129Xe NMR study of Xe adsorption on multiwall carbon nanotubes

¹²⁹Xe NMR spectroscopy has been used to study the adsorption of Xe on multi-wall carbon nanotubes (MWCNT). The results obtained have shown the ¹²⁹Xe NMR ability to probe the intercrystalline (aggregate) and the inner porosity of CNT. In particular, the effects on porosity of tubes openings by hydrogen exposure and of ball milling were examined. Dramatic changes observed in the ¹²⁹Xe NMR spectra after moderate ball milling of MWCNTs were attributed to the destruction of the initial intercrystalline pore structure and to the Xe access inside the nanotubes. To examine the exchange dynamics the mixture of as-made and milled MWCNTs was studied with one- and two-dimensional (1D and 2D) ¹²⁹Xe NMR. The exchange between the interior of milled nanotubes and the aggregate pores of as-made MWCNTs was fast on the NMR acquisition time scale. The Xenon exchange between the interior of the as-made MWCNTs and the large aggregate pores occurred on a longer time scale of 10 ms, as was established by 2D ¹²⁹Xe NMR exchange spectroscopy. Variable temperature ¹²⁹Xe NMR data were also discussed and analyzed in terms of the fast exchange approximation.     

超极化129Xe自动收集-升华装置研究

因其较高的核自旋极化度所提供的探测灵敏度，超极化¹²⁹Xe气体已被成功应用于动物和人体磁共振成像（MRI）.但是，在超极化¹²⁹Xe的收集-升华过程中，多种因素会导致¹²⁹Xe核自旋弛豫，进而限制其应用范围.本文通过理论模型分析和实验测量，验证了温度、磁场、螺旋冷阱材质等对冷冻恢复过程中超极化¹²⁹Xe弛豫的影响；同时，测量了自动收集-升华装置的稳定性.研究结果表明，升华方式和冷阱材质对¹²⁹Xe极化度损耗的影响显著；自制收集-升华装置的自动化程度高、长时间稳定，¹²⁹Xe极化度的恢复率可达到85.6% ± 4.7%.本研究非常有助于提升超极化¹²⁹Xe在动物和人体MRI中的使用效率.     

新型葫芦[6]脲纳米颗粒超极化129Xe"分子笼"研究

在相同浓度下,超极化¹²⁹Xe的核磁共振（NMR）灵敏度是传统质子NMR的10 000倍以上,但单原子Xe不具有靶向性,只有单一NMR信号.若超极化¹²⁹Xe与“分子笼”相结合,就能获得新的“笼”内Xe信号,为发展超极化¹²⁹Xe分子探针奠定基础.因此,构建新型的“分子笼”是发展新型超极化¹²⁹Xe分子探针的一个重要方向.葫芦[6]脲纳米颗粒的出现能改善以葫芦[6]脲为主体的¹²⁹Xe分子探针水溶性差、信号弱等缺点.本文构建了水溶性的葫芦[6]脲纳米颗粒,并发现其具有葫芦[6]脲/纳米颗粒内部两个“笼”内¹²⁹Xe信号.这一发现使这种纳米颗粒具有成为超极化¹²⁹Xe分子探针的潜力,能降低检测结果中假阳性和假阴性的发生率,值得更深入的探索和研究.     

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.     

超极化129Xe磁共振分子影像学

磁共振分子影像学发展的主要瓶颈之一在于灵敏度的限制,基于激光光泵和自旋交换技术能获得增强4~5个量级的超极化¹²⁹Xe磁共振信号,因此超极化¹²⁹Xe磁共振分子影像学相对于传统MRI在灵敏度上表现出巨大的优势. 围绕提高灵敏度这一核心MRI问题及其在科学研究中的应用,该文介绍了目前基于超极化¹²⁹Xe的生物分子探针的基本结构和原理,阐述了与之相关的分子影像学方法和技术,同时评述了当前的最新研究进展和发展方向.     

MEASUREMENTS OF 129Xe NUCLEAR MAGNETIC RESONANCE IN GASEOUS,LIQUID AND SOLID XENON

Natural xenon, contained in a ceil at a pressure of 6.5 atm, is frozen from 303 to 137 K on an WP-80SY NMR spectrometer. NMR signals of ¹²⁹Xe atoms in gaseous, liquid and solid phases are measured at various temperatures, We found that the chemical shift of NMR signal of liquid ¹²⁹Xe (expressed as ΔH) is directly proportional to the density of the sample with a coefficient of (4.73±0.05)×10^-7; and the chemical shift of NMR signal of solid ¹²⁹Xe (expressed as ΔH) is nearly proportional to the density of the sample with a coefficient of (5.00±0.08)×10^-7.     

Parameter analysis for a nuclear magnetic resonance gyroscope based on bf133Cs-129Xe/131Xe

We theoretically investigate several parameters for the nuclear magnetic resonance gyroscope based on ¹³³Cs-¹²⁹Xe/¹³¹Xe. For a cell containing a mixture of ¹³³Cs at saturated pressure, we investigate the optimal quenching gas (N₂) pressure and the corresponding pump laser intensity to achieve 30% ¹³³Cs polarization at the center of the cell when the static magnetic field B₀ is 5 μT with different ¹²⁹Xe/¹³¹Xe pressure. The effective field produced by spin-exchange polarized ¹²⁹Xe or ¹³¹Xe sensed by ¹³³Cs can also be discussed in different ¹²⁹Xe/¹³¹Xe pressure conditions. Furthermore, the relationship between the detected signal and the probe laser frequency is researched. We obtain the optimum probe laser detuning from the D2 (6²S_1/2→6²P_3/2) resonance with different ¹²⁹Xe/¹³¹Xe pressure owing to the pressure broadening.     

组织蛋白酶B响应的超极化129Xe MRI探针对肺癌细胞的超灵敏探测

组织蛋白酶B（Cat B）是一种溶酶体半胱氨酸蛋白酶,在细胞代谢中起重要作用.已有研究表明Cat B在肺癌细胞中会过表达.因此,细胞内Cat B水平的检测非常重要.迄今为止,细胞内Cat B的检测方法主要为荧光成像,但该技术受限于渗透性和自发荧光背景干扰.为了解决这些问题,我们设计了一种基于超极化¹²⁹Xe磁共振成像的新型探针.它由一个作为¹²⁹Xe核磁共振（NMR）报告基团的穴番分子笼和一个作为Cat B特异性可裂解基团的酰胺键组成.当探针与Cat B相互作用时,酰胺键的断裂会导致其¹²⁹Xe化学位移发生变化.结合超极化-化学交换饱和转移（Hyper-CEST）技术,可为Cat B提供一种新颖的检测方法.     

固体核磁共振技术在甲醇制烯烃反应中的应用

甲醇制烯烃过程是由非石油路线生成低碳烯烃的重要途径之一.分子筛因具备独特的孔结构和可调变的酸性质,而成为甲醇制烯烃过程的核心催化剂.固体核磁共振(NMR)是鉴定物质结构、阐释催化反应机理的强有力的工具,在甲醇制烯烃的研究中被广泛应用.本文主要总结了近年来利用原位固体NMR、多维多核NMR、脉冲梯度场NMR等固体NMR技术研究甲醇制烯烃反应机理取得的重要进展.原位固体NMR可以在真实反应条件下监测催化反应中反应物、中间体和产物的动态演变过程;多维多核NMR可以在不破坏催化剂结构情况下确定反应中间体结构信息,特别是¹²⁹Xe NMR可以很灵敏探测反应中催化剂的孔道结构变化;脉冲梯度场NMR可用于测定孔道内分子的扩散系数,阐明分子筛的扩散机制.     

Studies on the track formation mechanism of the heavy ions in CR-39

The bulk etch rate for two types of CR-39 detector was measured as a function of temperature and the activation energies of bulk etching was determined. Experimental values of track etch rate were derived directly from the function of the succesive measured track length vrs. etching time for ²⁰⁹Bi, ¹²⁹Xe and ²⁰Ne ions.

The maximum etchable length of 13 MeV/u ²⁰⁹Bi and 13.04 MeV/u ¹²⁹Xe ions have been measured at and below these energies. A comparison of the measured and calculated track length data is presented.     

ZSM-5 zeolite synthesis in the presence of a copper-phthalocyanine complex characterization by ESR and Xe NMR

In the presence of a copper phthalocyanine complex (CuPc), it is possible to synthesize ZSM-5 zeolite containing the complex, and the crystallinity is good, provided that the amount of CuPc trapped is lower than the number of channel intersections where it can be located without too much distortion. The crystallinity is retained after decomposition of the CuPc in a stream of air at 500 °C. The copper-ZSM-5 system is characterized by the combined application of xenon adsorption, ESR and ¹²⁹Xe NMR spectroscopy.     

New approach of fragment charge correlations in Xe+Sn central collisions

A previous analysis of the charge (Z) correlations in the ΔZ−Z plane for ¹²⁹Xe+^natSn central collisions at 32 MeV/n has shown an enhancement in the production of equally sized fragments (low ΔZ) which was interpreted as an evidence for spinodal decomposition. However, the signal is weak and rises the question of the estimation of the uncorrelated yield. After a critical analysis of its robustness, we propose in this paper a new technique to build the uncorrelated yield in the charge correlation function. The application of this method to ¹²⁹Xe+^natSn central collision data at 32, 39, 45 and 50 MeV/n does not show any particular enhancement of the correlation function in any ΔZ bin.     

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。     

The role of polarization of Xe by di- and monovalent cations in Xe NMR studies in zeolite A

We consider the role of polarization in the adsorption of Xe in zeolites of type A by direct comparative analysis of the adsorption isotherms, distributions of occupancies, and ¹²⁹Xe NMR chemical shifts of Xe_n in cages containing Ca_xNa_{12 −2x} ions per alpha cage (x = 0, 1, 2, 3, 5). We find that the qualitative trends in the adsorption isotherms, and in the progressions of Xe_n chemical shifts (for n = 0–8 in cages with x = 0, 1 Ca²⁺ ions and for n = 0–5 in cages with x = 2, 3 Ca²⁺ ions) upon increasing the level of Ca²⁺ ion for Na⁺ ion substitution could only be accounted for by including polarization of the Xe atom by the zeolite framework and its ions. This system, which permits observation of individual Xe_n peaks and of directly comparable adsorption isotherms in several cage types, provides a good model system for the interpretation of the more general case in which only the overall average ¹²⁹Xe NMR chemical shift is observed in open network zeolites, arising from free exchange of Xe among cavities of variable occupancy and variable cation distribution.     

胶束型磁共振成像分子探针的设计与应用

飞速发展的分子影像学在肿瘤的早期诊断及检测中发挥着越来越重要的作用.磁共振成像(MRI)是分子影像学的重要分支，具有其他成像技术不可比拟的优越性和广阔的发展前景.它不需要放射性示踪剂，没有电离辐射，具有高的空间、时间分辨率和组织对比度.近年来，新型磁共振分子探针及成像序列取得了一系列进展，包括环境响应型分子探针、¹⁹F成像、¹²⁹Xe超极化成像以及化学交换饱和转移成像等，进一步拓展了MRI的应用范围.研究和开发靶向性好、弛豫效率高且安全性好的新型多模态MRI造影剂，进一步提高灵敏度是MRI领域的一项重要课题，例如将胶束的特性与一些MRI新方法结合，寻找合适的胶束体系，以提高MRI分子探针的灵敏度；或者引入多模态分子探针，弥补磁共振方法的不足.本文综述了胶束型MRI分子探针核心技术的研究进展与应用，并指出分子影像技术在生物医学工程研究和临床诊断中的重要性.     

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.     

Magnetic resonance imaging of convection in laser-polarized xenon

We demonstrate nuclear magnetic resonance (NMR) imaging of the flow and diffusion of laser-polarized xenon (129Xe) gas undergoing convection above evaporating laser-polarized liquid xenon. The large xenon NMR signal provided by the laser-polarization technique allows more rapid imaging than one can achieve with thermally polarized gas-liquid systems, permitting shorter time-scale events such as rapid gas flow and gas-liquid dynamics to be observed. Two-dimensional velocity-encoded imaging shows convective gas flow above the evaporating liquid xenon, and also permits the measurement of enhanced gas diffusion near regions of large velocity variation.     

通过惰性气体氙判断核试验信息的方法

全面禁止核试验条约的达成是防止核武器扩散的重要手段. 如何判断一次核试验的发生是一个关键课题. 研究了基于测量惰性气体氙同位素^133mXe,¹³³Xe,¹³⁵Xe和^131mXe来鉴别核试验和民用反应堆泄漏的方法. 通过分析这些处于复杂衰变链上核素的数量随时间的变化,寻找核试验与反应堆泄露事件的区别. 对两次朝鲜可疑的事件进行了测量和分析. 为了验证理论计算结果,设计了一次热中子辐照钚的模拟实验. 关键词： 全面禁止核试验条约核查 气体裂变产物 核试验判据 惰性气体氙核素     

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.     

High-spin study of Xe

High-spin states have been populated in ₅₄¹¹⁹Xe via the ⁹⁶Mo(²⁷Al,p3n) reaction at 133 MeV, using the γ-ray spectrometer to record triple γ-ray coincidences. The known level scheme has been significantly extended and several band crossings identified. In particular, the νh_11/2 yrast band has been extended to I^π = (83/2⁻) and shows features which are consistent with those of smooth band termination at high spin. Theoretical results for ¹¹⁹Xe at high spin are discussed within the framework of cranked Nilsson-Strutinsky calculations, together with results for ¹¹⁷Xe.