Advances in Fast Atom Bombardment Mass-Spectrometry (Glycosphingolipids, Nucleotides, Markers, Negative Ion)

Abstract

180 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1986.The capabilities and limitations of the recently introduced technique of fast atom bombardment mass spectrometry were explored. A comparison of fast atom bombardment and field desorption mass spectrometry was made to determine relative sensitivity and applicability. A series of glycosphingolipids and a series of protected oligonucleotides of known structure were analyzed to ascertain the potential utility of fast atom bombardment mass spectrometry in the structural elucidation of novel compounds in these classes. Negative ion mass markers, necessary for accurate mass measurements of the aforementioned classes of compounds and in newly proposed scanning accurate mass measurement methods, were also developed.Fast atom bombardment was found to be one-to-two orders of magnitude more sensitive than field desorption based on the analysis of a limited number of compounds from several classes. Superior sensitivity was not universal and field desorption was clearly better in certain cases. In the negative ion mode in particular, fast atom bombardment was found to be a useful tool for the determination of the primary structure of glycosphingolipids and oligonucleotides. Carbohydrate sequence and branching information, and fatty acid and lipid base composition were readily obtained from the mass spectra of glycosphingolipids while bidirectional nucleotide sequence, nucleotide base, and protecting group assignments were obtained for oligonucleotides. Based on this knowledge, a tentative structure of a human peripheral nervous system glycosphingolipid implicated in certain cases of disorders such as amyotrophic lateral sclerosis, Lou Gehrig's Disease, was proposed. Suitable negative ion mass markers were found in dispersions of poly(ethylene) and poly(propylene) glycols in a triethylenetetramine matrix, a matrix which also proved useful in the analysis of glycosphingolipids. These polyglycol dispersions provided ions for calibration to 2300 daltons.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD