~(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。     

129Xe核自旋极化转移增强分子的核磁共振信号

激光极化的129Xe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129Xe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。     

NMR Study of Laser polarized ~(129) Xe in Low Pressure Natural Xenon Gas

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NMR Study of Laser-polarized 129Xe in Low Pressure Natural Xenon Gas

The NMR signal from the laser-polarized t29 Xe in low-pressure natural xenon gas has been observed with a Bruker WP-80SY NMR spectrometer. The laser-polarized 129 Xe was produced by the method of laser pumping and spin exchange in a magnetic field of 1.87 Tesla. It is obtained experimentally that the nuclear spin relaxation rate 1/T1 of laser-polarized 129Xe are (4.03±1.97)×10-3/see～(2.21±0.78)×10-3/see in the range of the 3.33×103 Pa～8.29×104 Pa Xe gas pressures, the apparent wall relaxation rate 1/Tw* =(1.98±0.18)×10-3/see, and the relaxation rate coefficient C of 133Cs-129Xe spin exchange is (2.81±0.74)×10-16 em3/sec.     

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     

Consequences of (129)Xe-(1)H cross relaxation in aqueous solutions.

We have investigated the transfer of polarization from (129)Xe to solute protons in aqueous solutions to determine the feasibility of using hyperpolarized xenon to enhance (1)H sensitivity in aqueous systems at or near room temperatures. Several solutes, each of different molecular weight, were dissolved in deuterium oxide and although large xenon polarizations were created, no significant proton signal enhancement was detected in l-tyrosine, alpha-cyclodextrin, beta-cyclodextrin, apomyoglobin, or myoglobin. Solute-induced enhancement of the (129)Xe spin-lattice relaxation rate was observed and depended on the size and structure of the solute molecule. The significant increase of the apparent spin-lattice relaxation rate of the solution phase (129)Xe by alpha-cyclodextrin and apomyoglobin indicates efficient cross relaxation. The slow relaxation of xenon in beta-cyclodextrin and l-tyrosine indicates weak coupling and inefficient cross relaxation. Despite the apparent cross-relaxation effects, all attempts to detect the proton enhancement directly were unsuccessful. Spin-lattice relaxation rates were also measured for Boltzmann (129)Xe in myoglobin. The cross-relaxation rates were determined from changes in (129)Xe relaxation rates in the alpha-cyclodextrin and myoglobin solutions. These cross-relaxation rates were then used to model (1)H signal gains for a range of (129)Xe to (1)H spin population ratios. These models suggest that in spite of very large (129)Xe polarizations, the (1)H gains will be less than 10% and often substantially smaller. In particular, dramatic (1)H signal enhancements in lung tissue signals are unlikely.     

A rapid and precise probe for measurement of liquid xenon polarization

The relaxation time of liquid (129)Xe is very long (>15 min) and the signal at thermal equilibrium is weak. Therefore, determination of the absolute polarization enhancement of hyperpolarized (129)Xe by direct measurement is tedious. We demonstrate a fast and precise alternative, based on the dipolar field created by liquid hyperpolarized (129)Xe contained in a cylindrical sample tube. The dipolar field is homogeneous in the bulk of the tube and adds to the external field, causing a shift in the Larmor frequencies of all nuclear spins. We show that the frequency shift of the proton in CHCl(3) (chloroform), which dissolves homogeneously in xenon over a fairly broad temperature range, is an excellent probe for (129)Xe polarization. Frequency measurements are precise and the experiment is much faster than by direct measurement. Furthermore the (129)Xe polarization is minimally disturbed since no rf pulses are applied directly to (129)Xe and since chloroform is a fairly weak source of (129)Xe relaxation. The experiments are reproducible and require only standard NMR instrumentation.     

Free precession and transverse relaxation of hyperpolarized <Superscript>129</Superscript>Xe gas detected by SQUIDs in ultra-low magnetic fields

We studied the free precession of the nuclear magnetization of hyperpolarized ¹²⁹Xe gas in external magnetic fields as low as B₀ = 4.5 nT, using SQUIDs as magnetic flux detectors. The transverse relaxation was mainly caused by the restricted diffusion of ¹²⁹Xe in the presence of ambient magnetic field gradients. Its pressure dependence was measured in the range from 30 mbar to 850 mbar and compared quantitatively to theory. Motional narrowing was observed at low pressure, yielding transverse relaxation times of up to 8000 s.     

Nonlinear amplification of small spin precession using long-range dipolar interactions

In measurements of small signals using spin precession the precession angle usually grows linearly in time. We show that a dynamic instability caused by spin interactions can lead to an exponentially growing spin-precession angle, amplifying small signals and raising them above the noise level of a detection system. We demonstrate amplification by a factor of greater than 8 of a spin-precession signal due to a small magnetic field gradient in a spherical cell filled with hyperpolarized liquid 129Xe. This technique can improve the sensitivity in many measurements that are limited by the noise of the detection system, rather than the fundamental spin-projection noise.     

Nuclear spin resonance of (129)Xe doped with O(2)

Spin-lattice relaxation of (129)Xe nuclei in solid natural xenon has been investigated in detail over a large range of paramagnetic O(2) impurity concentrations. Direct measurements of the ground state magnetic properties of the O(2) are difficult because the ESR (electron spin resonance) lines of O(2) are rather unstructured, but NMR measurements in the liquid helium temperature region (1.4-4 K) are very sensitive to the effective magnetic moments associated with the spin 1 Zeeman levels of the O(2) molecules and to the O(2) magnetic relaxation. From these measurements, the value of the D[Sz(2)-(1/3)S(2)] spin-Hamiltonian term of the triplet spin ground state of O(2) can be determined. The temperature and magnetic field dependence of the measured paramagnetic O(2)-induced excess line width of the (129)Xe NMR signal agree well with the theoretical model with the spin-Hamiltonian D=0.19 meV (2.3 K), and with the reasonable assumption that the E[S(x)(2)-S(y)(2)] spin-Hamiltonian term is close to 0 meV. An anomalous temperature dependence between 1.4 K and 4.2K of the (129)Xe spin-lattice relaxation rate, T(1n)(-1)(T), is also accounted for by our model. Using an independent determination of the true O(2) concentration in the Xe-O(2) solid, the effective spin lattice relaxation time (which will be seen to be transition dependent) of the O(2) at 2.3 K and 0.96 T is determined to be approximately 1.4 x 10(-8)s. The experimental results, taken together with the relaxation model, suggest routes for bringing highly spin-polarized (129)Xe from the low temperature condensed phase to higher temperatures without excessive depolarization.     

Wall relaxation of spin polarized 129Xe nuclei

The wall relaxation of spin polarized ¹²⁹Xe nuclei is much longer in silicone coated pyrex cells than in uncoated cells. In contrast to uncoated glass cells where the wall relaxation times are unpredictable and usually only a few tens of seconds, the relaxation time of ¹²⁹Xe in silicone-coated cells is usually 20 minutes or longer.     

Development of co-located 129Xe and 131Xe nuclear spin masers with external feedback scheme

We report on the operation of co-located ¹²⁹Xe and ¹³¹Xe nuclear spin masers with an external feedback scheme, and discuss the use of ¹³¹Xe as a comagnetometer in measurements of the ¹²⁹Xe spin precession frequency. By applying a correction based on the observed change in the ¹³¹Xe frequency, the frequency instability due to magnetic field and cell temperature drifts are eliminated by two orders of magnitude. The frequency precision of 6.2 μHz is obtained for a 10⁴ s averaging time, suggesting the possibility of future improvement to ≈ 1 nHz by improving the signal-to-noise ratio of the observation.     

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。     

Intermolecular dipole-dipole relaxation of (129)Xe dissolved in water

Intermolecular (129)Xe-(1)H nuclear Overhauser effects and (129)Xe longitudinal relaxation time measurements were used to demonstrate that the dipole-dipole coupling is the dominant relaxation mechanism for (129)Xe in water, at room temperature. (129)Xe-(1)H cross-relaxation rates were derived to be sigma(XeH) approximately 3.2 +/- 0.3 x 10(-3) s(-1), independent of xenon pressure (in the range of 1-10 bar) and of the presence of oxygen. Corresponding xenon-proton internuclear distances were calculated to be 2.69 +/- 0.12 A. Using the magnitude of the dipole-dipole coupling and the spin density ratio between dissolved xenon and bulk water, it is estimated that (129)Xe-(1)H spin polarization-induced nuclear Overhauser effects would yield little net proton signal enhancement in water.     

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.     

MEASUREMENTS OF RELAXATION OF SPIN POLARIZED 129Xe NUCLEI IN HIGH MAGNETIC FIELDS

We observed the NMR signal of low-pressure gas ¹²⁹Xe by laser enhanced method on an MSL-400 NMR spectrometer and measured nuclear spin relaxations of ¹²⁹Xe gas at various temperatures. The relaxation rate constant of ¹²⁹Xe-¹³³Cs spin exchange was obtained as (6.8±0.5)×10^-16cm^-3s^-1.     

Motion dependence of myocardial transverse relaxation time in magnetic resonance imaging

We discuss the effects of motion on the computation of the myocardial transverse relaxation time by use of magnetic resonance imaging. Equations describing its behavior are derived and illustrated graphically under different conditions. It is shown that the myocardial transverse relaxation time calculated from magnetic resonance images depends on the actual myocardial transverse relaxation time ex vivo (T2) as well as the phase of the cardiac cycle in which it is computed, heart rate, cardiac wall velocity, choice of spin-echoes used in the calculation, and the spin-echo times employed. In particular, the error in T2 decreases when both the first and third echoes are employed in the calculation, rather than only the first two echoes. However, the myocardial transverse relaxation time is more strongly dependent on heart rate in the former case rather than in the latter. Furthermore, the error in T2, when both the first and second spin echoes are used in the calculation, is seen to increase as the spin-echo time shortens. On the other hand, the error in T2 decreases for shorter spin-echo times when both the first and third spin echoes are used instead. The results are relevant to the noninvasive assessment of ischemia, cardiac transplantation rejection, and other myocardial disorders.     

NMR phase noise in bitter magnets

We have studied the temporal instability of a high field resistive Bitter magnet through nuclear magnetic resonance (NMR). This instability leads to transverse spin decoherence in repeated and accumulated NMR experiments as is normally performed during signal averaging. We demonstrate this effect via Hahn echo and Carr--Purcell--Meiboom--Gill (CPMG) transverse relaxation experiments in a 23-T resistive magnet. Quantitative analysis was found to be consistent with separate measurements of the magnetic field frequency fluctuation spectrum, as well as with independent NMR experiments performed in a magnetic field with a controlled instability. Finally, the CPMG sequence with short pulse delays is shown to be successful in recovering the intrinsic spin--spin relaxation even in the presence of magnetic field temporal instability.     

Gas flow MRI using circulating laser-polarized 129Xe.

We describe an experimental approach that combines multidimensional NMR experiments with a steadily renewed source of laser-polarized 129Xe. Using a continuous flow system to circulate the gas mixture, gas phase NMR signals of laser-polarized 129Xe can be observed with an enhancement of three to four orders of magnitude compared to the equilibrium 129Xe NMR signal. Due to the fact that the gas flow recovers the nonequilibrium 129Xe nuclear spin polarization in 0.2 to 4 s, signal accumulation on the time scale of seconds is feasible, allowing previously inaccessible phase cycling and signal manipulation. Several possible applications of MRI of laser-polarized 129Xe under continuous flow conditions are presented here. The spin density images of capillary tubes demonstrate the feasibility of imaging under continuous flow. Dynamic displacement profiles, measured by a pulsed gradient spin echo experiment, show entry flow properties of the gas passing through a constriction under laminar flow conditions. Further, dynamic displacement profiles of 129Xe, flowing through polyurethane foams with different densities and pore sizes, are presented.     

Nuclear Spin Maser Oscillation of 129Xe by Means of Optical-Detection Feedback

We have developed the nuclear spin maser oscillating at a low frequency of 34 Hz with highly polarized nuclear spins of the noble gas element ¹²⁹Xe. The system is advantageous for detecting a small frequency shift of the nuclear spin precession. We are thus planning to apply this system to the search for an atomic electric dipole moment of ¹²⁹Xe. We here report the development of the system and its performance.