Concepts in Magnetic Resonance Part A最新文献

Here we describe the selective inversion methodology for quantifying the rates of site-specific ion exchange in materials such as lithium ion battery cathode frameworks. This strategy is shown to be robust in the presence of paramagnetic centers and viable and efficient for the evaluation of hopping rates, in spite of varying initial conditions for the NMR experiment. This is contrasted with 2D EXSY methodology, and selective inversion is shown to be preferable for a number of reasons articulated herein. Work in this area in our group was guided by insights into chemical exchange processes provide by our friend and colleague, Prof. Alex D. Bain. We dedicate this short review to him.

Using a Cartesian operator basis set, precession equations have previously been derived for spin-1 systems using some 23 Cartesian operator commutators. We avoid the explicit evaluation of these commutators, and use instead fundamental properties of irreducible tensor operators (ITO) to obtain these precession equations. First, advantage is taken of the angle-axis parametrization of the rotation matrices that transform second-rank ITO under rotation to define the unitarily equivalent rotation matrix that transforms second-rank Cartesian tensors. From this latter transformation, and using simple matrix analysis techniques, all the equations that describe spin-1 precession in the presence of radiofrequency fields and resonance offsets are obtained. Second, information on the ITO commutation relations can be encoded in angular momentum coupling coefficients in a generalized spin precession equation. In the case of spin-1, this leads to a set of coupled differential equations for the statistical tensor components . After transformation of these components to their Cartesian counterparts, the corresponding vector differential equations that define the time evolution of the Cartesian operator expectation values are easily solved, again using simple matrix analysis. This solution yields all the equations that describe spin-1 precession in the presence of radiofrequency fields, resonance offsets, and the quadrupolar interaction.

This article reviews the use of long-range shift correlation spectra for structure elucidation of natural products and other complex organic compounds from the early 1980's to the present. Much of it is written from the personal viewpoint of someone who has been involved in this area of research since its earliest days. The first section covers the early use of long-range correlation spectra in the 1980's. The second section covers the development of specialized pulse sequences for this type of acquisition. It begins with three ¹³C-detected sequences, followed by heteronuclear multiple bond correlation (HMBC) and some modified versions of HMBC and, finally, longer range correlation sequences based on the heteronuclear single quantum multiple bond correlation sequence. The third section covers various sequences designed to distinguish between 2-bond and longer range ¹³C-¹H correlations. Unfortunately, none of these can make this distinction for non-protonated carbons. Only the 1,1-ADEQUATE sequence can make this distinction but its very low sensitivity limits its usefulness. The next section focuses on ways of avoiding getting incorrect structures of organic compounds, an ongoing problem in natural product research. The last section includes likely short-term developments and possible long-term developments in NMR methodology that would be beneficial for small molecule structure elucidation.

The SPI/SPRITE class of techniques in magnetic resonance imaging are pure phase encode methods that are well established for systems with short transverse signal lifetimes. Applying a broadband radio-frequency pulse in the presence of a magnetic field gradient is unconventional in MRI but fundamental to these methods. Ordinarily, it is assumed that the excitation is instantaneous and any possible phase evolution during the RF pulse is ignored. High quality, quantitative imaging of a variety of samples over many years suggests that the off-resonance effects of the RF pulse, with consequent phase accumulation during the pulse, are not significant. However, a reconsideration of the RF pulse behavior in related work has shown that phase accumulation during the pulse may be non-negligible in some circumstances.

The effect of phase accumulation during the RF pulse is investigated through simulation of one-dimensional SPI experiments and is shown to manifest as a systematic scaling of the image field-of-view (FOV). The FOV scaling effect is also verified experimentally. One-dimensional profiles of a cylindrical elastomer sample were acquired employing a 2.4 T horizontal bore magnet. Experiments were undertaken with variation of the experimental RF pulse duration. Under typical experimental parameters, neglecting the phase accumulation during the RF pulse is acceptable.

The use of frequency-hopped pulse pairs and pulse pair trains for exciting NMR signals is introduced. Pairs of pulses, each pair lasting one nutation period about the effective field in the rotating frame, can be used to efficiently tip nuclear spin magnetization. In the limit where the frequency difference between the partners in a pair is large, the magnetization dynamics mimic those of an ordinary rectangular rf pulse with rf amplitude scaled down by a factor of π/2. When the amplitude of the applied rf begins to approach the offset frequency however, the excitation bandwidth broadens dramatically in a manner reminiscent of a composite pulse. The effects of the frequency-hopped pulse pairs is described with analytical calculations and numerical simulations, and are shown to agree well with experiment.

Understanding the dynamics of electron or nuclear spins during a magnetic resonance experiment requires to solve the Schrödinger equation for the spin system considering all contributions to the Hamiltonian from interactions of the spins with each other and their surroundings. In general, this is a difficult task as these interaction terms can be both time-dependent and might not commute with each other. A powerful tool to analytically approximate the time evolution is average Hamiltonian theory, in which a time-independent effective Hamiltonian is taking the place of the time-dependent Hamiltonian. The effective Hamiltonian is subjected to the Magnus expansion, allowing to calculate the effective Hamiltonian to a certain order. The goal of this paper is to introduce average Hamiltonian theory in a rigorous but educational manner. The application to two composite pulses in NMR spectroscopy is used to demonstrate important aspects of average Hamiltonian theory.

Solid-state nuclear magnetic resonance (SSNMR) spectroscopy has largely overtaken nuclear quadrupole resonance (NQR) spectroscopy for the study of quadrupolar nuclei. In addition to information on the electric field gradient, SSNMR spectra may offer additional information concerning other NMR interactions such as magnetic shielding. With continued technological advances contributing to developments such as higher magnetic fields, SSNMR boasts several practical advantages over NQR. However, NQR is still a relevant technique, as it may often be the most practical approach in cases of extremely large quadrupolar coupling constants. Here, we discuss the advantages and disadvantages of SSNMR and NQR spectroscopies, with the quadrupolar halogens serving as examples. The purpose of this article is to serve as a guide on using SSNMR and NQR as complementary tools, covering some of their practicalities, limitations, and experimental challenges.

In this article, we discuss the progress achieved with the use of evolutionary algorithms for the analysis of ¹H Nuclear Magnetic Resonance spectra of solutes in orientationally ordered liquids. With these tools the analysis of extremely complex spectra that were hitherto impossible to solve has now become eminently feasible. We discuss applications to 2 molecules of special interest: (a) hexamethylbenzene, which is a text book example of steric hindrance between adjacent rotating methyl groups; and (b) cyclohexane which is the standard example of interconversion between various molecular conformations. New interesting physics is obtained in both cases.