Front-end Electron Transfer Dissociation

Compton, Philip Daniel, Department of Chemistry, University of Virginia
Hunt, Donald F., Department of Chemistry, University of Virginia
Venton, Jill, Department of Chemistry, University of Virginia
Harrison, Ian, Department of Chemistry, University of Virginia
Demas, James, Department of Chemistry, University of Virginia

In this thesis, we describe a method and apparatus that enables electron transfer dissociation (ETD) to be performed in the quadrupole ion trap ofa hybrid mass spectrometer. Advantages of this technology include increased throughput bottom-up analyses by enabling fewer mass analyses per sample as well as reducing database search times by providing accurate intact mass and precursor charge state information. Topand middle-down methodologies are also aided by the possibility of detecting fragment ions with high resolution and mass accuracy, extending the upper mass limit of precursors that can be adequately analyzed via mass spectrometric methods. Further, the apparatus is simplified in comparison to current technologies, allowing for simpler, more robust and less expensive implementation of ETD. Finally, the parameters governing the rate of ETD reactions are optimized, minimizing the time required for a single ETD scan event. In combination, optimized ETD parameters and a new reagent ion source reduce the acquisition time of an ETD scan significantly from current standards, thereby increasing dynamic range in the context of online liquid chromatography/mass spectrometry (LC/MS) experiments.

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PHD (Doctor of Philosophy)
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