The effects of nitroxide structure upon ¹H Overhauser dynamic nuclear polarization efficacy at ultralow-field

The efficacy in ¹H Overhauser dynamic nuclear polarization in liquids at ultralow magnetic field (ULF, B₀ = 92 ± 0.8 µT) and polarization field (B_p = 1-10 mT) was studied for a broad variety of 26 different spin probes. Among others, piperidine, pyrrolidine, and pyrroline radicals specifically synthesized for this study, along with some well-established commercially available nitroxides, were investigated. Isotope-substituted variants, some sterically shielded reduction-resistant nitroxides, and some biradicals were included in the measurements. The maximal achievable enhancement, E_max, and the radio frequency power, P_1/2, needed for reaching E_max/2 were measured. Physico-chemical features such as molecular weight, spectral linewidth, heterocyclic structure, different types of substituents, deuteration, and ¹⁵N-labeling as well as the difference between monoradicals and biradicals were investigated. For the unmodified nitroxide radicals, the E_max values correlate with the molecular weight. The P_1/2 values correlate with the spectral linewidth and are additionally influenced by the type of substituents neighboring the nitroxide group. The nitroxide biradicals with high intramolecular spin-spin coupling show low performance. Nitroxides enriched with ¹⁵N and/or ²H afford significantly higher |E_max| and require lower power to do so, compared to their unmodified counterparts containing at natural abundance predominantly ¹⁴N and ¹H. The results allow for a correlation of chemical features with physical hyperpolarization-related properties and indicate that small nitroxides with narrow spectral lines have clear advantages for the use in Overhauser dynamic nuclear polarization experiments. Perdeuteration and ¹⁵N-labeling can be used to additionally boost the spin probe performance.