Fundamental reactive and mechanistic aspects of mass spectrometry

Analysis of the mass spectra of organic and biological compounds to gain insight to the nature of the ionization process and gas phase reactions that occur in liquid secondary ion mass spectrometry (LSIMS) and electrospray ionization mass spectrometry (ESIMS) is the primary focus of the research described in this thesis. Dynamics of the ionization processes in electron impact ionization (EI) and chemical ionization (CI) mass spectrometry are well established, but there remains considerable debate as to the nature of the ionization processes in LSIMS and ESI. In a very practical application of analytical chemistry, the last chapter of this thesis discusses the monitoring of hydrogen and benzene gas evolution for two drums containing tetraphenylborate slurries from the Savannah River Site (SRS). This was accomplished through the design and implementation of a system that allowed for the analysis of gases in the headspace of irradiated slurry.; Chapter 2 of this thesis presents the results of some LSIMS experiments on a class of compounds that form cluster and adduct ions that are exclusive to the LSIMS ionization process. Chapter 3 presents the results of some LSIMS experiments on a class of compounds in which the effects of different LSIMS matrices on ion production were explored. Chapters 4 and 5 compare the energetics of two different ionization methods, LSIMS and ESI, via different MS/MS experiments: high- and low-energy collision-induced dissociation (CID) and surface induced dissociation (SID). These chapters also explain how experimental conditions of the MS/MS techniques influence product ion production in charge-remote fragmentation (CRF) Chapter 6 investigates the mechanism of an enzyme-inhibitor interaction utilizing ESI and matrix assisted laser desorption (MALDI) ionization methods. Chapter 7 discusses the development and implementation of a head-space analysis system used to determine gas evolution rates from large scale radiolysis of surrogate slurries from the Savannah River Site (SRS).