FAST ATOM BOMBARDMENT MASS SPECTROMETRY OF BIOLOGICAL COMPOUNDS (INSULIN, FABMS)
Abstract
Fast atom bombardment was spectrometry (FABMS) is a relatively new analytical tool, yet it has already had a dramatic impact on analytical chemistry in general and mass spectrometry in particular. Since its commercial introduction in 1981, there has been a virtual explosion in its applications. There are few, if any, organic or inorganic classes of compounds to which FABMS has not been applied. This dissertation expounds the application of FABMS to peptides (Part I), nucleotides and acridines (Part II), and organometallic complexes (Part IV). A specific study into the ionization processes and matrix-analyte interactions in FABMS is also presented (Part III). The peptides examined in Part I are all insulins or insulin-like compounds. A new method of pepsin digestion/reverse phase high-performance liquid chromatography (HPLC)/FABMS is described. New human insulin B-chain structures and human insulin degradation products are proposed. Part II presents background mass spectral data for the further study on the mutagenic activity of the acridines. Nucleotides, nucleosides, protected nucleotides, and acridines were analyzed to provide a data base for future studies of acridine-DNA interactions. In Part III inorganic salts are primarily used to study ionization processes and matrix-analyte interactions. Direct desorption of performed ions, fragmentation processes, and metal reduction are observed. Using glycerol as a matrix, structural rearrangements showing strong glycerol-analyte interactions are proposed. Part IV shows the limitations of using FABMS for analysis of technetium (Tc)-complexes. Although some of the spectra implied the presence of polynuclear species, the anionic complexes displayed a tendency to decompose upon irradiation. These data show a few of the broad range of topics which can be addressed using FABMS. Many analytical problems previously anathematical to mass spectroscopists have become essentially routine. FABMS has been shown to be a valuable analytical tool for analysis of proteins, nucleotides, acridines, and inorganic salts, but to be of limited value for analysis of Tc complexes.
Degree
Ph.D.
Subject Area
Pharmacology
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