Propagation of dynamic nuclear polarization across the xenon cluster boundaries: elucidation of the spin-diffusion bottleneck.

Earlier Dynamic Nuclear Polarization (DNP) experiments with frozen xenon/1-propanol/trityl mixtures have demonstrated spontaneous formation of pure xenon clusters above 120 K, enabling spectrally-resolved real-time measurements of (129)Xe nuclear magnetization in the clusters and in the surrounding radical-rich matrix. A spin-diffusion bottleneck was postulated to explain the peculiar time evolution of (129)Xe signals in the clusters as well as the apparent discontinuity of (129)Xe polarization across the cluster boundaries. A self-contained ab initio model of nuclear spin diffusion in heterogeneous systems is developed here, incorporating the intrinsic T1 relaxation towards the temperature-dependent equilibrium polarization and the spin-diffusion coefficients based on the measured NMR line widths and the known atomic densities in each compartment. This simple model provides the physical basis for the observed spin-diffusion bottleneck and is in a good quantitative agreement with the earlier measurements. A simultaneous fit of the model to the time-dependent NMR data at two different DNP frequencies provides excellent estimates of the cluster size, the intrinsic sample temperature, and (129)Xe T1 constants. The model was also applied to the NMR data acquired during relaxation towards the thermal equilibrium after the microwaves were turned off, to estimate T1 relaxation time constants inside and outside the clusters. Fitting the model to the data during and after DNP provides consistent estimates of the cluster size.

Lineshape-based polarimetry of dynamically-polarized (15)N2O in solid-state mixtures.

Dynamic nuclear polarization (DNP) of (15)N2O, known for its long-lived singlet-state order at low magnetic field, is demonstrated in organic solvent/trityl mixtures at ∼1.5 K and 5 T. Both (15)N polarization and intermolecular dipolar broadening are strongly affected by the sample's thermal history, indicating spontaneous formation of N2O clusters. In situ (15)N NMR reveals four distinct powder-pattern spectra, attributed to the chemical-shift anisotropy (CSA) tensors of the two (15)N nuclei, further split by the intramolecular dipolar coupling between their magnetic moments. (15)N polarization is estimated by fitting the free-induction decay (FID) signals to the analytical model of four single-quantum transitions. This analysis implies (10.2±2.2)% polarization after 37 h of DNP, and provides a direct, instantaneous probe of the absolute (15)N polarization, without a need for time-consuming referencing to a thermal-equilibrium NMR signal.

Cluster formation restricts dynamic nuclear polarization of xenon in solid mixtures.

During dynamic nuclear polarization (DNP) at 1.5 K and 5 T, (129)Xe nuclear magnetic resonance (NMR) spectra of a homogeneous xenon/1-propanol/trityl-radical solid mixture exhibit a single peak, broadened by (1)H neighbors. A second peak appears upon annealing for several hours at 125 K. Its characteristic width and chemical shift indicate the presence of spontaneously formed pure Xe clusters. Microwave irradiation at the appropriate frequencies can bring both peaks to either positive or negative polarization. The peculiar time evolution of (129)Xe polarization in pure Xe clusters during DNP can be modelled as an interplay of spin diffusion and T(1) relaxation. Our simple spherical-cluster model offers a sensitive tool to evaluate major DNP parameters in situ, revealing a severe spin-diffusion bottleneck at the cluster boundaries and a significant sample overheating due to microwave irradiation. Subsequent DNP system modifications designed to reduce the overheating resulted in four-fold increase of (129)Xe polarization, from 5.3% to 21%.

Metabolism of hyperpolarized [1-¹³C]pyruvate in the isolated perfused rat lung - an ischemia study.

We report studies of the effect of ischemia on the metabolic activity of the intact perfused lung and its restoration after a period of reperfusion. Two groups of rat lungs were studied using hyperpolarized 1-(13) C pyruvate to compare the rate of lactate labeling differing only in the temporal ordering of ischemic and normoxic acquisitions. In both cases, a several-fold increase in lactate labeling was observed immediately after a 25-min ischemia event as was its reversal back to the baseline after 30-40 min of resumed perfusion (n = 5, p < 0.025 for both comparisons). These results were corroborated by (31) P spectroscopy and correspond well to measured changes in lactate pool size determined by (1) H spectroscopy of freeze-clamped specimens.

Measurements of the persistent singlet state of N2O in blood and other solvents--potential as a magnetic tracer.

The development of hyperpolarized tracers has been limited by short nuclear polarization lifetimes. The dominant relaxation mechanism for many hyperpolarized agents in solution arises from intramolecular nuclear dipole-dipole coupling modulated by molecular motion. It has been previously demonstrated that nuclear spin relaxation due to this mechanism can be removed by storing the nuclear polarization in long-lived, singlet-like states. In the case of N(2)O, storing the polarization of the nitrogen nuclei has been shown to substantially increase the polarization lifetime. The feasibility of utilizing N(2)O as a tracer is investigated by measuring the singlet-state lifetime of the N(2)O when dissolved in a variety of solvents including whole blood. Comparison of the singlet lifetime to longitudinal relaxation and between protonated and deuterated solvents is consistent with the dominance of spin-rotation relaxation, except in the case of blood.

Push-pull optical pumping of pure superposition states.

A new optical pumping method, "push-pull pumping," can produce very nearly pure, coherent superposition states between the initial and the final sublevels of the important field-independent 0-0 clock resonance of alkali-metal atoms. The key requirement for push-pull pumping is the use of D1 resonant light which alternates between left and right circular polarization at the Bohr frequency of the state. The new pumping method works for a wide range of conditions, including atomic beams with almost no collisions, and atoms in buffer gases with pressures of many atmospheres.

Intense, narrow atomic-clock resonances.

We present experimental and theoretical results showing that magnetic resonance transitions from the "end" sublevels of maximum or minimum spin in alkali-metal vapors are a promising alternative to the conventional 0-0 transition for small-size gas-cell atomic clocks. For these "end resonances," collisional spin-exchange broadening, which often dominates the linewidth of the 0-0 resonance, decreases with increasing spin polarization and vanishes for 100% polarization. The end resonances also have much stronger signals than the 0-0 resonance, and are readily detectable in cells with high buffer-gas pressure.

Fast nuclear spin relaxation in hyperpolarized solid 129Xe.

We report extensive new measurements of the longitudinal relaxation time T1 of 129Xe nuclear spins in solid xenon. For temperatures T<120 K and magnetic fields B>0.05 T, we found T1 on the order of hours, in good agreement with previous measurements and with the predicted phonon-scattering limit for the spin-rotation interaction. For T>120 K, our new data show that T1 can be much shorter than the phonon scattering limit. For B = 0.06 T, a field often used to accumulate hyperpolarized xenon, T1 is approximately 6 s near the Xe melting point T(m) = 161.4 K. From T = 50 K to T(m), the new data are in excellent agreement with the theoretical prediction that the relaxation is due to (i) modulation of the spin-rotation interaction by phonons, and (ii) modulation of the dipole-dipole interaction by vacancy diffusion.

Spectroscopic evidence for the localization of Skyrmions near nu = 1 as T --> 0.

Optically pumped nuclear magnetic resonance measurements of 71Ga spectra were carried out in an n-doped GaAs/Al(0.1)Ga0.9As multiple quantum well sample near the integer quantum Hall ground state nu = 1. As the temperature is lowered (down to T approximately 0.3 K), a "tilted plateau" emerges in the Knight shift data, which is a novel experimental signature of quasiparticle localization. The dependence of the spectra on both T and nu suggests that the localization is a collective process. The frozen limit spectra appear to rule out a 2D lattice of conventional Skyrmions.