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Acquired and Partially De Novo Synthesized Pyrrolizidine Alkaloids in Two Polyphagous Arctiids and the Alkaloid Profiles of Their Larval Food-Plants

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Abstract

The profiles of pyrrolizidine alkaloids (PAs) in the two highly polyphagous arctiids Estigmene acrea and Grammia geneura and their potential PA sources in southeastern Arizona were compiled. One of four species of Boraginaceae, Plagiobothrys arizonicus, contained PAs; this is the first PA record for this plant species. The principle PA sources are Senecio longilobus (Asteraceae) and Crotalaria pumila (Fabaceae). The known PA pattern of S. longilobus was extended; the species was found to contain six closely related PAs of the senecionine type. Three novel PAs of the monocrotaline type, named pumilines A–C, were isolated and characterized from C. pumila, a species not studied before. The pumilines are the major PAs in the seeds, while in the vegetative organs they are accompanied by the simple necine derivatives supinidine and as the dominant compound subulacine (1β,2β-epoxytrachelanthamidine). In both plant species, the PAs are stored as N-oxides, except C. pumila seeds, which accumulate the free bases. Great variation in PA composition was observed between local populations of C. pumila. The PA profiles were established for larvae and adults of E. acrea that as larvae had fed on an artificial diet supplemented with crotalaria-powder and of G. geneura fed with S. longilobus. In both experiments, the larvae had a free choice between the respective PA source and diet or food plants free of PAs. The profiles compiled for the two species reflect the alkaloid profiles of their PA sources with one exception, subulacine could never be detected in E. acrea. Besides acquired PAs, insect PAs synthesized from acquired necine bases and necic acids of insect origin were detected in the two arctiid species. These insect PAs that do not occur in the larval food sources accounted for some 40–70% (E. acrea) and 17–37% (G. geneura) of total PAs extracted from the insects. A number of novel insect PAs were identified. Plant-acquired and insect PAs were found to accumulate as N-oxides. The results are discussed in relation to specific biochemical, electrophysiological, and behavioral mechanisms involved in PA sequestration by arctiids.

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Authors and Affiliations

  1. Institut für Pharmazeutische Biologie, Technische Universität Braunschweig, Mendelssohnstrasse 1, D-38106, Braunschweig, Germany

    T. Hartmann, C. Theuring & T. Beuerle

  2. NMR-Laboratorium der Chemischen Institute, Technische Universität Braunschweig, D-38106, Braunschweig, Germany

    L. Ernst

  3. Department of Entomology, University of Arizona, Tucson, Arizona, 85721, USA

    M. S. Singer & E. A. Bernays

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  1. T. Hartmann
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  2. C. Theuring
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  3. T. Beuerle
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  4. L. Ernst
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  5. M. S. Singer
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  6. E. A. Bernays
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Correspondence to T. Hartmann.

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Hartmann, T., Theuring, C., Beuerle, T. et al. Acquired and Partially De Novo Synthesized Pyrrolizidine Alkaloids in Two Polyphagous Arctiids and the Alkaloid Profiles of Their Larval Food-Plants. J Chem Ecol 30, 229–254 (2004). https://doi.org/10.1023/B:JOEC.0000017975.16399.c3

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