Experimental and Theoretical Studies in Solid-state Nuclear Magnetic Resonance

Solid-state nuclear magnetic resonance (SSNMR) has proven to be a powerful tool for probing molecular structure and dynamics. Deuterium SSNMR is particularly useful due to the presence of anisotropic interactions whose motional averaging contributes structural and dynamical insight. The magnitude and type of molecular motion can be determined from analysis of solid echo deuterium lineshapes and/or relaxation studies. This work uses various applications of solid-state NMR as well as ab initio and density functional computational methods to study three different areas of physical chemistry: biophysical chemistry, materials science and fundamental concepts of physical chemistry. The first project addressed the dynamics of biomolecules as an aid in understanding protein recognition and binding to damaged DNA by selectively labeling the [2′′-2 H] furanose ring in two deoxynucleosides. The next project uses 1 H, 2 H, and 13 C SSNMR to gain structural insight of self-assembling organic molecules by assessing experimental and theoretical nuclear magnetic parameters. Finally, variant isotopic labeling and deuterium SSNMR are used to understand fundamental thermodynamic isotope effects in amino acids. Of central importance is the dependence on electronic and magnetic parameters in chemical environment; hydrogen bond strength directly correlates to the magnitude of these parameters as obtained experimentally and theoretically. my three siblings, Rebecca, Derik and Jessica, for showing me nothing but love and support throughout this process. iv Acknowledgements I would first like to extend the deepest appreciation and gratitude to my advisor and mentor, Professor Gerard Harbison. Your guidance, knowledge and expertise in the field of NMR has provided me learning and other opportunities too numerous to mention. I extend a hearty thank you to those individuals that served on my supervisory committee: Professors Hui Li (reader), Robert Powers (reader), Robert Spreitzer and Xiao Cheng Zeng. I appreciate all the insight you have provided me throughout my tenure at UNL. To my lab mates that have taught me so much over the years, John sincere appreciation. I have to convey my utmost appreciation for Dr. Joe Dumais for patiently teaching me the ins and outs of experimental NMR. To the other individuals of the UNL John Persons and Jayson Kempinger; thank you so much for your patience, guidance and for the willingness to work around our crazy solid-state voodoo. To the many colleagues-turned-friends I have met at UNL, thank you. Judy, your friendships and intellectual collaborations mean very much to me. To the amazing and hardworking staff …