Chemotypes of two pyrrolizidine alkaloid-containing Senecio species

doi:10.1016/0031-9422(92)90038-R

Phytochemistry

Volume 31, Issue 2, February 1992, Pages 559-565

https://doi.org/10.1016/0031-9422(92)90038-R Get rights and content

Abstract

Evaluation of the pyrrolizidine alkaloids (PAs) of more than 100 populations of Senecio jacobaea and of ca 25 populations of S. erucifolius from different geographic locations revealed the existence of different chemotypes. Two chemotypes were established within each species. They are for S. jacobaea, (a) ‘jacobine chemotype’ with jacobine and its derivatives as major PAs, representing the well known ‘classical’ PA pattern of this species. (b)‘erucifoline chemotype’, with erucifoline and O-acetylerucifoline as dominating PAs, and for S. erucifolius, (a) ‘erucifoline chemotype’, erucifoline and O-acetylerucifoline as major PAs. (b) ‘eruciflorine chemotype’, with eruciflorine (21-hydroxyintegerrimine) as dominating PA. Eruciflorine was identified as a novel PA. Its structure was elucidated by means of NMR and mass spectrometry. Individual populations representing the different chemotypes within the respective species are indistinguishable from their morphological characters.

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Species of the genera Senecio and Jacobaea, particularly tansy ragwort (Jacobaea vulgaris, syn. S. jacobaea) and marsh ragwort (J. aquatica, syn. S. aquaticus) have spread as weeds in Western and Central Europe in poorly managed pastures and meadows during the last decades. Due to high level of numerous toxic pyrrolizidine alkaloids and their N-oxides (PAs) in contaminated forage they present a threat for livestock. Horses are of the greatest risk, while ruminants are more resistant due to a partial detoxification in the rumen. The susceptibility decreases in order cattle, goats and sheep. The risk during grazing is limited because animals mostly avoid the unpalatable weeds. During feeding stabled animals with cut fresh forage, hay or silage the risk however lasts. Haymaking preserves the PAs, whereas ensiling partly decreases their level. The carry-over to milk is dose-related and seems to be low. Even the observed low PA levels in cow milk may be of concern for human health as regards hepatotoxic and genotoxic properties. Recent data on PAs chemistry, toxicity, factors affecting their content, composition and distribution within the Senecio/Jacobaea plants, changes in silage and hay and carry-over to milk are reviewed.
Pyrrolizidine alkaloids and unusual millingtojanine A-B from Jacobaea vulgaris (syn. Senecio jacobaea L.)
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Four undescribed pyrrolizidine alkaloids (seneciojanine A-D), two enantiomeric pairs of unusual alkaloids (millingtojanine A-B) with a unique tricyclic core, and nine known pyrrolizidine alkaloids were isolated from whole plant extracts of Jacobaea vulgaris Gaertn. The structures of the undescribed compounds were established by extensive spectroscopic and spectrometric analyses and comparison of theoretical and experimental ECD data. Several of the structures were also confirmed by X-ray diffraction analysis. Seneciojanine A-D possess a rare natural necine moiety with an α,β-unsaturated carbonyl group located at C-3 and a hydroxyl substituent at C-8.
Biodegradation and utilization of crop residues contaminated with poisonous pyrrolizidine alkaloids
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Citation Excerpt :
In general, the total PA content was fairly similar to that observed for the Rostock plant material of 796 mg/kg (d.w.). The differences of the PA-composition of the identical plant species from two different locations is striking, but especially for S. jacobaea this is well known and documented as due to two different chemotypes (Macel et al., 2004; Witte et al., 1992), here representing the jacobine chemotype and the erucifoline chemotype as classical cases for Braunschweig and Rostock, respectively. Although quite different in their individual PA patterns, both chemotypes are characterized by closely related structures, all belonging to the PA-subclass of the senecionine-type-PAs consisting of macrocyclic (12-membered ring), 1,2-unsaturated retronecine-type diester PAs (Fig. 1A and B), one of the largest and most diverse class of PAs (Hartmann and Witte, 1995).
Disposal of noxious plant residues is a challenge for farmers and land management dealing with contaminated biomasses. Recent studies confirm the potential threat of transferring toxic plant constituents like pyrrolizidine alkaloids (PAs) from plant residues to non-toxic succeeding agricultural crops via the soil.
We studied the degree of biochemical degradation of PAs in the two most important processes, composting and biomethanization. We used lab composting and biogas batches to investigate the potential of PA-degradation of two common PA-containing plants, Lappula squarrosa and Senecio jacobaea.
The experiments demonstrated a virtually complete loss of PAs in three months during the composting process and a rapid decomposition of PAs from 3112.6 μg/kg to less than 21.5 μg/kg in L. squarrosa and from 6350.2 μg/kg to less than 539.6 μg/kg in S. jacobaea during biomethanization. The information obtained is a first guide on how to re-utilize PA-contaminated plant matter in a circular bioeconomy.
Genetic and chemical diversity of the toxic herb Jacobaea vulgaris Gaertn. (syn. Senecio jacobaea L.) in Northern Germany
2020, Phytochemistry
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J. vulgaris is one of the species that produce PAs and this becomes relevant for protection against generalist herbivores. Previous studies detected 27 different PAs in J. vulgaris (Joosten et al., 2011): the major ones are jacoline, jacozine, jacobine, seneciphylline, senecionine and erucifoline (Crews et al., 2009; Witte et al., 1992). Depending on the major PAs they contain, two different chemotypes were defined.
Tansy ragwort, Jacobaea vulgaris Gaertn. (syn. Senecio jacobaea L.), is a common Asteraceae in Europe and Asia and known to be an invasive pest in several regions in the world. Recently it is also spreading immensely in native regions like Northern Germany. Pyrrolizidine alkaloids (PAs), which are found in high amounts in Jacobaea vulgaris, are toxic for humans and potentially lethal for grazing animals. In this study we investigated 27 populations of tansy ragwort in Northern Germany for their PA concentration and composition using liquid chromatography coupled to high resolution mass spectrometry. Furthermore, we investigated the genetic structure of selected populations using amplified length polymorphism markers. We detected 98 different PAs in the samples and considerable differences of PA composition between populations. In contrast, PA content of populations did not differ significantly. Genetic (4%) differentiation among populations was low while average genetic diversity was high (0.35). There was no correlation between genetic and geographic distance. Neither genetic markers nor chemical composition revealed any connection to the geographic pattern. As we could not detect any pattern in genetic or chemical diversity, we suggest that the existence of this diversity is a result of a broad interaction with the environment rather than that of evolutionary constraints in the current selection process driving PA composition in J. vulgaris in certain chemotypes.
Local adaptation in oviposition choice of a specialist herbivore: The cinnabar moth
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The content of pyrrolizidine alkaloids (PAs), a diverse but structurally-related group of secondary metabolites in ragwort, differs between the two areas. Coastal ragworts are often rich in jacobine-like PAs while those rich in erucifoline-like PAs are predominant in inland ragworts (Witte et al., 1992; Vrieling and Boer, 1999; Macel et al., 2004). To test whether the different habitats of ragworts selected for different oviposition strategies of the cinnabar moth, we used moth populations from Meijendel, a regularly defoliated coastal area and Bertogne, a rarely defoliated inland area.
Specialist herbivores feed on a restricted number of related plant species and may suffer food shortage if overexploitation leads to periodic defoliation of their food plants. The density, size and quality of food plants are important factors that determine the host plant choice of specialist herbivores. To explore how all these factors influence their oviposition behaviour, we used the cinnabar moth Tyria jacobaeae and the hybrids of a cross between Jacobaea vulgaris and J. aquatica as a study system. While defoliation by the cinnabar moth is common in the coastal area of The Netherlands, it is relatively rare in inland ragwort population. Ragworts contain pyrrolizidine alkaloids (PAs) and those that are found in coastal areas are rich in jacobine-like PAs while those that occur inland are rich in erucifoline-like PAs. We tested how the oviposition preference was influenced by plant size, nitrogen and water content and PA composition. We used cinnabar moth populations from a regularly defoliated area, Meijendel, and Bertogne, a rarely defoliated area. Our results revealed no effects of nitrogen or water content on oviposition preference. Moths from both populations laid larger egg batches on the plants rich in jacobine-like PAs. Moths from Meijendel preferred larger plants and spread their eggs over more egg batches that were, on average, smaller than those of Bertogne moths. These results suggest that Meijendel moths adopted a oviposition strategy to cope with potential defoliation.
Characterisation and pathogenicity of Fusarium taxa isolated from ragwort (Jacobaea vulgaris) roots
2016, Fungal Ecology
Citation Excerpt :
The seeds also have extended persistence in the seed bank, remaining viable for up to 10 yr (Harper, 1958). Both fresh and dried ragwort plants may contain between 10 and 12 pyrrolizidine alkaloids (PAs), which are toxic to grazing livestock, particularly horses (Witte et al., 1992; Prakash et al., 1999). Consumption of PAs results in severe liver damage in susceptible animals and may lead to death (Mattocks, 1986).
We characterised the fungi isolated from necrotic lesions observed on roots of the noxious weed Jacobaea vulgaris and assessed their host range. ITS–rDNA sequence data identified twenty-one isolates of Fusarium and TEF-1α sequencing separated these isolates into four clades namely Fusarium avenaceum/Fusarium acuminatum, Fusarium redolens, Fusarium culmorum/Fusarium cerealis and Fusarium solani. Representatives of each clade were tested for virulence against ragwort seedlings. All isolates in the F. avenaceum/F. acuminatum clade caused visible disease symptoms. Host range of three isolates was tested using six pasture grass species along with Trifolium pratense and Trifolium repens. No disease symptoms were detected on the grasses. All three isolates, however, caused disease symptoms on T. repens, and two isolates also attacked T. pratense. The results demonstrate that several species of Fusarium can colonise ragwort roots but only isolates from one clade cause significant disease symptoms on ragwort seedlings.

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Chemotypes of two pyrrolizidine alkaloid-containing Senecio species

Abstract

Toxicol. Letters

Toxicol. Letters

Phytochemistry

J. Plant Physiol.

Naturwissenschaften

Z. Naturforsch.

J. Chromatogr.

Magn. Reson. Chem.

Collec. Czech. Chem. Commun.

Collec. Czech. Chem. Commun.

J. Toxicol. Enuiron. Health

Monath. Chem.