Progress in DNP theory and hardware

Dynamic nuclear polarisation is a technique that allows one to increase the signal-to-noise ratio in an NMR experiment substantially, by transferring the inherently larger electron polarisation to the nuclei. Quantum mechanical models of this effect have thus far been limited to the description of only a few nuclei. This is due to the exponential scaling of the matrices involved in the description of the system. In this thesis methods of reducing the state space needed to accurately describe the simulation of solid effect DNP were explored and tested. Krylov Bogoliubov averaging has been used to remove high frequency oscillations from the system Hamiltonian and confine the trajectory of the dynamics to the zero quantum coherence subspace. Truncation of the basis spanning the Liouville space to low spin correlation orders has been tested and a condition for a minimum truncation level was found. A strategy based on a projection method, which allows one to describe the spin polarisation transient with multi-exponential functions, is introduced. This results in a linear scaling of the propagator with the number of spins. The influence of the parameters involved in the solid effect on the dynamics of the polarisation build up is discussed. The second part of this thesis is concerned with a novel approach to detecting fast molecular dynamics with the use of multiple RF receive and transmit coils. A proof of principle probe with two decoupled RF coils is presented, as well as a field map based shimming strategy and fast 2D data acquired with the probe. Lastly a probe with six RF coils, based on the design of the dual coil probe, will be presented, and initial data shown. The potential for using this probe in hyper-polarisation experiments for protein binding and folding studies will be discussed.EThOS - Electronic Theses Online ServiceGBUnited Kingdo