To shield solutions carrying hyperpolarized nuclear magnetization from rapid relaxation during transfer through low fields, the transfer duct can be threaded through an array of permanent magnets. The advantages are illustrated for solutions containing hyperpolarized 1H and 13C nuclei in a variety of molecules.
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.
Long-lived states (LLS) involving pairs of magnetically inequivalent but chemically equivalent proton spins in aliphatic chains can be excited by simultaneous application of weak selective radio frequency fields at chemical shifts by polychromatic spin-lock induced crossing. The LLS are delocalized throughout the aliphatic chains by mixing of intrapair singlet states and by excitation of LLS comprising products of four and six spin operators. The measured lifetimes in a model compound are about 5 times longer than and are strongly affected by interactions with macromolecules.
15 March 2018 in Angewandte Chemie International Edition