Studies of ergot alkaloids using high-performance liquid chromatography-mass spectrometry andB/E linked scans

Abstract

A crude extract from an ergot fermentation broth has been examined by high-performance liquid chromatography mass spectrometry (LCIMS). The [Mcl]' ions formed from the mixture under chemical ionization conditions have also been studied using BIE linked scans with and without collision induced dissociation. Data obtained from high-performance liquid chromatography mass spectrometry have been used to identify 11 alkaloids in a mixture of at least 18 unknown molecules. BIE Linked scan spectra obtained with and without collision activated dissociation from pure samples proved useful in differentiating isomeric alkaloids and in providing stereochemical information. Problems were encountered in application of these latter techniques to studies of the crude extract; in particular in the identification of isomers and in the presence of peaks arising from fragment ions formed from higher mass alkaloids present in the mixture.

Quadrupole mass spectrometry/mass spectrometry of ergot cyclol alkaloids

“…For example, detection of ergosine or /S-ergosine and + H+, respectively, demonstrating that the alkaloids were being volatilized intact and that the fragments analyzed did indeed come from the alkaloid molecules. Eckers et al (1982) concluded from their linked B/E scan studies of ergot clavine alkaloids that the use of MS/MS alone for the study presented problems. They reported that isomeric mixtures were difficult to resolve and that interferences of fragment ions of other clavine alkaloids caused problems.…”

“…Also, the alkaloids as a class are not amenable to GC, so chromatographic cleanup of sample is necessary before mass spectrometric analysis. Recently, in a report dealing with HPLC/MS and B/E-linked scans of ergot clavine alkaloids (Eckers et al, 1982), LC/MS analysis of one of the cyclol alkaloids, ergokryptine, was reported. We have recorded quadrupole MS/MS spectra for 12 of the 14 known ergopeptine alkaloids (Bianchi et al, 1982) and report that all 12 can be differentiated by MS/MS experiments.…”

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

“…Eckers et al 7, 8 applied HPLC coupled via moving belt interface to EI‐ and CI‐MS to identify 11 known alkaloids in chloroform extracts of Claviceps purpurea ; this represented a step forward since HPLC is more amenable to clavine and ergopeptide compounds than GC. In a similar chromatographic advance, Porter's group9 combined thin‐layer chromatography with both EI‐ and CI‐MS by introduction of extracts from C. purpurea sclerotia by direct insertion to identify nine alkaloids in fescue, barley and wheat, with estimation of relative peptide alkaloid percentages from MS/MS data using the relative ratios of respective signals for the major daughter ion fragments.…”

Analytical techniques for trace organic compounds - VI. Application of liquid chromatography-mass spectrometry (Technical Report)

“…Alkaloids have been analyzed rather early in the development of LC/MS, and in an impressive study on ergot alkaloids the potential of the moving belt has been demonstrated ( 194). Recently, CFFAB (195) and thermospray has been used to study catharanthus alkaloids ( 196), castanospermine related alkaloids ( 197) and senecio alkaloids ( 198).…”