Nuclear spin relaxation

This article attempts to explain what nuclear relaxation is, why it can be a friend, why it can also be a foe, and how the destructive qualities of relaxation may sometimes be held at bay using the symmetry properties of the quantum states and of the relaxation processes

Extremely low-frequency spectroscopy in low-field nuclear magnetic resonance

We demonstrate a new phenomenon in nuclear magnetic resonance spectroscopy, in which nuclear spin transitions are induced by radio frequency irradiation at extremely low frequencies (of the order of a few Hz). Slow Rabi oscillations are observed between spin states of different exchange symmetry. These “forbidden” transitions are rendered weakly allowed by differential electronic shielding effects on the radio frequency field. We generate coherence between the singlet and triplet states of 15N-labeled nitrous oxide in solution, and estimate the scalar coupling between the two 15N nuclei with a precision of a few mHz

Symmetry constraints on spin dynamics: application to hyperpolarized NMR

Spin dynamical evolution is constrained by the symmetries of the spin Hamiltonians that generate the quantum dynamics. The consequences of symmetry-induced constraints are examined for some common hyperpolarized NMR experiments, including the excitation of singlet order in spin-pair systems, and the transfer of parahydrogen-induced hyperpolarized singlet order to magnetization in systems displaying chemical and magnetic equivalence

Symmetry-based pulse sequences in solid-state NMR and applications to biological systems

We present some applications of solid-state nuclear magnetic resonance to model compounds and biological systems. We highlight a class of pulse sequences that are designed based on symmetry properties of the internal spin interactions. Examples are given showing resonance assignments, determination of internuclear distances, and torsion angle determinations in representative model systems as well as true biological systems

Theory and applications of supercycled symmetry-based recoupling sequences in solid-state NMR

We present the theoretical principles of supercycled symmetry-based recoupling sequences in solid-state magic-angle-spinning NMR. We discuss the construction procedure of the SR26 pulse sequence, which is a particularly robust sequence for double-quantum homonuclear dipole-dipole recoupling. The supercycle removes destructive higher-order average Hamiltonian terms and renders the sequence robust over long time intervals. We demonstrate applications of the SR26 sequence to double-quantum spectroscopy, homonuclear spin counting, and determination of the relative orientations of chemical shift anisotropy tensors

Direct enhancement of nuclear singlet order by dynamic nuclear polarization

Hyperpolarized singlet order is available immediately after dissolution DNP, avoiding need for additional preparation steps. We demonstrate this procedure on a sample of [1,2–13C2]pyruvic aci

Scalable dissolution-dynamic nuclear polarization with rapid transfer of a polarized solid

In dissolution-dynamic nuclear polarization, nuclear spins are hyperpolarized at cryogenic temperatures using radicals and microwave irradiation. The hyperpolarized solid is dissolved with hot solvent and the solution is transferred to a secondary magnet where strongly enhanced magnetic resonance signals are observed. Here we present a method for transferring the hyperpolarized solid. A bullet containing the frozen, hyperpolarized sample is ejected using pressurized helium gas, and shot into a receiving structure in the secondary magnet, where the bullet is retained and the polarized solid is dissolved rapidly. The transfer takes approximately 70 ms. A solenoid, wound along the entire transfer path ensures adiabatic transfer and limits radical-induced low-field relaxation. The method is fast and scalable towards small volumes suitable for high-resolution nuclear magnetic resonance spectroscopy while maintaining high concentrations of the target molecule. Polarization levels of approximately 30% have been observed for 1-13C-labelled pyruvic acid in solution