Distant Dipolar Field Research Articles

Robust parahydrogen-induced polarization at high concentrations.

Parahydrogen-induced polarization (PHIP) is a potent technique for generating target molecules with high nuclear spin polarization. The PHIP process involves a chemical reaction between parahydrogen and a target molecule, followed by the transformation of nuclear singlet spin order into magnetization of a designated target nucleus through magnetic field manipulations. Although the singlet-to-magnetization polarization transfer process works effectively at moderate concentrations, it is observed to become much less efficient at high molar polarization, defined as the product of polarization and concentration. This strong dependence on the molar polarization is attributed to interference due to the field produced by the sample magnetization during polarization transfer, which leads to complex dynamics and can severely affect the scalability of the technique. We address this challenge with a pulse sequence that suppresses the influence of the distant dipolar field, while simultaneously achieving singlet-to-magnetization polarization transfer to the desired target spins, free from restrictions on the molar polarization.

Approaching the Ultimate Limit in Measurement Precision with RASER NMR

Radio-frequency Amplification by Stimulated Emission of Radiation (RASER) is a promising tool to study nonlinear phenomena or measure NMR parameters with unprecedented precision. Magnetic fields, J-couplings, and chemical shifts can be recorded over long periods of time without the need for radiofrequency excitation and signal averaging. One key feature of RASER NMR spectroscopy is the improvement in precision, which grows with the measurement time T_{{text{m}}}^{3/2}, unlike conventional NMR spectroscopy, where the precision increases with T_{{text{m}}}^{1/2}. However, when detecting NMR signals over minutes to hours, using available NMR magnets (ppb homogeneity), the achieved frequency resolution will eventually be limited by magnetic field fluctuations. Here, we demonstrate that full compensation is possible even for open low-field electromagnets, where magnetic field fluctuations are intrinsically present (in the ppm regime). A prerequisite for compensation is that the spectrum contains at least one isolated RASER line to be used as a reference, and the sample experiences exclusively common magnetic field fluctuations, that is, ones that are equal over the entire sample volume. We discuss the current limits of precision for RASER NMR measurements for two different cases: The single-compartment RASER involving J-coupled modes, and the two-compartment RASER involving chemically shifted species. In the first case, the limit of measurable difference approaches the Cramér-Rao lower bound (CRLB), achieving a measurement precision {sigma }_{f}<{10}^{-4} Hz. In the second case, the measured chemical shift separation is plagued by independently fluctuating distant dipolar fields (DDF). The measured independent field fluctuation between the two chambers is in the order of tens of mHz. In both cases, new limits of precision are achieved, which paves the way for sub-mHz detection of NMR parameters, rotational rates, and non-linear phenomena such as chaos and synchrony.

Signal feedback applications in low-field NMR and MRI.

Tuned pick-up coils with high quality factors Q are used in NMR and MRI for high-sensitivity and low-noise detection. However, large Q-factors introduce bandwidth issues at low frequency and the associated enhanced currents may cause significant radiation damping effects, especially with hyperpolarised samples. Signal feedback can be used to actively control these currents and adjust the detection bandwidth without resistive losses. Capacitive and inductive coupling methods are compared using detailed models and the operating conditions for efficient feedback with negligible noise penalty are discussed. Several high-impedance commercial preamplifiers have been found to affect the resonance characteristics of tuned coils in a gain-dependent way, or could not be used in low-frequency NMR because of oscillations at large positive gain. This is attributed to an undocumented internal feedback, and could be neutralised using external feedback. The implementation of an inductive coupling scheme to feed a suitably amplified phase-adjusted signal back into the PU coils of low-field NMR systems is described, and three experimental applications are reported. One system is used for NMR studies of distant dipolar field effects in highly polarised liquid 3He without or with radiation damping. The moderate intrinsic Q-factor (≈7) could be reduced (down to 1) or increased (up to 100) to control transient maser oscillations. Another system was used for MRI of water samples around 2 mT with Q≈190 litz-wire detection coils. The detection bandwidth was increased by actively reducing the Q-factor to obtain uniform sensitivities in images and avoid artifacts introduced by intensity corrections. Finally, parallel acquisition in MRI was performed using two separately tuned detection coils placed above and below the sample. They were actively decoupled using two feedback systems. For an imaging field of view smaller than the sample, artifact-free unfolded images demonstrate the efficiency of this active coil decoupling scheme.

A Numerical Study on the Dynamics of Distant Dipolar Field in Solution NMR: Understanding Spatial Aspect of Magnetizations

Magnetization in k-space with a CRAZED-type pulse sequence (90°-{G,T}-90°-{G, 2T}-100ms) including the distant dipolar field and radiation damping.

Remote detection of hyperpolarized 129Xe resonances via multiple distant dipolar field interactions with 1H.

A remote detection scheme utilizing the distant dipolar field interaction between two different spin species was proposed by Granwehr et al. [J. Magn. Reson. 176(2), 125 (2005)]. In that sequence 1H spins were detected indirectly via their dipolar field interaction with 129Xe spins, which served as the sensing spins. Here we propose a modification of the proposed detection scheme that takes advantage of the longer T1 relaxation time of xenon to create a long lasting dipolar field with which the fast relaxing 1H spins are allowed to interact many times during a single acquisition. This new acquisition scheme improves detection sensitivity, but it also presents some challenges.

A heteronuclear intermolecular single-quantum coherence scheme for high-resolution 2D J-resolved 1H NMR spectra in inhomogeneous magnetic fields

ABSTRACTBased on heteronuclear intermolecular single-quantum coherences between proton (1H) and quadrupolar nuclei (i.e. deuterium 2H), a three-dimensional nuclear magnetic resonance (NMR) pulse sequence is proposed for recovering high-resolution two-dimensional J-resolved NMR spectra from samples mixed with a deuterated solvent in the presence of large magnetic field inhomogeneities. Benefitting from excitation of spins via two different radio frequency (RF) transmit channels, this sequence is suitable for applications in randomly large inhomogeneous fields and the solvent suppression generally required in homonuclear intermolecular multiple-quantum coherence approaches is no longer necessary. Systematic theoretical analyses are given based on the distant dipolar field treatment. Experiment on a sample of corn oil in deuterated acetone and ethyl 3-bromopropionate and acetone dissolved in DMSO-d6 in a deshimmed field with severe inhomogeneous broadening is performed to show the feasibility and applicability of this sequence.

Remote detection of hyperpolarized 129 Xe resonances via multiple distant dipolar field interactions with 1 H

Remote detection of hyperpolarized 129 Xe resonances via multiple distant dipolar field interactions with 1 H

High-resolution heteronuclear multi-dimensional NMR spectroscopy in magnetic fields with unknown spatial variations

Heteronuclear NMR spectroscopy is an extremely powerful tool for determining the structures of organic molecules and is of particular significance in the structural analysis of proteins. In order to leverage the method’s potential for structural investigations, obtaining high-resolution NMR spectra is essential and this is generally accomplished by using very homogeneous magnetic fields. However, there are several situations where magnetic field distortions and thus line broadening is unavoidable, for example, the samples under investigation may be inherently heterogeneous, and the magnet’s homogeneity may be poor. This line broadening can hinder resonance assignment or even render it impossible. We put forth a new class of pulse sequences for obtaining high-resolution heteronuclear spectra in magnetic fields with unknown spatial variations based on distant dipolar field modulations. This strategy’s capabilities are demonstrated with the acquisition of high-resolution 2D gHSQC and gHMBC spectra. These sequences’ performances are evaluated on the basis of their sensitivities and acquisition efficiencies. Moreover, we show that by encoding and decoding NMR observables spatially, as is done in ultrafast NMR, an extra dimension containing J-coupling information can be obtained without increasing the time necessary to acquire a heteronuclear correlation spectrum. Since the new sequences relax magnetic field homogeneity constraints imposed upon high-resolution NMR, they may be applied in portable NMR sensors and studies of heterogeneous chemical and biological materials.

A novel detection scheme for high-resolution two-dimensional spin-echo correlated spectra in inhomogeneous fields.

BackgroundTwo-dimensional (2D) nuclear magnetic resonance (NMR) spectroscopy is a powerful and non-invasive tool for the analysis of molecular structures, conformations, and dynamics. However, the inhomogeneity of magnetic fields experienced by samples will destroy spectral information and hinder spectral analysis. In this study, a new pulse sequence is proposed based on the modulation of distant dipolar field to recover high-resolution 2D spin-echo correlated spectroscopy (SECSY) from inhomogeneous fields.Method and MaterialBy using the new sequence, the correlation information between coupled spins and the J coupled information with straightforward multiplet patterns can be obtained free from inhomogeneous line broadening. In addition, the new sequence is also suitable for non-J coupled spin systems. Although three-dimensional acquisition is needed, the evolution of indirect detection dimensions is carefully designed and the ultrafast acquisition scheme is utilized to improve the acquisition efficiency. A chemical solution of butyl methacrylate (C8H14O2) in DMSO (C2H6SO) in a deshimmed magnetic field was tested to demonstrate the implementation details of the new sequence. The performance of the new sequence relative to the conventional SECSY sequence was shown by using an aqueous solution of main brain metabolites in a deshimmed magnetic field.ConclusionThe results reveal that the new sequence provides an attractive way to eliminate the inhomogeneous spectral line broadening for the spin-echo correlated spectrum and is a promising tool for the study of metabolites in metabonomics, even for the applications on in vivo and in situ high-resolution 2D NMR spectroscopy.

Ultrafast 1H J-resolved spectroscopy via 2H distant dipolar field in magnetic fields with unknown spatial variations

Spatially encoded ultrafast NMR accelerates the acquisition of 2D NMR spectra by orders of magnitude, but it is affected by field inhomogeneity. To circumvent this influence, various approaches have been proposed. Here we propose a new scheme to ultrafast achieve 2D J-resolved spectroscopy in inhomogeneous fields via the distant dipolar field of deuterium nuclei. Compared to the methods via homonuclear distant dipolar field, the trouble of selective excitation and solvent suppression when the peaks of solvent and solute spins are close to each other in inhomogeneous fields will be avoided. Theoretical analyses and experimental results are presented for verification.

Probing of susceptibility structures through the distant dipolar field effect

In this paper, the utilization of the distant dipolar field (DDF) signal to extract the properties of susceptibility structures over a subvoxel length scale is investigated. Numerical simulations are performed to study a system of randomly distributed blood vessels with a susceptibility offset inside a voxel. It is shown that the DDF signal of the system as a function of the strength of the correlation gradient field manifests a peak that depends on the volume ratio, size, and susceptibility offset of the blood vessels. In particular, the location of the signal peak is found to vary as powers of these parameters. As a result, by varying the strength of the correlation gradient field, the characteristic properties of the blood vessels can be extracted from the peak position of the DDF signal. It is also found that, for a given volume ratio of the blood vessels, a smaller size of the blood vessels can be probed when the susceptibility offset is increased. Nevertheless, it is demonstrated that, owing to the broad width of the signal peak, the DDF effect generally cannot be used for the preferential selection of the signal arising from the blood vessels on the length scale determined by the correlation length.

Intermolecular double-quantum coherence imaging without coherence selection gradients and its application in in vivo MRI

In the COSY Revamped with Asymmetric Z-gradient Echo Detection (CRAZED) experiments, magnetization is modulated by the distant dipolar field (DDF) generated by coherence selection gradient (CSG) commonly in sinusoidal wave-form and results in detectable intermolecular multiple-quantum coherence (iMQC) signal. IMQCs have some attractive features, but their intrinsic weak signal intensity prevents their widespread applications. In this paper, a new phase cycling scheme was applied to obtain intermolecular double-quantum coherence (iDQC) signal. It is found that DDF can arise from nonspherical sample geometry or background inhomogeneous field in the absence of CSGs, which is more efficient than that created from CSGs. The experimental results show that the resulting DDF can refocus the ±iDQC signals simultaneously and thus enhance the signal intensity to about two folds of that from the conventional CRAZED sequence. Theoretical prediction and experiments give coincident results.

Hadamard encoded 2D correlation spectroscopy in inhomogeneous fields

In this Letter, we present a new approach to obtain two-dimensional high-resolution COSY spectra in inhomogeneous fields based on Hadamard encoding. It is an extension of one-dimensional high-resolution intermolecular double-quantum coherence Hadamard encoding approach. The approach is time-efficient and can recover useful structural information even when the inhomogeneous line broadening leads to overlap of neighboring resonances in the conventional COSY spectrum. Theoretical expression of the resulting signals was deduced based on intermolecular multiple-quantum coherence treatment in combination with distant dipolar field treatment. Experiments were performed to verify its feasibility and advantages over previous methods.

Multiple echoes due to distant dipolar fields in NMR of hyperpolarized noble gas solutions

We report on multiple echo measurements in hyperpolarized liquids using optically pumped spin-1/2 noble gas atoms: either 129Xe dissolved in cyclohexane or 3He dissolved in superfluid 4He. An NMR pulse sequence 90° − τ − 90° (with slice-selective flipping pulses for 129Xe experiments) was used and long echo trains have been observed in the presence of applied gradients due to average dipolar fields typically one order of magnitude larger than those of bulk water in high magnetic fields. We show that a mean field description is valid for explaining the multiple echoes observed in these liquids, even for spin temperatures as low as 10mK for 129Xe or 10μK for 3He, and the echoes originate from the distant dipolar fields within the samples. Numerical lattice simulations have been used to assess the effects of slice selection and of finite sample size in addition to those of atomic diffusion. They account for the observed echo widths and amplitudes much better than previously published models, which disregard finite size effects that appear to be of key importance. This opens the way to using multiple echoes resulting from distant dipolar fields for the determination of the absolute magnetization in hyperpolarized liquids without signal calibration.

Revisiting the mean-field picture of dipolar effects in solution NMR

For more than three decades, the classical or mean-field picture describing the distant dipolar field has been almost always simplified to an effective field proportional to the local longitudinal magnetization, differing only by a scale factor of 1.5 for homomolecular (identical resonance frequency) and heteromolecular interactions. We re-examine the underlying assumptions, and show both theoretically and experimentally that the mathematical framework needs to be modified for modern applications such as imaging. We demonstrate new pulse sequences which produce unexpected effects; for example, modulating an arbitrarily small fraction of the magnetization can substantially alter the frequency evolution. Thus, matched gradient pulse pairs (a seemingly innocuous module in thousands of existing pulse sequences) can alter the time evolution in highly unexpected ways, particularly with small flip angle pulses such as those used in hyperpolarized experiments. We also show that specific gradient pulse combinations can retain only dipolar interactions between unlike spins, and the dipolar field can generate a secular Hamiltonian proportional to I(x).

Flat pancake distant dipolar fields for enhancement of intermolecular multiple-quantum coherence signals

Intermolecular multiple-quantum coherences (iMQCs) originated from distant dipolar field (DDF) possess some appealing unique properties for magnetic resonance imaging (MRI). DDF is usually induced with continuous wave (i.e., sine- or square-wave) magnetization modulation in the whole sample. In this article, a spatially localized and enhanced DDF was optimally tailored in a thin slice with an adiabatic inversion pulse. Evidence was provided to show that careful tailoring of the spatially localized DDF can generate highly efficient iMQC signals, with more than two-fold enhancement compared to the conventional sine-wave magnetization modulation method, and 1.5 times of that with the square-wave modulation under the similar condition. Theoretical predictions, simulation results, and experimental verifications agree well with each other. Practical implementation of this approach for efficient iMQC MRI was explored.

Apparent diffusion behaviors of spins in the presence of distant dipolar field in two-component solution NMR

The diffusion behaviors of spins in the presence of distant dipolar field in two-component spin systems during the second evolution period of a modified CRAZED sequence before acquisition were investigated. Theoretical formulas were deduced based on the distant dipolar field model. The simulation results and experimental observations are consistent with the theoretical predictions. This study shows that the relative intensities of signals from intermolecular zero-quantum coherences (iZQCs) and intermolecular double-quantum coherences (iDQCs) have the same diffusion attenuation characteristic under the combined effect of diffusion weighting gradients and distant dipolar field during the second evolution period. This diffusion attenuation may be different from that of conventional single-quantum coherence signal, depending on the relative orientation of the diffusion weighting gradients to the coherence selection gradients. The results presented herein are helpful for understanding the effect of distant dipolar field from a spin system on the diffusion behavior of other spin system and the signal properties in the iZQC or iDQC magnetic resonance imaging.

Highly efficient square wave distant dipolar field and its application for in vivo MRI

Intermolecular multiple quantum coherences generated by distant dipolar field (DDF) have some attractive properties, but the intrinsic weak signal intensity prevents their widespread applications. Recently, Branca et al. (J Chem Phys 2008;129:054502) suggested that square wave DDF was more efficient than conventional sinusoidal DDF because it could simultaneously produce intermolecular multiple quantum coherences signal with various major orders. In this article, instead of a series of adiabatic inversion pulses proposed previously, a more efficient composite adiabatic inversion pulse was applied to create square wave DDF. The square wave DDF was applied to in vivo MRI for the first time, and the corresponding simulations were performed. Both experimental and simulated results show that square wave DDF with composite adiabatic inversion pulse improves over the original Z-modulation enhanced to binary for self-refocused acquisition implementation and can enhance the signal intensity to about 2-fold of that from conventional correlation spectroscopy (COSY) revamped with asymmetric Z-gradient echo detection sequence for in vivo MRI, close to the theoretical prediction.

High-resolution two-dimensional correlation spectroscopy in inhomogeneous fields: New application of intermolecular zero-quantum coherences

A new pulse sequence is proposed based on intermolecular zero-quantum coherences (iZQCs) to obtain high-resolution two-dimensional (2D) correlation spectroscopy (COSY) in inhomogeneous fields via three-dimensional (3D) acquisition. This sequence extends the high-resolution iZQC approaches from one dimension to two dimensions. Since the iZQC evolution periods in the new sequence are insensitive to the field inhomogeneities, high-resolution COSY spectra can be recovered from inhomogeneous fields by projecting the 3D data onto the indirectly acquired 2D plane. Theoretical expressions were derived according to the distant dipolar field treatment combined with product operator formalism. Both the experimental observations and computer simulations are consistent with the theoretical predictions. The new sequence thus provides an attractive way to eliminate the influences of field inhomogeneity on the conventional COSY methods, which may be useful for the study of chemical and biological materials.

Theoretical analysis of the sensitivity of dipolar field signal to local field variations by perturbative expansion of the magnetization

A perturbation method based on the integral form of the Bloch equation is used to calculate the distant dipolar field (DDF) signal formed by the correlation spectroscopy revamped by asymmetric z-gradient echo detection (CRAZED) sequence in the presence of a susceptibility-induced field. The properties of the DDF signal are analyzed through the series expansion of the magnetization, and the first order DDF result is applied to study the use of the DDF effect to probe sub-voxel field distributions. Numerical calculations are carried out with the sub-voxel field distributions modeled by rectangular tubes of uniform frequency shifts (the block model) and cylinders of a finite susceptibility difference (the blood vessel model) using the parameters for brain at 9.4 T. The DDF signal is found to exhibit features arising from the sub-voxel structures.