Access Type

Open Access Dissertation

Date of Award

January 2013

Degree Type


Degree Name




First Advisor

Sarah Trimpin


Matrix-assisted laser/desorption ionization (MALDI) and electrospray ionization (ESI) have made a huge impact in the analysis of biological materials. ESI has gained its popularity involving liquid based analysis, efficient fragmentation, chromatographic and electrophoretic separations but has a limitation for solubility restricted materials and surface analysis. MALDI is applicable to large biomolecule analysis and for surface methods useful for tissue imaging but is limited for structural characterization due to poor fragmentation and is ill suited for liquid based separation methods. The research presented here relates to new ionization methods that encompass the benefits of ESI and MALDI. These novel ionization methods produce multiply charged ions similar to ESI but directly from surfaces similar to MALDI. The formation of multiply charged ion extends the mass range of high performance mass spectrometers with advanced features for structural characterization such as ultra-high mass resolution and mass accuracy, and electron transfer dissociation. The surface method approach enables the detection, characterization, and identification of compounds directly from native environments such as tissue. The use of gas phase ion mobility separation reduces spectral complexity and improves the dynamic range of the experiment. Among the three novel ionization methods presented, MAIV has the potential to analyze fragile molecules and protein complexes, and is applicable for both atmospheric pressure and vacuum conditions. The laser-based method, LSII has the potential to improve the spatial resolution for tissue imaging and LSIV to enhance sensitivity.