Journal of magnetic resonance最新文献

The use of parahydrogen – the isomer of molecular hydrogen with zero nuclear spin – is important for promising and actively developing methods for spin hyperpolarization of nuclei called parahydrogen induced polarization (PHIP). However, the dissolved parahydrogen in PHIP experiments quickly loses its spin order, resulting in the formation of orthohydrogen and reduction of the overall nuclear polarization of the substrate. This process is due to the difference of chemical shifts of hydride protons, as well as spin–spin couplings between nuclei, in the intermediate catalytic complexes, and it has not been rigorously explained so far. We proposed a new experimental technique based on magnetic field cycling for measuring the rate of molecular hydrogen para–ortho conversion in solution and applied it for non-hydrogenative PHIP Signal Amplification By Reversible Exchange (SABRE) experiments. The para–ortho conversion rate was measured over a wide range of magnetic field from 0.5 mT to 9.4 T. It was found that the conversion rate strongly depends on the magnetic field in which the reaction occurs, as well as on the concentrations of reactants. The rate decreases with increasing the concentration of pyridine ligand and increases with increasing the concentration of iridium catalyst. The model, which takes into account the reversible exchange of molecular hydrogen with the catalyst, nuclear spin–spin interaction of hydride protons with nuclei of ligands within catalytic complex and nuclear Zeeman interactions, qualitatively describes the experimental data. Two types of complexes with different spin system symmetry contribute to the molecular hydrogen conversion. In asymmetric complexes possessing hydride protons with different chemical shifts due to the presence of chlorine anion ligand the para–ortho conversion rate increases with magnetic field, while for symmetric complexes this mechanism is not operable. In the magnetic field where level anti-crossing occurs the resonant feature for the rate of para–ortho conversion is found. The results of this work can be utilized for finding the optimal conditions for obtaining the maximum hyperpolarization in the experiments employing parahydrogen.

Very-low field (VLF) magnetic resonance imaging (MRI) offers advantages in term of size, weight, cost, and the absence of robust shielding requirements. However, it encounters challenges in maintaining a high signal-to-noise ratio (SNR) due to low magnetic fields (below 100 mT). Developing a close-fitting radio frequency (RF) receive coil is crucial to improve the SNR. In this study, we devised and optimized a helmet-shaped dual-channel RF receive coil tailored for brain imaging at a magnetic field strength of 54 mT (2.32 MHz). The methodology integrates the inverse boundary element method (IBEM) to formulate initial coil structures and wiring patterns, followed by optimization through introducing regularization terms. This approach frames the design process as an inverse problem, ensuring a close fit to the head contour. Combining theoretical optimization with physical measurements of the coil's AC resistance, we identified the optimal loop count for both axial and radial coils as nine and eight loops, respectively. The effectiveness of the designed dual-channel coil was verified through the imaging of a CuSO4 phantom and a healthy volunteer's brain. Notably, the in-vivo images exhibited an approximate 16–25 % increase in SNR with poorer B₁ homogeneity compared to those obtained using single-channel coils. The high-quality images achieved by T1, T2-weighted, and fluid-attenuated inversion-recovery (FLAIR) protocols enhance the diagnostic potential of VLF MRI, particularly in cases of cerebral stroke and trauma patients. This study underscores the adaptability of the design methodology for the customization of RF coil structures in alignment with individual imaging requirements.

Triaxial magnetic field coils are one of the most important components of magnetic resonance sensors. Traditional measurement methods for coil constants and non-orthogonal angles using fluxgate magnetometers are no longer suitable for small-volume nuclear magnetic resonance sensors. This study presents a method for measuring the coil constants and nonorthogonal angles of triaxial nuclear magnetic resonance coils using the dynamics of the electron paramagnetic resonance magnetometer without requiring any additional calibration equipment. After constructing the in-situ magnetometer, we measured the coil constants of the z- and the x-axes as 1189 nT/mA and 45.53 nT/mA, respectively. We obtained the nonorthogonal angle of approximately 0.18° between the z-axis and the x-y plane with a standard deviation of about 0.03° by solving the relevant trigonometric function. Additionally, the non-orthogonal angle between the x- and y-axes is approximately 1.70° with a standard deviation of about 0.17°. This study is significant for evaluating and reducing signal crosstalk errors and improving the accuracy of NMR sensors.

Dynamic nuclear polarization (DNP) combined with high magnetic fields and fast magic angle spinning (MAS) has opened up a new avenue for the application of exceptionally sensitive ¹H NMR detection schemes to study protonated solids. Recently, it has been shown that DNP experiments at fast MAS rates lead to slower spin diffusion and hence reduced DNP enhancements for impregnated materials. However, DNP enhancements alone do not determine the overall sensitivity of a NMR experiment. Here we measure the overall sensitivity of one-dimensional ¹H detected relayed DNP experiments as a function of the MAS rate in the 20–60 kHz regime using 0.7 mm diameter rotors at 21.2 T. Although faster MAS rates are detrimental for the DNP enhancement on the target material, due to slower spin diffusion, we find that with increasing spinning rates the gain in sensitivity due to ¹H line-narrowing and the folding-in of sideband intensity compensates a large part of the loss of overall hyperpolarization. We find that sensitivity depends on the atomic site in the molecule, and is maximised at between 40 and 50 kHz MAS for the sample of L-histidine.HCl·H₂O studied here. There is a 10–20 % difference in sensitivity between the optimum MAS rate and the fastest rate currently accessible (60 kHz).

High-field electron paramagnetic resonance (EPR) measurements are indispensable for a better understanding of dynamic nuclear polarization (DNP), which relies on polarization transfer between electron and nuclear spins. DNP experiments are typically performed at high > 7 T magnetic fields and low ≤ 100 K temperatures, while EPR instrumentation capable of EPR measurements under these conditions is scarce. In this paper, we describe the CW EPR capabilities of a dual DNP/EPR spectrometer that is designed to carry out EPR experiments under “DNP conditions” at 14 and 7 T. In the first part, we present the design of this instrument, highlighting the choices made to allow for both DNP and EPR operations. The spectrometer uses a sweepable cryogen-free magnet with NMR-grade homogeneity, a closed-cycle cooling system, a quasi-optical induction mode bridge, and a superheterodyne receiver system. The probe design is optimized for low heat load and fast sample exchange under cryogenic conditions. The spectrometer can operate in frequency and field sweep modes, including wide field sweeps using the main coil of the magnet. In the second part, we present EPR spectra acquired over a wide range of samples and operating conditions, illustrating the CW EPR capabilities of the instrument.

Nuclear Magnetic Resonance (NMR) techniques display an inherently low sensitivity due to a small equilibrium magnetisation. Nowadays this issue is easily overcome through the use of hyperpolarisation methods. This however raises the question as to what precisely do we mean by “hyperpolarisation”. Recently a formal definition of hyperpolarisation has been given based on the von Neumann entropy of a system. Ideally this definition should conform with the general usage in the magnetic resonance community, where hyperpolarisation is often used synonymously with “larger” NMR signals. Within this article I show that an entropy-based hyperpolarisation criterion does not always conform with the general usage. Based on this observation I introduce an alternative hyperpolarisation criterion utilising the concept of latent polarisation, where latent polarisation is a measure of the highest possible amount of polarisation that may be extracted from a system. I show that a hyperpolarisation criterion based on latent polarisation correlates more strongly with the general usage within the magnetic resonance community. Ultimately however our results show that there are several possible notions of hyperpolarisation, and the choice depends upon the questions of interest.

Serial NMR experiments are commonly applied in variable-temperature studies, reaction monitoring, and other tasks. The resonance frequencies often shift linearly over the series, and the shift rates help to characterize the studied system. They can be determined using a classical fitting of peak positions or a more advanced method of Radon transform. However, the optimal procedure for data collection remains to be determined. In this paper, we discuss how to invest experimental time, i.e., whether to measure more scans at the expense of the number of spectra or vice versa. The results indicate that classical fitting provides slightly less error than the Radon transform, although the latter can be the method of choice for a low signal-to-noise ratio. We demonstrate this fact through theoretical consideration, simulations, and an experiment. Finally, we extend our considerations to the linear fitting of peak amplitudes. Interestingly, the optimal setup for measuring peak height changes differs from the one for resonance frequency changes — fewer spectra with more scans provide better results.

CPMG relaxation dispersion studies of biomolecular dynamics on the μs–ms timescale can provide detailed kinetic, thermodynamic, and structural insights into function. Frequently, the ¹⁵N spin serves as the probe of choice, as uniform incorporation of the ¹⁵N isotope is facile and cost-effective, and the interpretation of the resulting data is often relatively straightforward. In conventional CPMG relaxation dispersion experiments the application of CPMG pulses with constant radiofrequency (RF) phase can lead to artifactual dispersion profiles that result from off-resonance effects, RF field inhomogeneity, and pulse miscalibration. The development of CPMG experiments with the [0013]-phase cycle has significantly reduced the impact of pulse imperfections over a greater bandwidth of frequency offsets in comparison to constant phase experiments. Application of ¹⁵N-TROSY-based CPMG schemes to studies of the dynamics of large molecules is necessary for high sensitivity, yet the correct incorporation of the [0013]-phase cycle is non-trivial. Here we present TROSY- and anti-TROSY-based ¹⁵N CPMG experiments with the [0013]-phase cycling scheme and demonstrate, through comprehensive numerical simulations and experimental validation, enhanced resistance to pulse imperfections relative to traditional schemes utilizing constant phase CPMG pulses. Notably, exchange parameters derived from the new experiments are in good agreement with those obtained using other, more established, ¹⁵N-based CPMG approaches.

This study comprehensively assesses radiofrequency (RF) volumetric wireless coils utilizing artificial materials for clinical breast MRI. In particular, we evaluated the transmit efficiency, RF safety, and homogeneity of magnetic field amplitude distribution for four structures electromagnetically coupled with a whole-body birdcage coil: extremely high permittivity ceramic coil, solenoid coil, Helmholtz coil, and metamaterial-inspired coil based on periodically coupled split-loop resonators. These coils exhibit favorable attributes, including lightweight construction, compactness, cost-effectiveness, and ease of manufacturing. The results of this study demonstrated that the metamaterial-inspired coil outperforms other wireless coils considered for addressing a specific problem in terms of the set of characteristics. In particular, the metamaterial-inspired coil achieved 85% and 88% homogeneity in magnetic field amplitude distribution at 3 T and 1.5 T MRI, respectively. Also, the 1.5 T metamaterial-inspired coil demonstrated the best performance, increasing the efficiency gain of the birdcage coil by 4.93 times and improving RF safety by 2.96 times. This research explains the limitations and peculiarity of utilizing the volumetric wireless coils in 1.5 and 3 T MRI systems.

Accumulating several scans of free induction decays is always needed to improve the signal-to-noise ratio of NMR spectra, especially for the low gyromagnetic ratio solid-state NMR. In this study, we present a new denoising approach based on the correlations between multiple similar NMR spectra. Contrary to the simple averaging of multiple scans or denoising the final averaged spectrum, we propose a Wavelet-based Denoising technique for Multiple Similar scans(WDMS). Firstly, the stationary wavelet transform is applied to decompose every spectrum into approximation coefficients and detail coefficients. Then, the detail coefficients are multiplied by weights calculated based on Pearson's correlation coefficient and structural similarity index between approximation coefficients of different spectra. Finally, the average of these detailed components is used to denoise the spectra. The proposed method is carried on the assumption that noise between multiple spectra is uncorrelated while peak signal information is similar between different spectra, thus preserving the possibility of applying further processing to the data. As a demonstration, the standard wavelet denoise is applied to the WDMS-processed spectra, achieving a further increase in the S/N ratio. We confirm the reliability of the denoising approach based on multiple scans on 1D/2D solid-state MAS/static NMR spectra. In addition, we also show that this method can be used to deal with a single Car-Purcell-Meiboom-Gill (CPMG) echo train.