Several studies concerning the analysis and quantification of biologic
al and pharmaceutical compounds have been effected during the past 20-
30 years using different techniques of desorption-ionization. In most
cases, however, the authors have not been interested in the mass spect
rometric fragmentation mechanisms of these products. Plasma desorption
mass spectrometry (PDMS) is a powerful technique for analysing, witho
ut matrix interferences, solid biological and pharmaceutical compounds
. In this work, we use PDMS in order to study the influence of the ami
ne (amide) function on the fragmentation processes of nitrogen-contain
ing compounds. For this work, quaternary ammonium salts, trisubstitute
d amines, disubstituted amines and a compound with an amide function w
ere chosen. Classical PD mass spectra, accurate mass measurements, tra
nsitions in the field free region (FFR), labelled compound spectra and
thermodynamical data are reported for the structural study of these c
ompounds. Our results allow us to propose fragmentation rules for posi
tively charged polyfunctional biological nitrogen compounds. These rul
es relate to a class of structurally informative decomposition reactio
ns that can be applied to the determination and of identification of s
tructural unknowns.