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

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

On the accuracy of the state space restriction approximation for spin dynamics simulations

We present an algebraic foundation for the state space restriction approximation in spin dynamics simulations and derive applicability criteria as well as minimal basis set requirements for practically encountered simulation tasks. The results are illustrated with NMR, ESR, DNP and Spin Chemistry simulations. It is demonstrated that state space restriction yields accurate results in systems where the time scale of spin relaxation processes approximately matches the time scale of the experiment. Rigorous error bounds and basis set requirements are derived.Comment: Submitted for publicatio

Developing Fine-Grained Actigraphies for Rheumatoid Arthritis Patients from a Single Accelerometer Using Machine Learning

In addition to routine clinical examination, unobtrusive and physical monitoring of Rheumatoid Arthritis (RA) patients provides an important source of information to enable understanding the impact of the disease on quality of life. Besides an increase in sedentary behaviour, pain in RA can negatively impact simple physical activities such as getting out of bed and standing up from a chair. The objective of this work is to develop a method that can generate fine-grained actigraphies to capture the impact of the disease on the daily activities of patients. A processing methodology is presented to automatically tag activity accelerometer data from a cohort of moderate-to-severe RA patients. A study of procesing methods based on machine learning and deep learning is provided. Thirty subjects, 10 RA patients and 20 healthy control subjects, were recruited in the study. A single tri-axial accelerometer was attached to the position of the fifth lumbar vertebra (L5) of each subject with a tag prediction granularity of 3 s. The proposed method is capable of handling unbalanced datasets from tagged data while accounting for long-duration activities such as sitting and lying, as well as short transitions such as sit-to-stand or lying-to-sit. The methodology also includes a novel mechanism for automatically applying a threshold to predictions by their confidence levels, in addition to a logical filter to correct for infeasible sequences of activities. Performance tests showed that the method was able to achieve around 95% accuracy and 81% F-score. The produced actigraphies can be helpful to generate objective RA disease-specific markers of patient mobility in-between clinical site visits

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

Quantum mechanical simulation of solid effect dynamic nuclear polarisation using Krylov–Bogolyubov time averaging and a restricted state-space

A strategy is described for simulations of solid effect dynamic nuclear polarisation that reduces substantially the dimension of the quantum mechanical problem. Averaging the Hamiltonian in the doubly rotating frame is used to confine the active space to the zero quantum coherence subspace. A further restriction of the Liouville space is made by truncating higher spin order states, which are weakly populated due to the presence of relaxation processes. Based on a dissipative transport equation, which is used to estimate the transport of the magnetisation starting from single spin order to higher spin order states, a minimal spin order for the states is calculated that needs to be taken into account for the spin dynamics simulation. The strategy accelerates individual spin calculations by orders of magnitude, thus making it possible to simulate the polarisation dynamics of systems with up to 25 nuclear spins.<br/