化学位移各向导性对半整数自旋四极核的2D NMR章动的影响(英文)

考察了化学位移各向异性对半整数自旋四极核2DNMR章动的影响．用数值方法对2DNMR章动实验的演化期的Hamiltonian矩阵进行对角化，然后用帐篷法进行粉末平均，获得了自旋为I＝3／2、5／2、7／2和9／2的四极核在不同化学位移各向异性下的2DNMR章动谱．实验结果与理论计算符合较好．     

三能级体系的Z回波核磁共振粉末谱

本文提出一个Z回波核磁共振(NMR)脉冲序列,可以获得三能级体系的纯偶极或纯四极谱。Z回波NMR谱不仅与化学位移各向异性无关,而且在强射频场条件下,与射频场非均匀性无关。该方法明显优于章动NMR技术。以上结论经过理论分析和实验结果的验证。 关键词：     

四极核旋转边带的抑制

本文从自旋-1体系自旋空间的旋转特性的讨论建议了抑制四极核旋转边带的4(π/2)脉冲系列,进而给出了一种4(π/2)-4π脉冲系列,该系列可用于获得该四极核体系的化学位移各向同性固体高分辨谱。文中给出了相应的实验结果。     

2DNMR鉴定吗啉付产物的结构

本文用~H—NMR,反门控定量~(13)C—NMR,异核丁—分解2D、同核化学位移相关2D、异核化学位移相关2D等技术,鉴定了二种未见报道的吗啉付产物结构。     

自旋I=3/2核四极共振体系对梳状脉冲的响应

用密度矩阵理论和计算机模拟较详细地讨论了自旋I=3/2核四极共振(NQR)粉末体系对梳状脉冲的响应以及偏共振效应的影响.在偏共振强度(包括谱线的非均匀增宽)较小的条件下.由它获得的谱与二维章动谱是相似的.但是实验所需时间能够减少近两个数量级. 关键词：     

玻璃和晶体粉末样品的核磁共振谱的计算机拟合

文本介绍了存在各向异性化学位移效应和电四极矩相互作用时,自旋为半整数核的固体NMR中心跃迁粉末谱的计算机拟合方法,讨论了谱拟合步骤和模拟谱中的"噪声"和误差。     

当能级间隔较小时三能级核四极共振自旋系统对脉冲的响应

用虚拟自旋-1/2算符理论考察了I=1的核四极共振自旋系统在其能级间隔较小时对1-2个脉冲的响应.由于核四极相互作用表象中的射频场与核自旋的相互作用(H_rf)包含时间,因而用Dyson时序算符来计算密度算符在H_rf作用下的演化.     

14N核四极共振自旋系统自旋-晶格弛豫时间的测量

¹⁴N核四极共振自旋系统的自旋-晶格弛豫是一种双指数弛豫。本文介绍了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间的3种测量方法,利用可变多面体方法对实验数据进行拟合,获得了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间T_1s和T₁₁,对有关文献中关于核四极共振弛豫时间的测量的3个观点提出了质疑。     

先进固体NMR技术研究高分子结构与动力学

随着固体NMR理论和谱仪硬件技术的不断发展,近年来固体NMR技术在高分子多尺度结构与动力学研究领域中正发挥着越来越重要的作用. 多脉冲及高速魔角旋转（MAS）等质子高分辨技术的发展使得高灵敏度的¹H谱可有效地用于高分子化学结构与链间相互作用的检测;基于化学键（J-耦合）相关和通过空间（偶极耦合）相互作用的各种二维异核相关谱NMR新技术,使得复杂高分子的链结构得以严格解析. 基于MAS下同核和异核偶极-偶极相互作用、化学位移各向异性等各向异性相互作用重聚的系列新技术,使得研究者可在采用高分辨¹H或¹³C 检测信号的同时检测准静态下的各向异性相互作用,进而获得与之密切相关的结构和动力学信息. 通过质子偶极滤波技术可有效检测多相聚合物中的界面相与相区尺寸、高分子共混物中的相容性等问题. 在动力学的研究中,通过质子间自旋扩散的有效压制技术和化学位移各向异性的重聚,目前已经可以有效地获取链段上单个化学键的快速局域运动以及链段的超慢分子运动. 上述丰富的多尺度NMR技术可以使研究者在不同空间和时间尺度上对高分子聚合物的微观结构、相分离和动力学行为等进行详细的研究,进而阐明高分子微观结构与宏观性能的关联. 该文以固体NMR中最主要的2类核（¹H和¹³C）的检测技术为主线,简单介绍近年来固体NMR领域的一些最新研究进展及其在高分子结构和动力学研究中的应用.     

魔角旋转核磁共振波谱学

样品绕与外加恒定磁场方向成魔角β_M=cos^-1(1)/√3的轴向快速旋转(MAS)可以消除固体NMR的多种谱增宽。本文首先介绍了固体中的几种主要的各向异性相互作用,即偶极-偶极,核四极,自旋-自旋或称间接偶极-偶极以及化学位移相互作用。然后用平均哈密顿理论阐述了MAS对这些相互作用的影响。现今的固体高分辨方法有四种,即多脉冲(MP),多量子(MQ),交叉极化和大功率异核去耦合(CP)以及MAS,在这些方法中MAS方法是唯一可以获得各向同性化学位移的。因而要得到类似于液体谱的固体高分辨,MAS往往是最后的手段。以上这些方法的联合运用以及极为广泛的应用研究使得固体高分辨NMR兴旺发达起来了。本文引述了大量原始和最新的文献,力图概述当前该领域中的大部分成就。评论这一领域的理论和实验技术的发展。     

Determination of mutual orientation of tensor interactions from two-dimensional nutation NQR-spectra of solids

Expressions for singularities of 2D correlation nutation NQR-spectra are obtained. A method is proposed for measuring orientation of two tensor interactions in powder specimens, which relies on specimen re-orientation in an rf-coil within the pulse period between the second and third pulses of a sequence of stimulated echo signal and detection of a 2D nutation NQR spectrum. Feasibilities of the method are discussed and simulated spectra for the case of nuclei with the spin I = 3/2 are reported. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 29–32, January, 2008.     

Single- and multiple-quantum cross-polarization in NMR of quadrupolar nuclei in static samples

Cross-polarization from a spin I=1/2 nucleus (e.g., ¹H) to a spin S = 3/2 nucleus (e.g., ²³Na) or a spin S = 5/2 nucleus (e.g., ²⁷A1 or ⁿO) in static powder samples is investigated. The results of conventional (single-quantum), three-quantum, and five-quantum cross-polarization experiments are presented and discussed. Based on a generalization of an existing theory of cross-polarization to quadrupolar nuclei, computer simulations are used to model the intensity and lineshape variations observed in cross-polarized NMR spectra as a function of the radio-frequency field strengths of the two simultaneous spin-locking pulses. These intensity and lineshape variations can also be understood in terms of the spin S = 3/2 or 5/2 nutation rates determined from experimental quadrupolar nutation spectra. The results of this study are intended as a preliminary step towards understanding single- and multiple-quantum cross-polarization to quadrupolar nuclei under MAS conditions and the application of these techniques to the MQMAS NMR experiment.     

Sample patterning on NMR surface microcoils

Aligned microcontact printing for patterning the sample in areas of homogeneous RF-field on the highly sensitive surface of planar NMR microprobes is presented. We experimentally demonstrate that sample patterning allows drastic improvement of the spin excitation uniformity. The NMR microprobes are designed for cell analysis and characterized using lipid vesicles as cell substitutes. Lipid vesicles are advantageous as composition and concentration of the confined solution are precisely controlled and because of their similarity to living cells. Using aligned microcontact printing, a monolayer of lipid vesicles is immobilized on the surface of the planar NMR microprobe in a patterned way. 1H NMR spectra and CPMG spin echoes of sucrose solution confined within the lipid vesicles are successfully recorded. Nutation curves of the sample structured in different patterns demonstrate the impact of patterning on the spin excitation uniformity. The total detection volumes are between 1 and 2 nL and derived with help of a theoretic model based on 3D finite element simulation. This model predicts the signal-to-noise ratio and the progression of the nutation curves.     

Selective Injection of Magnetization by Slow Chemical Exchange in NMR

In a system in slow dynamic equilibrium two NMR methods are shown to be suitable for injecting magnetization from one resonance to another by means of slow chemical exchange. The combined outputs of the methods may be employed to measure the value of the off-rate constant kappa(off) in the complex. The methods are implemented experimentally using the complex of molecules composed of the enzyme Escherichia coli dihydrofolate reductase (DHFR) and the ligand folate. In an equilibrium solution with DHFR, folate is known to undergo chemical exchange between a free state and a bound state. The modified synchronous nutation method is applied to a spin of the folate molecule in the free and bound states; magnetization transfer occurs between the two sites due to the underlying exchange process. As a preliminary step for the application of the synchronous nutation method, a new one-dimensional 1H NMR technique is proposed which facilitates the assignment of the resonance of a spin in the bound state, provided the resonance of its exchange partner in the free state is known. This experiment is also used to obtain quantitative estimates of the transverse relaxation rate constant of the bound resonance. The numerical procedure necessary to analyze the experimental results of the synchronous nutation experiment is presented.     

Y型沸石脱铝机制和铝状态的NMR研究

对Y型沸石原粉及几种不同脱铝样品进行了几种不同NMR方法的测量,确定了不同处理过程的脱铝机制和骨架内外铝状态的变化,²⁹Si MAS NMR谱给出了骨架Si、Al分布的信息,反映了不同方法处理样品其脱铝机制的差异,据此可以控制Y沸石脱铝过程获得更高的硅铝比,²⁷Al MAS NMR谱、二维章动NMR及¹H-²⁷Al CP/MAS NMR测量表明:水热处理的Y沸石中存在4种不同的铝状态。综合²⁹Si和²⁷Al MAS NMR观测,可相当程度地推断Y型沸石分子筛脱铝改性所发生的内部过程。     

N@C60 and P@C60 as quantum bits

Due to their long electron spin relaxation times, the endohedral fullerenes N@C₆₀ and P@C₆₀ are good candidates for the implementation of qubits in an electron spin quantum computer. A central operation in this context is the rotation of the spin direction by an arbitrary angle. In the present experiment, this nutation behavior was studied in pulsed electron spin resonance measurements. We show that, even at room temperature, about 50 Rabi oscillations (about 100 qubit operations) can be performed without refocusing the spin system, although inhomogeneities are present. A special feature of the group V endohedral fullerenes is the electron spinS=3/2, which complicates the nutation behavior. The zero-field splitting at low temperature gives rise to different nutation frequencies for the (1/2,?1/2) transition and the (±3/2, ±1/2) transitions. The frequency ratio is 2/3^1/2.     

Spin nutation in the quasi-isotropic A-like superfluid phase of 3He

The order parameter of the quasi-isotropic A-like superfluid phase of ³He has been reduced to a simple form. The frequencies of the spatially homogeneous oscillations of the spin and the spin part of the order parameter of this phase have been obtained taking into account the anisotropy of its magnetic susceptibility. It has been shown that the anisotropy of susceptibility strongly affects the low-frequency oscillation mode, which is similar to the nutation of an asymmetric top. The possibility of observing this mode using the NMR method is discussed.     

Pure-phase two-dimensional niobium-93 nutation spectroscopic study of lead metaniobate and the piezoelectric lead magnesium niobate

An NMR technique to measure pure-phase two-dimensional nutation NMR spectra, that yields higher resolution than traditional nutation experiments is reported. Using this technique 93Nb nutation NMR spectra of PbNb2O6 and the technologically important Pb(Mg1/3Nb2/3)O3 (PMN) have been measured and the quadrupolar coupling constant of the niobium site in PbNb2O6 (C(Q) = 19 +/- 2 MHz) determined. Estimates of the quadrupolar coupling constants for three different resonances associated with different niobium(V) sites in PMN (C(Q) < 1.2 MHz, approximately 17 MHz, and > 62 MHz) are also reported.