Improved Spin-Echo-Edited NMR Diffusion Measurements

The need for simple and robust schemes for the analysis of ligand-protein binding has resulted in the development of diffusion-based NMR techniques that can be used to assay binding in protein solutions containing a mixture of several ligands. As a means of gaining spectral selectivity in NMR diffusion measurements, a simple experiment, the gradient modified spin-echo (GOSE), has been developed to reject the resonances of coupled spins and detect only the singlets in the (1)H NMR spectrum. This is accomplished by first using a spin echo to null the resonances of the coupled spins. Following the spin echo, the singlet magnetization is flipped out of the transverse plane and a dephasing gradient is applied to reduce the spectral artifacts resulting from incomplete cancellation of the J-coupled resonances. The resulting modular sequence is combined here with the BPPSTE pulse sequence; however, it could be easily incorporated into any pulse sequence where additional spectral selectivity is desired. Results obtained with the GOSE-BPPSTE pulse sequence are compared with those obtained with the BPPSTE and CPMG-BPPSTE experiments for a mixture containing the ligands resorcinol and tryptophan in a solution of human serum albumin.     

A novel technique for imaging with inhomogeneous fields

We introduce a simple, efficient, low-SAR method for magnetic resonance imaging in the presence of a static field with a permanent, and possibly large gradient. The technique, which is called slant-slice imaging is essentially a spin-echo imaging sequence except that the imaging slice is oriented such that the static field gradient can be used in conjunction with applied gradients during readout. Data are collected for 2D slices. Unlike single point imaging techniques, entire lines of k-space are acquired with each readout. The slant-slice pulse sequence is used to obtain high quality images, using a clinical scanner to simulate a static field with a large permanent gradient. The effects of the inhomogeneity are quantified by two parameters nu and q, which are useful for assessing the utility of a magnet design for 3D-MR imaging.     

A multi-plane scout sequence using flash imaging

A new pulse sequence is presented for multi-plane imaging which simultaneously acquires images in the axial, coronal, and sagittal planes. Combined with FLASH imaging or other similar techniques, T1- and T2-weighted images in all three planes can be acquired in approximately 12 and 30 seconds, respectively. The sequence is easily implemented by modifying a multi-slice sequence to provide a rotation of gradient assignments between slice excitations. This sequence has been used extensively as a rapid "scout" scan. Several clinical examples are included.     

Very slow in-plane flow with gradient echo imaging

It is well appreciated that gradient-echo imaging techniques with short recovery times are highly sensitive to flow. This article analyzes the effect of in-plane flow in gradient recalled acquisition in the steady state (GRASS). It is shown that there is loss of signal due to velocity-dependent dephasing effects at velo cities as slow as 0.2 mm per second. It is also shown that striations appear in GRASS images of flow phantoms. This effect, which has not been previously described, arises from a modulation of K-space in the phase-encoding direction during the transient approach to steady state. Although these bands can give the appearance of flow lines, they are completely artifactual and not readily interpretable. Thus, the appearance of in-plane fluid movement in clinical GRASS images is a complex combination of signal loss due to dephasing and artifactual banding. Therefore, the interpretation of flow in GRASS images should be attempted only with caution.     

Multiecho multimoment refocussing of motion in magnetic resonance imaging: MEM-MO-RE

Gradient moment nulling techniques for refocussing of spin dephasing resulting from movement during application of magnetic resonance imaging gradients have gained widespread application. These techniques offer advantages over conventional imaging gradients by reducing motion artifacts due to intraview motion, and by recovering signal lost from spin dephasing. This paper presents a simple technique for designing multiecho imaging gradient waveforms that refocus dephasing from the interaction of imaging gradients and multiple derivatives of position. Multiple moments will be compensated at each echo. The method described relies on the fact that the calculation of time moments for nulled moment gradient waveforms is independent of the time origin chosen. Therefore, waveforms used to generate the second echo image for multiple echo sequences with echo times given by TEn = TE1 + (n - 1) * (TE2 - TE1) may also be used for generation of the third and additional echo images. All echoes will refocus the same derivatives of position. Multiecho, multimoment refocussing (MEM-MO-RE) images through the liver in a patient with ampullary adenocarcinoma metastatic to the liver demonstrate the application of the method in clinical scanning.     

Heteronuclear Correlation Spectroscopy with RF Gradients

The applicability of RF gradients for suppressing the resonances of uncoupled spins in inverse-detected heteronuclear spectroscopy has been investigated. Pulse sequences were designed which incorporate RF gradients in heteronuclear single-quantum-correlation experiments (HSQC), and they can be divided into three categories based on how the RF gradients are used. In the first type of experiment, the desired coherences are spin locked in the RF-gradient held, while unwanted terms, placed perpendicular to the direction of the RF-gradient held, are dephased. In a second type of experiment, the dephasing action of the gradient and the coherence-transfer RF pulses are combined into a single RF-gradient pulse. A second RF-gradient pulse is then used to rephase the desired spin terms. The third type of experiment uses a period of longitudinal storage of the heteronuclear magnetization, during which time the magnetization of the uncoupled spins is destroyed by an RF-gradient pulse. Experimental results are shown from all three techniques, and the techniques are compared.     

Effective dipolar couplings determined by dipolar dephasing of double-quantum coherences

It is shown how homonuclear distances and homonuclear dipolar lattice sums between spin-1/2 nuclei can be measured by a pulsed solid-state NMR experiment under magic-angle spinning conditions. The presented technique is based on double-quantum coherence filtering. Instead of measuring a build-up of double-quantum coherence the pulse sequence is designed to dephase double-quantum coherence. This is achieved by exciting double-quantum coherence either with the help of the through-space dipolar coupling or the through-bond dipolar coupling while the dephasing relies on the through-space dipolar coupling as selected by a gamma-encoded pulse sequence from the C/R symmetry class. Since dephasing curves can be normalized on zero dephasing, it is possible to analyze the initial dephasing regime and hence determine dipolar lattice sums (effective dipolar couplings) in multiple-spin systems. A formula for the effective dipolar coupling is derived theoretically and validated by numerical calculations and experiments on crystalline model compounds for (13)C and (31)P spin systems. The double-quantum dephasing experiment can be combined with constant-time data sampling to compensate for relaxation effects, consequently only two experimental data points are necessary for a single distance measurement. The phase cycling overhead for the constant-time experiment is minimal because a short cogwheel phase cycle exists. A 2D implementation is demonstrated on [(13)C(3)]alanine.     

The matrix formalism for generalised gradients with time-varying orientation in diffusion NMR

Protein backbone 15N NMR spin relaxation rates are useful in characterizing the protein dynamics and structures. To observe the protein nuclear-spin resonances a pulse sequence has to include a water suppression scheme. There are two commonly employed methods, saturating or dephasing the water spins with pulse field gradients and keeping them unperturbed with flip-back pulses. Here different water suppression methods were incorporated into pulse sequences to measure 15N longitudinal T1 and transversal rotating-frame T1ρ spin relaxation. Unexpectedly the 15N T1 relaxation time constants varied significantly with the choice of water suppression method. For a 25-kDa Escherichiacoli. glutamine binding protein (GlnBP) the T1 values acquired with the pulse sequence containing a water dephasing gradient are on average 20% longer than the ones obtained using a pulse sequence containing the water flip-back pulse. In contrast the two T1ρ data sets are correlated without an apparent offset. The average T1 difference was reduced to 12% when the experimental recycle delay was doubled, while the average T1 values from the flip-back measurements were nearly unchanged. Analysis of spectral signal to noise ratios (s/n) showed the apparent slower 15N relaxation obtained with the water dephasing experiment originated from the differences in 1HN recovery for each relaxation time point. This in turn offset signal reduction from 15N relaxation decay. The artifact becomes noticeable when the measured 15N relaxation time constant is comparable to recycle delay, e.g., the 15N T1 of medium to large proteins. The 15N relaxation rates measured with either water suppression schemes yield reasonable fits to the structure. However, data from the saturated scheme results in significantly lower Model-Free order parameters (=0.81) than the non-saturated ones (=0.88), indicating such order parameters may be previously underestimated.     

An analysis of the intrinsic resonance offset dependence of magnetization generated by stimulated echo pulse sequences for noncoupled spins.

It is demonstrated that the basic radiofrequency pulse train used to generate stimulated echoes (90x-tau TE-90x-tau TM-90x-tau TE-Acq.) is in general characterized by strong amplitude and phase modulations of the transverse magnetization as a function of the resonance offset. Two dephasing techniques which eliminate the modulations are investigated both theoretically and experimentally, and a simple formula is derived for calculating the relative modulation across a spectrum as a function of gradient strength and duration, echo delay, and spectral linewidth.     

13C PGSE NMR experiment with heteronuclear dipolar decoupling to measure diffusion in liquid crystals and solids

A new PGSE NMR experiment, designed to measure molecular diffusion coefficients in systems with nonvanishing static dipolar coupling, is described. The fast static dipolar dephasing of the single-quantum (13)C coherences is removed by multiple-pulse heteronuclear decoupling. The resulting slow dephasing of the (13)C coherences allows for inserting appropriate gradient pulses into the pulse sequence. The presence of the large magnetic field gradient reduces the efficiency of the decoupling sequences which is compensated for by introducing a scheme of sequential slice selection across the sample. The method is demonstrated by (19)F-decoupled (13)C PGSE NMR experiments in a lyotropic nematic and lamellar liquid crystal.     

Combined relaxation and displacement experiment: a fast method to acquire T2, diffusion and velocity maps

A fast method for quantitative imaging of T2 and displacement (flow and diffusion) is presented. The pulse sequence combines multi-PGSE NMR with multi-echo acquisition and compensates for flow effects in the read gradient and diffusion during multi-echo trains. The impact of the gradient pulses in a multi-echo train on the signal phase and amplitude is discussed. It is shown that separate T2 and displacement images with microscopic resolution can be obtained within minutes. The capability for 3D flow imaging is demonstrated. The sequence is then used to investigate forced detachment of a biofilm in a tube.     

Fast Field Echo imaging: an overview and contrast calculations

Current fast imaging techniques are based on gradient echo sequences with reduced flip angle excitation pulses and very short repetition times TR. Practical T2 values may be of the order of TR or longer. In this situation, a different image contrast can be obtained, depending on details of the sequence. Four essentially different versions of the basic Fast Field Echo (FFE) sequence can be distinguished and are described systematically in this article. For these sequences, image contrast formulas are presented. Practical imaging should tolerate small field inhomogeneities. This requirement can be satisfied by only three of the four versions. Numerical simulations are used to study the influence of a modified phase alternation scheme on image contrasts of two of the remaining sequences. The results of the calculations are verified by phantom studies on a 1.5-T whole-body imager. Implications for contrast in clinical images are discussed in relation to head images obtained on the same machine.     

SAR reduced pulse sequences

Three techniques were considered for reducing the RF (radiofrequency) power deposition in the body while maintaining scan time efficiency: reducing the RF peak amplitude while increasing the pulse width, substituting gradient echoes for spin echoes, and reducing the flip angle of the phase reversal pulse. The use of gradient echoes was found to be the most efficient means to reduce the power delivered to the patient and to obtain rapid data acquisition. The effect upon SAR (specific absorption rate) and SNR (signal-to-noise ratio) was demonstrated on a phantom when the phase reversal pulse was reduced from the standard 180 degrees to 90 degrees. Data in the body indicated a fairly constant SNR down to a refocusing flip angle between 110 degrees and 135 degrees. An initial clinical evaluation was performed at three institutions using the method of reducing the flip angle of the phase reversal pulse. The scan with theta = 120 degrees was rated by readers in a blinded study as having acceptable diagnostic image quality while the 135 degrees scan had comparable image quality to a conventional 90 degrees - 180 degrees pulse sequence. The use of reduced phase reversal pulses was seen as an efficient protocol to obtain T1-weighted images at rapid data rates while reducing the power delivered to the body by about 40%.     

Nuclear magnetic resonance for cultural heritage

Nuclear magnetic resonance (NMR) portable devices are now being used for nondestructive in situ analysis of water content, pore space structure and protective treatment performance in porous media in the field of cultural heritage. It is a standard procedure to invert T(1) and T(2) relaxation data of fully water-saturated samples to get "pore size" distributions, but the use of T(2) requires great caution. It is well known that dephasing effects due to water molecule diffusion in a magnetic field gradient can affect transverse relaxation data, even if the smallest experimentally available half echo time tau is used in Carr-Purcell-Meiboom-Gill experiments. When a portable single-sided NMR apparatus is used, large field gradients due to the instrument, at the scale of the sample, are thought to be the dominant dephasing cause. In this paper, T(1) and T(2) (at different tau values) distributions were measured in natural (Lecce stone) and artificial (brick samples coming from the Greek-Roman Theatre of Taormina) porous media of interest for cultural heritage by a standard laboratory instrument and a portable device. While T(1) distributions do not show any appreciable effect from inhomogeneous fields, T(2) distributions can show strong effects, and a procedure is presented based on the dependence of 1/T(2) on tau to separate pore-scale gradient effects from sample-scale gradient effects. Unexpectedly, the gradient at the pore scale can be, in some cases, strong enough to make negligible the effects of gradients at the sample scale of the single-sided device.     

Spectroscopic imaging from spatially-encoded single-scan multidimensional MRI data

We have recently proposed a protocol for retrieving multidimensional magnetic resonance images within a single scan, based on a spatial encoding of the spin interactions. This methodology relies on progressively dephasing spin coherences throughout a sample; for instance, by sweeping a radiofrequency pulse in the presence of a magnetic field gradient. When spins are suitably refocused by a second (acquisition) field gradient, this yields a time-domain signal reflecting in its magnitude the spatial distribution of spins throughout the sample. It is hereby shown that whereas the absolute value of the resulting signals conveys such imaging information, the hitherto unutilized phase modulation of the signal encodes the chemical shift offsets of the present speciae. Spectroscopically-resolved multidimensional images can thereby be retrieved in this fashion at no additional expense in either experimental complexity, sensitivity or acquisition time--simply by performing an additional analysis of the collected data. The resulting approach to single-scan spectroscopic imaging can also incorporate "RF shimming" compensating abilities, capable of providing high-resolution spectral and high-definition imaging data even under the presence of substantial magnetic field inhomogeneities. The principles of these methodologies as applied to spectroscopic imaging are briefly reviewed and compared against the background of traditional Fourier-based single-scan spectroscopic imaging protocols. Demonstrations of these new multidimensional spectroscopic MRI experiments on simple phantoms are also given.     

Echo spectroscopy and quantum stability of trapped atoms

We investigate the dephasing of ultra cold 85Rb atoms trapped in an optical dipole trap and prepared in a coherent superposition of their two hyperfine ground states by interaction with a microwave pulse. We demonstrate that the dephasing, measured as the Ramsey fringe contrast, can be reversed by stimulating a coherence echo with a pi pulse between the two pi / 2 pulses, in analogy to the photon echo. We also demonstrate that "echo spectroscopy" can be used to study the quantum dynamics in the trap even when more than 10(6) states are thermally populated and to study the crossover from quantum to classical dynamics.     

颅脑梯度回波成像:呼吸伪影和导航回波矫正

梯度回波序列是磁共振成像中常用的脉冲序列,然而梯度回波对主磁场波动非常敏感,呼吸等生理运动引起的信号波动会导致图像伪影.该文报道了采用导航回波技术获取呼吸运动导致的局部磁场波动,用以矫正图像回波中随时间变化的相位波动,并将该技术应用于三维多回波梯度回波成像和T2*定量图研究.研究结果显示:矫正前,相位波动幅度随回波时间增长而增大,模图和T2*定量图在相位编码方向有明显伪影,并且男女呼吸伪影水平有显著性差异;矫正后,相位波动幅度大幅下降,图像伪影水平有显著性下降.     

FID-acquired-echos (FAcE): a short echo time imaging method for flow artefact suppression.

The FID-Acquired-Echo sequence (FAcE) is a magnetic resonance imaging technique using fractional-echo acquisitions, with sequential separate sampling of the right and left k-space half planes. It reduces the minimal echo times by about a factor of two, compared to conventional full-(gradient)-echo sampling schemes. With this sequence, implemented on a commercial 1.5 Tesla whole body system, high resolution images are acquired with typical echo times between 3 and 4.5 msec. Using short echo times the signal dephasing caused by velocity and higher order spin motion is reduced. Further, due to the modified sampling scheme, the sequence exhibits, for triggered studies, partially a compensation of motion-induced phase shifts in the frequency-encoding direction. Thus, the sequence offers an alternative means for the reduction of motion-induced image artefacts to the use of flow compensating gradients, which usually makes a sequence more sensitive to higher order motion and introduces further eddy currents. Besides potential application for imaging of nuclei and tissues with short T2 relaxation times, and non-ECG-triggered in-flow angiography, the main application seems to be triggered-phase contrast imaging with focus on quantitation of blood flow. Its usefulness is largest in cases with irregular flow patterns, where considerable in-plane flow occurs.