Magic Echo Solid-State NMR Imaging without a Rapidly Switchable Field Gradient

To relax the high-speed requirement imposed on the gradient system used in solid-state proton imaging, we propose two simple modifications of the magic echo imaging sequence, TREV-16TS. In the first modification, the applied gradient is inverted in the middle of the RF irradiation; the second modification utilizes a sinusoidal gradient synchronized with the RF sequence. It is estimated by experiments that as long as the RF amplitude is at least about 10 times stronger than the resonance offset induced by the gradient, the spatial resolution is not degraded significantly by the line narrowing deterioration due to the gradient applied during the on-resonance RF irradiation. The modifications allow commercially available standard gradients to be used for the magic echo imaging of solids.     

Orientational analysis of the Achilles tendon and enthesis using an ultrashort echo time spectroscopic imaging sequence

Tendons and entheses are magnetic resonance (MR) “invisible” when imaged with conventional clinical pulse sequences. When the highly ordered, collagen-rich fibers in tendons and entheses are placed at the magic angle, dipolar interactions are decreased and their T2s are often considerably increased. The bulk magnetic susceptibility of tendons and entheses also varies with orientation to B₀, leading to a direction-dependent resonance frequency shift. Ultrashort echo time (UTE) sequences with a minimum TE of 8 μs provide high signal from both tendons and entheses. The combination of a UTE sequence with an interleaved undersampled variable TE acquisition scheme provides a new approach for fast spectroscopic imaging of short T2 tissues. This UTE spectroscopic imaging (UTESI) technique provides quantitative information including T2?, chemical shift and resonance frequency shift due to bulk susceptibility effect. In this article, the orientational effects on tendons and entheses were investigated using a UTESI sequence on a clinical 3-T scanner. T2? was found to increase fivefold for tendons and twofold for entheses due to the magic angle effect. A resonance frequency shift up to 1.2 ppm was observed for both tendons and entheses due to the bulk susceptibility effect when their orientation was changed from 0° to 90° relative to B₀.     

Symmetric echo acquisition for absolute-value display in solid-state NMR imaging

A method of solid-state NMR imaging that permits echo Fourier transformation (FT) has been devised using a magic echo train. The echo FT imaging can be implemented simply by modifying the gradient pulse sequence in the previous magic echo imaging (TREV-16TS) so that the one-dimensional k-space trajectory follows the sampling points which are symmetric about the k origin. The implemented ability of echo FT improves the performance of the magic echo imaging: the sensitivity gained by radical2, the phase correction is made unnecessary, and the digital resolution is doubled. One- and two-dimensional imaging experiments have been conducted on some solid samples, confirming the improved performance and revealing a TREV-16TS adjustment parameter that is critical for the successful echo FT imaging.     

Multinuclear MRI of Solids: from Structure to Transport

Direct multinuclear imaging of rigid solids has been performed using the conventional two-pulse spin-echo pulse sequence and liquids magnetic resonance imaging (MRI) hardware. Two-dimensional ²⁷Al and ⁵¹V images of an Al₂O₃-V₂O₅-glass composite sample and ¹¹B, ²³Na, ²⁷Al and ²⁹Si images of glass have been detected, extending the range of nuclei and solid materials that can be studied by this approach. For a spinning cylinder packed with Al₂O₃ powder, quantitative velocity maps have been obtained by directly detecting the ²⁷Al nuclear magnetic resonance signal of the solid phase. The two velocity components in the imaging plane transverse to the rotation axis have been mapped using the three-pulse stimulated echo sequence. Some possibilities to improve sensitivity in the MRI experiments on rigid solids have been considered. In particular, inversion of the satellite transitions by a double frequency sweep adiabatic passage has led to a signal enhancement by a factor of two in ²⁷Al MRI of a glass sample despite a short repetition time (0.5 s) of the imaging pulse sequence. Authors' address: Igor V. Koptyug, International Tomography Center, Russian Academy of Sciences, 3A Institutskaya ulitsa, Novosibirsk 630090, Russian Federation     

T1ρ space dependence in rigid polymers by effective radio frequency gradient

An extension of the solid-state nuclear magnetic resonance (NMR) imaging based on magic angle in the rotating frame (MARF) line narrowing approach is presented. The modified magic angle in the rotating frame imaging sequence is able to yield T_1ρ maps of large band polymers with remarkable contrast sensitivity and without contrast parameter alteration referable to the narrowing procedure. This last feature is examined closely in order to outline the actual effectiveness of the method. Further experimental details, especially regarding probe coil design, recently improved, are discussed and some new results are presented.     

Proton NMR studies of the NaAlH4 structure

Advanced nuclear magnetic resonance (NMR) techniques were applied to study the local environments of hydrogen in NaAlH₄. Through a combined application of the magic echo (ME) and the magic Hahn echo (MHE) sequences the hetero- and homonuclear contributions to the dipolar second moment (M₂) were determined separately. The obtained values are compared with the second moments calculated by the van Vleck formulae, using structural data determined by neutron scattering on NaAlD₄. This comparison indicates structural differences between NaAlH₄ and NaAlD₄. A model is suggested for the orientation of the [AlH₄]⁻ tetrahedra in NaAlH₄, for which the calculated second moments are in good agreement with the experimentally observed values.     

Generalized MAGSTE with bipolar diffusion-weighting gradient pulses

The generalized magic asymmetric gradient stimulated echo (generalized MAGSTE) sequence compensates background gradient cross-terms and can be adjusted to asymmetric timing boundary conditions which for instance are present in echo-planar MR imaging. However, its efficiency is not optimal because one of the two diffusion-weighting gradients applied in each interval usually must have a reduced amplitude to ensure the desired cross-term compensation. In this work, a modification of generalized MAGSTE is investigated where this gradient pulse is replaced by two gradient pulses with full amplitude but opposite polarities. It is shown that with these bipolar gradients (i) the sequence retains the cross-term compensation capability for an appropriate choice of the gradient pulse durations and (ii) the diffusion-weighting efficiency is improved, i.e. higher k and b values can be achieved without prolonging the echo time. These results are confirmed in MR imaging experiments on phantoms and in vivo in the human brain at 3 T using spin-echo and echo-planar MR imaging. In the examples shown, the b value could be increased between about 30% and 200% when using the bipolar gradient pulses. Thus, bipolar gradients may help to improve the applicability of the generalized MAGSTE sequence.     

Fast magic-angle sample spinning solid-state NMR at 60–100 kHz for natural abundance samples

In spite of tremendous progress made in pulse sequence designs and sophisticated hardware developments, methods to improve sensitivity and resolution in solid-state NMR (ssNMR) are still emerging. The rate at which sample is spun at magic angle determines the extent to which sensitivity and resolution of NMR spectra are improved. To this end, the prime objective of this article is to give a comprehensive theoretical and experimental framework of fast magic angle spinning (MAS) technique. The engineering design of fast MAS rotors based on spinning rate, sample volume, and sensitivity is presented in detail. Besides, the benefits of fast MAS citing the recent progress in methodology, especially for natural abundance samples are also highlighted. The effect of the MAS rate on ¹H resolution, which is a key to the success of the ¹H inverse detection methods, is described by a simple mathematical factor named as the homogeneity factor k. A comparison between various ¹H inverse detection methods is also presented. Moreover, methods to reduce the number of spinning sidebands (SSBs) for the systems with huge anisotropies in combination with ¹H inverse detection at fast MAS are discussed.     

SHA+脉冲序列用于g-C3N4样品15N-15N相关性的固体核磁共振研究

利用固体核磁共振实验研究了15N标记的g-C3N4样品中的15N-15N空间相关性,在高场和魔角旋转条件下对比两种不同的脉冲序列PDSD和SHA+的实验效果。发现当某个氮上连有质子的时候,脉冲序列SHA+比PDSD可以更好地检测15N原子间的极化转移。该研究可以为材料科学领域,特别是含氮掺杂的碳材料,提供一种有价值的研究方法。     

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.     

Cross-term-compensated pulsed-gradient stimulated echo MR with asymmetric gradient pulse lengths

The magic asymmetric gradient stimulated echo (MAGSTE) sequence developed to compensate background-gradient cross-terms in the preparation and readout interval independently, assumes identical lengths for the two gradient pulses applied in each interval. However, this approach is rather inefficient if some extra delay time is present in one half of an interval, e.g. as required for special RF excitations or spatial encoding prior to the stimulated echo in MR imaging. Therefore, a generalized version of the sequence is presented that considers different gradient pulse lengths within an interval. It is shown theoretically that (i) for any pulse lengths a "magic" amplitude ratio exists which ensures the desired cross-term compensation in each interval and that (ii) prolonging one of the gradients can deliver a considerably higher diffusion weighting efficiency. These results are confirmed in MR imaging experiments on phantoms and in vivo in the human brain at 3T using an echo-planar trajectory. In the examples shown, typically 10 times higher b values can be achieved or an echo time reduction with a 40% signal gain in brain white matter. Thus, in case of asymmetric timing requirements, the generalized MAGSTE sequence with different gradient pulse lengths may help to overcome signal-to-noise limitations in diffusion weighted MR.     

A phase rotation scheme for achieving very short echo times with localized stimulated echo spectroscopy

In a single-voxel stimulated echo localization sequence in magnetic resonance spectroscopy, magnetic field gradients are inserted within the echo time (TE) to filter signals generated through coherence pathways other than that leading to the stimulated echo. There is a significant penalty for these gradients as they increase the minimum TE, thereby leading to significant signal loss from spin-spin relaxation and phase distortions in coupled spin systems. Here, an RF phase rotation technique is described for a stimulated echo localization sequence that allows removal of the gradients in the TE intervals and, subsequently, reduction of the minimum TE to only 6 ms. Experiments carried out on six healthy volunteers on a 1.5-T whole-body MR system show a significant signal increase in the metabolite concentrations when measured with a 6-ms TE (N-acetyl-aspartate, 12%, P=.002; creatine, 15%, P=.04; and glutamate+glutamine, 92%, P=.02) compared to concentrations measured with data collected at TEs of 15 and 20 ms.     

Structural Analysis of Relaxation Curves in MRI

In magnetic resonance imaging, the gradient recalled echo sequence preserves information about spatial heterogeneities of magnetic field within a voxel, providing additional opportunity for classification of biological tissues. All the information, composed of physically meaningful parameters, like proton density, spin–spin relaxation time T ₂, gradients of magnetic field and spin–spin relaxation, effective relaxation time \(T_{2}^{*}\), and many others, is encoded in the shape of a relaxation curve, which is more complicated than a pure monoexponent, traditionally observed in spin echo sequences. The previous work [A. Protopopov, Appl. Magn. Reason. 48, 255-274 (2017)], introduced the theory and basic algorithms for separation of those parameters. The present work further expands this theory to the case of spin–spin relaxation gradients, improves reliability of the algorithms, introduces physical explanation of the phenomenon previously known as “multiexponentiality”, and presents new validation of the algorithms on volunteers. The entire approach may be named the structural analysis of relaxation curves.     

Simultaneous measurement of perfusion and oxygenation changes using a multiple gradient-echo sequence: application to human muscle study

We have developed a magnetic resonance imaging (MRI) technique based on a multiple gradient-echo sequence designed to probe perfusion and oxygenation simultaneously within skeletal muscle. Processing of the images acquired at successive echo times (TEs) generates two functional maps: one of the signal intensity (SI) extrapolated to zero echo time, which is sensitive to perfusion; and a second one of R21, which reflects oxygenation. An advantage of the processing procedure lies in the selection of tissue of interest through the profile of T₂1 decay, leading to automatic rejection of pixels containing small vessels. This allows a more specific assessment of tissue perfusion and oxygenation. This technique was demonstrated successfully during post-ischemic reactive hyperemia in human calf. A perfusion peak of 123 mL ×100 g⁻¹ × min⁻¹ was measured immediately after ischemia, whereas R21 value showed an 11.5% decrease at the same time, essentially reflecting blood oxygenation changes. Differences in the time courses of reperfusion and re-oxygenation were observed, oxygenation presenting a slower recovery. The mechanisms responsible for such a differential dynamic response are discussed.     

Quantitative T2 Imaging of Plant Tissues By Means Of Multi-Echo MRI Microscopy

A method for quantitative T₂ imaging is presented which covers the large range of T₂ values in plants (5 to 2000 ms) simultaneously. The transverse relaxation is characterized by phase-sensitive measurement of many echo images in a multi-echo magnetic resonance imaging sequence. Up to 1000 signal-containing echo images can be measured with an inter-echo time of 2.5 ms at 0.47 T. Separate images of water density and of T₂ are obtained. Results on test samples, on the cherry tomato and on the stem of giant hogweed are presented. The effects of field strength, spatial resolution and echo time on the observed T₂ values is discussed. The combination of a relatively low magnetic field strength, short echo time and medium pixel resolution results in excellent T₂ contrast and in images hardly affected by susceptibility artifacts. The characterization of transverse relaxation by multi-echo image acquisition opens a new route for studies of water balance in plants.     

Imaging of the H NMR Second Moment with C Chemical-Shift Resolution

A method of ¹³C chemical-shift-resolved ¹H second moment imaging is proposed for molecular mobility imaging of heterogeneous materials. For evaluating the ¹H second moment, the method relies on the curve fitting procedure using spin-echo shapes indirectly: The information of ¹H echo shapes is transferred to the ¹³C signal amplitude through ¹H–¹³C cross polarization and then the curve fitting is made using the ¹³C signal amplitude. The ¹³C signal is detected under ¹H dipolar decoupling and magic angle spinning, resulting in the incorporation of ¹³C chemical-shift resolution. Imaging information is included in the ¹³C signal by application of phase-encoding gradients. The second moment images obtained can reflect the molecular mobility at every molecular site separated by ¹³C chemical shifts, yielding detailed information on the molecular mobility. The method is demonstrated by spatially 1D experiments performed on a model sample.     

Direct Detection of Al–O–Al Structure in Aluminosilicate Specimens: A Use of Homo-Nuclear DQMAS NMR

A general strategy of Al–O–Al structure in various aluminosilicate was evaluated by combining triple-quantum magic angle spinning (3QMAS) and double-quantum homo-nuclear correlation under magic angle spinning (DQMAS) solid-state nuclear magnetic resonance (NMR) measurements with the aid of high magnetic field NMR (800 MHz for ¹H Larmor frequency). The results show that in many cases the direct detection of Al–O–Al sites in aluminosilicate crystals and glasses is possible; hence the extent of aluminum avoidance can be directly elucidated. Specifically, experimental evidence of Al–O–Al linkages in several aluminosilicate materials with Si/Al >1 was straightforwardly confirmed; and the existence of Al–O–Al is considered to have little correlation with the Si/Al ratio, but it may be strongly related to the cation and local structural arrangement. In addition, the presence of tri-clusters of (Si, Al)O₄-tetrahedra in aluminosilicate framework was proposed, which was thought to act as nuclei for formation and incorporation of cations to achieve charge neutrality.     

In vivo lactate editing in single voxel proton spectroscopy and proton spectroscopic imaging by homonuclear polarisation transfer

Volume-selective lactate editing has been performed successfully in vitro and in vivo in the brain on a clinical scanner using a PRESS-based single voxel ¹H spectroscopy and a ¹H spectroscopic imaging sequence. The PRESS sequence was made sensitive to homonuclear polarisation by replacing the standard 180° refocusing pulses with 90° pulses. Two acquisitions were made at a total echo time around 2/J (J is the coupling constant for CH and CH₃ spins in lactate ≈7 Hz) whose individual echo times differed by 5.5 ms. Subtraction of one signal from the other yielded the lactate resonance alone. The technique is an effective method of separating the overlapping signals of lactate and lipids. Furthermore this editing method can be performed without state of the art MRI scanner hardware.     

MR imaging of teeth using a silent single point imaging technique

Magnetic resonance imaging (MRI) of teeth is an emerging application area which is still in development. Previous investigations did not fully focus on potential in vivo applications. Using ¹H and ³¹P MRI, we obtained ex vivo microimages of teeth with a silent single point imaging (SPI) technique. ¹H Images with an in-plane resolution of 310×310 μm² were obtained. Utilizing sine-shaped gradient ramps significantly reduced the sound pressure level of the experiment to that of background noise. ¹H magnetic resonance spectroscopy (MRS) was used to characterize the major components in the observed resonance. The spin–spin (T₂) relaxation times of water in enamel and dentin differed by at least one order of magnitude. Three-dimensional surface reconstruction of the data allowed for complete visualization of the tooth’s surface while volume reconstruction displayed the internal geometry. PACS 82.56.Na; 83.85.Fg; 87.61.-c; 87.19.-j; 43.50.Cb     

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.