Enhanced NMR signal from the laser-polarized129Xe produced by spin exchange at a high magnetic field

Nuclear-magnetic-resonance (NMR) measurement of laser-polarized gaseous¹²⁹Xe produced by spin-exchange optical pumping with a narrow-linewidth laser at a high magnetic field of 4.7 T is reported. The samples are contained in the glass tubes. The nuclear spin polarization of the laserpolarized¹²⁹Xe is 3.9%, and this corresponds to an enhancement of 9· 10³ compared to the equilibrium value at 311 K and at the same magnetic field. The laser-enhanced¹²⁹Xe NMR signals can be used in MR imaging.     

Performance assessment of a new laser system for efficient spin exchange optical pumping in a spin maser measurement of <Superscript>129</Superscript>Xe EDM

We demonstrate spin-exchange optical pumping of ¹²⁹Xe atoms with our newly made laser system. The new laser system was prepared to provide higher laser power required for the stable operation of spin maser oscillations in the ¹²⁹Xe EDM experiment. We studied the optimum cell temperature and pumping laser power to improve the degree of ¹²⁹Xe spin polarization. The best performance was achieved at the cell temperature of 100 ^°C with the presently available laser power of 1 W. The results show that a more intense laser is required for further improvement of the spin polarization at higher cell temperatures in our experiment.     

129Xe and131Xe NMR of xenon on silica surfaces at 77 K

Little is known about¹²⁹Xe NMR spectral features and spin-lattice relaxation behavior, and the dynamics of xenon atoms, for xenon adsorbed on solid surfaces at cryogenic temperatures (≤77 K), where exchange with gas-phase atoms is not a significant complication. We report¹²⁹Xe NMR experiments at 9,4 T that provide such information for xenon adsorbed onto the hydroxylated surface of a number of microporous silica samples at 77 K. A convenient design for these cryogenic experiments is described. Dynamics of surface-adsorbed xenon atoms on the time scale of seconds can be observed by¹²⁹Xe NMR hole-burning experiments; much slower dynamics occurring over hours and days are evidenced from changes with time of the¹²⁹Xe NMR chemical shifts. The peak maxima occur in the region ca. 180–316 ppm, considerably downfield of¹²⁹Xe shifts previously reported on surfaces at higher temperatures, and closer to the shift of xenon bulk solid (316.4±1 ppm). The¹²⁹Xe spin-lattice relaxation timesT ₁ range over five orders of magnitude; possible explanations for both nonexponential relaxation behavior and extremely shortT ₁ values (35 ms) are discussed. Preliminary¹³¹Xe and¹H NMR results are presented, as well as a method for greatly increasing the sensitivity of¹²⁹Xe NMR detection at low temperatures by using closely-spaced trains of rf pulses.     

激光极化129Xe的生物磁共振成像研究进展

激光光抽运自旋交换方法能够极大地增强＾１２９Ｘｅ核自旋极化,其获得的非平衡极化度远远高于在相同磁场里玻尔兹曼平衡值。     

Nuclear orientation measurements of the magnetic dipole moments of the 11/2− Isomeric states in129Xe,131Xe and133Xe

The low-temperature nuclear orientation technique was used to measure the magnetic moments of¹²⁹ mXe,¹³¹ mXe and¹³³ mXe implanted in iron by isotope separator. The magnitudes of the magnetic dipole moments, extracted from the gamma-ray anisotropy measurements areμ=?0.80(10)μ _N for^129m Xe,μ=?0.80(10)μ _N for¹³¹Xe andμ=?0.87(12)% for¹³³Xe. The results for these 11/2^? isomers agree with theoretical calculations by the spin polarization procedure using wave functions from the pairing-plus-quadrupole model.     

NMR of Xe on CO/Ir(1 1 1) and on multilayer Xe/Ir(1 1 1)

Nuclear magnetic resonance (NMR) is performed on monolayer (ML) amounts of adsorbed ¹²⁹Xe on a single crystal substrate. The inherently low sensitivity of NMR is overcome by using highly nuclear spin polarized ¹²⁹Xe that has been produced by optical pumping. A polarization of 0.8 is regularly achieved which is 10⁵ times the thermal (Boltzmann) polarization. The experiments are performed with a constant flux of xenon atoms impinging on the surface, typically 4 ML/s. The chemical shift (σ) of ¹²⁹Xe is highly sensitive to the Xe local environment. We measured profoundly different shifts for the Xe bulk, for the surface of the Xe bulk, and for Xe on CO/Ir(1 1 1). The growth of the bulk is seen in a phase transition like change of σ as a function of temperature at constant Xe flux. At temperatures where no bulk forms at a flux of 4 ML/s, the xenon exchange rate was measured by a spin inversion/recovery method. The exchange time of Xe is found to be 0.24 s at 63.4 K and 64.4 K and somewhat longer at 61.2 K. An analysis is given involving the desorption out of the second layer and fast mixing of first and second layer atoms at these temperatures.     

Production of nitrogen-free, hyperpolarized 129Xe gas

129 Xe with a nuclear polarization far above the thermal equilibrium value (hyperpolarized) is used in NMR studies to increase sensitivity. Gaseous, adsorbed, or dissolved xenon is utilized in physical, chemical, and medical applications. With the aim in mind to study single-crystal surfaces by NMR of adsorbed hyperpolarized ¹²⁹Xe, three problems have to be solved. The reliable production of ¹²⁹Xe with highest nuclear polarization possible, the separation of the xenon gas from the necessary quench gas nitrogen without polarization loss, and the dosing/delivery of small amounts of polarized xenon gas to a sample surface. Here we describe an optical pumping setup that regularly produces xenon gas with a ¹²⁹Xe nuclear polarization of 0.7(±0.07). We show that a freeze–pump–thaw separation of xenon and nitrogen is feasible without a significant loss in xenon polarization. The nitrogen partial pressure can be suppressed by a factor of 400 in a single separation cycle. Dosing is achieved by using the low vapor pressure of a frozen hyperpolarized xenon sample. Received: 12 June 1998     

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 P_Xe = 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.     

Hyperpolarized (131)Xe NMR spectroscopy

Hyperpolarized (hp) (131)Xe 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 T(1) 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 (131)Xe 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 (129)Xe SEOP. (131)Xe 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 (131)Xe 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 (131)Xe spectrum shows differential line broadening, suggesting the presence of strong adsorption sites. Beyond hp (131)Xe NMR spectroscopy studies, a general equation for the high temperature, thermal spin polarization, P, for spin I ≥ 1/2 nuclei is presented.     

流动系统中的激光增强固体和液体129Xe核磁共振信号

在流动系统中,用半导体阵列激光器在低磁场下抽运Cs原子,由自旋交换碰撞产生极化的129Xe气体,在SY80M核磁共振谱仪中,冻成固体和液体后的极化度分别为216%和145%,和相同条件下未光泵的129Xe极化度相比,分别增强6000和5000倍.为将激光增强固体和液体129Xe用于量子计算提供了基础和可能.并对输运和相变过程中极化损失作了讨论 关键词： 光泵 激光极化 核磁共振信号 光和原子相互作用     

Control of the nuclear spin of the <Superscript>129</Superscript>Xe and <Superscript>131</Superscript>Xe isotopes in the spin-exchange interaction with <Superscript>87</Superscript>Rb atoms

Nuclear spin dynamics of the ¹²⁹Xe and ¹³¹Xe isotopes in an external magnetic field B ₀ is considered. Nuclear spin is pumped by the laser through ⁸⁷Rb, which transfers the electron spin to the ¹²⁹Xe and ¹³¹Xe nuclei in the spin-exchange interaction. The nuclear spin dynamics is controlled with a transverse magnetic field that causes nuclear magnetic resonance in both ¹²⁹Xe and ¹³¹Xe isotopes. Numerical calculations are performed to find conditions at which the transverse component of the nuclear spin in the established motion is of maximum and the slope angle relative to the vector of the constant magnetic field B ₀ is 45°. This regime is taken to be optimal for simulation of practical applications. It is also found that the pump of the nuclear spin of xenon is strongly attenuated when the rubidium polarization vector is turned to the plane perpendicular to the external magnetic field vector B ₀.     

~(129)Xe核自旋极化转移增强分子的核磁共振信号

激光极化的12 9Xe核具有极高的非平衡极化度和长的弛豫时间 ,这一特点使得它能够极化转移增强液体、固体或者固体表面分子中原子核自旋极化。因而 ,提高了它们的核磁共振探测灵敏度和扩展了在材料和表面科学研究中的应用。综述激光极化12 9Xe核与其它分子中原子核之间的极化转移研究与进展 ,介绍相关物理机制和参数的测量。     

High capacity production of >65% spin polarized xenon-129 for NMR spectroscopy and imaging

A rubidium spin exchange optical pumping system for high capacity production of >65% spin polarized 129Xe gas is described. This system is based on a fiber coupled multiple laser diode array capable of producing an unprecedented 210 W of circularly polarized light at the pumping cell with a laser line width of 1.6 nm. The 129Xe nuclear spin polarization is measured as a function of flow rate, pumping cell pressure, and laser power for varying pumping gas compositions. A maximum 129Xe nuclear polarization of 67% was achieved using a 0.6% Xe mixture at a Xe flow rate of 2.45 sccm. The ability to generate 12% polarized 129Xe at rates in excess of 1L-atm/h is also demonstrated. To achieve production of 129Xe gas at even higher polarization will rely on further optimization of the pumping cell and laser beam geometries in order to mitigate problems associated with temperature gradients that are encountered at high laser power and Rb density.     

Present status of the 129Xe comagnetometer development for neutron EDM measurement

A ¹²⁹Xe comagnetometer designed for the measurement of neutron electric dipole moment (nEDM) as precisely as 1 × 10^?27e cm is presented. Highly nuclear spin polarized ¹²⁹Xe are introduced into an EDM cell where the ¹²⁹Xe spin precession is detected by means of the two-photon transition. The geometric phase effect (GPE) which generates the false nEDM was quantitatively discussed and the systematic error of nEDM from the GPE was estimated considering the buffer-gas suppression due to Xe atomic collisions. Research and development are in progress to construct the ¹²⁹Xe comagnetometer with a field sensitivity of 0.3 fT. At present, about 70 % nuclear spin polarized ¹²⁹Xe atoms have been obtained in a spin exchange opitial pumping cell, that are in the process of being transferred into the EDM cell via a cold trap.     

Time resolved spectroscopic NMR imaging using hyperpolarized Xe

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.     

Study of the124Xe and126Xe structure

The level structure of¹²⁴Xe and¹²⁶Xe is studied on the basis ofβ ⁺ decay of¹²⁴Cs and¹²⁶Cs. The Cs isotopes were produced in the Xe(p, n) Cs reactions at a proton energy ofE≈9.5 MeV. Decay schemes are proposed for these nuclei. The available experimental data are compared with the predictions of various models.     

Intravascular delivery of hyperpolarized129Xenon forin vivo MRI

The nuclear polarization of¹²⁹Xe and³He can be enhanced by several orders of magnitude by using optical pumping techniques, thus allowing NMR detection of xenon and helium in very low concentrations. The benefits of optically enhanced magnetic resonance (MR) are already exploited in MR imaging of the lungs using optically polarized³He. The high solubility of xenon in blood and lipids suggests a variety ofin vivo MR applications, for instance perfusion measurements or functional MR studies. This article reviews some current work directed towards delivery of optically polarized xenon forin vivo MR applications.     

XeNA: An automated ‘open-source’ Xe hyperpolarizer for clinical use

Here we provide a full report on the construction, components, and capabilities of our consortium’s “open-source” large-scale (~ 1 L/h) ¹²⁹Xe hyperpolarizer for clinical, pre-clinical, and materials NMR/MRI (Nikolaou et al., Proc. Natl. Acad. Sci. USA, 110, 14150 (2013)). The ‘hyperpolarizer’ is automated and built mostly of off-the-shelf components; moreover, it is designed to be cost-effective and installed in both research laboratories and clinical settings with materials costing less than $125,000. The device runs in the xenon-rich regime (up to 1800 Torr Xe in 0.5 L) in either stopped-flow or single-batch mode—making cryo-collection of the hyperpolarized gas unnecessary for many applications. In-cell ¹²⁹Xe nuclear spin polarization values of ~ 30%–90% have been measured for Xe loadings of ~ 300–1600 Torr. Typical ¹²⁹Xe polarization build-up and T₁ relaxation time constants were ~ 8.5 min and ~ 1.9 h respectively under our spin-exchange optical pumping conditions; such ratios, combined with near-unity Rb electron spin polarizations enabled by the high resonant laser power (up to ~ 200 W), permit such high P_Xe values to be achieved despite the high in-cell Xe densities. Importantly, most of the polarization is maintained during efficient HP gas transfer to other containers, and ultra-long ¹²⁹Xe relaxation times (up to nearly 6 h) were observed in Tedlar bags following transport to a clinical 3 T scanner for MR spectroscopy and imaging as a prelude to in vivo experiments. The device has received FDA IND approval for a clinical study of chronic obstructive pulmonary disease subjects. The primary focus of this paper is on the technical/engineering development of the polarizer, with the explicit goals of facilitating the adaptation of design features and operative modes into other laboratories, and of spurring the further advancement of HP-gas MR applications in biomedicine.     

A129Xe NMR study of highly cadmium-exchanged zeolite Y

The adsorption isotherms of carbon monoxide and xenon as well as the¹²⁹Xe NMR chemical shifts of xenon in highly (68 and 87%) cadmium-exchanged zeolite NaY were measured. The complete set of experimental data can quantitatively be reproduced with a model that considers localized adsorption of both adsorbate molecules on cadmium and sodium cation sites in the supercages. The concentrations of the supercage cadmium cations as well as their characteristics like adsorption constants for Xe and CO and¹²⁹Xe NMR chemical shifts were determined.     

Novel MRI applications of laser-polarized noble gases

Gas-phase nuclear magnetic resonance (NMR) has great potential as a probe for a variety of interesting physical and biomedical problems that are not amenable to study by water or similar liquid. However, NMR of gases was largely neglected due to the low signal obtained from the thermally polarized gases with very low sample density. The advent of optical pumping techniques for enhancing the polarization of the noble gases³He and¹²⁹Xe has bought new life to this field, especially in medical imaging where³He lung inhalation imaging is approaching a clinical application. However, there are numerous applications in materials science that also benefit from the use of these gases. We review primarily nonmedical applications of laser-polarized noble gases for both NMR imaging and spectroscopy and highlight progress with examples from our laboratory including high-resolution imaging at millitesla applied field strength and velocity imaging of convective flow. Porous media microstucture has been probed with both thermal and laser-polarized xenon, as xenon is an ideal probe due to low surface interaction with the grains of the porous media.