A new solvent suppression method via radiation damping effect

Radiation damping effects induced by the dominated solvent in a solution sample can be applied to suppress the solvent signal. The precession pathway and rate back to equilibrium state between solute and solvent spins are different under radiation damping. In this paper, a series of pulse sequences using radiation damping were designed for the solvent suppression in nuclear magnetic resonance (NMR) spectroscopy. Compared to the WATERGATE method, the solute signals adjacent to the solvent would not be influenced by using the radiation damping method. The one-dimensional (1D) ¹H NMR, two-dimensional (2D) gCOSY, and J-resolved experimental results show the practicability of solvent suppression via radiation damping effects in 1D and 2D NMR spectroscopy.     

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.     

Multiple Nonlinear Stimulated Echoes

Three-pulse sequences in the presence of magnetic field gradients at high magnetic fields produce multiple nonlinear stimulated echoes (NOSE) at timesnτ₁after the third pulse, wherenis an integer and τ₁the interval between the first two pulses. These phenomena are due to the demagnetizing field produced by the spatial modulation of the nuclear magnetization arising in the sample after the first two pulses. The theory is presented and compared with experiments. The dependence of the NOSE amplitudes on the flip angles and on the pulse intervals is described. Implications for multidimensional NMR experiments based on sequences of three or more pulses in the presence of field gradients are discussed.     

Ultra-low field NMR measurements of liquids and gases with short relaxation times

Interest in nuclear magnetic resonance measurements at ultra-low magnetic fields (ULF, approximately microT fields) has been motivated by various benefits and novel applications including narrow NMR peak-width, negligible susceptibility artifacts, imaging of samples inside metal containers, and possibility of directly imaging neuronal currents. ULF NMR/MRI is also compatible with simultaneous measurements of biomagnetic signals. However the most widely used technique in ULF NMR-prepolarization at high field and measurement at lower field-results in large transient signals which distort the free induction decay signal. This is especially severe for the measurement of signals from samples and materials with short T1 time. We have devised an approach that largely cancels the transient signals. The technique was successfully used to measure NMR signals from liquids and gases with T1 in the range 1-4 ms.     

Radiation damping in microcoil NMR probes

Radiation damping arises from the field induced in the receiver coil by large bulk magnetization and tends to selectively drive this magnetization back to equilibrium much faster than relaxation processes. The demand for increased sensitivity in mass-limited samples has led to the development of microcoil NMR probes that are capable of obtaining high quality NMR spectra with small sample volumes (nL-microL). Microcoil probes are optimized to increase sensitivity by increasing either the sample-to-coil ratio (filling factor) of the probe or quality factor of the detection coil. Though radiation damping effects have been studied in standard NMR probes, these effects have not been measured in the microcoil probes. Here a systematic evaluation of radiation damping effects in a microcoil NMR probe is presented and the results are compared with similar measurements in conventional large volume samples. These results show that radiation-damping effects in microcoil probe is much more pronounced than in 5 mm probes, and that it is critically important to optimize NMR experiments to minimize these effects. As microcoil probes provide better control of the bulk magnetization, with good RF and B0 inhomogeneity, in addition to negligible dipolar field effects due to nearly spherical sample volumes, these probes can be used exclusively to study the complex behavior of radiation damping.     

NMR signal averaging in 62T pulsed fields

Nuclear Magnetic Resonance (NMR) experiments in pulsed high magnetic fields up to 62T at the Dresden High Magnetic Field Laboratory (Hochfeld-Magnetlabor Dresden) are reported. The time dependence of the magnetic field is investigated by observing various free induction decays (FIDs) in the vicinity of the maximum of the field pulse. By analyzing each FID's phase and its evolution with time the magnetic field's time dependence can be determined with high precision. Assuming a quadratic or cubic dependence on time near the field maximum its confidence is found to be better than ± 0.03ppm at low fields and ± 0.8ppm near 62T. In turn, the thus obtained time dependence of the field can be used to demodulate and phase-correct all FIDs so that they appear phase-locked to each other. As a consequence signal averaging is possible. The increase in signal-to-noise ratio is found to be close to that expected theoretically. This shows that the intrinsic time dependence of the pulsed fields can be removed so that the NMR signals appear to be taken at rather stable static field. This opens up the possibility of performing precise shift measurements and signal averaging also of unknown, weak signals if a reference signal is measured during the same field pulse with a double-resonance probe.     

A simulation algorithm based on Bloch equations and product operator matrix: application to dipolar and scalar couplings

A product operator matrix is proposed to describe scalar couplings in liquid NMR. Combination of the product operator matrix and non-linear Bloch equations is employed to describe effects of chemical shift, translational diffusion, dipolar field, radiation damping, and relaxation in multiple spin systems with both scalar and dipolar couplings. A new simulation algorithm based on this approach is used to simulate NMR signals from dipolar field effects in the presence of scalar couplings. Several typical coupled spin systems with both intra-molecular scalar couplings and inter-molecular dipolar couplings are simulated. Monte Carlo methods are incorporated into simulations as well to analyze diffusion process in these complicated spin systems. The simulated results of diffusion and relaxation parameters and 2D NMR spectra are coincident with the experimental measurements, and agree with theoretical predictions as well. The simulation algorithm presented herein therefore provides a convenient means for designing pulse sequences and quantifying experimental results in complex coupled spin systems.     

Simulating the effects of time-varying magnetic fields with a realistic simulated scanner

Transient magnetic fields induce changes in magnetic resonance (MR) images ranging from small, visually undetectable effects (caused, for instance, by neuronal currents) to more significant ones, such as those created by the gradient fields and eddy currents. Accurately simulating these effects may assist in correcting or optimising MR imaging for many applications (e.g., diffusion imaging, current density imaging, use of magnetic contrast agents, neuronal current imaging, etc.). Here we have extended an existing MR simulator (POSSUM) with a model for changing magnetic fields at a very high-resolution time-scale. This simulator captures a realistic range of scanner and physiological artifacts by modeling the scanner environment, pulse sequence details and subject properties (e.g., brain geometry and air-tissue boundaries).     

Toroid cavity detectors for high-resolution NMR spectroscopy and rotating frame imaging: capabilities and limitations

The capabilities of toroid cavity detectors for simultaneous rotating frame imaging and NMR spectroscopy have been investigated by means of experiments and computer simulations. The following problems are described: (a) magnetic field inhomogeneity and subsequent loss of chemical shift resolution resulting from bulk magnetic susceptibility effects, (b) image distortions resulting from off-resonance excitation and saturation effects, and (c) distortion of lineshapes and images resulting from radiation damping. Also, special features of signal analysis including truncation effects and the propagation of noise are discussed. B(0) inhomogeneity resulting from susceptibility mismatch is a serious problem for applications requiring high spectral resolution. Image distortions resulting from off-resonance excitation are not serious within the rather narrow spectral range permitted by the RF pulse lengths required to read out the image. Incomplete relaxation effects are easily recognized and can be avoided. Also, radiation damping produces unexpectedly small effects because of self-cancellation of magnetization and short free induction decay times. The results are encouraging, but with present designs only modest spectral resolution can be achieved.     

On concomitant gradients in low-field MRI

Growing interest in magnetic resonance imaging (MRI) at ultra-low magnetic fields (ULF, approximately muT fields) has been motivated by several advantages over its counterparts at higher magnetic fields. These include narrow line widths, the possibility of novel imaging schemes, reduced imaging artifacts from susceptibility variations within a sample, and reduced system cost and complexity. In addition, ULF NMR/MRI with superconducting quantum interference devices is compatible with simultaneous measurements of biomagnetic signals, a capability conventional systems cannot offer. Acquisition of MRI at ULF must, however, account for concomitant gradients that would otherwise result in severe image distortions. In this paper, we introduce the general theoretical framework that describes concomitant gradients, explain why such gradients are more problematic at low field, and present possible approaches to correct for these unavoidable gradients in the context of a non-slice-selective MRI protocol.     

Intermolecular multiple-quantum coherence NMR signals modulated by double distant dipolar fields

A modified CRAZED pulse sequence was applied to obtain the intermolecular multiple-quantum coherence NMR signals from double distant dipolar fields in highly polarized spin systems. Complete theoretical analyses were explicitly derived from the dipolar field treatment combined with product operator formalism. Two typical samples containing several different components were chosen for the experimental verifications. The computer simulations and experimental observations are consistent with the theoretical predictions. The results presented herein provide a convenient way to understand the combined effects of multiple distant dipolar fields from the different components in complicated chemical or biological solutions. When experimental conditions such as selective radio-frequency pulses are not optimal, it may be helpful to identify possible unexpected signals or artefacts of high-resolution NMR spectroscopy in inhomogeneous fields.     

Modulation effects in non-drilling NMR in the Earth’s field

The paper describes the variant of nuclear magnetic resonance (NMR) in the Earth’s field using no prepolarization. This method can be employed to record the NMR signal of underground proton-containing liquids, such as water, located at the depth of more than 100 m without drilling. The non-drilling NMR in the Earth’s field is recorded by locating on the surface the circular wire with a diameter of about 100 m. This wire serves as an antenna for the exciting field source and the NMR signal receiver. The radiofrequency pulse with the carrier frequency equal to that of proton resonance in the Earth’s field is passed through the wire. When the exciting pulse is switched off, the induction e.m.f. signal caused by the free Larmor nuclear precession in the geomagnetic fields is observed. An important case when in the non-drilling NMR in the Earth’s field the signal is excited and observed at different frequencies is studied both from theoretical and practical viewpoints. The resulting modulation effects are considered. Such situations arise e.g. either in magnetic rocks or upon magnetic storms.     

High spatial resolution NMR imaging of polymer layers on metallic substrates

High spatial resolution NMR imaging techniques have been developed recently to measure the spatial inhomogeneity of a polymer coating film. However, the substrates of the polymer coatings for such experiments are generally required to be non-metallic, because metals can interact with static magnetic fields B(0) and RF fields B(1) giving rise to artifacts in NMR images. In this paper we present a systematic study on the effects of metallic substrates on 1D profiles obtained by high resolution NMR imaging. The off-resonance effect is discussed in detail in terms of the excitation profile of the RF pulses. We quantitatively show how the NMR signal intensities change with frequency offset at different RF pulse lengths. The complete NMR profiles were simulated using a Finite Element Analysis method by fully considering the inhomogeneities in both B(1) and B(0). The excellent agreement between the calculated and measured NMR profiles on both metallic and non-metallic substrates indicates that the experimental NMR profiles can be reproduced very well by numerical simulations. The metallic substrates can disturb the RF field of the coil by eddy current effect and therefore change the NMR profiles. To quantitatively interpret the NMR profile of a polymer layer on a metallic substrate, the profile has to be divided by the profile of a reference on the same metallic substrate located at the same distance from the coil.     

Field propagation phenomena in ultra high field NMR: a Maxwell-Bloch formulation

The principal advantage of NMR at high field is the concomitant increase in signal-to-noise ratio (SNR). This can be traded for improved spatial resolution and combined with parallel imaging to achieve higher temporal resolution. At high field strength, the RF-wavelength and the dimension of the human body complicate the development of NMR coils. For example, at 7 T, the wavelength in free space corresponds to about 1m. The dielectric constant in tissue with a high water content can be as high as 70 and at a larmor frequency of 300 MHz, this corresponds to a wavelength inside tissue of less than 15 cm. The operating wavelength is thus comparable to the diameter of most body parts. To this end, both temporal and spatial variations of the excitation field must be taken into account in addition to the expected increase in conductivity. For all these reasons, we find the propagation of radiation at ultra high fields (>4 T) new phenomena commonly observed in quantum optics but traditionally negligible in NMR such as phase modulation of the excitation field such that the identity between pulse area and flip angle is no longer valid. In this paper, the emergence of field propagation phenomena in NMR experiments is analytically and numerically demonstrated. It is shown that in addition to the well-studied dielectric resonance phenomena at high magnetic fields (>4 T), field propagation effects transform the excitation pulse into an adiabatic excitation. The high field strength also mean that nonlinear effects such as self-induced transparency are now possible in NMR experiments.     

脉冲梯度场NMR实验中的弛豫和辐射阻尼效应

使用梯度脉冲压制水峰已广泛地应用于生物样品的NMR实验,一个选择性90°脉冲接一个纵向的散相梯度脉冲破预期能得到好的去水峰效果,然而基于下面的三方面的原因,梯度脉冲去水峰的效果受到了限制,其一是梯度散相的动力学过程表明总磁化强度的衰减是需要时间的,其二是纵向弛豫T₁机制在梯度脉冲作用过程中不可避免,其三是辐射阻尼效应力图将磁化强度推向z方向.在本文中我们定量地分析了这三种机制在压水峰过程中的作用.     

消磁场对纳米铁磁线磁畴壁动力学行为的影响

为了实现基于磁畴壁运动的自旋电子学装置, 掌握磁畴壁动力学行为是重要争论之一.研究了在外磁场驱动下L-型纳米铁磁线磁畴壁的动力学行为. 通过微磁学模拟,在各种外磁场的驱动下考察了纳米铁磁线磁畴壁的动力学特性; 在较强外磁场的驱动下, 在不同厚度纳米线上考察了纳米线表面消磁场对磁畴壁动力学行为的影响. 为了进一步证实消磁场对磁畴壁动力学的影响, 在垂直于纳米线表面的外磁场辅助下分析了磁畴壁的动力学行为变化. 结果表明, 随着纳米线厚度和外驱动磁场强度的增加, 增强了纳米线表面的消磁场的形成, 使得磁畴壁内部自旋结构发生周期性变化, 导致磁畴壁在纳米线上传播时出现Walker崩溃现象. 在垂直于纳米线表面的外磁场辅助下, 发现辅助磁场可以调节消磁场的强度和方向. 这意味着利用辅助磁场可以有效地控制纳米铁磁线磁畴壁的动力学行为.     

The role of magnetic damping in the r-mode evolution of accreting neutron stars

The magnetic damping rate was introduced in the evolution equations of r-modes,which shows that r-modes can generate strong toroidal magnetic fields in the core of accreting millisecond pulsars inducing by differential rotation.With consideration of the coupling evolution of r-modes,spin and thermal evolution,we investigated the influence of the magnetic damping on the differential rotation of nonlinear r-modes of accreting neutron stars.We derived the coupling evolution equations of the star involving the magnetic damping rate in the framework of second-order r-mode theory.The numerical results show that the magnetic damping suppressed the nonlinear evolution of r-modes since the saturation amplitude is reduced to a great extent.In particular,because of the presence of the generated toroidal magnetic field,the spin-down of the stars is terminated and the viscous heating effects are also weakened.Moreover,we could obtain a stronger generated toroidal magnetic field in the second-order r-mode theory.The gravitational radiation may be detected by the advanced laser interferometer detector LIGO if the amount of differential rotation is small when the r-mode instability becomes active and the accretion rate is not very high.     

Mapping eddy current induced fields for the correction of diffusion-weighted echo planar images

Diffusion-weighted echo-planar magnetic resonance imaging is potentially of great importance as a diagnostic imaging tool; however, the technique currently suffers a number of limitations, including the image distortion caused by the eddy current induced fields when the diffusion-weighting magnetic field gradient pulses are applied. The distortions cause mis-registration between images with different diffusion-weighting, that then results in artifacts in quantitative diffusion images. A method is presented to measure the magnetic fields generated from the eddy currents for each of three orthogonal gradient pulse vectors, and then to use these to ascertain the image distortion that occurs in subsequent diffusion-weighted images with arbitrary gradient pulse vector amplitude and direction, and image plane orientation. The image distortion can then be reversed. Both temporal and spatial dependence of the residual eddy current induced fields are included in the analysis. Image distortion was substantially reduced by the correction scheme, for arbitrary slice position and angulation. This method of correction is unaffected by the changes in image contrast that occur due to diffusion weighting, and does not need any additional scanning time during the patient scan. It is particularly suitable for use with single-shot echo planar imaging.     

DIRECT MEASUREMENT OF TRANSVERSE RELAXATION TIME OF INTERMOLECULAR MULTIPLE QUANTUM COHERENCES IN NMR

A one-dimensional NMR method is presented for measuring the transverse relaxation time, T_2,n, of intermolecular multiple quantum coherences (IMQCs) of coherence order n in highly polarized spin systems. The pulse sequence proposed in this paper effectively suppresses the effects of radiation damping, molecular diffusion, inhomogeneity of magnetic field, and variations of dipolar correlation distance, all of which may affect quantitation of T_2,n. This pulse sequence can be used to measure not only IMQC transverse relaxation time T_2,n(n>1) quickly and directly, but also the conventional transverse relaxation time. Experimental results demonstrate that the quantitative relationship between T_2,n(n≥1) and T₂ is T_2,n≈T₂/n. These results will be helpful for understanding the fundamental properties and mechanisms of IMQCs.     

Theoretical limit of the minimal magnetization switching field and the optimal field pulse for Stoner particles

The theoretical limit of the minimal magnetization switching field and the optimal field pulse design for uniaxial Stoner particles are investigated. Two results are obtained. One is the existence of a theoretical limit of the smallest magnetic field out of all possible designs. It is shown that the limit is proportional to the damping constant in the weak damping regime and approaches the Stoner-Wohlfarth (SW) limit at large damping. For a realistic damping constant, this limit is more than 10 times smaller than that of so-called precessional magnetization reversal under a noncollinear static field. The other is on the optimal field pulse design: if the magnitude of a magnetic field does not change, but its direction can vary during a reversal process, there is an optimal design that gives the shortest switching time. The switching time depends on the field magnitude, damping constant, and magnetic anisotropy.