不均匀不稳定磁场下高分辨液体核磁共振新技术的研究进展

高分辨核磁共振（Nuclear Magnetic Resonance,NMR）谱的获得通常需要高度稳定且均匀的强静磁场. 阻抗磁体或阻抗－超导混合磁体可获得比超导磁体高得多的磁场, 但它们的磁场的稳定性与均匀性比较差;另一方面, 在活体定域波谱研究中,样品内部组分的磁化率差异,运动或生理活动等作用将不可避免地导致磁场的不均匀不稳定,并且这些不稳定不均匀性无法通过锁场匀场等传统的方法消除. 基于分子间零量子相干的方法、空间编码单扫描快速方法、反卷积技术等日渐成为在不均匀不稳定磁场下获取高分辨率的NMR谱的研究热点.     

Fast high-resolution nuclear magnetic resonance spectroscopy through indirect zero-quantum coherence detection in inhomogeneous fields

In many cases, high-resolution nuclear magnetic resonance （NMR） spectra are virtually impossible to obtain by con- ventional nuclear magnetic resonance methods because of inhomogeneity of magnetic field and inherent heterogeneity of sample. Although conventional intramolecular zero-quantum coherence （ZQC） can be used to obtain high-resolution spectrum in inhomogeneous field, the acquisition takes rather long time. In this paper, a spatially encoded intramolecular ZQC technique is proposed to fast acquire high-resolution NMR spectrum in inhomogeneous field. For the first time, the gradient-driven decoding technique is employed to selectively acquire intramolecular ZQC signals. Theoretical analyses and experimental observations demonstrate that high-resolution NMR spectral information can be retrieved within several scans even when the field inhomogeneity is severe enough to erase most spectral information. This work provides a new way to enhance the acquisition efficiency of high-resolution intramolecular ZQC spectroscopy in inhomogeneous fields.     

High-resolution NMR with resistive and hybrid magnets: deconvolution using a field-fluctuation signal

A method for compensating effect of field fluctuation is examined to attain high-resolution NMR spectra with resistive and hybrid magnets. In this method, time dependence of electromotive force induced for a pickup coil attached near a sample is measured synchronously with acquisition of NMR. Observed voltage across the pickup coil is converted to field fluctuation data, which is used to deconvolute NMR signals. The feasibility of the method is studied by (79)Br MAS NMR of KBr under a 30T magnetic field of a hybrid magnet. Twenty single-scan NMR signals were accumulated after the manipulation, resulting in a high-resolution NMR spectrum.     

Magnetic field homogeneity: a new approach to orthogonalizing and optimizing shim gradients

A new approach to optimizing shim coil currents for magnetic resonance magnets is presented. The new approach orthogonalizes the shim coil gradients to allow a simple one-dimensional optimization for each orthogonalized "composite shim." The technique demands no specialized equipment, requiring only the acquisition of simple one-dimensional NMR spectra. Examples from two high-resolution NMR spectrometers are presented, where the shim currents found by the new algorithm provide higher resolution than was obtained by the spectrometer vendor's installation engineers using field-mapping techniques. The examples shown demonstrate the advantages of the technique for high-resolution NMR, but we expect the approach will also find application in a broad variety of areas including imaging and in vivo spectroscopy.     

Single-sided sensor for high-resolution NMR spectroscopy

The unavoidable spatial inhomogeneity of the static magnetic field generated by open sensors has precluded their use for high-resolution NMR spectroscopy. In fact, this application was deemed impossible because these field variations are usually orders of magnitude larger than those created by the microscopic structure of the molecules to be detected. Recently, chemical shift resolved NMR spectra were observed for the first time outside a portable single-sided magnet by implementing a method that exploits inhomogeneities in the rf field designed to reproduce variations of the static magnetic field. In this communication, we describe in detail the magnet system built from permanent magnets as well as the rf coil geometry used to compensate the static field variations.     

First2H NMR at 58 T

The first nuclear magnetic resonance (NMR) experiments in pulsed field magnets at fields up to 58 T are reported. The basic features of the pulsed field source and the strategy to observe the first spectra are described. A²H NMR spectrum at 58 T is shown and the first results are discussed.     

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.     

Fast-field-cycling NMR: Applications and instrumentation

Magnetic field cycling in nuclear magnetic resonance (NMR) experiments has been used since the early days of NMR. Originally such time-dependent magnetic field experiments were motivated to study cross relaxation, spin system thermodynamics and indirect detection of quadrupolar resonance. The first apparatus used mechanical or pneumatic systems to shoot the sample between two magnets, the typical “flying time” being a few hundreds of milliseconds. As a natural evolution of the experimental technique and the need to extend its application to samples with higher relaxation rates, faster magnetic field switching devices were developed during the last years. Special electric networks combined with sophisticated air core magnets allowed one to switch magnetic fields between zero and fields of the order of 0.5 T in a few milliseconds. Today we refer to this new generation of instruments as “fast-field-cycling” devices. The technique has been successfully used during the last years to obtain information on the molecular dynamics and order in different materials, ranging from organic solids, metals, polymers, liquid crystals, porous media to biological systems. At present it is also turning to be an important tool for the design of contrast agents for magnetic resonance imaging. Fast field cycling was mainly oriented toT ₁ relaxometry as a unique technique offering a dynamic window of several decades, ranging from few kilohertz to several megahertz. However, there exist less conventional applications of the technique that can also provide relevant information concerning molecular dynamics, structure and molecular order. In this article we will briefly deal with basic aspects of the technique, its evolution, present-day relevant applications and the last improvements concerning specialized instrumentation.     

Mobile high resolution xenon nuclear magnetic resonance spectroscopy in the earth's magnetic field

Conventional high resolution nuclear magnetic resonance (NMR) spectra are usually measured in homogeneous, high magnetic fields (>1 T), which are produced by expensive and immobile superconducting magnets. We show that chemically resolved xenon (Xe) NMR spectroscopy of liquid samples can be measured in the Earth's magnetic field (5 x 10(-5) T) with a continuous flow of hyperpolarized Xe gas. It was found that the measured normalized Xe frequency shifts are significantly modified by the Xe polarization density, which causes different dipolar magnetic fields in the liquid and in the gas phases.     

Velocity distributions remotely measured with a single-sided NMR sensor

The pulsed field gradient nuclear magnetic resonance (PFG NMR) method has proved to be a powerful non-invasive technique to measure molecular displacement in various systems. It has been largely implemented with conventional NMR magnets where the volume for housing the flow setup is restricted. In this work we present the first approach to measure velocity distributions ex situ implementing a pulsed field gradient sequence on a single-sided NMR sensor. The open geometry of these sensors provides access to NMR measurements of a large number of applications previously excluded by the geometry of conventional closed magnets. Both, the distortions to the displacement encoding observed when implementing a PFG sequence in the presence of strongly inhomogeneous B0 and B1 fields, and the performance of the modifications proposed to eliminate these distortions are shown by means of numerical simulations. An alternating stimulated spin-echo PFG sequence implemented to remotely measure velocity distributions was combined with a multi-echo acquisition scheme to significantly increase the sensitivity of the method. The technique was implemented to measure the velocity propagator in a fluid undergoing laminar flow and good agreement with the theoretical result is observed.     

High-resolution, >1 GHz NMR in unstable magnetic fields

Resistive or hybrid magnets can achieve substantially higher fields than those available in superconducting magnets, but their spatial homogeneity and temporal stability are unacceptable for high-resolution NMR. We show that modern stabilization and shimming technology, combined with detection of intermolecular zero-quantum coherences (iZQCs), can remove almost all of the effects of inhomogeneity and drifts, while retaining chemical shift differences and J couplings. In a 25-T electromagnet (1 kHz/s drift, 3 kHz linewidth over 1 cm(3)), iZQC detection removes >99% of the remaining inhomogeneity, to generate the first high-resolution liquid-state NMR spectra acquired at >1 GHz.     

HL-2M中性束负离子试验源磁场位形及引出结构模拟分析

采用CST电磁工作室和粒子工作室软件对负离子试验源的会切磁场、过滤磁场、电子偏转磁场的位形及引出束流的光学进行了模拟计算。通过扫描会切磁体、过滤磁体、电子偏转磁体的表面磁场参数,确定了最佳的磁体结构和运行参数：周边6圈会切磁体,会切磁体表面磁场4kG,过滤磁体表面磁场5.5kG,电子偏转磁体表面磁场2.5kG,引出电压5~20kV,加速电压50~160kV,引出负离子束的光学性能满足NBI注入要求。     

HL-2M装置低温冷凝泵在抽气工况下的热负荷分析

采用理论计算和有限元实体模型的方法,对HL-2M装置低温冷凝泵及与其相连接的真空穿透结构进行了温度分布和液氦管热负荷分析。结果显示,低温冷凝泵中液氦管的热稳态热负荷为5.45W,粒子沉积的热负荷为75.68W,真空穿透部分的热负荷为5.04W。所得结果为后续的热应力分析、低温泵流速控制和低温系统的设计提供了参考。     

磁爆加载下强磁体的磁场研究

 为了研究磁爆压缩发生器加载下强磁体形成的磁场,对磁爆加载过程进行分析,建立了磁爆加载下强磁体形成磁场的理论模型。按照此模型,对6种不同结构强磁体的磁场进行对比研究,得到了强磁体的磁场变化规律。结果表明：在加载初始阶段,磁爆压缩发生器的自身参数为主要影响因素,各磁体的磁场峰值和范围差别较小;在磁通压缩阶段,电路过程的改变使得磁体结构的影响逐渐显著,各磁体的磁场峰值和范围发生了明显变化;磁体结构对磁场的空间分布具有决定性作用,磁场分布不受加载过程的影响。     

Magnetic field compensation for field-cycling NMR Relaxometry in the ULF band

In setting up field-cycling experiments aimed to study physical phenomena in the low-field region, magnetic field contributions from external sources (earth’s field, environment, other magnets, etc.) become important. Indeed, a compensation of these contributions has successfully been used for the application of field-cycling methods to nuclear magnetic relaxation and double resonance experiments. This feature becomes relevant in samples where local fields are stronly averaged due to motional narrowing, on the ground that relaxation experiments can therefore be extended to lower fields. Compensation of external contributions is also crucial for the study of kinky processes related to internal local fields. In this article we outline NMR field-cycling experiments aimed to detect and quantify the external net magnetic field sensed by the spin-system. Both parallel and normal components with respect to the high-field Zeeman axis can be determined separately by using different experimental protocols.     

An Efficacious Target-Field Approach to Design Shim Coils for Halbach Magnet of Mobile NMR Sensors

The main magnetic fields of mobile nuclear magnetic resonance (NMR) magnets differ from those of conventional NMR and magnetic resonance imaging (MRI) magnets. In the Halbach magnet, the main field B ₀ is perpendicular to the longitudinal axis, the symmetry of the current distribution with respect to the symmetry of the magnetic field differs from that in conventional target-field applications, and the current distribution on the coil surface cannot be expressed in terms of periodic basis functions. To obtain the winding pattern of the coil, an efficacious target-field approach. The surface of a coil is divided into small discrete elements, where each element is represented by a magnetic dipole. From the stream function of the elements, the resultant magnetic field is calculated. The optimization strategy follows an objective function defined by the power dissipation or efficiency of the coil. This leads to the optimum stream function on the coil surface, whose contour lines define the winding patterns of the coil. This paper shows winding patterns designed of shim coils for Halbach magnet and illustrates the craft of a shim coil using flexible printed circuit board. The performance of the coils is verified by simulating the fields they produce over the sensitive volume.     

不均匀场下基于分子间双量子相干核磁共振技术的果肉检测

核磁共振（NMR）谱图可在不破坏生物样品的状态下提供组织成分组成及其含量的信息,已被广泛应用于生物、医学和食品检测等领域.NMR谱图分辨率越高,提供的与组织成分相关的信息越丰富、越准确,也越有利于未知成分的定性和定量分析.传统的高分辨NMR谱图通常要在均匀磁场下采集.但在实际应用中,均匀的磁场较难获得.这就使得我们采集的NMR谱图的分辨率,以及由此获得的生物组织成分组成和含量等信息的准确性受到影响.源于远程偶极相互作用的分子间双量子相干（iDQC）技术对磁场均匀度不敏感,可在不均匀场下获得高分辨率NMR谱图.本文采用基于iDQC技术的IDEAL-Ⅱ序列对甲基丙烯酸丁酯、蕃茄和西瓜三种样品进行了NMR实验,结果证明基于iDQC技术在不均匀场下获得水果的高分辨NMR谱图是可行的,这对食品科学以及食品检测具有积极的意义.     

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 portable Halbach magnet that can be opened and closed without force: the NMR-CUFF

Portable equipment for nuclear magnetic resonance (NMR) is becoming increasingly attractive for use in a variety of applications. One of the main scientific challenges in making NMR portable is the design of light-weight magnets that possess a strong and homogeneous field. Existing NMR magnets can provide such magnetic fields, but only for small samples or in small regions, or are rather heavy. Here we show a simple yet elegant concept for a Halbach-type permanent magnet ring, which can be opened and closed with minimal mechanical force. An analytical solution for an ideal Halbach magnet shows that the magnetic forces cancel if the structure is opened at an angle of 35.3° relative to its poles. A first prototype weighed only 3.1 kg, and provided a flux density of 0.57 T with a homogeneity better than 200 ppm over a spherical volume of 5mm in diameter without shimming. The force needed to close it was found to be about 20 N. As a demonstration, intact plants were imaged and water (xylem) flow measured. Magnets of this type (NMR-CUFF = Cut-open, Uniform, Force Free) are ideal for portable use and are eminently suited to investigate small or slender objects that are part of a larger or immobile whole, such as branches on a tree, growing fruit on a plant, or non-metallic tubing in industrial installations. This new concept in permanent-magnet design enables the construction of openable, yet strong and homogeneous magnets, which aside from use in NMR or MRI could also be of interest for applications in accelerators, motors, or magnetic bearings.     

Field Calculations for Permanent Magnets used for Glow Discharges

If a permanent magnet has both a homogeneous polarization inside the material and a linear demagnetization characteristic in external fields, its magnetic field can be expressed using a surface pole model. For magnets satisfying these conditions and, in addition, having a rectangular shape, the fields at any given point in space can be calculated analytically. An algorithm for this calculation is presented in a form that can easily be implemented into a computer program. In our experiments we used Nd₂Fe₁₄B magnets to support low pressure glow discharges by magnetic fields. The magnets can be seen as composed of elementary magnets with rectangular shape, for which the magnetic field distribution is calculable. We present results of field calculations for various configurations of permanent magnets that we used in hollow cathode and Penning discharges.