Journal of magnetic resonance最新文献

Nuclear spin hyperpolarization techniques, such as dynamic nuclear polarization (DNP) and parahydrogen-induced polarization (PHIP), have revolutionized nuclear magnetic resonance and magnetic resonance imaging. In these methods, a readily available source of high spin order, either electron spins in DNP or singlet states in hydrogen for PHIP, is brought into close proximity with nuclear spin targets, enabling efficient transfer of spin order under external quantum control. Despite vast disparities in energy scales and interaction mechanisms between electron spins in DNP and nuclear singlet states in PHIP, a pseudo-spin formalism allows us to establish an intriguing equivalence. As a result, the important low-field polarization transfer regime of PHIP can be mapped onto an analogous system equivalent to pulsed-DNP. This establishes a correspondence between key polarization transfer sequences in PHIP and DNP, facilitating the transfer of sequence development concepts. This promises fresh insights and significant cross-pollination between DNP and PHIP polarization sequence developers.

We reveal an interplay between temperature and radical concentration necessary to establish thermal mixing (TM) as an efficient dynamic nuclear polarization (DNP) mechanism. We conducted DNP experiments by hyperpolarizing widely used DNP samples, i.e., sodium pyruvate-1-¹³C in water/glycerol mixtures at varying nitroxide radical (TEMPOL) concentrations and microwave irradiation frequencies, measuring proton and carbon-13 spin temperatures. Using a cryogen consumption-free prototype-DNP apparatus, we could probe cryogenic temperatures between 1.5 and 6.5 K, i.e., below and above the boiling point of liquid helium. We identify two mechanisms for the breakdown of TM: (i) Anderson type of quantum localization for low radical concentration, or (ii) quantum Zeno localization occurring at high temperature. This observation allowed us to reconcile the recent diverging observations regarding the relevance of TM as a DNP mechanism by proposing a unifying picture and, consequently, to find a trade-off between radical concentration and electron relaxation times, which offers a pathway to improve experimental DNP performance based on TM.

One of the most essential prerequisites for the development of pulse Dynamic Nuclear Polarization (DNP) is the ability to generate high-power coherent mm-wave pulses at the electron precession frequencies corresponding to the magnetic fields of modern high-resolution NMR spectrometers. As a major step towards achieving this goal, an Extended Interaction Klystron (EIK) pulse amplifier custom-built by the Communications and Power Industries, Inc. and producing up to 140 W at 197.8 GHz, was integrated with in-house built NMR/DNP/EPR spectrometer operating at 7 T magnetic field. The spectrometer employs a Thomas Keating, Ltd. quasioptical bridge to direct mm-waves into a homebuilt DNP probe incorporating photonic bandgap (PBG) resonators to further boost electronic B_1e fields. Three-pulse electron spin echo nutation experiments were employed to characterize the B_1e fields at the sample by operating the homodyne 198 GHz bridge in an induction mode. Room-temperature experiments with a single-crystal high-pressure, high-temperature (HPHT) diamond and a polystyrene film doped with BDPA radical yielded < 9 ns π/2 pulses at ca. 50 W specified EIK output at the corresponding resonance frequencies and the PBG resonator quality factor of Q≈300. DNP experiments carried out in a “gated” mode by supplying 20 μs mm-wave pulses every 1 ms yielded ¹³C solid-effect DNP with gains up to 20 for the polystyrene-BDPA sample at natural ¹³C abundance. For a single-crystal HPHT diamond, the gated DNP mode yielded almost the same ¹³C enhancement as a low-power continuous wave (CW) mode at 0.4 W, whereas no DNP effect was observed for the BDPA/polystyrene sample in the latter case. To illustrate the versatility of our upgraded DNP spectrometer, room-temperature Overhauser DNP enhancements of 7–14 for ³¹P NMR signal were demonstrated using a liquid droplet of 1 M tri-phenyl phosphine co-dissolved with 100 mM of BDPA in toluene‑d₈.

MRI systems have a thin conducting layer placed between the gradient and RF coils, this acts as a shield at the RF-frequency, minimizing noise coupled into the experiment, and decreasing the coupling between the RF and gradient coils. Ideally, this layer should be transparent to the gradient fields to reduce eddy currents. In this work the design of such a shield, specifically for low-field point-of-care Halbach based MRI devices, is discussed. A segmented double layer shield is designed and constructed based on eddy current simulations. Subsequently, the performance of the improved shield is compared to a reference shield by measuring the eddy current decay times as well as using noise measurements. A maximum reduction factor of 2.9 in the eddy current decay time is observed. The segmented shield couples in an equivalent amount of noise when compared to the unsegmented reference shield. Turbo spin echo images of a phantom and the brain of a healthy volunteer show improvements in terms of blurring using the segmented shield.

The rapid advancement of parahydrogen-induced hyperpolarization (PHIP) and its diverse array of applications highlights the critical need for enhanced signals in both ¹H NMR and heteronuclear NMR spectroscopy. Simultaneously, there is an increasing interest in utilizing benchtop NMR analysis across various laboratory settings. However, due to their lower magnetic fields, benchtop NMR spectrometers inherently produce weaker signal intensities. Here, PHIP is a well-established solution to this challenge. Consequently, we are expanding our cost-effective PHIP setup from a high-field NMR spectrometer (11.7 T) to include an additional benchtop NMR spectrometer (1.4 T), thereby enabling concurrent execution of PHIP experiments and measurements. Through the implementation of automated experimental protocols, we aim to minimize experiment time while increasing reproducibility. In this work, a non-isotope labelled propargyl alcohol sample is used at low concentrations to demonstrate our setup’s capabilities. It could be shown that single-scan PASADENA experiments can be run with comparable signal enhancements at the benchtop as well as the high-field spectrometer. At 1.4 T, fully automated PHIP pseudo-2D measurements will also be demonstrated. Additionally, two different field profiles for the spin-order transfer of p-H₂ to ¹³C at zero- to ultralow fields are elaborated upon. The setup facilitates the measurement of carbon signal enhancement of more than 2000 on the benchtop NMR spectrometer, employing a straightforward one-pulse, one-scan experiment.

Two-dimensional (2D) J-resolved spectroscopy provides valuable information on J-coupling constants for molecular structure analysis by resolving one-dimensional (1D) spectra. However, it is challenging to decipher the J-coupling connectivity in 2D J-resolved spectra because the J-coupling connectivity cannot be directly provided. In addition, 2D homonuclear correlation spectroscopy (COSY) can directly elucidate molecular structures by tracking the J-coupling connectivity between protons. However, this method is limited by the problem of spectral peak crowding and is only suitable for simple sample systems. To fully understand the intuitive coupling relationship and coupling constant information, we propose a three-dimensional (3D) COSY method called CTCOSY-JRES (Constant-Time COrrelation SpectroscopY and J-REsolved Spectroscopy) in this paper. By combining the J-resolved spectrum with the constant-time COSY technique, a doubly decoupled COSY spectrum can be provided while preserving the J-coupling constant along an additional dimension, ensuring high-resolution analysis of J-coupling connectivity and J-coupling information. Moreover, compression sensing and fold-over correction techniques are introduced to accelerate experimental acquisition. The CTCOSY-JRES method has been successfully validated in a variety of sample systems, including industrial, agricultural, and biopharmaceutical samples, revealing complex coupling interactions and providing deeper insights into the resolution of molecular structures.

Proton-detected INADEQUATE NMR experiments are widely used for structure elucidation of small molecules, in particular the implementations that display ¹³C single-quantum rather than double-quantum frequencies in the indirect dimension of 2D spectra. But unfortunately, such spectra in addition to the desired ¹H–¹³C two-bond correlations also contain HSQC artifacts of comparable magnitude. The redesigned versatile experiment presented in this paper requires no compromise based on different ¹³C multiplicities and suppresses the HSQC artifacts that are a source of possible spectral misinterpretation. Demonstration of the new method is shown by applications to typical small molecules of different complexity.

The open-source console MaRCoS, which stands for “Magnetic Resonance Control System”, combines hardware, firmware and software elements for integral control of Magnetic Resonance Imaging (MRI) scanners. Previous developments have focused on making the system robust and reliable, rather than on users, who have been somewhat overlooked. This work describes a Graphical User Interface (GUI) designed for intuitive control of MaRCoS, as well as compatibility with clinical environments. The GUI is based on an arrangement of tabs and a renewed Application Program Interface (API). Compared to the previous versions, the MaRGE package (“MaRCoS Graphical Environment”) includes new functionalities such as the possibility to export images to standard DICOM formats, create and manage clinical protocols, or display and process image reconstructions, among other features conceived to simplify the operation of MRI scanners. All prototypes in our facilities are commanded by MaRCoS and operated with the new GUI. Here we report on its performance on an experimental 0.2 T scanner designed for hard-tissue, as well as a 72 mT portable scanner presently installed in the radiology department of a large hospital. The possibility to customize, adapt and streamline processes has substantially improved our workflows and overall experience.

The measurement of translational diffusion coefficients by NMR generally makes use basically of two magnetic field gradient pulses separated by a so-called diffusion interval. The magnetic field gradient arises either from the static magnetic field (denoted by B₀ used for polarizing the nuclear spins) or from the radio-frequency field (denoted by B₁ used for inducing NMR transitions). The B₀ method may be hampered by short effective transverse relaxation times ($T_2^{\ast }$), by important gradient rise and fall times or by eddy currents. This does not occur with B₁ gradients. Moreover, the effect of short transverse relaxation times during the gradient pulses is reduced by at least a factor of two. However, for B₁ gradients, one might face with the limited volume in which the gradient is uniform and with the effect of short relaxation times which imply to reduce the various intervals in the diffusion experiment (this is as well true for the B₀ method). Examples will be given for which the measurement of the diffusion coefficient by B₀ gradients turned out to be impossible while a proper result was obtained with B₁ gradients as far as a correction taking into account the limited volume is applied, together with a correction about the gradient calibration especially when dealing with samples containing paramagnetic species.

Solution NMR spectroscopy has tremendous potential for providing atomic resolution insights into the interactions between proteins and nucleic acids partitioned into condensed phases of phase-separated systems. However, the highly viscous nature of the condensed phase challenges applications, and in particular, the extraction of quantitative, site-specific information. Here, we present a delayed decoupling-based HMQC pulse sequence for methyl-TROSY studies of ‘client’ proteins and nucleic acids partitioned into ‘scaffold’ proteinaceous phase-separated solvents. High sensitivity and excellent quality spectra are recorded of a nascent form of superoxide dismutase and of a small RNA fragment partitioned into CAPRIN1 condensates.