thesis
Overhauser dynamic nuclear polarisation studies in solution-state at 3.4T
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Abstract
Studies of Overhauser DNP in liquids are presented in this thesis, where the
polarisation is achieved in-situ using TEMPO-derived radicals at a magnetic field
of 3.4 T (143 MHz/94 GHz 1H NMR/EPR frequency).
The dielectric heating of lossy water solvent is unavoidable at high field, and
so knowledge of temperature effects is important to properly compare enhancement
results. It is shown that the temperature dependent DNP enhancement of water
protons can be determined provided that the 1H NMR shift is sufficiently resolved
and the nuclear relaxation T1I is sufficiently fast. Considerable sensitivity gains are
made at modest temperatures, e.g. [E] ~ 40 at ~40 degrees C, and much greater enhancements
are achievable at elevated temperatures, e.g. [E]~ 130 at ~ 100 degrees C. Since high
radical concentrations (100 mM TEMPOL) are used, the leakage and saturation
factors approach 1, enabling an experimental determination of the coupling factor
from the enhancement. A value of E = 0:055+0:003 is found at 25 degrees C, which agrees
well with values in the literature calculated from molecular dynamics simulations.
The DNP enhancement is measured as a function of temperature for three
organic compounds dissolved in water: glycine, L-proline and acrylic acid; with enhancements
of -17, -16 and -11 at ~40 degrees C. To the author's knowledge, this is the
first report of solute molecule enhancements for direct in-situ liquid DNP at this
field. Significant enhancements are obtained, however, further analysis of the results
reveals significantly weaker coupling of the electron spin to the solute molecule
protons than to the solvent molecule protons. Discrepancies between experimental
coupling factor ratios and those calculated from a force-free hard-sphere model
suggest that the classical analytical models used to describe Overhauser DNP may
require refinement.
In addition to these temperature studies, simultaneous saturation of two EPR
hyperfine lines is investigated and achieved, resulting in an increase in observed DNP
enhancement