Thesis (Ph.D.) - Indiana University, Chemistry, 2011A number of atmospheric-pressure ionization sources for mass spectrometry has recently appeared in the literature to yield a field that is collectively referred to as Ambient Desorption/Ionization-Mass Spectrometry (ADI-MS). These sources include, among others, Desorption ElectroSpray Ionization (DESI), Direct Analysis in Real Time (DART), the Flowing Atmospheric-Pressure Afterglow (FAPA), and the Low-Temperature Plasma (LTP) probe. Collectively, these ADI-MS sources offer numerous advantages over conventional ionization sources, including direct analysis of solid, liquid, and gaseous samples, high ionization efficiency, and soft ionization. Additionally, their ability to analyze samples directly with no pretreatment dramatically reduces analysis times.
The ultimate ambient ionization source would be one that is capable of desorbing and ionizing a broad range of analytes (polar, non-polar, small molecules, biopolymers, etc.) while being minimally influenced by matrix effects. While the plasma-based ADI-MS sources, such as FAPA, DART, and LTP, have been shown to be capable of efficiently ionizing a range of small molecules, few investigations have been aimed at understanding desorption and ionization processes or matrix effects that occur with them.
At present, the performance and fundamental characteristics of the FAPA source, developed in our research group, and the LTP probe, developed at Purdue University, are being evaluated through optical and mass-spectrometric methods. The FAPA source consists of a direct-current, atmospheric-pressure glow discharge in a pin-to-plate configuration. A hole in the plate allows ionized and excited plasma species to interact directly with a sample, while physically and electrically isolating the discharge from the sample-introduction region. Conversely, the LTP probe is a high-voltage, alternating-current, dielectric-barrier discharge that interacts directly with a sample. While the fundamental processes governing these discharges are quite different, mass spectra produced with both sources are very similar. The major differences are in achievable detection limits and susceptibility to matrix effects, with the FAPA sources routinely performing better. Direct, fundamental comparisons among the FAPA source, the LTP probe, and DART are made
