Advances in high-resolution nuclear magnetic resonance methods in inhomogeneous magnetic fields using intermolecular multiple quantum coherences

Strong and extremely homogeneous static magnetic field is usually required for high-resolution nu-clear magnetic resonance (NMR). However, in the cases of in vivo and so on, the magnetic field inho-mogeneity owing to magnetic susceptibility variation in samples is unavoidable and hard to eliminate by conventional methods such as shimming. Recently, intermolecular multiple quantum coherences (iMQCs) have been employed to eliminate inhomogeneous broadening and obtain high-resolution NMR spectra, especially for in vivo samples. Compared to other high-resolution NMR methods, iMQC method exhibits its unique feature and advantage. It simultaneously holds information of chemical shifts, multiplet structures, coupling constants, and relative peak areas. All the information is often used to analyze and characterize molecular structures in conventional one-dimensional NMR spec-troscopy. In this work, recent technical developments including our results in this field are summarized; the high-resolution mechanism is analyzed and comparison with other methods based on interactions between spins is made; comments on the current situation and outlook on the research directions are also made.     

High-resolution heteronuclear correlation spectroscopy based on spatial encoding and coherence transfer in inhomogeneous fields

Two-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy has been proven to be a powerful technique for chemical, biological, and medical studies. Heteronuclear single quantum correlation (HSQC) and heteronuclear multiple bond correlation (HMBC) are two frequently used 2D NMR methods. In combination with spatially encoded techniques, a heteronuclear 2D NMR spectrum can be acquired in several seconds and may be applied to monitoring chemical reactions. However, it is difficult to obtain high-resolution NMR spectra in inhomogeneous fields. Inspired by the idea of tracing the difference of precession frequencies between two different spins to yield high-resolution spectra, we propose a method with correlation acquisition option and J-resolved-like acquisition option to ultrafast obtain high-resolution HSQC/HMBC spectra and heteronuclear J-resolved-like spectra in inhomogeneous fields.     

Observation of intermolecular double-quantum coherence signal dips in nuclear magnetic resonance

The correlated spectroscopy revamped by asymmetric Z-gradient echo detection (CRAZED) sequence is modified to investigate intermolecular double-quantum coherence nuclear magnetic resonance signal dips in highly polarized spin systems. It is found that the occurrence of intermolecular double-quantum coherence signal dips is related to sample geometry, field inhomogeneity and dipolar correlation distance. If the field inhomogeneity is refocused, the signal dip occurs at a fixed position whenever the dipolar correlation distance approaches the sample dimension. However, the position is shifted when the field inhomogeneity exists. Experiments and simulations are performed to validate our theoretic analysis. These signal features may offer a unique way to investigate porous structures and may find applications in biomedicine and material science.     

High-resolution NMR spectra in inhomogeneous and unstable fields via the three-pulse method

In modern solution nuclear magnetic resonance (NMR), the spectral resolution is mainly dependent on the spatial homogeneity and temporal stability of the magnetic field. The spectral linewidths are usually proportional to the overall field homogeneity and the stability experienced by the sample. Many high-resolution NMR methods have been developed, but few are applicable in inhomogeneous and unstable fields. In this paper, a high-resolution three-pulse method based on intermolecular zero-quantum coherences (iZQCs) is proposed. Since this method is insensitive to field inhomogeneity and instability, spectral information such as the chemical shift can be retained in the resulting spectra. In comparison with the CPMG-HOMOGENIZED method, the new method provides almost pure solvent–solute iZQC signals.     

A heteronuclear intermolecular single-quantum coherence scheme for high-resolution 2D J-resolved 1H NMR spectra in inhomogeneous magnetic fields

Based on heteronuclear intermolecular single-quantum coherences between proton (¹H) and quadrupolar nuclei (i.e. deuterium ²H), a three-dimensional nuclear magnetic resonance (NMR) pulse sequence is proposed for recovering high-resolution two-dimensional J-resolved NMR spectra from samples mixed with a deuterated solvent in the presence of large magnetic field inhomogeneities. Benefitting from excitation of spins via two different radio frequency (RF) transmit channels, this sequence is suitable for applications in randomly large inhomogeneous fields and the solvent suppression generally required in homonuclear intermolecular multiple-quantum coherence approaches is no longer necessary. Systematic theoretical analyses are given based on the distant dipolar field treatment. Experiment on a sample of corn oil in deuterated acetone and ethyl 3-bromopropionate and acetone dissolved in DMSO-d₆ in a deshimmed field with severe inhomogeneous broadening is performed to show the feasibility and applicability of this sequence.     

Nuclear magnetic resonance in inhomogeneous magnetic fields

The response of the spin system has been investigated by numerical simulations in the case of a nuclear magnetic resonance (NMR) experiment performed in inhomogeneous static and radiofrequency fields. The particular case of the NMR-MOUSE was considered. The static field and the component of the radiofrequency field perpendicular to the static field were evaluated as well as the spatial distribution of the maximum NMR signal detected by the surface coil. The NMR response to various pulse sequences was evaluated numerically for the case of an ensemble of isolated spins (1/2). The behavior of the echo train in Carr-Purcell-like pulse sequences used for measurements of transverse relaxation and self-diffusion was simulated and compared with the experiment. The echo train is shown to behave qualitatively differently depending on the particular phase schemes used in these pulse sequences. Different echo trains are obtained, because of the different superposition of Hahn and stimulated echoes forming mixed echoes as a result of the spatial distribution of pulse flip angles. The superposition of Hahn and stimulated echoes originating from different spatial regions leads to distortions of the mixed echoes in intensity, shape, and phase. The volume selection produced by Carr-Purcell-like pulse sequences is also investigated for the NMR-MOUSE. The developed numerical simulation procedure is useful for understanding a variety of experiments performed with the NMR-MOUSE and for improving its performance. Copyright 2000 Academic Press.     

Selective NMR excitation in strongly inhomogeneous magnetic fields

The NMR-MOUSE is a unilateral and mobile NMR sensor which operates with highly inhomogeneous magnetic fields. To produce a mobile NMR unit, RF excitation is sought, which can be produced with the most simple equipment, in particular nonlinear, low-power amplifiers, and to observe a free induction decay in strongly inhomogeneous fields, the excitation needs to be selective. The possibility to produce selective excitation by sequences of hard low-power radiofrequency pulses in the strongly inhomogeneous magnetic fields of the NMR-MOUSE is explored. The use of the DANTE sequence for selection of magnetization from parts of the sensitive volume was investigated for longitudinal and transverse magnetization by computer simulations and experiments. The spectra of the recorded FIDs and echo signals are in good agreement with those simulated for the excitation, which verifies the concept of the DANTE excitation. The results obtained are an important step towards a low-power operation of the NMR-MOUSE to improve its mobility.     

Study of natural diamonds by dynamic nuclear polarization-enhanced C nuclear magnetic resonance spectroscopy

The results of a study of two types of natural-diamond crystals by dynamic nuclear polarization (DNP)-enhanced high-resolution solid-state ¹³C nuclear magnetic resonance (NMR) are reported. The home-built DNP magic-angle spinning (MAS) ¹³C NMR spectrometer operates at 54 GHz for electrons and 20.2 MHz for carbons. The power of the microwave source was about 30 W and the highest DNP enhancement factor came near to 10³. It was shown that in the MAS spectra the ¹³C NMR linewidths of the I_b-type diamond were broader than those of I_aB3-type diamond. From the hyperfine structure of the DNP enhancement as a function of frequency, four kinds of nitrogen-centred and one kind of carbon-centred free radicals could be identified in the I_b-type diamond. The hyperfine structures of the DNP enhancement curve that originated from the anisotropic hyperfine interaction between electron and nuclei could be partially averaged out by MAS. The ¹³C polarization time of DNP was rather long, i.e. 1500 s, and the spin—lattice relaxation time (without microwave irradiation) was about 300 s, which was somewhat shorter than anticipated. Discussions on these experimental results have been made in this report.     

Pulsed nuclear magnetic resonance signals in magnetically ordered materials

We have obtained an analytical expression for nuclear precession and nuclear echo signals generated in magnetically ordered materials upon resonant excitation of the nuclear subsystem by two pulses of identical amplitude but different durations. We show that in a nuclear subsystem with inhomogeneous broadening of the spectroscopic transition and an inhomogeneous gain distribution, the two-pulse precession and echo signals are split into four and nine components respectively. We have analytically established a correlation between the macroscopic parameters of the components of the two-pulse signals (relative amplitudes, signal formation times) and the microscopic parameters of the magnetically ordered media (inhomogeneous half-width of the spectral line, half-width of the gain distribution function, average gain). The theoretically calculated formation times for the components of the nuclear precession and nuclear echo signals agree with the experimental data obtained for the alloy FeNiCo (70% Co). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 529–538, July–August, 2008.     

不均匀场下空间编码超快速高分辨NMR研究进展

二维核磁共振(2D NMR)的提出和发展,为NMR技术的研究和应用提供了广阔的空间. 然而当样品或磁场本身不均匀时,高分辨的2D NMR谱难以获得. 此外,常规2D NMR实验通常需要长的采样时间. 空间编码超快速采样方法利用空间编码技术,只需单次扫描即可获得2D甚至多维NMR谱,极大地缩短了采样时间. 目前相位补偿、相干转移和分子间多量子相干等技术与空间编码技术相结合,已成功实现不均匀场下超快速获得高分辨NMR谱. 该文对不均匀场下空间编码超快速NMR方法进行了介绍,对其未来发展进行了展望.     

Dynamic H nuclear magnetic resonance of rotating solids

The sensitivity of one-dimensional dynamic magic-angle spinning (MAS) and off-MAS ²H nuclear magnetic resonance spectra to changes in the parameters of jump-type molecular motions is studied. The Floquet theory approach is used to simulate spectra of spins with I = 1, which are involved in exchange processes in rotating solids. The solution of the Bloch-McConnell equations for rotating samples are derived and some simulated frequency spectra are shown. The dependence of the lineshapes of the center and sidebands of the MAS and off-MAS spectra on the exchange parameters are discussed. Experimental results of ²H spectra of perdeuterated dimethyl sulfone, obtained in the temperature range 20–55 °C, are demonstrated. The methyl groups in this molecule undergo π flips at rates that can be detected by MAS and off-MAS NMR. The shapes of the experimental sidebands are compared with simulated results.     

核磁共振量子信息处理研究的新进展

过去的二十年中,量子信息相关研究取得了显著的进展,重要的理论和实验工作不断涌现.与其他量子信息处理系统相比,基于自旋动力学的核磁共振系统,不仅具有丰富而且成熟的控制技术,还拥有相干时间长、脉冲操控精确、保真度高等优点.这也是核磁共振体量子系统能够精确操控多达12比特的量子系统的原因.因此,核磁共振量子处理器在量子信息领域一直扮演着重要角色.本文介绍核磁共振量子计算的基本原理和一些新研究进展.研究的新进展主要包括量子噪声注入技术、量子机器学习在核磁共振平台上的实验演示、高能物理和拓扑序的量子模拟以及核磁共振量子云平台等.最后讨论了液态核磁共振的发展前景和发展瓶颈,并对未来发展方向提出展望.     

扫场对核磁共振测量的影响

在连续波核磁共振实验中，通常采用低频扫场产生重复再现的共振吸收信号。当处于磁场中的射频线圈引线回路等效面积不为零时，简谐扫场必然引起该闭合回路的磁通量变化，由此而产生同频简谐感生电动势并与核磁共振信号叠加共同构成振荡器输出信号。由于扫场上升和下降过程的感生电动势方向相反，从而扫场前半周和后半周所对应的共振吸收测量信号存在差异。实验结果表明：扫场强度及方向对核磁共振测量影响来源于实验测量技术缺陷，而非核磁共振的物理本质。     

磁共振波谱与成像技术

文章简要介绍了核磁共振的基本原理,详细阐述了液体核磁共振在蛋白质结构、功能和动力学等方面的研究进展,论述了增强固体核磁共振分辨率的方法及其应用,讲述了磁共振成像的原理并综述了不同磁共振成像方法的应用研究进展,并对核磁共振的发展作了展望。     

核磁共振中的量子控制

近年来, 随着量子信息科学的发展, 对由量子力学原理描述的微观世界的主动调控已成为重要的前沿研究领域. 为构造实际的量子信息处理器, 一个关键的挑战是: 如何对处于噪声环境下的量子体系实现一系列高精度的任意操作, 以完成目标量子信息处理任务. 为此, 人们将经典系统控制论的思想方法延伸到量子体系的领域, 提出了大量的量子控制方法以及相关的数值技术(如量子优化控制、量子反馈控制等), 并取得了丰富的研究成果. 核磁共振自旋体系具备成熟的系统理论和操控技术, 为量子控制方法的实用性研究提供了优秀的实验测试平台. 因此, 基于核磁共振的量子控制成为量子控制领域的重要方向. 本文简要介绍了量子控制的基本概念和方法; 从系统控制论的角度对核磁共振自旋体系的基本原理和重要控制任务做了阐述; 介绍了近些年来在该领域发展的相关控制方法及其应用; 对基于核磁共振体系的量子控制的进一步的研究做了几点展望.     

Study on signal intensity of low field nuclear magnetic resonance via an indirect coupling measurement

We carry out an ultra-low-field nuclear magnetic resonance (NMR) experiment based on high-T c superconducting quantum interference devices (SQUIDs). The measurement field is in a micro-tesla range (～10 μT-100 μT) and the experiment is conducted in a home-made magnetically-shielded-room (MSR). The measurements are performed by the indirect coupling method in which the signal of nuclei precession is indirectly coupled to the SQUID through a tuned copper coil transformer. In such an arrangement, the interferences of applied measurement and polarization field to the SQUID sensor are avoided and the performance of the SQUID is not destroyed. In order to compare the detection sensitivity obtained by using the SQUID with that achieved using a conventional low-noise-amplifier, we perform the measurements using a commercial room temperature amplifier. The results show that in a wide frequency range (～1 kHz-10 kHz) the measurements with the SQUID sensor exhibit a higher signal-to-noise ratio. Further, we discuss the dependence of NMR peak magnitude on measurement frequency. We attribute the reduction of the peak magnitude at high frequency to the increased field inhomogeneity as the measurement field increases. This is verified by compensating the field gradient using three sets of gradient coils.     

THz spectroscopy of diluted magnetic semiconductors and semiconductor quantum structures in ultrahigh magnetic fields

Magneto-absorption spectra in ferromagnetic semiconductor In_1−xMn_xAs films and self-organized PbSe/PbEuTe quantum dot superlattices have been studied in the terahertz range at very high magnetic fields up to 500 T. Both heavy hole (HH) and light hole (LH) cyclotron resonance (CR) have been observed in bulk In_1−xMn_xAs thin films with different Mn concentrations. The detailed Landau level calculation in terms of the effective mass approximation well explained the CR peak positions, line shapes and the dependence of the circular polarization of the incident light on the CR spectra. In InMnAs/GaSb heterostructures that have higher ferromagnetic transition temperature (T_c) than the bulk samples, the observed HH and LH cyclotron masses are larger than that in the bulk thin films. We found that the CR peak position and its line shape suddenly change in the vicinity of the ferromagnetic transition temperature, suggesting the change in the electronic structure due to the ferromagnetic transition. Electron CR in PbSe/PbEuTe quantum dots has been observed and it was found that the effective mass of the electrons is considerably modified by the quantum confinement potential and the lattice strain around the dots. A large wavelength dependence of the absorption intensity was observed due to the interference effect of the radiation inside the sample.     

基于核磁共振的子空间量子过程重构

基于三核自旋量子系统实现了内嵌两量子位子空间量子过程重构.通过输入完备态集合对执行的量子过程进行了表征.由于量子过程内嵌于子空间,使得重构实验所需输入次数及时间显著减少,同时实验尽量避免使用时间较长的J偶合演化,有效控制了系统的退相干。     

Indirect detection of nuclear magnetic resonance via geometrically induced long-range dipolar fields

We report the indirect detection of the magnetization of one spin species via the NMR signal of a second species. Our method relies on the control of long-range dipolar fields between two separate objects, in this case, a water droplet (sensor) immersed in a tube containing mineral oil (sample). Unlike prior experiments, no gradient pulses are used; rather, the setup geometry is exploited to select the part of the sample to be probed and modulate the spin alignment in the sensor. Our results are discussed in the context of Dipolar Field Microscopy, a proposed strategy in which the detector is a hyperpolarized tip.     

电阻式核磁共振测量的最新进展

电阻式核磁共振(RDNMR)测量是1988年由德国马普所的von Klitzing研究小组针对GaAs二维电子气中少量核自旋的探测而提出的一种具有超高灵敏度的实验技术. 目前, RDNMR已经成为研究单层或双层GaAs二维电子气核自旋和电子自旋特性的重要手段. 由于为实现电阻式核磁共振测量所建立的动态核极化方法强烈依赖于GaAs特有的材料属性, 至今这一技术一直没有扩展应用到其他半导体低维系统中. 最近,本研究小组发展了一种动态核极化新方法,成功实现了对典型窄带半导体锑化铟(InSb) 二维电子气的电阻式核磁共振测量.本文在介绍电阻式核磁共振测量工作原理及已建立的典型动态核极化方法的基础上,着重讨论所提出的动态核极化新方法的机理、 实验结果以及对今后研究的展望.