Date of Award


Document Type


Degree Name

Doctor of Philosophy (PhD)



First Advisor

Patrick A. Limbach


The application of mass spectrometry for the analysis of biomolecules and metalloporphyrins is the aim of the work presented within this document. Part A of this document addresses the use of Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS) for the analysis of oligonucleotides. The goal of Part A is to develop a better understanding of the matrix/analyte relationship in the condensed phase required for MALDI analysis of oligonucleotides. Part A also focuses on the employment of novel co-matrices to help improve oligonucleotide mass resolution and ion abundance. The objectives for Part B was to study the use of Electrospray Ionization (ESI) for the analysis of metalloporphyrins. The first half of Part B focuses on the characteristic behavior observed for each of the model porphyrin systems used in this study. The second half of Part B presents the data collected from the positive ion ESI-MS analysis of homogeneous and heterogeneous porphyrin solutions. The ion abundance of each of the porphyrins present in these solutions was monitored as a function of the ESI flow rate, porphyrin concentration, ESI needle voltage, and solvent polarity. These systematic investigations revealed the influence of these parameters on the ion abundance of one porphyrin relative to another porphyrin in a heterogeneous solution. Furthermore, certain experimental conditions have been observed to separately optimize the detection of each of the components of such mixtures.