Progress in Nuclear Magnetic Resonance Spectroscopy最新文献

Swelling layered clay minerals form an important sub-group of the phyllosilicate family. They are characterized by their ability to expand or contract in the presence or absence of water. This property makes them useful for a variety of applications, ranging from environmental technologies to heterogeneous catalysis, and including pharmaceutical and industrial applications. Solid State Nuclear Magnetic Resonance (SS-NMR) has been extensively applied in the characterization of these materials, providing useful information on their dynamics and structure that is inaccessible using other characterization methods such as X-ray diffraction. In this review, we present the key contributions of SS-NMR to the understanding of the mechanisms that govern some of the main applications associated to swelling clay minerals. The article is divided in two parts. The first part presents SS-NMR conventional applications to layered clay minerals, while the second part comprises an in-depth review of the information that SS-NMR can provide about the different properties of swelling layered clay minerals.

Porous carbonaceous materials have many important industrial applications including energy storage, water purification, and adsorption of volatile organic compounds. Most of their applications rely upon the adsorption of molecules or ions within the interior pore volume of the carbon particles. Understanding the behaviour and properties of adsorbate species on the molecular level is therefore key for optimising porous carbon materials, but this is very challenging owing to the complexity of the disordered carbon structure and the presence of multiple phases in the system. In recent years, NMR spectroscopy has emerged as one of the few experimental techniques that can resolve adsorbed species from those outside the pore network. Adsorbed, or “in-pore” species are shielded with respect to their free (or “ex-pore”) counterparts. This shielding effect arises primarily due to ring currents in the carbon structure in the presence of a magnetic field, such that the observed chemical shift differences upon adsorption are independent of the observed nucleus to a first approximation. Theoretical modelling has played an important role in rationalising and explaining these experimental observations. Together, experiments and simulations have enabled a large amount of information to be gained on the adsorption and diffusion of adsorbed species, as well as on the structural and magnetic properties of the porous carbon adsorbent. Here, we review the methodological developments and applications of NMR spectroscopy and related modelling in this field, and provide perspectives on possible future applications and research directions.

Magnetic Resonance Imaging (MRI) scanners produce loud acoustic noise originating from vibrational Lorentz forces induced by rapidly changing currents in the magnetic field gradient coils. Using zero echo time (ZTE) MRI pulse sequences, gradient switching can be reduced to a minimum, which enables near silent operation. Besides silent MRI, ZTE offers further interesting characteristics, including a nominal echo time of TE = 0 (thus capturing short-lived signals from MR tissues which are otherwise MR-invisible), 3D radial sampling (providing motion robustness), and ultra-short repetition times (providing fast and efficient scanning). In this work we describe the main concepts behind ZTE imaging with a focus on conceptual understanding of the imaging sequences, relevant acquisition parameters, commonly observed image artefacts, and image contrasts. We will further describe a range of methods for anatomical and functional neuroimaging, together with recommendations for successful implementation.

Single-crystal (SC) NMR spectroscopy is a solid-state NMR method that has been used since the early days of NMR to study the magnitude and orientation of tensorial nuclear spin interactions in solids. This review first presents the field of SC NMR instrumentation, then provides a survey of software for analysis of SC NMR data, and finally it highlights selected applications of SC NMR in various fields of research. The aim of the last part is not to provide a complete review of all SC NMR literature but to provide examples that demonstrate interesting applications of SC NMR.

The nuclear Overhauser effect (NOE) is a consequence of cross-relaxation between nuclear spins mediated by dipolar coupling. Its sensitivity to internuclear distances has made it an increasingly important tool for the determination of through-space atom proximity relationships within molecules of sizes ranging from the smallest systems to large biopolymers. With the support of sophisticated FT-NMR techniques, the NOE plays an essential role in structure elucidation, conformational and dynamic investigations in liquid-state NMR. The efficiency of magnetization transfer by the NOE depends on the molecular rotational correlation time, whose value depends on solution viscosity. The magnitude of the NOE between ¹H nuclei varies from +50% when molecular tumbling is fast to −100% when it is slow, the latter case corresponding to the spin diffusion limit. In an intermediate tumbling regime, the NOE may be vanishingly small. Increasing the viscosity of the solution increases the motional correlation time, and as a result, otherwise unobservable NOEs may be revealed and brought close to the spin diffusion limit. The goal of this review is to report the resolution of structural problems that benefited from the manipulation of the negative NOE by means of viscous solvents, including examples of molecular structure determination, conformation elucidation and mixture analysis (the ViscY method).

In recent years, new molecular symmetry-based approaches for magnetic resonance have been invented. The implications of these discoveries will be significant for molecular imaging via magnetic resonance, in vitro as well as in vivo, for quantum computing and for other fields. Since the initial observation in 2004 in Southampton that effective spin symmetry can be instilled in a molecule during magnetic resonance experiments, spin states that are resilient to relaxation mechanisms have been increasingly used. Most of these states are related to the nuclear singlet in a pair of J-coupled spins. Tailored relaxation rate constants for magnetization became available in molecules of different sizes and structures, as experimental developments broadened the scope of symmetry-adapted spin states. The ensuing access to timescales longer than the classically-attained ones by circa one order of magnitude allows the study of processes such as slow diffusion or slow exchange that were previously beyond reach. Long-lived states formed by differences between populations of singlets and triplets have overcome the limitations imposed by longitudinal relaxation times (T₁) by factors up to 40. Long-lived coherences formed by superpositions of singlets and triplets have overcome the limit of classical transverse coherence (T₂) by a factor 9. We present here an overview of the development and applications of long-lived states (LLS) and long-lived coherences (LLC’s) and considerations on future perspectives.

Quantitative cardiac magnetic resonance has emerged in recent years as an approach for evaluating a range of cardiovascular conditions, with T₁ and T₂ mapping at the forefront of these developments. Cardiac Magnetic Resonance Fingerprinting (cMRF) provides a rapid and robust framework for simultaneous quantification of myocardial T₁ and T₂ in addition to other tissue properties. Since the advent of cMRF, a number of technical developments and clinical validation studies have been reported. This review provides an overview of cMRF, recent technical developments, healthy subject and patient studies, anticipated technical improvements, and potential clinical applications. Recent technical developments include slice profile and pulse efficiency corrections, improvements in image reconstruction, simultaneous multislice imaging, 3D whole-ventricle imaging, motion-resolved imaging, fat–water separation, and machine learning for rapid dictionary generation. Future technical developments in cMRF, such as B₀ and B₁ field mapping, acceleration of acquisition and reconstruction, imaging of patients with implanted devices, and quantification of additional tissue properties are also described. Potential clinical applications include characterization of infiltrative, inflammatory, and ischemic cardiomyopathies, tissue characterization in the left atrium and right ventricle, post-cardiac transplantation assessment, reduction of contrast material, pre-procedural planning for electrophysiology interventions, and imaging of patients with implanted devices.

Hyperpolarised gas lung MRI using xenon-129 can provide detailed 3D images of the ventilated lung airspaces, and can be applied to quantify lung microstructure and detailed aspects of lung function such as gas exchange. It is sensitive to functional and structural changes in early lung disease and can be used in longitudinal studies of disease progression and therapy response. The ability of ¹²⁹Xe to dissolve into the blood stream and its chemical shift sensitivity to its local environment allow monitoring of gas exchange in the lungs, perfusion of the brain and kidneys, and blood oxygenation. This article reviews the methods and applications of in vivo ¹²⁹Xe MR in humans, with a focus on the physics of polarisation by optical pumping, radiofrequency coil and pulse sequence design, and the in vivo applications of ¹²⁹Xe MRI and MRS to examine lung ventilation, microstructure and gas exchange, blood oxygenation, and perfusion of the brain and kidneys.

The family of resolution enhancement and spectral reconstruction techniques collectively known as covariance NMR continues to expand, along with the list of applications for these techniques. Recent advances in covariance NMR include the utilization of covariance to reconstruct pure shift NMR spectra, and the growing use of covariance NMR in processing non-uniformly sampled data, especially in solid state NMR and metabolomics. This review describes theoretical and practical considerations for direct and indirect covariance NMR techniques, and summarizes recent additions to the covariance NMR family. The review also outlines some of the applications of covariance NMR, and places covariance NMR in the larger context of methods that use statistical and algebraic approaches to enhance and combine various kinds of spectroscopic data, including tensor-based approaches for multidimensional NMR and heterocovariance spectroscopy.