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I. Gas-phase reactions of polycyclic aromatic hydrocarbons with model DNA bases. II. Evaluation of laboratory techniques for the analysis of peptides

Andy Bob Whitehill, University of Nebraska - Lincoln

Abstract

This dissertation is split in two main subject areas, gas-phase ion chemistry and analysis of peptides. The first subject area reports reactions of polycyclic aromatic hydrocarbons (PAHs) with model DNA bases through chemical ionization mass spectrometry. Collaborative research with Dr. Cavalieri and coworkers at the Eppley Institute in Omaha, NE have shown mass spectrometry to be effective in the analysis of PAH-DNA adducts derived from solution-phase reactions of PAH radical cations with DNA. This project uses these analytical results as a driving force in the following manner; since PAH radical cations are reactive toward DNA in solution phase and the reaction products identifiable with mass spectrometry, then gas-phase reactions of PAH radical cations with model DNA bases may show a correlation between biological activity and inherent reactivity. The study of inherent gas-phase reactivity is first approached with reactions of benzene and naphthalene with N-methylimidazole (Chapter 1). A detailed study of reactants and product structure for these systems are applied to reactions of higher mass PAHs with the model DNA bases pyridine and N-methylimidazole (Chapter 2). The second area of this dissertation reports on instrument development and analytical approach to analyze low amounts (pico to femtomole) of synthetic and isolated peptides in the m/z 500 to 2000 range. Our lab is interested in the analysis of peptides that are a result of the immune systems response to antigens, often resulting in the presentation of peptides at cell surfaces. Determination of these peptides, through molecular weight and peptide sequencing, can help in understanding the complex function of the immune system. The mass spectrometric methods; static FAB, continuous-flow FAB, electrospray, and matrix-assisted laser desorption, are evaluated to determine, limit of detection, the effect of presence of other peptides, sample consumption, sample handling, mass accuracy, and ease of analysis (Chapter 3).

Subject Area

Analytical chemistry|Biochemistry

Recommended Citation

Whitehill, Andy Bob, "I. Gas-phase reactions of polycyclic aromatic hydrocarbons with model DNA bases. II. Evaluation of laboratory techniques for the analysis of peptides" (1996). ETD collection for University of Nebraska-Lincoln. AAI9620347.
https://digitalcommons.unl.edu/dissertations/AAI9620347

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