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 (Bp = 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. Isotopesubstituted 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.