| dc.description | For more than two centuries, the medicinal potential of bismuth compounds has been exploited to yield positive health effects in humans. Pepto-Bismol RTM, De-NolRTM, and PyloridRTM are modern remedies for gastrointestinal ailments, containing bismuth subsalicylate, colloidal bismuth subcitrate, and ranitidine bismuth citrate, respectively. Given the strength of bismuth-sulfur bonds compared to bonds between bismuth and other heteroatoms, it is likely that sulfur is involved in biological transformations of bismuth compounds. However, the biological chemistry of bismuth is still not understood at a molecular level. Among other characterization techniques, electrospray ionization mass spectrometry (ESI-MS) has recently been established as a data-rich tool for examining reaction mixtures containing metals and biological molecules. To build on previous studies and to further investigate the utility of ESI-MS as a method for examining bioinorganic chemical systems, this thesis primarily describes endeavours to examine new, biologically significant combinations of bismuth and biological molecules. For comparison, the chemistry of relatively toxic metals---mercury, thallium, and lead, which reside in the same row as bismuth in the periodic table---has also been examined. From these experiments, numerous new complex ions have been observed containing bismuth or other metals and various biologically relevant ligands, including amino acids and monosaccharides. In particular, the first bismuth-citrate complexes to be observed by mass spectrometry are described. This research not only contributes to a growing library of known metal-biomolecule complexes, but also confirms that mass spectrometry is a valid and preferred technique for the examination of bioinorganic complexes. Because bismuth compounds are effective in many different medicinal applications, and particularly with respect to gastrointestinal disorders, the fundamental work presented herein may be helpful to other medicinal chemists who are interested in the biological chemistry of bismuth, and particularly to those involved in the future production of new bismuth-based pharmaceuticals. | en_US |
