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′′-2H] furanose ring in two deoxynucleosides. The next project uses 1H, 2H, and 13C 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