Two Defensive Lines in Juvenile Leaf Beetles; Esters of 3-nitropropionic Acid in the Hemolymph and Aposematic Warning

Pauls, Gerhard; Becker, Tobias; Rahfeld, Peter; Gretscher, René R.; Paetz, Christian; Pasteels, Jacques; Reuß, Stephan H. von; Burse, Antje; Boland, Wilhelm

doi:10.1007/s10886-016-0684-0

Cited by 22 publications

(36 citation statements)

References 44 publications

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“…In a living larva, release of free 3-NPA is cured by activation as a CoA-ester and re-esterification to the C(6′) of isoxazolinone glucoside. 1 The identification and cloning of the enzymes catalyzing the transformation of the amino group of β-alanine to the functionally relevant nitro group are the next and urgent steps to understand the underlying mechanisms and the regulation of defense production in leaf beetle larvae.…”

Section: Resultsmentioning

confidence: 99%

Biosynthesis of isoxazolin-5-one and 3-nitropropanoic acid containing glucosides in juvenile Chrysomelina

2016

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Stable-isotope-labeled precursors were used to establish the biosynthetic pathway leading from β-alanine towards isoxazolin-5-one glucoside 1 and its 3-nitropropanoate (3-NPA) ester 2 in Chrysomelina larvae. Both structural elements originate from sequestered plant-derived β-alanine or from propanoyl-CoA that is derived from the degradation of some essential amino acids, e.g. valine. β-Alanine is converted into 3-NPA and isoxazolinone 5 by consecutive oxidations of the amino group of β-Ala. Substituting the diphospho group of α-UDP-glucose with 5 generates the isoxazolin-5-one glucoside 1, which serves in the circulating hemolymph of the larva as a platform for esterification with 3-nitropropanoyl-CoA. The pathway was validated with larvae of Phaedon cochleariae, Chrysomela populi as well as Gastrophysa viridula.

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Section: Resultsmentioning

confidence: 99%

Biosynthesis of isoxazolin-5-one and 3-nitropropanoic acid containing glucosides in juvenile Chrysomelina

2016

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“…Like other species of the subtribe Chrysomelina, both larvae and adults of C. lapponica are defended against natural enemies by toxic and/or deterrent chemicals, which differ in larvae and adults (Pasteels et al 1984). Adults synthesise de novo isoxazolinone derivatives that are released from pronotal and elytral exocrine glands upon disturbance (Pasteels et al 1989;Sugeno and Matsuda 2002) and act as a defence against predators (Pauls et al 2016). Beetle unpalatability is advertised by two different types of aposematic coloration: a red-and-black pattern or a metallic black with blue iridescence ( Fig.…”

Section: Leaf Beetle Chrysomela Lapponicamentioning

confidence: 99%

Differential Bird Responses to Colour Morphs of an Aposematic Leaf Beetle may Affect Variation in Morph Frequencies in Polymorphic Prey Populations

et al. 2018

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The selection of prey by predators should, theoretically, favour uniformity in the warning signals displayed by unpalatable prey. Nevertheless, some aposematically coloured species are polymorphic. We tested the hypothesis that colour morphs of unpalatable prey differ in the efficacy of their aposematic signal for birds, thereby affecting the selective advantages of these morphs. We used colour morphs (red-and-black light, red-and-black dark and metallic) of the chemically defended leaf beetle Chrysomela lapponica. In laboratory experiments, naïve great tits (Parus major) attacked live beetles of all colour morphs at the same rate. By contrast, wild-caught tits attacked light beetles at first encounter at the same rate as a novel control prey, but significantly avoided both dark and metallic beetles. Beetles of all colour morphs were similarly unpalatable for birds, and about half of the attacked beetles were released unharmed. Avoidance learning was similarly fast for all three leaf beetle morphs. However, in the next-day memory test, the dark beetles were attacked at a greater rate than beetles of two other morphs, indicating their lower memorability. A field experiment suggests that at low C. lapponica population densities, dark beetles have a survival advantage over light beetles, potentially due to the lesser conspicuousness of the dark pattern; however, when the density is high, dark beetles lose this advantage due to the low memorability of their pattern. Thus, the direction of selective bird predation on prey colour morphs may depend on prey density and thereby contribute to temporal shifts in colour morph frequencies following population fluctuations.

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“…46 In the eggs, concentrations around 10 À2 M (M ¼ mol L À1 ) of compound 4 were reported for Gastrophysa viridula, Chrysomela tremulae and C. populi. 44 The same concentration ranges were determined for this compound in the larval hemolymph, 41 and show increasing tendencies with respect to the larval body weight. 5,41 To gain a comprehensive picture of the occurrence of 3-NPA and its derivatives in natural samples, it is of interest whether 3-NPA can be found only in its unaltered free form, or if it is found as a derivative, e.g.…”

Section: Introductionmentioning

confidence: 53%

“…[41][42][43][44][45][46] In these organisms, compound 4 is present in all life stages of the insect, occurring as a major secondary metabolite in the eggs, the larval hemolymph, the pupae and the adult hemolymph and their defensive secretions. 6,[41][42][43][44][45][47][48][49][50][51] Additionally, in adult secretions of the four leaf beetle species Gastrophysa atrocyanea, Plagiodera versicolora distincta, Chrysomela vigintipunctata costella, and Gastrolina depressa, belonging to the subtribe Chrysomelina, diverse esters of glucose containing 3-NPA and isoxazolin-5-one motifs were indicated by TLC and their structures were determined by HPLC, MS and NMR analyses. 46 These ndings describe structures without the isoxazolin-5-one heterocycle, bearing up to three 3-NPA moieties in different positions on the sugar.…”

Section: Introductionmentioning

confidence: 99%

A tale of four kingdoms – isoxazolin-5-one- and 3-nitropropanoic acid-derived natural products

et al. 2017

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Covering up to September 2016This review reports on natural compounds that derive from the isoxazolinone ring as well as the 3-nitropropanoic acid (3-NPA) moiety. These structural elements occur in compounds that have been identified in plants, insects, bacteria and fungi. In particular, plants belonging to the family of legumes produce such compounds. In the case of insects, isoxazolin-5-one and 3-NPA derivatives were found in leaf beetles of the subtribe Chrysomelina. A number of these natural products have been synthesized so far. In the case of the single compound 3-NPA, several synthetic strategies have been reported and some of the most efficient routes are reviewed. The toxicity of 3-NPA results from its ability to bind covalently to the catalytic center of succinate dehydrogenase causing irreversible inhibition of mitochondrial respiration. As a motif that is produced by many species of plants, leaf beetles and fungi, different detoxification mechanisms for 3-NPA have evolved in different species. These mechanisms are based on amide formation of 3-NPA with amino acids, reduction to β-alanine, ester formation or oxidation to malonic acid semialdehyde. The biosynthetic pathways of 3-NPA and isoxazolin-5-one moieties have been studied in fungi, plants and leaf beetles. In the case of fungi, 3-NPA derives from aspartate, while leaf beetles use essential amino acids such as valine as ultimate precursors. In the case of plants, it is supposed that malonate serves as a precursor of 3-NPA, as indicated by feeding of C-labeled precursors to Indigofera spicata. In other leguminous plants it is suggested that asparagine is incorporated into compounds that derive from isoxazolin-5-one, which was indicated byC-labeled compounds as well. In the case of leaf beetles it was demonstrated that detection of radioactivity after C-labeling from a few precursors is not sufficient to unravel biosynthetic pathways.

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Two Defensive Lines in Juvenile Leaf Beetles; Esters of 3-nitropropionic Acid in the Hemolymph and Aposematic Warning

Cited by 22 publications

References 44 publications

Biosynthesis of isoxazolin-5-one and 3-nitropropanoic acid containing glucosides in juvenile Chrysomelina

Biosynthesis of isoxazolin-5-one and 3-nitropropanoic acid containing glucosides in juvenile Chrysomelina

Differential Bird Responses to Colour Morphs of an Aposematic Leaf Beetle may Affect Variation in Morph Frequencies in Polymorphic Prey Populations

A tale of four kingdoms – isoxazolin-5-one- and 3-nitropropanoic acid-derived natural products

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