Journal of Magnetic Resonance Open最新文献

Liquid-state Overhauser Dynamic Nuclear Polarization (ODNP) is an emerging technique, aimed at shortening NMR experiment times. It achieves this by increasing the otherwise poor nuclear polarization at room temperature, by polarization transfer from excited electron spins. The present work explores two ideas, aimed at achieving the optimal signal-to-noise per time unit for a given system, and quantitation of spectra showing a large disparity in ODNP enhancements at high magnetic fields (≥ 9.4 T). Both of these ideas are predicated on, perhaps counterintuitively, not allowing full dynamic nuclear polarization to build up, either by rapid rf pulsing, or gating of the microwave irradiation.

Dynamic nuclear polarization (DNP) is a powerful tool to polarize nuclear spins and enhance the intensity of their magnetic resonance signal. For DNP a sample is doped with an agent providing unpaired electron spins. Then the sample is cooled in a strong magnetic field to polarize these electron spins and a microwave field is applied to transfer this polarization to the nuclear spins. While DNP is very efficient, it has two inherent issues: the electron spins needed to polarize the nuclear spins are also the main source of polarization decay. Furthermore, polarizing the electron spins requires strong magnets and powerful cryogenics, that may obstruct further use of the polarized nuclear spins.

These issues can be addressed by using the electron spin of photo-excited triplet states for DNP. After DNP the light creating the electron spins can be shut off, thus eliminating the main source of decay of the nuclear polarization. Moreover, for some well-chosen molecules the photo-excitation process creates the triplet state in a highly polarized state, so magnets and cryogenics can be significantly simplified.

The present article presents the state of the art of producing a high proton polarization – up to 0.80 – with a long lifetime – typically 50 h at liquid nitrogen temperature and in a field of 0.75 T – using the photo-excited triplet state of pentacene in a naphthalene host. It describes sample preparation, experimental equipment and procedures required to obtain this result, as well the theoretical background required to maximize the polarization transfer from the triplet spins to the proton spins and to optimize the photo-excitation process. It finishes with methods for long-distance transport and final application of polarized samples.

The basic physics of magnetic fields is presented for a target audience of NMR workers. This group often does not have formal training in electromagnetism, but could benefit from an understanding of a selected subset of topics. The focus here is on a relatively non-mathematical view, intended to deliver an intuitive understanding of the topic. The covered topics start with the fields arising from simple idealized currents, including long straight wires, short flat coils, infinite current sheets, long solenoids, and magnetic dipole moments. The generation of field gradients and shim fields is discussed. All of these can be unified by considering the divergence and curl of the magnetic field. Magnetic materials are treated, both linear magnetizable materials (including the sample itself) and permanently magnetized materials; the approaches of equivalent currents and Ampere's theorem for magnetic circuits are presented.

Conventional diagnostic images from Magnetic Resonance Imaging (MRI) are typically qualitative and require subjective interpretation. Alternatively, quantitative MRI (qMRI) methods have become more prevalent in recent years with multiple clinical and preclinical imaging applications. Quantitative MRI studies on preclinical MRI scanners are being used to objectively assess tissues and pathologies in animal models and to evaluate new molecular MRI contrast agents. Low-field preclinical MRI scanners ($\le$3.0T) are particularly important in terms of evaluating these new MRI contrast agents at human MRI field strengths. Unfortunately, these low-field preclinical qMRI methods are challenged by long acquisition times, intrinsically low MRI signal levels, and susceptibility to motion artifacts. In this study, we present a new rapid qMRI method for a preclinical 3.0T MRI scanner that combines a Spiral Acquisition with a Matching-Based Algorithm (SAMBA) to rapidly and quantitatively evaluate MRI contrast agents. In this initial development, we compared SAMBA with gold-standard Spin Echo MRI methods using Least Squares Fitting (SELSF) in vitro phantoms and demonstrated shorter scan times without compromising measurement accuracy or repeatability. These initial results will pave the way for future in vivo qMRI studies using state-of-the-art chemical probes.

We describe a method and an apparatus for producing hyperpolarized (HP) Xe gas of high concentration without Xe condensation. The HP Xe generator works under atmospheric pressure and employs a quasi-continuous method to provide a continuous supply of HP Xe gas by adopting technologies for supplying a highly pure gas, a gas control system and precise pressure control. The apparatus has a glass cell containing solid Rb metal and solid Xe in vacuum at a low temperature and is heated so that the Xe becomes a gas and Rb exists in a gas-liquid mixture. Then a magnetic field is applied with laser beam irradiation to produce polarized Xe gas of high concentration. The device was evaluated using a 2T magnetic resonance imaging (MRI) scanner. Long-term experimental operation demonstrated the continuous collection of 30 ml syringes of HP Xe gas with a sufficient polarization rate for fast one scan acquisition. A practical device for the automated manufacture of HP ¹²⁹Xe gas was thus successfully developed.

Layered rare earth hydroxides (LREHs) are a new family of ion-exchangeable layered metal hydroxides, which have extensive applications in various fields due to the unique properties of rare earth cations in the layered structure and the anion exchange capacity. The transformation of layered metal hydroxides to new layered phases that can be restored through the memory effect is critical for their chemistry and applications. However, the structure details of these new phases such as the coordination environments of rare earth cations/counterions and their evolution as a function of calcination temperature remain unclear to date. Herein, a comprehensive ⁸⁹Y/³⁵Cl solid-state NMR (ssNMR) and theoretical modeling approach was used to reveal the structural evolution of a representative LREH, namely LYH-Cl, upon calcination. We first identified partial decomposition products of Y₃O(OH)₅Cl₂ and Y(OH)₃ during the dehydration stage, then uncovered the preferential removal of hydroxide ions on yttrium sites coordinated with chlorine during the dehydroxylation stage, and finally determined the preferential removal of chlorine exposed to the surface of layers during the dechlorination stage. The coordination environments of Y³⁺ and Cl⁻ undergo significant changes upon calcination, revealed by ssNMR experiments. These findings thus help us to overcome the obstacles impeding the rational design and synthesis of LREH-based functional materials via memory effect, underscoring the vast potential of ssNMR in deepening the understanding of layered metal hydroxides and related materials.

In this tutorial paper, we describe some basic principles and practical considerations for designing probe circuits for NMR or MRI. The goal is building a bridge from material that is familiar from undergraduate physics courses to more specialized information needed to put together and tune a resonant circuit for magnetic resonance. After a brief overview of DC and AC circuits, we discuss the properties of circuit elements used in an NMR probe and how they can be assembled into building blocks for multi-channel circuits. We also discuss the use of transmission lines as circuit elements as well as practical considerations for improving circuit stability and power handling.

A versatile strategy for synthesizing tailored peptide based biradicals is presented. By labeling the protected amino acid hydroxyproline with PROXYL via the OH functionality and using this building block in solid phase peptide synthesis (SPPS), the obtained peptides become polarization agents for DNP enhanced solid-state NMR in biotolerant media. To analyze the effect of the radical position on the enhancement factor, three different biradicals are synthesized. The PROXYL spin-label is inserted in a collagen inspired artificial peptide sequence by binding through the OH group of the hydroxyproline moieties at specific position in the chain. This labeling strategy is universally applicable for any hydroxyproline position in a peptide sequence since solid-phase peptide synthesis is used to insert the building block. High performance liquid chromatography (HPLC) and mass spectrometry (MS) analyses show the successful introduction of the spin label in the peptide chain and electron paramagnetic resonance (EPR) spectroscopy confirms its activity. Dynamic nuclear polarization (DNP) enhanced solid-state nuclear magnetic resonance (NMR) experiments performed on frozen aqueous glycerol-d₈ solutions containing these peptide radicals show significantly higher enhancement factors of up to 45 in ¹H→¹³C cross polarization magic angle spinning (CP MAS) experiments compared to an analogous mono-radical peptide including this building block (ε ≈ 14). Compared to commercial biradicals such as AMUPol for which enhancement factors > 100 have been obtained in the past and which have been optimized in their structure, the obtained enhancement up to 45 for our biradicals presents a significant progress in radical design.

The discovery of novel experimental techniques often lags behind contemporary theoretical understanding. In particular, it can be difficult to establish appropriate measurement protocols without analytic descriptions of the underlying system-of-interest. Here we propose a statistical learning framework that avoids the need for such descriptions for ergodic systems. We validate this framework by using Monte Carlo simulation and deep neural networks to learn a mapping between nuclear magnetic resonance spectra acquired on a novel low-field instrument and proton exchange rates in ethanol-water mixtures. We found that trained networks exhibited normalized-root-mean-square errors of less than 1 % for exchange rates under 150 s⁻¹ but performed poorly for rates above this range. This differential performance occurred because low-field measurements are indistinguishable from one another for fast exchange. Nonetheless, where a discoverable relationship between indirect measurements and emergent dynamics exists, we demonstrate the possibility of approximating it in an efficient, data-driven manner.

Benchtop NMR is enjoying a renaissance with numerous manufacturers bringing products to the market over the last decade. The improved accessibility, lower cost of ownership and ease of use (vs high field NMR), is attracting new users into NMR spectroscopy, which is highly beneficial for the field in general. As benchtop NMR systems seldom require deuterated solvents, this allows samples to be analyzed “as is”, without extraction or alteration. However, many interesting samples, be it an organic reaction mixture, beer, or a biofluid, contain one or more solvent/water signals, which often require suppression. Due to the lower spectral dispersion of benchtop NMR's (vs high field) the frequency of solvent/water is much closer to the analytes of interest, making solvent suppression more challenging. As such, there is a conundrum, where novel users wish to analyze unaltered samples but are quickly faced with the challenge of water suppression, and the wealth of options in the high field literature can be overwhelming. It is important to note that all manufacturers offer some sort of automated water suppression that can be performed with a “single click” that are sufficient for “walk-up” applications or occasional users. This primer is aimed as an accessible guide to those wishing to take the next step and is suitable for users who; 1) would like to pick the optimal water suppression approach for their sample type and 2) wish to understand how water suppression works. The guide focuses on water suppression approaches that are easy to apply, namely presaturation based sequences, binomial sequences for aggressive suppression, and WET for multiple signal suppression, across a range of samples including sucrose standards, espresso, human blood serum and wine. The primer finishes with a flow chart that can be used to guide users in choosing the optimal water suppression approach for their specific sample type, with considerations, including exchangeable signals and the preservation of macromolecular signals, amongst others. In addition, the primer includes 3 fully interactive videos based on H5P technology, focusing on how to acquire data using the approaches described here. The videos include quizzes, with a first-person-perspective of the spectrometer software with interactive elements, as if the users were acquiring the data themselves. In summary, the primer is aimed at advanced undergraduates, graduate students, new users, or users wishing to expand their water/solvent suppression skills/knowledge using benchtop NMR.