Zackary I. Cleveland

Hyperpolarized 131Xe NMR spectroscopy

Hyperpolarized (hp) 131Xe with up to 2.2% spin polarization (i.e., 5000-fold signal enhancement at 9.4 T) was obtained after separation from the rubidium vapor of the spin-exchange optical pumping (SEOP) process. The SEOP was applied for several minutes in a stopped-flow mode, and the fast, quadrupolar-driven T1 relaxation of this spin I = 3/2 noble gas isotope required a rapid subsequent rubidium removal and swift transfer into the high magnetic field region for NMR detection. Because of the xenon density dependent 131Xe quadrupolar relaxation in the gas phase, the SEOP polarization build-up exhibits an even more pronounced dependence on xenon partial pressure than that observed in 129Xe SEOP. 131Xe is the only stable noble gas isotope with a positive gyromagnetic ratio and shows therefore a different relative phase between hp signal and thermal signal compared to all other noble gases. The gas phase 131Xe NMR spectrum displays a surface and magnetic field dependent quadrupolar splitting that was found to have additional gas pressure and gas composition dependence. The splitting was reduced by the presence of water vapor that presumably influences xenon-surface interactions. The hp 131Xe spectrum shows differential line broadening, suggesting the presence of strong adsorption sites. Beyond hp 131Xe NMR spectroscopy studies, a general equation for the high temperature, thermal spin polarization, P, for spin I⩾1/2 nuclei is presented.

Exploring hyperpolarized Kr83 by remotely detected NMR relaxometry

For the first time, a hyperpolarized (hp) noble gas with a nuclear electric quadrupole moment is available for high-field nuclear-magnetic-resonance (NMR) spectroscopy and magnetic-resonance imaging. Hp Kr83 (I=9∕2) is generated by spin-exchange optical pumping and separated from the rubidium vapor used in the pumping process. Optical pumping occurs under the previously unstudied condition of high krypton gas densities. Signal enhancements of more than three orders of magnitude compared to the thermal equilibrium Kr83 signal at 9.4T magnetic-field strength are obtained. The spin-lattice relaxation of Kr83 is caused primarly by quadrupolar couplings during the brief adsorption periods of the krypton atoms on the surrounding container walls and significantly limits the currently obtained spin polarization. Measurements in macroscopic glass containers and in desiccated canine lung tissue at field strengths between 0.05 and 3T using remotely detected hp Kr83 NMR spectroscopy reveal that the longitudinal relax...

Hyperpolarized 83Kr MRI of lungs

Hyperpolarized (hp) (83)Kr (spin I=9/2) is a promising gas-phase contrast agent that displays sensitivity to the surface chemistry, surface-to-volume ratio, and surface temperature of the surrounding environment. This proof-of-principle study demonstrates the feasibility of ex vivo hp (83)Kr magnetic resonance imaging (MRI) of lungs using natural abundance krypton gas (11.5% (83)Kr) and excised, but otherwise intact, rat lungs located within a custom designed ventilation chamber. Experiments comparing the (83)Kr MR signal intensity from lungs to that arising from a balloon with no internal structure inflated to the same volume with krypton gas mixture suggest that most of the observed signal originated from the alveoli and not merely the conducting airways. The (83)Kr longitudinal relaxation times in the rat lungs ranged from 0.7 to 3.7s but were reproducible for a given lung. Although the source of these variations was not explored in this work, hp (83)Kr T(1) differences may ultimately lead to a novel form of MRI contrast in lungs. The currently obtained 1200-fold signal enhancement for hp (83)Kr at 9.4T field strength is found to be 180 times below the theoretical upper limit.

Studying porous materials with krypton-83 NMR spectroscopy

This report is the first review of 83Kr nuclear magnetic resonance as a new and promising technique for exploring the surfaces of solid materials. In contrast to the spin I = 1/2 nucleus of 129Xe, 83Kr has a nuclear spin of I = 9/2 and therefore possesses a nuclear electric quadrupole moment. Interactions of the quadrupole moment with the electronic environment are modulated by surface adsorption processes and therefore affect the 83Kr relaxation rate and spectral lineshape. These effects are much more sensitive probes for surfaces than the 129Xe chemical shielding and provide unique insights into macroporous materials in which the 129Xe chemical shift is typically of little diagnostic value. The first part of this report reviews the effect of quadrupolar interactions on the 83Kr linewidth in zeolites and also the 83Kr chemical shift behavior that is distinct from that of its 129Xe cousin in some of these materials. The second part reviews hyperpolarized (hp) 83Kr NMR spectroscopy of macroporous materials in which the longitudinal relaxation is typically too slow to allow sufficient averaging of thermally polarized 83Kr NMR signals. The quadrupolar‐driven T1 relaxation times of hp 83Kr in these materials are sensitive to surface chemistry, surface‐to‐volume ratios, coadsorption of other species on surfaces, and surface temperature. Thus, 83Kr T1 relaxation can provide information about surfaces and chemical processes in macroscopic pores and can generate surface‐sensitive contrast in hp 83Kr MRI. Copyright

Binary-collision-induced longitudinal relaxation in gas-phase Kr83

Density dependent NMR relaxation measurements of noble gases can provide complementary information to that obtained from relaxation studies of molecular gases. However, conventional noble gas NMR is typically hindered by low sensitivity or prohibitively long relaxation times. In this work, the low sensitivity of (83)Kr (I=92) was overcome by spin exchange optical pumping, and the quadrupolar interaction dominated (83)Kr T(1) times of 40-400 s enabled rapid collection of relaxation data. The density dependence of the (83)Kr longitudinal relaxation in pure krypton was found to be about 1.6 x 10(-3) amagat(-1) s(-1). Experiments were also performed in krypton mixtures containing either helium or nitrogen as a buffer gas. By varying the composition and the density of these mixtures, the density dependence of buffer gas induced relaxation and the relaxation efficiency of (83)Kr-buffer gas collisions were determined. The results from these gas mixtures are compared with those from pure krypton.