns.
Mentions: The enrichment by [13C3]propionate is given by the integration ratio of the satellite lines by the sum of all carbon signals1112 (Fig. 2, Table 1). Positions C-1, C-2, C-5, C-6 and C-7 were labeled, and at C-1 and C-2 the enrichment was weaker. All labeled positions showed increased satellite lines.

Bottom Line: Our analysis also indicates the presence of methylmalonyl-CoA mutase, converting acetate into propionyl-CoA via succinyl-CoA, together with other C₃ unit routes.This is the first biosynthetic study of alkyl vinyl ketones in arthropods.Our results shed light on the origin and diversification of chemical compounds in a major arthropod group.

View Article: PubMed Central - PubMed

Affiliation: Chemistry Institute, State University of Campinas, POB 6154, 13083-970 Campinas, SP, Brazil.

ABSTRACT
Arthropods produce a great variety of natural compounds, many of which have unexplored biosynthesis. Among the armored harvestmen (Arachnida: Opiliones) of the suborder Laniatores, the defensive gland exudates contain vinyl ketones and other constituents of supposed polyketide origin. We have studied the biosynthesis of 1-hepten-3-one in the Neotropical harvestman Iporangaia pustulosa by feeding individuals with ¹³C-labeled precursors, demonstrating its mixed acetate/propionate origin. ¹³C NMR spectroscopy showed an unusual labeling pattern suggesting different propionate sources for starting and extender units. Our analysis also indicates the presence of methylmalonyl-CoA mutase, converting acetate into propionyl-CoA via succinyl-CoA, together with other C₃ unit routes. This is the first biosynthetic study of alkyl vinyl ketones in arthropods. Our results shed light on the origin and diversification of chemical compounds in a major arthropod group.

Show MeSH