Suppression of Radiation Damping in High-Resolution NMR

The radiation damping field induced by an intense NMR line can be counterbalanced by a DANTE sequence of small flip angle pulses of opposite phase applied during the free induction decay. The transient NMR signal is acquired, one complex data point at a time, in the intervals between these DANTE pulses. As the intense signal decays, reducing the radiation damping field, the flip angles of the DANTE pulses are reduced at a matching rate. An experimental test on an aqueous solution ofd-glucose demonstrates a reduction in linewidth at half height from 13.5 to 0.8 Hz, revealing a weak doublet response previously hidden under the broad water line.     

Combined simulated annealing and Shinnar-Le Roux pulse design of slice-multiplexed RF pulses for multi-slice imaging

Slice-multiplexed RF pulses have recently been introduced for simultaneous multi-slice imaging. Their novel aspect is that each slice is given a different linear phase profile, and hence a different slice-rephasing requirement, by the pulse. During readout, extra slice gradients are applied such that when one slice is rephased, the others are dephased to prevent aliasing. In this paper, an improved method of designing slice-multiplexed RF pulses is presented: component pulses which are optimized with simulated annealing for a specific rephasing are combined using Shinnar-Le Roux methods. In this way, non-linearities at higher flip angles are taken into account and more slices can be excited. Bloch simulations show the phase and amplitude profile of component pulses are faithfully preserved in the multiplexed pulse. Three- and four-slice multiplex pulses are demonstrated in gradient- and spin-echo in-vivo imaging.     

Optimization schemes for selective excitations: application to the DIGGER pulses.

In this work, two distinct approaches to the tailoring of selective radiofrequency (RF) pulses were applied to a cos-sinc pulse of the DIGGER sequence used in localized spectroscopy. Ideally, three such pulses combined with a gradient in each direction destroy the Mz component of the magnetization everywhere but in the volume of interest. In the first approach, the optimal RF amplitude modulation is found by minimizing the difference between the ideal and the computed Mz profiles. In the second strategy, the RF pulse envelope is adjusted by optimization of the tip angle profile. Computed slice profiles optimized by each of these methods have been compared to experimental results. Simulations as well as experiments show that the second approach, which optimizes tip angles, is the most efficient.     

Improvement of resolution in solid state NMR spectra with J-decoupling: an analysis of lineshape contributions in uniformly 13C-enriched amino acids and proteins

In magic angle spinning (MAS) NMR spectra of highly and uniformly 13C,15N-enriched amino acids and proteins, homo-nuclear coupling interactions contribute significantly to the 13C linewidths, particularly for moderate applied magnetic field strengths and sample spinning frequencies. In this work, we attempted to dissect, analyze, and control the contributions of J-coupling and residual homo-nuclear dipolar coupling interactions to the linewidths of uniformly 13C,15N-enriched crystalline alanine; these studies were carried out at 9.4 T using a range of spinning frequencies from 5 to 15 kHz. The anisotropic second-order dipolar shifts and the J-splittings are comparable in their contribution to the linewidths, but behave very differently in terms of experimental protocols for line narrowing. In contrast to the J-coupling interactions, the second-order dipolar broadening cannot be refocused using selective pulses on the passively coupled spin. We carried out experiments to remove or refocus the 13C J-coupling interactions (omega1 J-decoupling) using a selective DANTE pulse in the center of the indirect evolution period. Inversion profiles and bandwidths of selective DANTE pulses acting on transverse magnetization, in the regime of moderate spinning frequencies, were characterized computationally and experimentally. A dramatic improvement in the resolution of the 2D spectrum was achieved when this decoupling protocol was employed.     

Improvement of resolution in solid state NMR spectra with J-decoupling: an analysis of lineshape contributions in uniformly C-enriched amino acids and proteins

In magic angle spinning (MAS) NMR spectra of highly and uniformly 13C,15N-enriched amino acids and proteins, homo-nuclear coupling interactions contribute significantly to the 13C linewidths, particularly for moderate applied magnetic field strengths and sample spinning frequencies. In this work, we attempted to dissect, analyze, and control the contributions of J-coupling and residual homo-nuclear dipolar coupling interactions to the linewidths of uniformly 13C,15N-enriched crystalline alanine; these studies were carried out at 9.4 T using a range of spinning frequencies from 5 to 15 kHz. The anisotropic second-order dipolar shifts and the J-splittings are comparable in their contribution to the linewidths, but behave very differently in terms of experimental protocols for line narrowing. In contrast to the J-coupling interactions, the second-order dipolar broadening cannot be refocused using selective pulses on the passively coupled spin. We carried out experiments to remove or refocus the 13C J-coupling interactions (omega1 J-decoupling) using a selective DANTE pulse in the center of the indirect evolution period. Inversion profiles and bandwidths of selective DANTE pulses acting on transverse magnetization, in the regime of moderate spinning frequencies, were characterized computationally and experimentally. A dramatic improvement in the resolution of the 2D spectrum was achieved when this decoupling protocol was employed.     

Off-resonance effects of the radiofrequency pulses used in spectral editing with double-quantum coherence transfer

Spectral editing using gradient selected double-quantum (DQ) coherence transfer is often used for the selective observation of metabolites in vivo. In attempting to optimize the detection sensitivity of a conventional DQ spectral editing sequence, the effects of using radiofrequency (RF) pulses that are not at the resonance frequency of the observed peaks were investigated both theoretically and experimentally. The results show that spectral editing using pulses at the frequency of the observed resonance does not necessarily give the optimal detection sensitivity. At 7 T, the detection sensitivity of lactate observed using a DQ editing method can be increased by up to 30% by setting the RF pulses off resonance at the proper frequency. The results also suggest that slice selective RF pulses used in DQ spectral editing combined with PRESS localization may have slice profiles different from those when the same pulses are used for standard PRESS spatial localization.     

变延迟进动定制激发(DANTE)序列在工程中的优化设计

变延迟进动定制激发（Delays Alternating with Nutation for Tailored Excitation,DANTE）序列作为一种黑血预脉冲序列,通过连续施加小角度激发脉冲,以及结合散相梯度,使得流动物质和静态物质达到不同的稳态,从而抑制流动的血液.对于静态物质而言,施加DANTE序列后在图像等间隔的位置会出现暗条纹,暗条纹的宽度与梯度幅值和小单元持续时间乘积相关：乘积越大,暗纹宽度越小.对于动态物质而言,为达到较好的抑制效果,需要增加整个DANTE序列模块的准备时间,并且增大梯度幅值和小单元持续时间的乘积.因此,该方法对于梯度系统的要求较高,而实际梯度放大器（Gradient Amplifier,GPA）有一定的限额.在有限的GPA条件下,为使得DANTE序列具有更好抑制流动信号效果,本文在读出方向以及片层旋转两个方面进行了梯度优化,实现了更好的黑血效果.     

Design of Frequency-Selective RF Pulses by Optimizing a Small Number of Pulse Parameters

Slice-selective amplitude-modulated and adiabatic frequency-modulated π pulses are obtained by optimizing a small number of significant pulse parameters by unconstrained optimization of a suitable function. The method is also used to optimize the slice profile of AM pulses taking into account the RF inhomogeneity in the selection direction and to reduce the specific absorption rate and peak power. Experimental slice profiles are presented to verify the performance of the optimized pulses.     

Shaped pulses for selective inversion of magnetization in solids spinning at the magic angle

In order to achieve selective inversion of a chosen family of sidebands in NMR spectra of solids rotating at the magic angle (MAS spectra), a sequence of so-called DANTE pulses can be applied in synchronization with the sample rotation period. It is shown by simulation and experiment that the profiles of the offset dependence can be greatly improved by varying the amplitudes of the DANTE pulses, so that the envelope corresponds to that of a G³ Gaussian cascade. Alternatively, the DANTE pulses may be replaced by sandwiches composed of four hard pulses, adjusted so that the time-dependence of the nutation angles matches the envelope of a G³ Gaussian cascade. It is shown by simulations that in solids the profiles are affected by homogeneous decay of magnetization, in analogy to the influence of transverse relaxation in liquids. Applications to the intramolecular rearrangement (tautomerism) of polycrystalline tropolone illustrate that dynamic processes in the solid state can be monitored with great accuracy.     

A Generalized Estimate of the SLRBPolynomial Ripples for RF Pulse Generation

The nonlinearity of the parameter relations for the Shinnar–Le Roux RF pulse design algorithm has induced to performa classification based on the features of the slice profile dueto the RF pulse. In the present paper a generalization ofthe relation between the ripple amplitudes of the SLRBpolynomial and those of the slice profile is given. It allows generation of RF pulses with better slice profiles and slightly reduced energy, avoiding anya prioriclassification. The effect of our estimation has been shown by generating several pulses by generalized estimation ofBpolynomial ripples. In addition, their behavior has been compared to that of analogous pulses generated by means of the classification just mentioned.     

A chemical-shift-insensitive slice-selective RF pulse (CHISS)

In NMR imaging and in vivo spectroscopy, slice selection is usually achieved by applying a frequency-selective RF pulse in the presence of a magnetic field gradient. A serious limitation of this method of slice selection is that, in a system with many different chemical shifts, the selected slice is offset in space for each chemically shifted resonance. In the present study, a composite RF pulse that is insensitive to chemical-shift differences has been developed. The pulse involves applying a RF pulse of desired shape in the presence of an alternating magnetic field gradient, together with hard 180° pulses at each gradient transition. Calculations are presented to show that excitation with the proposed pulse averages the chemical-shift term to zero. An exact calculation for a rectangular RF excitation shape verifies this. Experiments based on observing the RF excitation profiles have been performed to demonstrate the validity of the proposed pulse.     

Selective NMR excitation in strongly inhomogeneous magnetic fields

The NMR-MOUSE is a unilateral and mobile NMR sensor which operates with highly inhomogeneous magnetic fields. To produce a mobile NMR unit, RF excitation is sought, which can be produced with the most simple equipment, in particular nonlinear, low-power amplifiers, and to observe a free induction decay in strongly inhomogeneous fields, the excitation needs to be selective. The possibility to produce selective excitation by sequences of hard low-power radiofrequency pulses in the strongly inhomogeneous magnetic fields of the NMR-MOUSE is explored. The use of the DANTE sequence for selection of magnetization from parts of the sensitive volume was investigated for longitudinal and transverse magnetization by computer simulations and experiments. The spectra of the recorded FIDs and echo signals are in good agreement with those simulated for the excitation, which verifies the concept of the DANTE excitation. The results obtained are an important step towards a low-power operation of the NMR-MOUSE to improve its mobility.     

Tagging of the magnetization with the transition zones of 360 degrees rotations generated by a tandem of two adiabatic DANTE inversion sequences

A new technique is presented for generating myocardial tagging using the signal intensity minima of the transition zones between the bands of 0 degrees and 360 degrees rotations, induced by a tandem of two adiabatic delays alternating with nutations for tailored excitation (DANTE) inversion sequences. With this approach, the underlying matrix corresponds to magnetization that has experienced 0 degrees or 360 degrees rotations. The DANTE sequences were implemented from adiabatic parent pulses for insensitivity of the underlying matrix to B(1) inhomogeneity. The performance of the proposed tagging technique is demonstrated theoretically with computer simulations and experimentally on phantom and on the canine heart, using a surface coil for both RF transmission and signal reception. The simulations and the experimental data demonstrated uniform grid contrast and sharp tagging profiles over a twofold variation of the B(1) field magnitude.     

Robust slice-selective broadband refocusing pulses

Slice-selective broadband refocusing pulses are of great interest in localized MR spectroscopy for improving spatial selectivity, reducing chemical-shift displacement errors, and reducing anomalous J modulation. In practice the bandwidth of RF pulses is limited by the maximum available B1 amplitude. The goal of the present work is to design slice-selective and broadband refocusing pulses which are tolerant against B1 deviations. Pulse design is performed by numerical optimization based on optimal control theory. A comprehensive study of different cost functions and their effect on the optimization is given. The optimized slice-selective broadband refocusing pulses are compared to conventional Shinnar-Le Roux (SLR), broadband SLR, and hyperbolic secant pulses. In simulations and experiments optimized pulses were shown to fulfill broadband slice specifications over a range of ±20% B1 scalings. Experimental validation showed a reduction of chemical-shift displacement error by a factor of 3 compared to conventional SLR pulses.     

The 'DANTE' experiment

The selective excitation scheme known as ‘DANTE’ emerged from a confluence of several ideas for new NMR experiments, some more fanciful than others. DANTE offers a simple and effective way to restrict excitation to a very narrow frequency band, usually that of a single resonance line. Initially applied to the study of individual proton-coupled carbon-13 spin multiplets, the method has been extended to water presaturation, relaxation measurements, and chemical exchange studies. Through the imposition of a magnetic field gradient it offers a simple method to enhance resolution by restricting the effective volume of the sample. Multiple DANTE excitation (with Hadamard encoding) can speed up multidimensional spectroscopy by orders of magnitude. Applied to magnetic resonance imaging, the DANTE sequence has been used to superimpose a rectangular grid onto a cardiac image, permitting motional distortions to be monitored in real time.     

Optimization of Adiabatic Selective Pulses

Adiabatic RF pulses play an important role in spin inversion due to their robust behavior in presence of inhomogeneous RF fields. These pulses are characterized by the trajectory swept by the tip of theB_effvector and the rate of motion upon it. In this paper, a method is described for optimizing adiabatic inversion pulses to achieve a frequency-selective magnetization inversion over a given bandwidth in a shorter time and to improve slice profile. An efficient adiabatic pulse is used as an initial condition. This pulse allows for flexibility in choosing its parameters; in particular, the transition sharpness may be traded off against the inverted bandwidth. The considerations for selecting the parameters of the pulse according to the requirements of the design are discussed. The optimization process then improves the slice profile by optimizing the rate of motion along the trajectory of the pulse while preserving the trajectory itself. The adiabatic behavior of the optimized pulses is fully preserved over a twofold range of variation in the RF amplitude which is sufficient for imaging applications in commercial high-field MRI machines. Design examples demonstrate the superiority of the optimized pulses over the conventional sech/tanh pulse.     

Triple quantum nutation in the two-level NMR system in the rotating frame

The authors present the detailed theory and the new results associated with the triple quantum (TQ) nutation and the line narrowing effect of the TQ resonance in the two-level NMR system which we reported previously. The TQ resonance is induced in the spin-locked system by the oscillating field produced by the sinusoidal phase modulation (PM) of the RF field. The theory predicts that the TQ nutation is accompanied by several higher frequency oscillations and we detected them experimentally by improving the detection system. These higher frequency oscillations are due to the fluctuation of the angle between the transverse or effective field causing the TQ nutation and the RF field. We obtain the result that the modulation index 2phim of the PM is the key parameter that essentially controls the conditions of the TQ resonance and the narrowing effect. Under the exact TQ resonance, the ratio of the TQ resonance frequency to the Larmor frequency of the RF field depends only on phim, and the secular part of the magnetic dipole Hamiltonian of a like spin system in the triply rotating frame disappears at a particular value of phim. The condition is different from that of the well-known magic angle condition.     

Tagging of the Magnetization with the Transition Zones of 360° Rotations Generated by a Tandem of Two Adiabatic DANTE Inversion Sequences

A new technique is presented for generating myocardial tagging using the signal intensity minima of the transition zones between the bands of 0° and 360° rotations, induced by a tandem of two adiabatic delays alternating with nutations for tailored excitation (DANTE) inversion sequences. With this approach, the underlying matrix corresponds to magnetization that has experienced 0° or 360° rotations. The DANTE sequences were implemented from adiabatic parent pulses for insensitivity of the underlying matrix to B₁ inhomogeneity. The performance of the proposed tagging technique is demonstrated theoretically with computer simulations and experimentally on phantom and on the canine heart, using a surface coil for both RF transmission and signal reception. The simulations and the experimental data demonstrated uniform grid contrast and sharp tagging profiles over a twofold variation of the B₁ field magnitude.     

Two-dimensional high-resolution NMR spectra in matched B(0) and B(1) field gradients

In a recent publication we presented a method to obtain highly resolved NMR spectra in the presence of an inhomogeneous B(0) field with the help of a matched RF gradient. If RF gradient pulses are combined with "ideal" 90 degrees pulses to form inhomogeneous z rotation pulses, the line broadening caused by the B(0) gradient can be refocused, while the full chemical shift information is maintained. This approach is of potential use for NMR spectroscopy in an inhomogeneous magnetic field produced by an "ex-situ" surface spectrometer. In this contribution, we extend this method toward two-dimensional spectroscopy with high resolution in one or both dimensions. Line narrowing in the indirect dimension can be achieved by two types of nutation echoes, thus leading to depth-sensitive NMR spectra with full chemical shift information. If the nutation echo in the indirect dimension is combined with a stroboscopic acquisition using inhomogeneous z-rotation pulses, highly resolved two-dimensional correlation spectra can be obtained in matched field gradients. Finally, we demonstrate that an INEPT coherence transfer from proton to carbon spins is possible in inhomogeneous B(0) fields. Thus, it is possible to obtain one-dimensional (13)C NMR spectra with increased sensitivity and two-dimensional HETCOR spectra in the presence of B(0) gradients of 0.4 mT/cm. These schemes may be of some value for ex-situ NMR analysis of materials and biological systems.