Identification of Ergobine, a New Natural Peptide Ergot Alkaloid

Perellino, Nicoletta Crespi; Małyszko, Jan; Ballabio, Marzia; Gioia, B.; Minghetti, A.

doi:10.1021/np50094a006

Cited by 8 publications

(6 citation statements)

References 4 publications

(5 reference statements)

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“…(Whichever was the ancestral ergopeptine cannot be discerned from the available data.) Remarkably, LpsA neofunctionalization appears to have accelerated dramatically in the Claviceps clade to give vast majority of known ergopeptines shown in Figure 3 (Blaney et al 2003; Cvak et al 1994, 1996, 2005; Eleuterius and Meyers 1977; Komarova and Tolkachev 2001; and references therein; Perellino et al 1993). …”

Section: Evolution Of Ergot-alkaloid Biosynthetic Pathwaysmentioning

confidence: 99%

Ergot Alkaloids of the Family Clavicipitaceae

2017

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Ergot alkaloids are highly diverse in structure, exhibit diverse effects on animals, and are produced by diverse fungi in the phylum Ascomycota, including pathogens and mutualistic symbionts of plants. These mycotoxins are best known from the fungal family Clavicipitaceae and are named for the ergot fungi that, through millennia, have contaminated grains and caused mass poisonings, with effects ranging from dry gangrene to convulsions and death. However, they are also useful sources of pharmaceuticals for a variety of medical purposes. More than a half-century of research has brought us extensive knowledge of ergot-alkaloid biosynthetic pathways from common early steps to several taxon-specific branches. Furthermore, a recent flurry of genome sequencing has revealed the genomic processes underlying ergot-alkaloid diversification. In this review, we discuss the evolution of ergot-alkaloid biosynthesis genes and gene clusters, including roles of gene recruitment, duplication and neofunctionalization, as well as gene loss, in diversifying structures of clavines, lysergic acid amides, and complex ergopeptines. Also reviewed are prospects for manipulating ergot-alkaloid profiles to enhance suitability of endophytes for forage grasses.

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Section: Evolution Of Ergot-alkaloid Biosynthetic Pathwaysmentioning

confidence: 99%

Ergot Alkaloids of the Family Clavicipitaceae

2017

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“…The known "ergot alkaloids" produced by Clauiceps spp. may be divided into five major classes: the clavine, lysergic acid, simple lysergic acid amides, ergopeptine, and ergopeptam alkaloids (Berde and Schild, 1978;Perellino et al, 1992Perellino et al, , 1993. The ergopeptines, simple lysergic acid amides, and clavines (Figures 1, 5, and 6 ) have been isolated from A. coenophialum-infected tall fescue (Yates et al, 1985;Lyons et al, 1986;Petroski and Powell, 1991).…”

Section: A Coenophialum-infected Fescuementioning

confidence: 99%

“…The major advantages of TLC are that several samples may be analyzed at the same time, TLC does not involve expensive instrumentation, and it may be used as a complement to MS in the confirmatory identification and analysis of mixtures of epimeric alkaloids (see below). Perellino et al (1993) have reported a TLC procedure on silica gel for the separation of most all of the known ergot alkaloids. By developing the TLC plates in methylene chloride: isopropyl alcohol (92:8, vol/vol) three times (drying the plates between runs), these alkaloids separate into the isolysergic acid group (i.e., -inine epimers), the ergotoxine group, the ergoxine group, and a mixture of the ergotamine and clavine groups.…”

Section: A Coenophialum-infected Fescuementioning

confidence: 99%

“…The major fragments used to identify the known ergopeptine alkaloids by this method are outlined in Table 1. Although ergovaline and its C-8 epimer ergovalinine produce the same three major fragments at 268 (AH), 267 (BH), and 197 ( C H ) amu and cannot be distinguished by this method, both compounds ( a s with the other ergopeptines and their C-8 epimers) separate nicely using TLC and(or) HPLC analysis (Porter et al, 1974(Porter et al, , 1979Yates and Powell, 1988;Rottinghaus et al, 1991Rottinghaus et al, , 1993Perellino et al, 1993). Tandem mass spectrometry (Plattner et al, 1983) also has been employed in the separation and analysis of ergopeptine alkaloids from both endophyte-infected tall fescue and perennial ryegrass (Yates et al, 1985;Lyons et al, 1986;Rowan and Shaw, 1987).…”

Section: Mass Spectrometry Identification and Quantitativementioning

confidence: 99%

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Analysis of endophyte toxins: fescue and other grasses toxic to livestock

1995

Journal of Animal Science

162

110

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Research on livestock toxicoses caused by Acremonium (endophyte)-infected grasses strongly implicate the ergopeptine alkaloids with A. coenophialum-infected fescue and paxilline and the lolitrem alkaloids with A. lolii-infected perennial ryegrass as the causative agents. Isolation, identification, and detection of these toxins involves extraction with appropriate solvents, clean-up procedures, and chromatographic methods with known standards. Thin-layer, high-performance liquid and gas chromatography along with ultraviolet and mass spectrometric (i.e., electron impact, chemical ionization, tandem mass) characterizations have been reported. These methods have varying degrees of success depending on the matrix from which the alkaloids have been extracted. Ergovaline is the primary ergopeptine alkaloid isolated from cultures of A. coenophialum and also from infected fescue grass and seeds toxic to livestock. Other compounds isolated from the endophyte-infected fescue include: lysergic acid amide (ergine), the clavine class of ergot alkaloids (chanoclavine I, agroclavine, elymoclavine, penniclavine), the pyrrolizidine alkaloids (N-formylloline, N-acetylloline, N-methyloline, N-acetylnorloline), and the unique pyrrolopyrazine alkaloid peramine. The loline alkaloids and peramine have been more associated with the insect-deterrent properties of the endophyte-infected fescue than with livestock toxicoses. Also, both peramine and the ergopeptine alkaloids (ergovaline, ergotamine) have been isolated from A. lolii-infected perennial ryegrass. More recently, paxilline and lolitrem B have been detected in laboratory cultures of A. coenophialum isolated from tall fescue. The ergot alkaloids in endophyte-infected perennial ryegrass may be more related to decreased animal productivity (weight gains, reproduction problems), whereas the lolitrems cause the staggers syndrome. The detection, isolation, identification, and analyses of these compounds from Acremonium-infected grasses is presented.

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“…These assignments were confirmed by long-range 1 H− 13 C correlation of the α-protons with both β- and γ-carbons and the correlations of the N -H with the α-carbon in each residue. Configurations of the remaining asymmetric centers, as shown, are the same as for the regular series of ergopeptines; − however, absolute configurations at the 2‘, 5‘, 8‘, and 9‘ positions of 1 remain to be determined.…”

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confidence: 99%