Mass Spectrometry Determination of Some Natural Clavines and Lysergic Acid Derivatives

Vokoun, J.; Sajdl, P.; Řeháček, Z.

doi:10.1016/s0044-4057(74)80016-x

Cited by 8 publications

(22 citation statements)

References 2 publications

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“…Voigt et al 4 applied electron impact mass spectrometry (EI‐MS) to similar clavines and ergopeptides via direct insertion probe to compare positive and negative ion modes, and dependably found ergopeptide M and M‐1 ions more easily by negative mode than by positive mode. Vokoun et al 5 carried out similar direct insertion EI‐MS of Δ 8–9 , Δ 9–10 and C8–9–10‐saturated clavines, which displayed intense M + ions, and ergopeptides, which did not, confirming the work of Barber et al ;3 spectra of C‐8 epimers were considered indistinguishable from one another. Porter and Betowski6 further expanded the repertoire of applied mass spectrometric techniques in reporting deconvolution of chemical ionization (CI) mass spectra of ergot alkaloids, claiming it a successful supplementary technique to EI‐MS which typically eliminates the molecular ion.…”

Section: Introductionsupporting

confidence: 53%

Electrospray[+] tandem quadrupole mass spectrometry in the elucidation of ergot alkaloids chromatographed by HPLC: screening of grass or forage samples for novel toxic compounds

et al. 2005

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Ergot alkaloids are mycotoxins generated by grass and grain pathogens such as Claviceps, for example. Ergot alkaloid-poisoning syndromes, such as tall fescue toxicosis from endophyte-infected tall fescue grass, are important veterinary problems for cattle, horses, sheep, pigs and chickens, with consequent impact on food, meat and dairy industries. Damage to livestock is of the order of a billion dollars a year in the United States alone. HPLC with UV and fluorescence detection are the predominant means of ergot alkaloid determination, with focus on quantitation of the marker compound ergovaline, although ELISA methods are undergoing investigation. These techniques are excellent for rapid detection, but of poor specificity in defining new or poorly characterized ergot alkaloids and related compounds. This paper demonstrates the facility of using electrospray(+) mass spectrometry with multiple reaction monitoring (MRM) detection during chromatographic examination of ergot alkaloid standards of lysergic acid, lysergol, ergonovine, ergovaline, ergotamine, ergocornine, ergocryptine and ergocrystine by HPLC. Ergoline-8 position epimers could be separated on the gradient HPLC system for ergocornine, ergocrystine and ergonovine and appeared as shoulders for ergotamine and ergovaline; epimers generally showed different patterns of relative intensity for specific MRM transitions. There was reasonable correspondence between retention of standards on the 2-mm ESI(+)MS phenyl-hexyl-based reverse phase column and those on the 4-mm C18-based column. Since up to 10% of clinical cases involving toxin exposure display unidentified chromatographic peaks, 11 samples of feed components associated with such cases were studied with developed MRM methods to attempt elucidation of crucial components if possible. Ergotamine appeared in all, ergovaline appeared in five and ergocornine appeared in six; ergonovine, ergocryptine, ergocrystine and lysergol also appeared in several. In addition, molecular weights of compounds newly revealed by mass spectrometry suggested ergosine, ergostine and ergoptine in four samples, for which standards were not available. Dehydrated products of ergotamine, ergocrystine and ergocornine were discovered, along with dihydrogenated ergocrystine and ergocryptine in seven of the samples, and the issue was raised as to whether dehydration was strictly an instrument-derived artifact. Finally, five of the samples, along with fescue seed standard, evidenced one or more of 14 new ergot alkaloids ranging in size from 381 to 611 molecular weight and with key mass spectral characteristics of ergot alkaloids, specifically the pair of peaks m/z 223 and 208, corresponding to the ergoline ring system and its demethylated variant, respectively. It is anticipated that findings such as these will provide impetus to future development of analytical methodology for these heretofore relatively rare ergot alkaloid species.

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Section: Introductionsupporting

confidence: 53%

Electrospray[+] tandem quadrupole mass spectrometry in the elucidation of ergot alkaloids chromatographed by HPLC: screening of grass or forage samples for novel toxic compounds

et al. 2005

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“…Dark-brown needles of 1 were filtered off, washed with ice-cold EtOH and Me 2 CO, and dried (yield 74%). The EIMS of the preparation was identical to that published previously, 9 and the NMR data are in qualitative agreement with previously published data of 1 in DMSO. 10 Lysergene (1): UV (MeOH) λ max (log ) 248 (4.22), 266 (sh, 4.07), 343 (4.01) nm; 1 H NMR (CDCl 3 ) δ 7.26 (1H, dd, J ) 6.8, 1.8 Hz, H-12), 7.24 (1H, dd, J ) 8.0, 1.8 Hz, H-14), 7.20 (1H, dd, J ) 8.0, 6.8 Hz, H-13), 6.98 (1H, m, H-9), 6.94 (1H, dd, J ) 2.0, 1.9 Hz, H-2), 5.07 (1H, m, H-17d), 4.96 (1H, m, H-17u), 3.52 (1H, ddd, J ) 14.6, 5.9, 0.5 Hz, H-4e), 3.51 (1H, d, J ) 13.2 Hz, H-7a), 3.62 (1H, dddd, J ) 11.4, 5.9, 2.0, 0.8 Hz, H-5), 3.22 (1H, ddd, J ) 13.2, 1.9, 1.8 Hz, H-7e), 2.77 (1H, ddd, J ) 14.6, 11.4, 1.9 Hz, H-4a), 2.59 (3H, s, N-Me); Feeding Experiments.…”

Section: Methodssupporting

confidence: 88%

“…Dark-brown needles of 1 were filtered off, washed with ice-cold EtOH and Me 2 CO, and dried (yield 74%). The EIMS of the preparation was identical to that published previously, and the NMR data are in qualitative agreement with previously published data of 1 in DMSO …”

Section: Methodssupporting

confidence: 88%

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Dimerization of Lysergene by Euphorbia calyptrata Cell Cultures

et al. 1996

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“…text). H20 + H), 206 (17), 196 (27), 183 (100), 168 (67), 167 (70), 155 (80), 154 (95), gave all indications that compound C was chanoclavine I (Cassady et al, 1973;Porter et al, 1979;Vokoun et al, 1974).…”

Section: Resultsmentioning

confidence: 99%

Ergosine, ergosinine, and chanoclavine I from Epichloe typhina

Porter¹,

Bacon²,

Robbins³

1979

J. Agric. Food Chem.

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Epichloé typhina, isolated from toxic K-31 tall fescue grass, was shown to produce ergot alkaloids in vitro. Ergosine, ergosinine, and chanoclavine I were isolated and identified by comparison with authentic standards with regard to thin-layer chromatography, ultraviolet absorption, and low-resolution mass spectra analyses. Total alkaloid production, colorimetrically determined as ergonovine maleate, was 5.5 mg/L for 28-day-old cultures. This is the first report of a fungus outside the genera of Claviceps and Balansia capable of producing alkaloids that are N-peptide-substituted amides of lysergic acid.The signs of the fescue toxicity syndrome have been described in cattle by Yates et al. (1971), in sheep by Biological Constituents Unit, Field

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Mass Spectrometry Determination of Some Natural Clavines and Lysergic Acid Derivatives

Cited by 8 publications

References 2 publications

Electrospray[+] tandem quadrupole mass spectrometry in the elucidation of ergot alkaloids chromatographed by HPLC: screening of grass or forage samples for novel toxic compounds

Electrospray[+] tandem quadrupole mass spectrometry in the elucidation of ergot alkaloids chromatographed by HPLC: screening of grass or forage samples for novel toxic compounds

Dimerization of Lysergene by Euphorbia calyptrata Cell Cultures

Ergosine, ergosinine, and chanoclavine I from Epichloe typhina

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