Hyperpolarization by DNP and Molecular Dynamics: Eliminating the Radical Contribution in NMR Relaxation Studies

Fast field cycling NMR relaxation dispersion represents a versatile method to elucidate the distribution of timescales of molecular motion for systems as diverse as polymers, proteins, and complex fluids. While electronic field switching accesses magnetic field strengths between about 1 T and Earth field, the method remains fundamentally insensitive and unspecific due to the low signal intensity at low fields and the inherently large field inhomogeneity that prohibits spectral resolution for most nuclei. These conditions limit the accessible concentrations and the detection of insensitive X-nuclei. Dynamic nuclear polarization (DNP) has been demonstrated to significantly enhance sensitivity, favoring low-field applications due to the increase in enhancement factors under these conditions. However, the required presence of radicals adds a significant and often dominating relaxivity to the system of nuclei, which has mostly precluded relaxation studies under DNP because of the need to separate several competing relaxation mechanisms. In this study, we present proof that the intrinsic relaxation dispersion of a substance can be completely recovered from experiments with different concentrations of radicals, irrespective of the nature of the DNP effect. This approach not only enhances detection sensitivity by at least one order of magnitude but also provides information about selective radical/molecule interaction that allows the separation of contributions from different molecular moieties from their differential enhancement and relaxation time.