Journal of Magnetic Resonance

Spectral diffusion of electron spin polarization plays a key part in dynamic nuclear polarization (DNP). It determines the distribution of polarization across the electron spin resonance (ESR) line and consequently the polarization that is available for transfer to the nuclear spins. Various authors have studied it experimentally by means of electron-electron double resonance (ELDOR) and proposed and used macroscopic models to interpret these experiments. However, microscopic models predicting the rate of spectral diffusion are scarce...

Biomolecular solid-state magic angle spinning (MAS) NMR spectroscopy frequently relies on selective 13 C-15 N magnetization transfers, for various kinds of correlation experiments. Introduced in 1998, spectrally induced filtering in combination with cross polarization (SPECIFIC-CP) is a selective heteronuclear magnetization transfer experiment widely used for biological applications. At MAS frequencies below 20 kHz, commonly used for 13 C-detected MAS NMR experiments, SPECIFIC-CP transfer between amide 15 N and 13 Cα atoms (NCA) is typically performed with radiofrequency (rf) fields set higher than the MAS frequency for both 13 C and 15 N channels, and high-power 1 H decoupling rf field is simultaneously applied...

MRI is essential for evaluating and diagnosing various conditions affecting the temporomandibular joint (TMJ) and surrounding structures, as it provides highly detailed images that enable healthcare professionals to assess the joints and surroundings in great detail. While commercial MRI scanners typically come equipped with basic receive coils, such as the head receive array, RF coils tailored for specialized applications like TMJ MRI must be obtained separately. Consequently, TMJ MRI scans are often conducted using the head receive array, yet this configuration proves suboptimal due to the lack of specialized coils...

In this work we achieve a significant overpopulation (PLLS ≈1%) of the long-lived spin state (LLS) of methylene protons in 2-bromoethan(2 H)ol (BrEtOD) obtained in a reaction between ethylene with non-equilibrium nuclear spin order and bromine water. Given all protons in ethylene are magnetically equivalent, its nuclear states are classified into nuclear spin isomers (NSIM) with total spin I = 2,1,0. Addition of parahydrogen to acetylene produces ethylene with a population of only those NSIMs with I = 1,0...

This study describes a technique to clean amplitude modulation (AM) noise of RF transmission waves, which is used to observe the sub-GHz CW-EPR spectrum. An RF transmitter amplifier that has the function of cleaning AM noise has been developed. Cleaning of the AM noise was owing to saturation of the output at the amplifier. Three stages of the amplifiers in series could effectively suppress the AM noise to about -176 dBc/Hz and -183 dBc/Hz at offset frequency of 10 kHz and 100 kHz, respectively at the carrier frequency of 750 MHz and the output power of 29 dBm...

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...

Fast Spin Echo MRI is now widely employed in biomedicine for proton density and T2 contrast imaging. Fast Spin Echo methods provide rapid data acquisition by employing multiple echoes to determine multiple k-space lines with single excitations. Due to the multi-exponential behavior of T2 in typical porous media, and the strong dependence of T2 on the details of the experiment, acquiring a proton density image with Fast Spin Echo methods requires favorable sample and acquisition parameters. In recent years, we have shown the value of pure phase encode Free Induction Decay based methods such as SPRITE...

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 1 H 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 1 H detected relayed DNP experiments as a function of the MAS rate in the 20-60 kHz regime using 0...

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...

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...

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...

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...

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...

CPMG relaxation dispersion studies of biomolecular dynamics on the μs-ms timescale can provide detailed kinetic, thermodynamic, and structural insights into function. Frequently, the 15 N spin serves as the probe of choice, as uniform incorporation of the 15 N 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...

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...

Spatially-encoded diffusion-ordered NMR spectroscopy (SPEN-DOSY) has emerged as a new time-efficient tool for the analysis of mixtures of small molecules in solution. Time efficiency is achieved using the concept of spatial parallelization of the effective gradient area, instead of the sequential incrementation used in conventional diffusion experiments. The data acquired with such sequences are then usually processed to extract diffusion coefficients, but cases when peak overlap in the 1 H spectrum are difficult to address...

Hartmann-Hahn cross polarization and INEPT polarization transfer are the most popular sequences to increase the polarization of low-γ nuclei in magic-angle spinning solid-state NMR. It is well known that the two methods preferentially lead to polarization transfer in different parts of molecules. Cross polarization works best in rigid segments of the molecule while INEPT-based polarization transfer is efficient in highly mobile segments where (nearly) isotropic motion averages out the dipolar couplings...

Rapid MR imaging of slowly relaxing samples is often challenging. The most commonly used solutions are found in multi spin-echo (RARE) sequences or gradient-echo (GE) sequences, which allow faster imaging of such samples with multiple acquisitions of k-space lines per excitation or imaging with very short repetition times (TRs). Another solution is the use of a spin-echo (SE) sequence superimposed with a driven equilibrium Fourier transform (DEFT) method. Such a (DE-SE) imaging sequence has two refocusing RF pulses that produce two spin-echoes...

Liquid-state low-concentration photochemically induced dynamic nuclear polarization (LC-photo-CIDNP) is an emerging technology tailored to enhance the sensitivity of NMR spectroscopy via LED- or laser-mediated optical irradiation. LC-photo-CIDNP is particularly useful to detect solvent-exposed aromatic residues (Trp, Tyr), either in isolation or within polypeptides and proteins. This study investigates the magnetic-field dependence of the LC-photo-CIDNP of Trp-α-13 C-β,β,2,4,5,6,7-d7 , a Trp isotopolog bearing a quasi-isolated 1 Hα -13 Cα spin pair (QISP)...

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...