It is shown by deuterium labelling, linked-scan measurements and collision activation that the [M -C,H,'I+ (a-cleavage) ion in the electron impact ionization spectrum of tributylamine loses C3H, with transfer of one hydrogen specifically from the y-position. The experimental data point towards a mechanism which involves the intermediate formation of a distonic diradical ion from an excited a-cleavage ion which then eliminates the neutral alkene.
A mass spectrometric screening method for barbiturates in serum was developed. Under electron impact conditions barbiturates fragment by loss of HNCO. A 'constant neutral loss' scan of 43 u provides, therefore, an indication of the presence of members of this toxicologically relevant class of compounds. Subsequent identification is possible either by 'daughter' or by 'parent ion' scans. The detection limit for propallylonal, buto- and phenobarbital was determined as better than 1 micrograms ml-1 serum.
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