EPR relaxation : progress in hardware and analysis methods

Dynamic nuclear polarization (DNP) is a technique for enhancing the sensitivity of nuclear magnetic resonance (NMR) experiments by increasing the polarization of the nuclear spins. DNP experiments are often characterized by the enhancement which is achieved, and the enhancement build-up rate. These...

Full description

Bibliographic Details
Main Author: Roberts, Peter Joseph
Format: Thesis (University of Nottingham only)
Language:English
Published: 2014
Subjects:
Online Access:https://eprints.nottingham.ac.uk/14119/
_version_ 1848791885542326272
author Roberts, Peter Joseph
author_facet Roberts, Peter Joseph
author_sort Roberts, Peter Joseph
building Nottingham Research Data Repository
collection Online Access
description Dynamic nuclear polarization (DNP) is a technique for enhancing the sensitivity of nuclear magnetic resonance (NMR) experiments by increasing the polarization of the nuclear spins. DNP experiments are often characterized by the enhancement which is achieved, and the enhancement build-up rate. These parameters are strongly influenced by electronic and nuclear relaxation processes. The purpose of the work presented in this thesis was to develop hardware and analysis methods for studying relaxation in electron paramagnetic resonance (EPR) and NMR. Two novel probes for combined NMR and longitudinally detected EPR experiments have been built. The first of these probes is designed for low temperature NMR, EPR and DNP experiments, with the main focus being relaxation studies in typical low-temperature DNP conditions. The second probe is designed for high temperature cryoporometry studies of lignin degradation. Relaxation data in magnetic resonance often exhibits multi-exponential decay. An algorithm for performing a Laplace inversion of multi-exponential relaxation data, and extracting distributions of time constants, is described. The algorithm, which is based on Tikhonov regularization, uses a uniform penalty and a zero-crossing penalty to stabilize the solution, but does not use a non-negativity constraint, so relaxation spectra with both positive and negative peaks can be produced. Two experiments to study relaxation and other dynamic processes in samples containing organic radicals have been performed. The first of these was designed to study saturation, relaxation and spectral diffusion processes in EPR during continuous microwave irradiation. The second experiment measured relaxation of DNP-enhanced nuclear polarization, and revealed an offset dependence of the relaxation behaviour. Both experiments were performed using the low-temperature probe, and the data was analysed using the Laplace inversion algorithm.
first_indexed 2025-11-14T18:35:37Z
format Thesis (University of Nottingham only)
id nottingham-14119
institution University of Nottingham Malaysia Campus
institution_category Local University
language English
last_indexed 2025-11-14T18:35:37Z
publishDate 2014
recordtype eprints
repository_type Digital Repository
spelling nottingham-141192025-02-28T11:28:57Z https://eprints.nottingham.ac.uk/14119/ EPR relaxation : progress in hardware and analysis methods Roberts, Peter Joseph Dynamic nuclear polarization (DNP) is a technique for enhancing the sensitivity of nuclear magnetic resonance (NMR) experiments by increasing the polarization of the nuclear spins. DNP experiments are often characterized by the enhancement which is achieved, and the enhancement build-up rate. These parameters are strongly influenced by electronic and nuclear relaxation processes. The purpose of the work presented in this thesis was to develop hardware and analysis methods for studying relaxation in electron paramagnetic resonance (EPR) and NMR. Two novel probes for combined NMR and longitudinally detected EPR experiments have been built. The first of these probes is designed for low temperature NMR, EPR and DNP experiments, with the main focus being relaxation studies in typical low-temperature DNP conditions. The second probe is designed for high temperature cryoporometry studies of lignin degradation. Relaxation data in magnetic resonance often exhibits multi-exponential decay. An algorithm for performing a Laplace inversion of multi-exponential relaxation data, and extracting distributions of time constants, is described. The algorithm, which is based on Tikhonov regularization, uses a uniform penalty and a zero-crossing penalty to stabilize the solution, but does not use a non-negativity constraint, so relaxation spectra with both positive and negative peaks can be produced. Two experiments to study relaxation and other dynamic processes in samples containing organic radicals have been performed. The first of these was designed to study saturation, relaxation and spectral diffusion processes in EPR during continuous microwave irradiation. The second experiment measured relaxation of DNP-enhanced nuclear polarization, and revealed an offset dependence of the relaxation behaviour. Both experiments were performed using the low-temperature probe, and the data was analysed using the Laplace inversion algorithm. 2014-07-10 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en arr https://eprints.nottingham.ac.uk/14119/1/PhDThesis_PeterRoberts.pdf Roberts, Peter Joseph (2014) EPR relaxation : progress in hardware and analysis methods. PhD thesis, University of Nottingham. Electron Paramagnetic Resonance Relaxation Saturation Inverse Laplace Transform Laplace Inversion Probe Low Temperature Probe Dual Frequency Probe Multimodal Probe Dynamic Nuclear Polarization Solid-State NMR EPR ILT DNP
spellingShingle Electron Paramagnetic Resonance
Relaxation
Saturation
Inverse Laplace
Transform Laplace
Inversion Probe
Low Temperature Probe
Dual Frequency Probe
Multimodal Probe
Dynamic Nuclear Polarization
Solid-State NMR
EPR
ILT
DNP
Roberts, Peter Joseph
EPR relaxation : progress in hardware and analysis methods
title EPR relaxation : progress in hardware and analysis methods
title_full EPR relaxation : progress in hardware and analysis methods
title_fullStr EPR relaxation : progress in hardware and analysis methods
title_full_unstemmed EPR relaxation : progress in hardware and analysis methods
title_short EPR relaxation : progress in hardware and analysis methods
title_sort epr relaxation : progress in hardware and analysis methods
topic Electron Paramagnetic Resonance
Relaxation
Saturation
Inverse Laplace
Transform Laplace
Inversion Probe
Low Temperature Probe
Dual Frequency Probe
Multimodal Probe
Dynamic Nuclear Polarization
Solid-State NMR
EPR
ILT
DNP
url https://eprints.nottingham.ac.uk/14119/