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.     

3D imaging with a single-sided sensor: an open tomograph

An open tomograph to image volume regions near the surface of large objects is described. The central achievement in getting such a tomograph to work is the design of a fast two-dimensional pure phase encoding imaging method to produce a cross-sectional image in the presence of highly inhomogeneous fields. The method takes advantage of the multi-echo acquisition in a Carr-Purcell-Meiboom-Gill (CPMG)-like sequence to significantly reduce the experimental time to obtain a 2D image or to spatially resolve relaxation times across the sensitive volume in a single imaging experiment. Depending on T(2) the imaging time can be reduced by a factor of up to two orders of magnitude compared to the one needed by the single-echo imaging technique. The complete echo train decay has been also used to produce T(2) contrast in the images and to spatially resolve the T(2) distribution of an inhomogeneous object, showing that variations of structural properties like the cross-link density of rubber samples can be distinguished by this method. The sequence has been implemented on a single-sided sensor equipped with an optimized magnet geometry and a suitable gradient coil system that provides two perpendicular pulsed gradient fields. The static magnetic field defines flat planes of constant frequency parallel to the surface of the scanner that can be selected by retuning the probe frequency to achieve slice selection into the object. Combining the slice selection obtained under the presence of the static gradient of the open magnet with the two perpendicular pulsed gradient fields, 3D spatial resolution is obtained.     

A single-scan method for measuring flow along an arbitrary direction

In this article, we demonstrate a single-scan method to measure an average flow velocity vector along an arbitrary direction. This method is based on the MMME sequence and utilizes static and pulsed magnetic field gradients along multiple directions for the optimal determination of flow velocity components in three-dimensional space. Experimentally measured average flow velocities from the flow induced phase shift with a single-scan MMME sequence show excellent agreements with the known flow rate, and the signal decay of each echo due to a velocity distribution is also quantitatively verified with known laminar flow patterns.     

Self-diffusion measurements by a mobile single-sided NMR sensor with improved magnetic field gradient

A simple and fast method of measuring self-diffusion coefficients of protonated systems with a mobile single-sided NMR sensor is discussed. The NMR sensor uses a magnet geometry that generates a highly flat sensitive volume where a strong and highly uniform static magnetic field gradient is defined. Self-diffusion coefficients were measured by Hahn- and stimulated echoes detected in the presence of the uniform magnetic field gradient of the static field. To improve the sensitivity of these experiments, a Carr-Purcell-Meiboom-Gill pulse sequence was applied after the main diffusion-encoding period. By adding the echo train the experimental time was strongly shortened, allowing the measurement of complete diffusion curves in less than 1min. This method has been tested by measuring the self-diffusion coefficients D of various organic solvents and poly(dimethylsiloxane) samples with different molar masses. Diffusion coefficients were also measured for n-hexane absorbed at saturation in natural rubber with different cross-link densities. The results show a dependence on the concentration that is in good agreement with the theoretical prediction. Moreover, the stimulated-echo sequence was successfully used to measure the diffusion coefficient as a function of the evolution time in systems with restricted diffusion. This type of experiment proves the pore geometry and gives access to the surface-to-volume ratio. It was applied to measure the diffusion of water in sandstones and sheep Achilles tendon. Thanks to the strong static gradient G(0), all diffusion coefficients could be measured without having to account for relaxation during the pulse sequence.     

Background gradient suppression in stimulated echo NMR diffusion studies using magic pulsed field gradient ratios

By evaluating the spin echo attenuation for a generalized 13-interval PFG NMR sequence consisting of pulsed field gradients with four different effective intensities (F(p/r) and G(p/r)), magic pulsed field gradient (MPFG) ratios for the prepare (G(p)/F(p)) and the read (G(r)/F(r)) interval are derived, which suppress the cross term between background field gradients and the pulsed field gradients even in the cases where the background field gradients may change during the z-store interval of the pulse sequence. These MPFG ratios depend only on the timing of the pulsed gradients in the pulse sequence and allow a convenient experimental approach to background gradient suppression in NMR diffusion studies with heterogeneous systems, where the local properties of the (internal) background gradients are often unknown. If the pulsed field gradients are centered in the tau-intervals between the pi and pi/2 rf pulses, these two MPFG ratios coincide to eta=G(p/r)/F(p/r)=1-8/[1+(1/3)(delta/tau)(2)]. Since the width of the pulsed field gradients (delta) is bounded by 0< or =delta< or =tau, eta can only be in the range of 5< or =-eta< or =7. The predicted suppression of the unwanted cross terms is demonstrated experimentally using time-dependent external gradients which are controlled in the NMR experiment as well as spatially dependent internal background gradients generated by the magnetic properties of the sample itself. The theoretical and experimental results confirm and extend the approach of Sun et al. (J. Magn. Reson. 161 (2003) 168), who recently introduced a 13-interval type PFG NMR sequence with two asymmetric pulsed magnetic field gradients suitable to suppress unwanted cross terms with spatially dependent background field gradients.     

MQ-PGSTE: A new multi-quantum STE-based PGSE NMR sequence

A new multi-quantum stimulated echo based pulsed gradient spin-echo sequence, MQ-PGSTE, has been developed for measuring translational diffusion. The new sequence provides a higher signal-to-noise ratio than the (Hahn spin-echo based) MAXY-D sequence at long diffusion times, and thus potentially affords better diffusion measurements on macromolecule samples. Based on multi-quantum coherence encoding, the MQ-PGSTE sequence needs considerably lower gradient strengths for diffusion characterization compared to standard single quantum pulsed gradient spin-echo sequences. By using the new sequence, the diffusion coefficient of l-[3-¹³C]-alanine was found to be 8.1 ± 0.1 × 10⁻¹⁰ m² s⁻¹, which is in line with the value obtained by the use of the standard stimulated echo based pulsed gradient spin-echo sequence.     

Multi-echo imaging in highly inhomogeneous magnetic fields

A new pulsed field gradient multi-echo imaging technique to encode position in the phase of every echo generated by a CPMG sequence in the presence of a strongly inhomogeneous static magnetic field is presented. It was applied to improve the sensitivity in an imaging experiment by adding the echo train acquired during the CPMG sequence and to spatially resolve relaxation times of inhomogeneous specimens using single-sided probes. The sequence was implemented in a new bar-magnet MOUSE equipped with a gradient coil system to apply a pulsed magnetic field with a constant gradient along one spatial coordinate. An important reduction by a factor larger than two orders of magnitude in the acquisition time was obtained compared to the previously published single-point imaging technique.     

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.     

超快速COSY类2D NMR实验弛豫假峰的抑制

在脉冲梯度场基础上研究了进一步缩短COSY类2D NMR实验数据采集时间的新方法.利用主动屏蔽梯度场线圈的梯度场恢复时间仅为100μs数量级这一特点,提出一类基于脉冲梯度场消除弛豫假峰的脉冲序列.并以DQF-COSY脉冲序列为例加以验证.实验结果表明:采用文中的方法,取序列重复时间远小于T₁和T₂是切实可行的;梯度场技术能很好地抑制弛豫假蜂以达到2D NMK数据的快速采集.     

Fast measurements of average flow velocity by Low-Field ¹H NMR

In this paper, we describe a method for measuring the average flow velocity of a sample by means of Nuclear Magnetic Resonance. This method is based on the Carr-Purcell-Meiboom-Gill (CPMG) sequence and does not require the application of any additional static or pulsed magnetic field gradients to the background magnetic field. The technique is based on analyzing the early-time behavior of the echo amplitudes of the CPMG sequence. Measurements of average flow velocity of water are presented. The experimental results show a linear relationship between the slope/y-intercept ratio of a linear fit of the first echoes in the CPMG sequence, and the average flow velocity of the flowing fluid. The proposed method can be implemented in low-cost Low-Field NMR spectrometers allowing a continuous monitoring of the average velocity of a fluid in almost real-time, even if the flow velocity changes rapidly.     

Estimation methods for flow imaging with high frequency ultrasound

This article proposes to estimate slow blood flow with high frequency ultrasound imaging. The proposed technique combines 2 methods. First, a statistical method, called Speckle Flow Imaging (SFI) based on the analysis of changes in the speckle pattern along time, gives an index directly related to the total velocity vector. Secondly, a block matching approach estimates the in-plane velocity components. Results on calibrated flow sequences of blood mimicking fluid have shown good agreement with the statistical model. The quantification of flow is achieved with pulsed flow and is also angle independent when the flow is perpendicular to the ultrasound beam. Speckle Tracking has been evaluated on the same data and has shown good estimation of the in-plane velocity vector when the component of velocity perpendicular to the imaging plane is inferior to 1mm/s. The results of these two methods permit the evaluation of the total 3D velocity field and the orthogonal velocity component relative to the imaging plane. This allows the quantification of blood flow (volumetric per time unit across the sequence).     

Measurement of sound field in cavitating media by an optical fibre-tip hydrophone

A fibre-optic technique was applied to measure the sound field in an ultrasonic cleaning vessel under practical conditions. A metal-coated fibre-tip is used as a sensor and a heterodyne interferometer detects the change in the optical path resulting from the movement of the fibre-tip in the sound field. Spectrally resolved sound field parameters such as the fundamental, the subharmonic or cavitation noise are extracted from the measurements and compared with results obtained by a piezo-electric hydrophone. It was found that the fibre sensor provides a signal related to the velocity in the sound field, but the information about cavitation-related parameters is similar to the information for pressure sensing techniques. The fibre-optic sensors have a uniquely high spatial resolution and the sound detection process is strongly influenced by single cavitation events close to the small fibre-tip. This paper shows that fibre-tip sensors are an alternative to common hydrophone techniques. They can open up new possibilities for measurement problems for which so far no solution exists, in particular when a high spatial resolution is required or when the measurement site is small.     

D-T2二维核磁共振脉冲序列及反演方法改进设计

面对日益复杂的勘探对象, D-T₂二维核磁共振技术在实际应用中面临无法兼顾扩散系数测量范围和横向弛豫分辨率的困境. 脉冲序列作为D-T₂二维核磁共振数据采集的核心技术, 其性能优劣直接影响应用效果, 在综合对比PFG, STE-PFG, BP-PFG、改良式CPMG, 扩散编程, 多回波间隔CPMG脉冲序列性能的基础上, 有效融合脉冲梯度场、恒定梯度场D-T₂脉冲序列的优点, 本文提出一种基于脉冲梯度场的双变量、两窗口D-T₂脉冲序列改进设计. 针对两个窗口的D-T₂二维核磁共振数据反演, 为突破现有反演方法无法兼顾反演精度和解谱效率的瓶颈, 本着第二个窗口回波信号为主、第一个窗口回波信号为辅的原则, 本文提出一种同时使用两个窗口数据参与解谱的联合TSVD反演方法. 气水、油水、稠油、油气水模型不同信噪比条件下的数值模拟结果表明, 本文提供的D-T₂改进脉冲序列达到了平衡扩散系数测量范围和横向弛豫分辨率的设计要求, 本文提供的联合TSVD反演方法也有效平衡了反演精度要求和解谱效率. 文中的D-T₂改进脉冲序列及联合TSVD反演方法在复杂油气藏流体识别和产能预测中具有广泛的应用前景, 可为促进国内D-T₂二维核磁共振岩心分析技术的发展提供有利条件.     

Experimental studies of pulsed signal propagation from the shelf to deep sea

Results of an experimental study of low-frequency broadband pulsed signal propagation in a waveguide that includes the shelf zone, the continental slope, and the deep sea region are presented. Using phase-manipulated signals with central frequencies of 366 and 600 Hz, pulsed characteristics are measured at six points along the propagation track, the maximal distance from the source being 368 km. It is experimentally demonstrated that, in the presence of a negative sound velocity gradient in the near bottom layer on the shelf with a small bottom slope, the choice of the source position at the shelf bottom near the shoreline provides the formation of a continuous illumination zone in the deep sea near the USC axis and a stable pulsed characteristic with two main sound energy arrivals. The propagation velocity of the pulse that is last to arrive is identical (within the measurement error) to the velocity of sound on the USC axis at the point of reception. Possibilities for practical application of the results obtained from the experiment are discussed.     

Gradient- and Sensitivity-Enhanced TOCSY Experiments

A pulsed field gradient version of the sensitivity-enhanced 2D TOCSY experiment is proposed which yields high-quality spectra with improved sensitivity and a minimum of two scans pert₁increment. For rapid acquisition of 1D TOCSY spectra, the 1D DPFGSE–TOCSY experiment was modified to include phase-encoded multiple-selective excitation followed by a simple spectral editing. Combination of these two building blocks is used in a sensitivity-enhanced 2D analog of the 3D TOCSY–TOCSY experiment which provides an efficient tool for resolving severely overlapped signals of oligomers in short experimental time.     

一维NOE NMR 技术用于蒂巴因衍生物的立体结构研究

基于高效镇痛剂双氢埃托啡游离碱,对蒂巴因衍生物的立体化学结构的NMR 测定方法进行了研究．结果表明,采用多频率位移选择激发一维NOESY(1D NOESY)和二维NMR(2D NMR)相结合的方法,可有效解决该类化合物¹H 和¹³C NMR 谱复杂重叠的信号归属困难的问题．同时在阐明溶液构象的基础上,提出采用一维NOE(1D NOE)测定C-7和差向异构体的新方法．该方法简单、有效、不受样品浓度影响和杂质信号干扰,结果可靠,不需要标准品对照等优点．该结果有助于此类化合物的立体结构与生物活性关系的研究．     

Line shape considerations in ultrafast 2D NMR

We have recently proposed and demonstrated an approach that enables the acquisition of 2D nuclear magnetic resonance (NMR) spectra within a single scan. The approach is based on spatially encoding the spins' evolution along the indirect domain with the aid of a magnetic field gradient, and subsequently decoding this information numerous times over the course of the signal acquisition while spins are subject to a train of gradient echoes. The present paper discusses further considerations pertaining the 2D line shapes arising from this new way of collecting NMR data. Specific issues that are hereby addressed include (i) the effects introduced by fast relaxation onto the spatial encoding process, particularly the line widths and line shapes that will then arise in the frequency domain; (ii) approaches capable of correcting for the mixed-phase kernels resulting in these fast-relaxation cases, corresponding in essence to spatially encoded analogs of the TPPI and hypercomplex time-domain acquisition procedures; (iii) the enveloping characteristics imposed by the use of discrete excitation pulses on the attainable spectral widths along the indirect domain; and (iv) an analysis of the signal-to-noise characteristics of the methodology, with experimental corroborations of theoretical predictions and an illustration of the method's capabilities to analyze protein solutions in the mM-range concentration.     

The virtual NMR spectrometer: a computer program for efficient simulation of NMR experiments involving pulsed field gradients

This paper presents a software program, the Virtual NMR Spectrometer, for computer simulation of multichannel, multidimensional NMR experiments on user-defined spin systems. The program is capable of reproducing most features of the modern NMR experiment, including homo- and heteronuclear pulse sequences, phase cycling, pulsed field gradients, and shaped pulses. Two different approaches are implemented to simulate the effect of pulsed field gradients on coherence selection, an explicit calculation of all coherence transfer pathways, and an effective approximate method using integration over multiple positions in the sample. The applications of the Virtual NMR Spectrometer are illustrated using homonuclear COSY and DQF COSY experiments with gradient selection, heteronuclear HSQC, and TROSY. The program uses an intuitive graphical user interface, which resembles the appearance and operation of a real spectrometer. A translator is used to allow the user to design pulse sequences with the same programming language used in the actual experiment on a real spectrometer. The Virtual NMR Spectrometer is designed as a useful tool for developing new NMR experiments and for tuning and adjusting the experimental setup for existing ones prior to running costly NMR experiments, in order to reduce the setup time on a real spectrometer. It will also be a useful aid for learning the general principles of magnetic resonance and contemporary innovations in NMR pulse sequence design.