UNDERSTANDING OF NOVEL CHEMISTRIES USING MASS SPECTROMETRY, DIFFERENTIAL ION MOBILITY SPECTROMETRY, AND THEORETICAL CALCULATIONS Public Deposited

Downloadable Content

Download PDF
Last Modified
  • March 20, 2019
Creator
  • Crizer, David
    • Affiliation: College of Arts and Sciences, Department of Chemistry
Abstract
  • Mass spectrometry is a very powerful analytical method that can be used to study a variety of interesting chemistries. The work in this dissertation is generally focused on the understanding of novel chemistries through the use of mass spectrometry, electron capture dissociation (ECD), electron transfer dissociation (ETD), differential ion mobility spectrometry (DIMS), electrospray ionization mass spectrometry, electrochemistry, and computational methods. The effects of cation recombination energy/Coulomb repulsion in electron capture dissociation and electron transfer dissociation processes were investigated using a set of peptides of the form X(AG)nX, where X is one of the three basic amino acid residues and n is 1, 2, or 4. DIMS has become a very useful post ionization separation technique in recent years and herein its applicability in the use of separating vitamin K2 protomers is discussed in detail. Unique ion types were observed when a series of halobenzoquniones were investigated using electrospray ionization mass spectrometry. These unique ion types were determined to be formed via electrochemical reduction. These electrochemical processes were studied using cyclic voltammetry and theoretical calculations to aid in the understanding of the mass spectrometry data. DIMS was also shown to be useful for separating different halobenzoquinone isomers. The energetics involved when ions move through the DIMS device was used to understand why mass spectra of different halobenzoquinone isomers had differing amounts of the previously mentioned unique ion types. Finally, a program is discussed that calculates theoretical properties of interest. The program was written using the Perl programming language and requires very little user input. It completely automates a variety of density functional theory calculations and manipulation of the output from these calculations into ionization energies, proton affinities, and heats of formation.
Date of publication
Keyword
DOI
Resource type
Rights statement
  • In Copyright
Advisor
  • Leibfarth, Frank
  • Wightman, R. Mark
  • Schoenfisch, Mark H.
  • Schauer, Cynthia
  • Glish, Gary
Degree
  • Doctor of Philosophy
Degree granting institution
  • University of North Carolina at Chapel Hill Graduate School
Graduation year
  • 2017
Language
Parents:

This work has no parents.

Items