固态样品中扩散的核磁共振测量

用脉冲梯度切核磁共振测量固态样品中的扩散遇到很多困难,对于一个不用内锁的电磁体系统,观测到脉冲场梯度过后涡流造成样品处的磁场强度的强烈振荡.提出了一个用该系统测量凝胶聚合物中锂离子扩散可获得较好结果的脉冲序列.     

核磁共振成像一维空间编码教学实验

利用梯度磁场实现检测信号的空间编码,是核磁共振成像(MRI)的关键技术.本文采用ccc系列样品将二维问题简化为一维,使用超小型教学用核磁共振成像仪进行了一维空间编码实验研究,并对实验过程及实验结果进行了计算模拟和分析.     

大白鼠脑中风模型的核磁共振成像(英文)

核磁共振成像现今已经成为临床神经影像的常规工具.在诊断、评估和监测中风从急性到慢性的各个阶段的脑组织的变化过程中,核磁共振成像扮演了一个重要的角色.该综述提供了多种核磁共振成像方法的描述,以及选择性地展示了作者在美国亨利福特医院神经科核磁共振成像实验室所获得的大白鼠栓塞中风模型的核磁共振成像研究成果.     

基于大功率LED的闪光成像速度测量系统(英文)

设计出一种非接触式高速运动物体速度测量系统,在CCD单帧曝光时间内利用闪光灯对飞行中的物体进行两次闪光照明,CCD对两个不同位置的飞行物体成像,设定两个光脉冲之间的时间间隔以及测量出两个物体像之间的距离即可算出其飞行速度.该系统能够进行实时测量,突破了空间单点测量技术的局限,可在同一幅图像上记录下不同时刻多个空间点目标的图像信息,以及同一时刻不同空间点目标的图像信息,从而可以获得目标运动的瞬时速度.     

Cross-relaxation effects in stimulated-echo-type PGSE NMR experiments by bipolar and monopolar gradient pulses

Exchange of longitudinal spin polarization by dipolar cross relaxation between nonequivalent spins results in a modulation of the stimulated echo signal on increasing the encoding/decoding delays and in a multiexponential decay on increasing the diffusion time. These artifacts are suppressed by 180° pulses inserted in the middle of the gradient encoding/decoding periods. The efficiency of the gradient encoding is preserved if bipolar gradient pulses are used instead of monopolar pulses. The behavior of the different pulse sequences is demonstrated by ¹⁹F PGSE NMR experiments in a lyotropic liquid crystal in both isotropic micellar and oriented nematic phases.     

C Selective Polarization and Spin Diffusion in a Lipid Bilayer-Bound Polypeptide by Solid-State NMR

While ¹⁵N solid-state NMR has proven to be very advantageous for the development of structural biological methods, ¹³C spectroscopy has increased sensitivity and spectral dispersion. However, large natural abundance signals and homonuclear dipolar interactions pose significant problems. Here we have used a pair of ¹³C-labeled sites in a lipid-solubilized polypeptide to show the selective polarization can be used in combination with spin diffusion to achieve simplified spectra. Both unoriented and oriented samples have been used, with the latter providing a well-resolved homonuclear dipolar splitting.     

NMR Imaging of Thermally Polarized Helium-3 Gas

It is shown that thermally polarized 3He gas can be used to measure important physical parameters and to design, test, and tune imaging sequences. The bulk values of T1, T2, and the diffusion coefficient were measured in a glass cell containing a mixture of helium-3 (0.8 bar) and oxygen (0.2 bar). They were found to be T1 = 7 s, T2 = 2.4 s, and D = 1.6 cm2 s(-1). The relaxation times T2* and T1 and the apparent diffusion coefficient of thermally polarized helium-3 gas were measured in the rat lung, and these parameters were used to design a helium-3 optimized multi-spin-echo sequence which was shown to increase the signal-to-noise ratio sufficiently to obtain the first NMR-images of thermally polarized helium-3 in the rat lung.     

Strategies for Diagnosing and Alleviating Artifactual Attenuation Associated with Large Gradient Pulses in PGSE NMR Diffusion Measurements

The generation of phase-based artifacts resulting from mismatch in the effective areas (i.e., the time integrals) of sequential gradient pulses is discussed in the context of large gradient pulsed-gradient spin-echo (PGSE) NMR diffusion measurements. Such effects result in artifactual attenuation and distortion in the spectra which, in the first instance, are similar to (and commonly mistaken for) the effects of eddy currents. Small degrees of mismatch cause "unphysical" concave downward curvature in PGSE attenuation plots of freely diffusing species. However, larger mismatches can result in artifactual diffraction peaks in the plots which could easily be confused for true restricted diffusion effects. Although "rectangular" gradient pulses are preferable from a theoretical viewpoint, we found that shaped gradient (e.g., half-sine) pulses, which due to their slower rise and fall times were more tractable for the current amplifier, were more sequentially reproducible. As well as generating fewer phase-based artifacts such shaped pulses also decrease the likelihood of vibration problems.     

Diffusion and relaxation effects in general stray field NMR experiments

We analyze the evolution of magnetization following any series of radiofrequency pulses in strongly inhomogeneous fields, with particular attention to diffusion and relaxation effects. When the inhomogeneity of the static magnetic field approaches or exceeds the strength of the RF field, the magnetization has contributions from different coherence pathways. The diffusion or relaxation induced decay of the signal amplitude is in general nonexponential, even if the sample has single relaxation times T(1), T(2) and a single diffusion coefficient D. In addition, the shape of the echo depends on diffusion and relaxation. It is possible to separate contributions from different coherence pathways by phase cycling of the RF pulses. The general analysis is tested on stray field measurements using two different pulse sequences. We find excellent agreement between measurements and calculations. The inversion recovery sequence is used to study the relaxation effects. We demonstrate two different approaches of data analysis to extract the relaxation time T(1). Finite pulse width effects on the timing of the echo formation are also studied. Diffusion effects are analyzed using the Carr--Purcell--Meiboom--Gill sequence. In a stray field of a constant gradient g, we find that unrestricted diffusion leads to nonexponential signal decay versus echo number N, but within experimental error the diffusion attenuation is still only a function of g(2)Dt(3)(E)N, where t(E) is the echo spacing.     

Identification of Spin Diffusion Pathways in Isotopically Labeled Biomolecules

One-dimensional NOE experiments applicable to labeled macromolecules are presented which allow the manipulation of specific spin diffusion pathways and thus unambiguously identify clandestine spins through which the direct NOE is mediated. A treatment of spin diffusion using average Liouvillian theory is shown to describe adequately these phenomena. Experiments are carried out on an 15N-labeled sample of human ubiquitin.     

NMR Relaxation and Diffusion Measurements on Iron(III)-Doped Kaolin Clay

Kaolin clay samples were mixed with various amounts of Fe₂O₃ powder. The influence of this magnetic impurity on NMR relaxation and diffusion measurements on the water in this porous material was investigated. The NMR relaxation measurements showed a nearly mono-exponential decay, leading to the conclusion that the pore size distribution of the clay samples is either narrow and/or that the pores are interconnected very well. Both the longitudinal and the transverse relaxation rate depend linearly on the concentration of the Fe₂O₃ impurity. The NMR diffusion measurements revealed that the Fe₂O₃ causes internal magnetic field gradients that largely exceed the maximum external gradient that could be applied by our NMR apparatus (0.3 T/m). Additional SQUID measurements yielded the magnetization and magnetic susceptibility of the samples at the magnetic field strength used in the NMR measurements (0.8 T). A theoretical estimate of the internal magnetic field gradients leads to the conclusion that the water in the porous clay samples cannot be described by the commonly observed motional averaging regime. Probably an intermediate or a localization regime is induced by the large internal gradients, which are estimated to be on the order of 1 to 10 T/m in the pore volume and may exceed 1000 T/m at the pore surface.     

基于WATERGATE的双溶剂峰抑制方法

WATERGATE（W3/W5）是NMR实验中使用较为广泛的溶剂峰抑制方法,但该方法通常仅能对一个溶剂信号进行有效抑制. 本文对WATERGATE的脉冲序列进行修饰、优化,发展了两种新的双溶剂峰抑制方法. 实验结果表明,经过修饰、优化后的WATERGATE,实验的设立非常简单,不需要复杂的优化过程就能够对双（多）溶剂峰进行有效抑制, 可用于常规1D & 2D NMR 实验、HPLC NMR实验,以及天然产物粗提取物的分析中.     

α-环糊精/水杨酸等包络物的NMR自扩散研究

用脉冲梯度场NMR测量自扩散系数的方法研究了水杨酸、水杨酸根、苯酚及苯甲酸根和α-环糊精（α-CD）形成包络物的相互作用. 研究发现4种客体的扩散系数均随着环糊精含量增加而减小. 利用测得的扩散系数计算出了4种客体和环糊精形成包络物的平衡常数，发现平衡常数随空间位阻变小而变大，同时也随着疏水性增强而增大，该结果和2D-ROESY（Rotating Frame Overhauser Effect Spectroscopy）谱均表明，在水杨酸等客体与α-环糊精相互作用过程中，芳香环与环糊精内腔的疏水相互作用起主导作用，不同客体和α-环糊精的结合比均为1∶1.     

A method for detection of spectral spin diffusion from minor peaks, and its application to F MAS NMR of antimony(III)-doped fluorapatite

A new technique for detecting spectral spin diffusion in solids under MAS NMR conditions that is particularly well suited for accurately measuring cross-relaxation from minor spectral components is presented. The pulse sequence, SINK (Saturation Inter-Nuclear Kinetics), selectively saturates the magnetization of a minor spectral component with a series of rotor-synchronized DANTE pulse trains and monitors spin diffusion to other peaks with a non-selective 90° pulse. We have used SINK with ¹⁹F MAS NMR on samples of calcium fluorapatite doped with Sb³⁺ to measure spin diffusion between a weak peak at 68.6 ppm due to fluoride ions associated with Sb³⁺ and other peaks in the spectrum. The SINK experiment clearly demonstrates that spin diffusion from the former peak to the main resonance of fluorapatite at 64.0 ppm is faster than spin diffusion to a second antimony-related peak at 65.6 ppm. These results strengthen our previous conclusion that antimony(III) occupies a phosphate site in the apatite lattice, with an SbO₃³⁻ group replacing a PO₄³⁻ group. The SINK experiment also enables the detection of a “hidden” peak at approximately 62.9 ppm that is otherwise obscured by the intense main peak at 64.0 ppm.