Senecio jacobaea, pyrrolizidine alkaloids

Macel G L, Klinkhamer P, Vrieling K and van der Meijden E (2002), Diversity of pyrrolizidine alkaloids in Senecio species does not affect the specialist herbivore Tyria jacobaeae , Oecologia, 133, 541-550. 

Pelser, P. B., Vos de, H., Theuring, C Beuerle, T., Vrieling, K. and Hartmann, T. 2005. Erequent gain and loss of pyrrolizidine alkaloids in the evolution of Senecio section Jacobaea (Asteraceae). Phytochemistry, 66 1285-1295. 

The presence of pyrrolizidine alkaloids in arctiid moths that had been reared on Senecio and Crotalaria species has been established by Rothschild et al.4S These alkaloids are stored in the moths, and serve as a deterrent to vertebrate predators and as precursors for insect sex pheromones. A pyrrolizidine alkaloid metabolite from the Cinnabar moth (Tyria jacobaea L.), named callimorphine, has been shown to have the structure (49) on the basis of mass-spectral and degradative evidence.46 The structure (49) was confirmed by synthesis of callimorphine and a diastereo-isomer by treatment of 9-chlororetronecine with the sodium salt of ( )-2-acetoxy-2-methylbutanoic acid. 

Fig. 13.14 The reversed phase HPLC-ESI-MS base ion (mjz 200-500) chromatograms for, and structures of some pyrrolizidine alkaloids identified in extracts of Senecio jacobaea and S. ovatus. The peak labels are referred to in the text.

Many species of Senecio, such as Senecio jacobaea (ragwort) and Senecio longilobus (thread leaf groundsel), contain hepatotoxic amounts of pyrrolizidine alkaloids (which are covered in a separate monograph). Honey made from Senecio plants also contains pjrrolizidine alkaloids (32). 

Analyses of the cinnibar moth, Tyria jacobaeae, revealed an interesting example for sequestration of defensive terpenoids. As with many other moths found within the family Actiidae, larvae of this species are able to sequester pyrrolizidine alkaloids (also see Section 2.04.6.4) from their plant host, in this case species from the genus Senecio. A population of T. jacobaeae was recendy identified, however, which lives on plants from the genus Petasites, from which it instead sequesters terpenoids such as petasol (26) and related compounds (Figure 9). ... 

An interesting sidelight on the metabolism of pyrrolizidines is that several butterfly and moth larvae that feed on plants containing these alkaloids metabolize them to products that serve the insects as pheromones or defensive substances. Thus the butterfly Idea leuconoe converts alkaloids from Parsonia laevigata to N-oxides [121]. The moth Creatonotos transiens makes its pheromone, R(-)-hydroxydanaidal from7(S)-heliotrine found in its host plant, Senecio jacobaea [122]. 

A large-scale extraction apparatus, employing ion-exchange resins, has been used for extracting pyrrolizidine alkaloids from Senecio jacobaea. Isolation of platy-phylline and seneciphylline (36) by electrodialysis of an extract from 5. platyphyl-loides has been achieved by Russian workers. Purification of the alkaloidal mixture was aided by electrochemical reduction of the extract. H.p.l.c. has been used to separate alkaloidal extracts from S. vulgaris S. longilobus ( = S.douglasii), and S. jacobaea. The major alkaloids were identified by mass... 

Serious livestock poisoning episodes are mentioned in literature from the effects of the pyrrolizidine alkaloid of the Senecio genus, especially Senecio riddellii, Senecio douglasii, and Senecio jacobaea The toxicity of... 

Kirk H, Vrieling K, Van der Meijden E, Klinkhamer PGL. Species by environment interactions affect pyrrolizidine alkaloid expression in Senecio jacobaea, Senecio aquatilis, and their hybrids. J Chem Ecol 2010 36(4) 378-87. 

Dimenna GP, Krick TP, Segall HJ (1980) Rapid high-performance liquid chromatography isolation of monoesters, diesters and macrocyclic diester pyrrolizidine alkaloids from Senecio jacobaea an Amsinckia intermedia. J Chromatogr 192 474-478 Edgar JA, Culvenor CCJ (1974) Pyrrolizidine ester alkaloid in danaid butterflies. Nature 248 614-616... 

Pyrrolizidine alkaloids also occur in honey made from Senecio jacobaea (tansy ragwort) and in milk of cattle that feed on this plant. 

Pyrrolizidine alkaloids Senecionine (D 17.1) Taken up by larvae of the moth s Arctia caja and Tyria jacobaeae from food source Senecio sp.), stored in the body, deterring birds... 

Vrieling K, van Wijk CAM (1994) Cost assessment of the production of pyrrolizidine alkaloids in ragwort (Senecio jacobaea L.). Oecologia 97 541-546... 

Crews C, Ehiffield M, Berthiller F, Krska R (2009) Loss of pyrrolizidine alkaloids on decomposition of ragwort (Senecio jacobaea) as measured by LC-TOF-MS. J Agric Food Chem 57 3669-3673... 

Hoi WHG, van Veen JA (2002) Pyrrolizidine alkaloids from Senecio jacobaea affect fimgal growth. J Chem Ecol 28 1763-1772... 

Deinzer ML, Thomson PA, Bingett DM, Isaacstm DL (1977) Pyrrolizidine alkaloids their occurrence in honey from tansy ragwort (Senecio jacobaea L.). Science 195 497-499... 

Macel, M., Vrieling, K. and Klinkhamer, P.G. (2004) Variation in pyrrolizidine alkaloid patterns of Senecio jacobaea. Phytochemistry, 65, 865-873. 

The ornate moth Utethesia ornatrix produces (i )-(-)-hydroxydanaidal (Figure 10.4) from pyrrolizidine alkaloids like monocrotaline N-oxide, and uses it as a sex attractant for females as the danaid butterflies do. The aphid Aphis jacobaeae also feeds on Senecio plants and stores these alkaloids. The ladybird Coccinella septempunctata (Plate 3) feeding on the aphids accumulates the pyrrolizidine alkaloids in turn, but does not accumulate cardiac glycosides (see earlier). 

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