Gas-phase reactivity of aromatic carbon-centered σ-type mono- and biradicals towards simple organic substrates and aliphatic amino acids using ion trap mass spectrometers

Enada F Archibold, Purdue University

Abstract

The study of radical reactions has become a rapidly growing area of research because radicals initiate many chemical processes. These chemical processes include reactions in the atmosphere that cause depletion of the ozone layer, combustion reactions and certain biochemical processes, which proceed through radical intermediates. Radicals' reactivity towards biomolecules, such as proteins and DNA, has become of great interest since para-benzyne derivatives were discovered to be the biologically active intermediates of the potent enediyne anti-tumor antibiotics. Understanding the factors that govern the reactivity of these para-benzyne derivatives would be beneficial in helping to control their reactivity. Unfortunately, only limited experimental data have been reported on the parameters that play a role on the reactivity of para-benzyne derivatives. Their short lifetimes and high reactivities make studies in solution challenging. Fortunately, these challenges can be avoided by carrying out gas-phase experiments. Utilizing the distonic ion approach and tandem mass spectrometers, the gas-phase reactivities of several para-benzyne derivatives, as well as related σ-type monoradicals and biradicals, are reported in this thesis.

Degree

Ph.D.

Advisors

Kenttamaa, Purdue University.

Subject Area

Organic chemistry|Physical chemistry

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