MS (Master of Science)
Date of Award
Committee Chair or Co-Chairs
Marina Roginskaya, David Close
Melatonin, a nontoxic natural antioxidant, is of interest as a possible spin trap for use in spectroscopic methods to observe and identify short-lived free radicals, which have been linked to oxidative stress that may result in serious health problems. However, the reaction mechanisms for the oxidation of melatonin to form the product N1-acetyl-N2-formyl-5-methoxykynuramine are still not well understood. Computational quantum chemistry studies have been done on four proposed reaction mechanisms, involving the following major intermediate structures: a dioxetane, an epoxide, a melatonin radical cation, and a spin radical adduct. Molecular geometries were optimized at the DFT/B3LYP/cc-pVTZ level of theory, and single point energies were extrapolated to the complete basis set limit at the Hartree-Fock and second-order Møller-Plesset perturbation levels of theory using the cc-pVXZ (X = D, T, Q) basis sets. The lowest energy pathway was found to be the single electron transfer pathway, involving the melatonin radical cation intermediate.
Thesis - Withheld
Warden, Constance E., "Computational Quantum Chemistry Studies of the Stabilities of Radical Intermediates Formed During the Oxidation of Melatonin" (2016). Electronic Theses and Dissertations. Paper 3135. https://dc.etsu.edu/etd/3135
Copyright by the authors.
Available for download on Sunday, October 11, 2020