Kiryutin, Alexey S., Bogdan A. Rodin, Alexandra V. Yurkovskaya, Konstantin L. Ivanov, Dennis Kurzbach, Sami Jannin, David Guarin, Daniel Abergel, and Geoffrey Bodenhausen. “Transport of Hyperpolarized Samples in Dissolution-DNP Experiments.” Physical Chemistry Chemical Physics 21, no. 25 (2019): 13696–705.
https://doi.org/10.1039/C9CP02600B.
Dissolution dynamic nuclear polarization (D-DNP) experiments rely on the transfer of a sample between two high-field magnets. During this transfer, samples might experience passage through regions where the stray fields of the magnets are very weak, can approach zero, and even change their sign. This can lead to unexpected spectral features in spin systems that undergo transitions from weak- to strong-coupling regimes and vice versa, much like in field cycling nuclear magnetic resonance experiments. We herein demonstrate that the spectral features observed in D-DNP experiments can be rationalized, provided the time-dependence of the spin Hamiltonian upon field cycling is sufficiently adiabatic. Under such conditions, a passage through a weak static field can lead to the emergence of a long-lived state (LLS) based on an imbalance between the populations of singlet and triplet states in pairs of nuclei that are strongly coupled during the passage through low field. The LLS entails the appearance of anti-phase multiplet components upon transfer to a high-field magnet for observation of NMR signals.