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Katharina Märker

Atomic-level structure determination of organic assemblies by dynamic nuclear polarization enhanced solid-state NMR

Published on 19 December 2017
Thesis presented December 19, 2017

Supramolecular structure determination of organic solids is of utter importance for understanding their properties and function. Structural insights at the atomic level can be provided by magic-angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) spectroscopy. However, this technique faces strong limitations in sensitivity due to the low natural isotopic abundance (NA) of the key nuclei 13C and 15N (1.1 % and 0.37 %, respectively). Sensitivity enhancement by several orders of magnitude can be achieved with dynamic nuclear polarization (DNP) which is based on polarization transfer from electron to nuclear spins. The recent progress in the practical implementation of DNP opens up new and exciting possibilities for structure determination of organic solids which are explored in this thesis.
The first step for structural studies with NMR is resonance assignment. The complete assignment of 13C and 15N resonances at NA is demonstrated here to be feasible based on DNP-enhanced 13C-13C and, for the first time, 13C-15N correlation spectra.
The focus is then laid on obtaining structural information in the form of carbon-carbon and carbon-nitrogen distances from the buildup of polarization in dipolar recoupling experiments. Several strategies are discussed for recording such polarization buildup curves at NA. A decisive advantage of these measurements is that dipolar truncation is reduced to a great extent in samples at NA, enabling undisturbed polarization transfer over long distances and a simple description of the spin dynamics by numerical simulations. This is demonstrated experimentally on the self-assembled cyclic diphenylalanine peptide (cyclo-FF). The 13C-13C and 13C-15N buildup curves obtained are indeed sensitive to long distances (up to ~ 7 Å) and are in excellent agreement with the crystal structure of cyclo-FF. Moreover, each buildup curve represents a superposition of multiple intra- and intermolecular distance contributions and can therefore provide a wealth of structural information.
It is subsequently shown that the high information content and the simple theoretical description of such polarization buildup curves enables determination of both the molecular and the supramolecular structure of cyclo-FF. This is achieved with the help of a dedicated computational code which creates structural models based on a systematic grid-search and ranks them according to their agreement with the experimental data.
The thesis concludes by presenting improvements for the homonuclear dipolar recoupling pulse sequence SR26 which is a powerful sequence for use in NA samples. These improvements enable increased recoupling efficiency and the acquisition of 2D correlation spectra with large spectral widths.
Overall, this thesis demonstrates that clear advantages lie in the use of NA samples for structural studies of organic solids, and that MAS-DNP enables structure determination which is mainly based on distance information from NMR data.

Structure determination, Dynamic nuclear polarization (DNP), Solid-State NMR, DFT

On-line thesis.