ergoline and ergosine

Cereals and feed contaminated with ergot alkaloids (EAs) have been of concern for several decades. Nowadays, analysis of EAs is focused on ergometrine, ergotamine, ergosine, ergocristine, ergocryptine (a mixture of α- and β-isomers) and ergocornine and their related -inine epimers as listed in the European Commission Recommendation 2012/154/EU. Liquid chromatography with fluorescence detection has been used for quantification of EAs for decades whilst LC-MS has become the work-horse for quantification of EAs in the last decade. However, in LC-MS analysis matrix effects of different magnitudes exist for each EA epimer, especially ergometrine/ergometrinine, even after different clean-up procedures. This leads to an underestimation or overestimation of EAs levels. Moreover, isotopic labelled standards for EAs are still not available in the market. This review aims to provide background information on different analytical methods, discuss their advantages and disadvantages and possible advancement. Moreover, the method performance requirements to support forthcoming regulations are also discussed.

Topics: Chemical Fractionation; Chromatography, High Pressure Liquid; Edible Grain; Ergolines; Ergot Alkaloids; Ergotamines; Food Contamination; Humans; Lipids; Spectrometry, Fluorescence; Tandem Mass Spectrometry; Toxins, Biological

The natural occurrence of six major ergot alkaloids, ergometrine, ergosine, ergotamine, ergocornine, ergokryptine and ergocristine, as well as their corresponding epimers, were investigated in 60 cereal samples (barley and wheat) from Algeria. Ultra-high performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) and a QuEChERS extraction method were used for sample analysis. The results revealed that 12 out of 60 samples (20%) were contaminated with ergot alkaloids. Wheat was the most contaminated matrix, with an incidence of 26.7% (8 out of 30 samples). The concentration of total ergot alkaloids ranged from 17.8 to 53.9 µg/kg for barley and from 3.66 to 76.0 μg/kg for wheat samples. Ergosine, ergokryptine and ergocristine showed the highest incidences in wheat, while ergometrine was the most common ergot in barley.

Topics: Algeria; Chromatography, High Pressure Liquid; Ergolines; Ergonovine; Ergot Alkaloids; Ergotamine; Ergotamines; Food Microbiology; Hordeum; Limit of Detection; Tandem Mass Spectrometry; Triticum

Topics: Avena; Carbonates; Chromatography, High Pressure Liquid; Ergolines; Ergonovine; Ergot Alkaloids; Ergotamines; Food Contamination; Functional Food; Solid Phase Extraction; Tandem Mass Spectrometry

In the present study, the genetic relationships and ergot-alkaloid production of the fungus Claviceps purpurea on grasses were investigated, to determine any associations between grass host specificity, ergot-alkaloid production, and geographic origin. C. purpurea sclerotia were obtained from wild and cultivated grasses along a 300-km climatic gradient, from sub-Mediterranean to continental climates. Twenty-one infected grass samples provided 39 sclerotia for analysis of the ergot alkaloids ergometrine, ergosine, ergotamine, ergocornine, ergocryptine, and ergocristine, and their "-inine" epimers, using liquid chromatography-tandem mass spectrometry. C. purpurea ribosomal DNA underwent molecular classification to determine any grass host or geographic specificity of ergot-alkaloid composition for the different operational taxonomic units. Molecular analysis of sclerotia ribosomal DNA showed three genetic groups, with some associations with specific grass host taxonomic groups. The ergot-alkaloid composition data were in agreement with the data obtained by molecular methods. The most frequent ergot-alkaloid epimers were ergocristine, and ergosine. The total ergot-alkaloid concentrations in sclerotia varied from 59 to 4,200 mg kg

Topics: Chromatography, High Pressure Liquid; Claviceps; DNA, Fungal; DNA, Ribosomal Spacer; Ergolines; Ergonovine; Ergot Alkaloids; Ergotamine; Ergotamines; Host Specificity; Phylogeny; Plant Diseases; Poaceae; Sequence Analysis, DNA; Slovenia; Tandem Mass Spectrometry

Ergot is a common disease of wheat and other cereal grains that is predominantly caused by Claviceps purpurea in the field, often affecting crop yield in addition to the environment. Infected grain can be contaminated with dark sclerotia, which contain fungal metabolites such as ergot alkaloids. The occurrence of ergot alkaloids in cereal grain is a major health concern for humans and livestock. Effective and rapid screening of these mycotoxins is crucial for producers, processors, and consumers of cereal-based food and feed grain. Established methods of ergot alkaloid screening based on LC-MS or GC-MS require laborious processes. A novel method using matrix-assisted laser desorption ionization (MALDI)-time-of-flight (TOF) MS was developed to identify four ergot alkaloids. Using dihydroxybenzoic acid as the matrix, ergosine, ergocornine, ergocryptine, and ergocristine were readily detected in individual sclerotia of C. purpurea. The accuracy of the identified ergot alkaloids was further confirmed by tandem MS analysis. MALDI-TOF MS is suitable for high-throughput screening of ergot alkaloids because it permits rapid and accurate identification, simple sample preparation, and no derivatization or chromatographic separation.

Topics: Claviceps; Ergolines; Ergot Alkaloids; Ergotamines; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Tandem Mass Spectrometry

An analysis of the 70 eV electron impact (EI) and fast atom bombardment (FAB) mass spectral features of a variety of ergoline and dihydroergoline derivatives of therapeutic importance is presented with emphasis upon analytical utility. Derivatives which carry non-peptide based C-8 substituents are fully characterized by EI-MS through provision of molecular wieght evidence and fragment ions diagnostic of both the ergoline skeleton and the C-8 substituent. Peptidic ergolines and dihydroergolines are poorly characterized by EI-MS, but their FAB-MS clearly reveal [M + 1]+ (high intensity) and [M - 1]- (high to low intensity) ions in positive and negative ion spectra, respectively. Negative FAB spectra of salts also display diagnostic anion-base conjugate ions.

Topics: Bromocriptine; Ergolines; Ergotamine; Ergotamines; Molecular Weight; Spectrometry, Mass, Fast Atom Bombardment

We determined the vasoconstrictive effects of selected ergot alkaloids, and a sample containing loline and its derivative alkaloids, on the isolated dorsal pedal vein of cattle, as a model system to study one of the toxic effects that result from cattle ingesting fescue forage infected with the endophytic fungus Acremonium coenophilalum. The ergot compounds ergotamine, ergosine, and agroclavine constricted this peripheral vein of cattle, but much less so than did the alpha-adrenergic agonist norepinephrine, which supports the ergots acting as partial agonists for these receptors. However, the sample of loline and loline-derivative alkaloids did not affect the dorsal pedal vein when given at concentrations similar to those of the ergot compounds. Loline and loline-derivative alkaloid sample at high concentrations partially inhibited norepinephrine-elicited vascular contraction, an effect that appeared to be unrelated to alpha-adrenoceptor activity. Thus, in the dorsal pedal vein model in cattle, the ergopeptide alkaloids were more venoconstrictive than were loline and its derivative alkaloids.

Topics: Acremonium; Alkaloids; Animals; Cattle; Dose-Response Relationship, Drug; Ergolines; Ergot Alkaloids; Ergotamine; Ergotamines; Hindlimb; Norepinephrine; Poaceae; Vasoconstriction; Veins

The total alkaloid content and individual alkaloid composition were determined by colorimetry and high performance liquid chromatography, respectively, for Canadian wheat ergot sclerotia. The total alkaloid content was highly variable between individual sclerotia from the same or different sources and ranged from 0.013 to 0.307%; the overall average for bulked samples from 75 sites was 0.163%. Ergocristine and its isomer ergocristinine were the major constituents (approximately 46%). Other alkaloid pairs observed were ergotamine (approximately 17%), ergocryptine (approximately 12%), ergocornine (approximately 11%), ergometrine (approximately 7%), and ergosine (approximately 5%), plus about 2% unidentified alkaloids.

Topics: Canada; Claviceps; Ergolines; Ergonovine; Ergot Alkaloids; Ergotamine; Ergotamines; Plant Diseases; Secale; Species Specificity; Triticum