Long-Lived Nuclear Singlet Order in Near-Equivalent ¹³C Spin Pairs

Molecules that support ¹³C singlet states with lifetimes of over 10 min in solution have been designed and synthesized. The ¹³C₂ spin pairs in the asymmetric alkyne derivatives are close to magnetic equivalence, so the ¹³C long-lived singlet states are stable in high magnetic field and do not require maintenance by a radiofrequency spin-locking field. We suggest a model of singlet relaxation by fluctuating chemical shift anisotropy tensors combined with leakage associated with slightly broken magnetic equivalence. Theoretical estimates of singlet relaxation rates are compared with experimental values. Relaxation due to antisymmetric shielding tensor components is significant

Long-Lived Nuclear Singlet Order in Near-Equivalent ¹³C Spin Pairs

Molecules that support ¹³C singlet states with lifetimes of over 10 min in solution have been designed and synthesized. The ¹³C₂ spin pairs in the asymmetric alkyne derivatives are close to magnetic equivalence, so the ¹³C long-lived singlet states are stable in high magnetic field and do not require maintenance by a radiofrequency spin-locking field. We suggest a model of singlet relaxation by fluctuating chemical shift anisotropy tensors combined with leakage associated with slightly broken magnetic equivalence. Theoretical estimates of singlet relaxation rates are compared with experimental values. Relaxation due to antisymmetric shielding tensor components is significant

Long-Lived Nuclear Singlet Order in Near-Equivalent ¹³C Spin Pairs

Molecules that support ¹³C singlet states with lifetimes of over 10 min in solution have been designed and synthesized. The ¹³C₂ spin pairs in the asymmetric alkyne derivatives are close to magnetic equivalence, so the ¹³C long-lived singlet states are stable in high magnetic field and do not require maintenance by a radiofrequency spin-locking field. We suggest a model of singlet relaxation by fluctuating chemical shift anisotropy tensors combined with leakage associated with slightly broken magnetic equivalence. Theoretical estimates of singlet relaxation rates are compared with experimental values. Relaxation due to antisymmetric shielding tensor components is significant

Synthesis of an Isotopically Labeled Naphthalene Derivative That Supports a Long-Lived Nuclear Singlet State

The synthesis of an octa-alkoxy substituted isotopically labeled naphthalene derivative, shown to have excellent properties in singlet NMR experiments, is described. This highly substituted naphthalene system, which incorporates an adjacent ¹³C spin pair, is readily accessed from a commercially available ¹³C₂-labeled building block via sequential thermal alkynyl- and arylcyclobutenone rearrangements. The synthetic route incorporates a simple desymmetrization approach leading to a small difference in the chemical shifts of the ¹³C spin pair, a design constraint crucial for accessing nuclear singlet order

Recycling and Imaging of Nuclear Singlet Hyperpolarization

The strong enhancement of NMR signals achieved by hyperpolarization decays, at best, with a time constant of a few minutes. Here, we show that a combination of long-lived singlet states, molecular design, magnetic field cycling, and specific radiofrequency pulse sequences allows repeated observation of the same batch of polarized nuclei over a period of 30 min and more. We report a recycling protocol in which the enhanced nuclear polarization achieved by dissolution-DNP is observed with full intensity and then returned to singlet order. MRI experiments may be run on a portion of the available spin polarization, while the remaining is preserved and made available for a later use. An analogy is drawn with a “spin bank” or “resealable container” in which highly polarized spin order may be deposited and retrieved