Xe Polarization Research Articles

Determination of the polarization of Xe nuclear spin using transverse and longitudinal Rb in-situ magnetometers in NMR co-magnetometers

NMR co-magnetometers, as novel atomic sensors, can measure the angular velocity information in inertial measurements by detecting the spin precession of Xe nuclei. The Xe polarization plays a crucial role in the sensing unit of co-magnetometers, as it enhances the signal-to-noise ratio (SNR) and sensitivity of NMR sensors. Here we elucidated the Rabi dynamics of Xe nuclear spin and demonstrated two methods to determine the Xe polarization based on the classical Bloch equations. By detecting the optical rotation angle signal, we acquired the amplitude and the phase variations information in two methods, respectively. The transverse magnetometer relies on the amplitude of the free induction decay (FID) signal and applies a short pulse to flip the Xe fields into the transverse plane, enabling precise measurements. On the other hand, the longitudinal magnetometer offers an intuitive approach to measuring the demodulated phase variations by capturing the repetitive flips of longitudinal Xe fields. This paper discusses the advantages and disadvantages of both proposed methods, with the aim of enhancing the accuracy and authenticity of nuclear spin polarization measurements for noble gas atoms in atomic sensors.

Synchronous Spin-Exchange Optical Pumping.

We demonstrate a new approach to precision NMR with hyperpolarized gases designed to mitigate NMR shifts due to the alkali spin-exchange field. The NMR bias field is implemented as a sequence of alkali (Rb) 2π pulses, allowing the Rb polarization to be optically pumped transverse to the bias field. When the Rb polarization is modulated at the noble-gas (Xe) NMR resonance, spin-exchange collisions buildup a precessing transverse Xe polarization. We study and mitigate novel NMR broadening effects due to the oscillating spin-exchange field. Spin-exchange frequency shifts are suppressed 2500×, and Rb magnetometer gain measurements project photon shot-noise limited NMR frequency uncertainties below 10 nHz/sqrt[Hz].

Optical hyperpolarization and NMR detection of 129Xe on a microfluidic chip.

Optically hyperpolarized (129)Xe gas has become a powerful contrast agent in nuclear magnetic resonance (NMR) spectroscopy and imaging, with applications ranging from studies of the human lung to the targeted detection of biomolecules. Equally attractive is its potential use to enhance the sensitivity of microfluidic NMR experiments, in which small sample volumes yield poor sensitivity. Unfortunately, most (129)Xe polarization systems are large and non-portable. Here we present a microfabricated chip that optically polarizes (129)Xe gas. We have achieved (129)Xe polarizations >0.5% at flow rates of several microlitres per second, compatible with typical microfluidic applications. We employ in situ optical magnetometry to sensitively detect and characterize the (129)Xe polarization at magnetic fields of 1 μT. We construct the device using standard microfabrication techniques, which will facilitate its integration with existing microfluidic platforms. This device may enable the implementation of highly sensitive (129)Xe NMR in compact, low-cost, portable devices.

Multidimensional mapping of spin-exchange optical pumping in clinical-scale batch-mode 129Xe hyperpolarizers.

We present a systematic, multiparameter study of Rb/129Xe spin-exchange optical pumping (SEOP) in the regimes of high xenon pressure and photon flux using a 3D-printed, clinical-scale stopped-flow hyperpolarizer. In situ NMR detection was used to study the dynamics of 129Xe polarization as a function of SEOP-cell operating temperature, photon flux, and xenon partial pressure to maximize 129Xe polarization (PXe). PXe values of 95 ± 9%, 73 ± 4%, 60 ± 2%, 41 ± 1%, and 31 ± 1% at 275, 515, 1000, 1500, and 2000 Torr Xe partial pressure were achieved. These PXe polarization values were separately validated by ejecting the hyperpolarized 129Xe gas and performing low-field MRI at 47.5 mT. It is shown that PXe in this high-pressure regime can be increased beyond already record levels with higher photon flux and better SEOP thermal management, as well as optimization of the polarization dynamics, pointing the way to further improvements in hyperpolarized 129Xe production efficiency.

A 3D-Printed High Power Nuclear Spin Polarizer

Three-dimensional printing with high-temperature plastic is used to enable spin exchange optical pumping (SEOP) and hyperpolarization of xenon-129 gas. The use of 3D printed structures increases the simplicity of integration of the following key components with a variable temperature SEOP probe: (i) in situ NMR circuit operating at 84 kHz (Larmor frequencies of (129)Xe and (1)H nuclear spins), (ii) <0.3 nm narrowed 200 W laser source, (iii) in situ high-resolution near-IR spectroscopy, (iv) thermoelectric temperature control, (v) retroreflection optics, and (vi) optomechanical alignment system. The rapid prototyping endowed by 3D printing dramatically reduces production time and expenses while allowing reproducibility and integration of "off-the-shelf" components and enables the concept of printing on demand. The utility of this SEOP setup is demonstrated here to obtain near-unity (129)Xe polarization values in a 0.5 L optical pumping cell, including ∼74 ± 7% at 1000 Torr xenon partial pressure, a record value at such high Xe density. Values for the (129)Xe polarization exponential build-up rate [(3.63 ± 0.15) × 10(-2) min(-1)] and in-cell (129)Xe spin-lattice relaxation time (T1 = 2.19 ± 0.06 h) for 1000 Torr Xe were in excellent agreement with the ratio of the gas-phase polarizations for (129)Xe and Rb (PRb ∼ 96%). Hyperpolarization-enhanced (129)Xe gas imaging was demonstrated with a spherical phantom following automated gas transfer from the polarizer. Taken together, these results support the development of a wide range of chemical, biochemical, material science, and biomedical applications.

Configuration and Performance of a Mobile 129Xe Polarizer

A stand-alone, self-contained and transportable system for the polarization of 129Xe by spin exchange optical pumping with Rb is described. This mobile polarizer may be operated in batch or continuous flow modes with medium amounts of hyperpolarized 129Xe for spectroscopic or small animal applications. A key element is an online nuclear magnetic resonance module which facilitates continuous monitoring of polarization generation in the pumping cell as well as the calculation of the absolute 129Xe polarization. The performance of the polarizer with respect to the crucial parameters temperature, xenon and nitrogen partial pressures, and the total gas flow is discussed. In batch mode the highest 129Xe polarization of PXe = 40 % was achieved using 0.1 mbar xenon partial pressure. For a xenon flow of 6.5 and 26 mln/min, P Xe = 25 % and P Xe = 13 % were reached, respectively. The mobile polarizer may be a practical and efficient means to make the applicability of hyperpolarized 129Xe more widespread.

Mobile High Resolution Xenon Nuclear Magnetic Resonance Spectroscopy in the Earth’s Magnetic Field

Conventional high resolution nuclear magnetic resonance (NMR) spectra are usually measured in homogeneous, high magnetic fields (>1 T), which are produced by expensive and immobile superconducting magnets. We show that chemically resolved xenon (Xe) NMR spectroscopy of liquid samples can be measured in the Earth's magnetic field (5 x 10(-5) T) with a continuous flow of hyperpolarized Xe gas. It was found that the measured normalized Xe frequency shifts are significantly modified by the Xe polarization density, which causes different dipolar magnetic fields in the liquid and in the gas phases.

Dynamic NMR spectroscopy of hyperpolarized (129)Xe in human brain analyzed by an uptake model.

Hyperpolarized (129)Xe (HpXe) NMR not only holds promise for functional lung imaging, but for measurements of tissue perfusion as well. To investigate human brain perfusion, several time-series of (129)Xe MR spectra were recorded from one healthy volunteer after HpXe inhalation. The time-dependent amplitudes of the MR spectra were analyzed by using a compartment model for xenon uptake modified to account for the loss of (129)Xe polarization due to RF-excitation and for the breathhold technique used in the experiments. This analysis suggests that the resonances detected at 196.5 +/- 1 ppm and 193 +/- 1 ppm originate from HpXe dissolved in gray and white matter, respectively, and that T(1) relaxation times of HpXe are different in gray and white matter (T(1g) > T(1w)).

Time resolved spectroscopic NMR imaging using hyperpolarized 129Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized 129Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.

Rubidium–xenon spin exchange and relaxation rates measured at high pressure and high magnetic field

The production of hyperpolarized Xe via spin exchange with optically pumped Rb atoms was studied at 47 000 G under high-pressure conditions. From variable pressure and temperature studies, the spin exchange efficiency was found to be pressure dependent and lower than comparable low-field measurements. Spin exchange due to short binary collisions is expected to be pressure independent, and the cross section was measured to be 〈σν〉SE=6.0 (±0.1)×10−17 cm3 s−1. The pressure dependent component was attributed to the formation of Rb–Xe van der Waals (vdW) complexes. The rate constant for spin exchange in Rb–Xe vdW complexes was measured to be κ=1400 (±100) s−1 in He buffer gas. This value is comparable, though somewhat smaller than vdW rates measured previously for other buffer gases. While it is well known that spin exchange occurs readily in vdW complexes when B0&amp;lt;200 G, vdW spin exchange at fields &amp;gt;10 000 G is not accounted for in current theories. Modulation of the hyperfine interaction during the vdW complex lifetime is proposed to account for these observations. Finally, relaxation by the walls of the pumping cell was found to increase with buffer gas pressure. These factors impact the equilibrium Xe polarization obtainable with high-field optical pumping.

Measurement of rubidium and xenon absolute polarization at high temperatures as a means of improved production of hyperpolarized (129)Xe.

We report on a rubidium-xenon (Rb-Xe) polarization unit for the continuous production of large quantities of hyperpolarized (129)Xe. The unit includes two diagnostic systems which enable the absolute measurement of both the (85)Rb and (129)Xe polarization in situ and at high temperatures. The Rb diagnostic system allows the measurement of one- or two-dimensional images of the absolute Rb polarization and thus enables the experimental study of light penetration into the optical pumping cell. The equilibrium Xe polarization measured in the optical pumping cell and in the freezing unit is typically approximately 20%, under optimal flowing conditions, and this is much lower than the volume-averaged rubidium polarization.

Cross-relaxation in laser-polarized liquid xenon

By dissolving compounds in hyperpolarized liquid Xe, we have successfully transferred the 129 Xe polarization to other spins in solution. We have observed signal enhancements of over 45 for 1 H, and over 70 for 13 C, compared to their thermal polarization signals at 200 K and 1.4 T. The lifetimes of the enhancements are on the order of 20 min. In addition, in dissolved toluene we have seen preferential enhancement of the ring protons over the methyl protons.

Crystal face specificity of xenon adsorption on iridium field emitters

Fundamental problems of the adsorption of noble gas atoms on metal surfaces are discussed on the basis of new data of xenon adsorption on well-defined crystal faces of iridium. These data include surface potentials ( = changes in work function), heats of adsorption and their decrease with increasing coverage; they have been obtained by using a field emitter probe-hole assembly. It is found that the heat of adsorption Q hkl is not simply additive in the number of Ir atoms contacting a Xe atom on a given site; in particular for the close-packed faces, Q 111 and Q 100 are relatively too high. Apparently, strong bonding is favoured by high work function of the adsorbing crystal face. This proves a significant contribution of a charge-transfer no-bond interaction to the adsorption bond. A model of Xe polarization by an electric surface field is rejected, as it predicts the wrong sign for the adsorption dipole. While at low coverage adsorption is confined to sites determined by the atomic topography of the adsorbing surface, several possibilities exist for high coverages. Either a two-dimensional close-packed layer is formed with little or no epitaxial relation to surface topography, or adsorption remains confined to certain sites. The present data favour the former possibility for atomically smooth faces in agreement with recent LEED results. For atomically rough faces however, the smallness of the decrease of Q hkl with coverage seems to favour site adsorption even at high coverage. The latter result is of relevance for surface area determinations by means of “physical” adsorption.