Solid state nuclear magnetic resonance最新文献

In MQMAS-based high-resolution solid-state NMR experiments of half-integer spin quadrupolar nuclei, the high radiofrequency (RF) field requirement for the MQ excitation and conversion steps with two hard-pulses is often a sensitivity limiting factor in many practical applications. Recently, the use of two cosine-modulated (cos) low-power (lp) pulses, lasting one-rotor period each, was successfully introduced for efficient MQ excitation and conversion of spin-3/2 nuclei with a reduced RF amplitude. In this study, we extend our previous investigations of spin-3/2 nuclei to systems with higher spin values and discuss the applicability of coslp-MQ excitation and conversion in MQMAS and MQ-HETCOR experiments under slow and fast spinning conditions. For the numerical simulations and experiments we used a moderate magnetic field of 14.1 T. Two spin-5/2 nuclei (⁸⁵Rb and ²⁷Al) are mainly employed with a large variety of C_Q values, but we show that the practical set up is also available for higher spin values, such as spin-9/2 with ⁹³Nb in Cs₄Nb₁₁O₃₀. We demonstrate for nuclei with spin value larger than 3/2 a preferential use of coslp-MQ acquisition for low-gamma nuclei and/or large C_Q values with a much reduced RF-field with respect to that of hard-pulses used with conventional methods.

Static satellite-transitions (ST) NMR line shapes from half-integer quadrupolar nuclei could be very informative: they can deliver insight about local motions over a wide range of timescales, and can report on small changes in the local electronic environments as reflected by variations in the quadrupolar parameters. Satellite transitions, however, are typically “invisible” for half-integer quadrupolar nuclei due to their sheer breadth, leading to low signal-to-noise ratio –especially for unreceptive low-gamma or dilute quadrupolar nuclei. Very recently we have introduced a method for enhancing the NMR sensitivity of unreceptive X nuclei in static solids dubbed PROgressive Saturation of the Proton Reservoir (PROSPR), which opens the possibility of magnifying the signals from such spins by repeatedly imprinting frequency-selective X-driven depolarizations on the much more sensitive ¹H NMR signal. Here, we show that PROSPR's efficacy is high enough for enabling the detection of static ST NMR for challenging species like ³⁵Cl, ³³S and even ¹⁷O –all at natural-abundance. The ensuing ST-PROSPR NMR experiment thus opens new approaches to probe ultra-wideline (6–8 MHz wide) spectra. These highly pronounced anisotropies can in turn deliver new vistas about dynamic changes in solids, as here illustrated by tracking ST line shapes as a function of temperature during thermally-driven events.

Recoupling, decoupling, and multidimensional correlation experiments in magic-angle-spinning (MAS) solid-state NMR can be designed by exploiting the symmetry of internal spin interactions. One such scheme, namely, ${C5}_2^1$, and its supercycled version ${SPC5}_2^1$, notated as a five-fold symmetry sequence, is widely used for double-quantum dipole-dipole recoupling. Such schemes are generally rotor synchronised by design. We demonstrate an asynchronous implementation of the ${SPC5}_2^1$ sequence leading to higher double-quantum homonuclear polarisation transfer efficiency compared to the normal synchronous implementation. Rotor-synchronisation is broken in two different ways: lengthening the duration of one of the pulses, denoted as pulse-width variation (PWV), and mismatching the MAS frequency denoted as MAS variation (MASV). The application of this asynchronous sequence is shown on three different samples, namely, U–¹³C-alanine and 1,4-¹³C-labelled ammonium phthalate which include ¹³C_α-¹³C_β, ¹³C_α-¹³C_o, and ¹³C_o–¹³C_o spin systems, and adenosine 5′- triphosphate disodium salt trihydrate (ATP⋅3H₂O). We show that the asynchronous version performs better for spin pairs with small dipole-dipole couplings and large chemical-shift anisotropies, for example, ¹³C_o–¹³C_o. Simulations and experiments are shown to corroborate the results.

Bone construction has been under intensive scrutiny for many years using numerous techniques. Solid-state NMR spectroscopy helped unravel key characteristics of the mineral structure in bone owing to its capability of analyzing crystalline and disordered phases at high-resolution. This has invoked new questions regarding the roles of persistent disordered phases in structural integrity and mechanical function of mature bone as well as regarding regulation of early events in formation of apatite by bone proteins which interact intimately with the different mineral phases to exert biological control.

Here, spectral editing tethered to standard NMR techniques is employed to analyze bone-like apatite minerals prepared synthetically in the presence and absence of two non-collagenous bone proteins, osteocalcin and osteonectin. A ¹H spectral editing block allows excitation of species from the crystalline and disordered phases selectively, facilitating analysis of phosphate or carbon species in each phase by magnetization transfer via cross polarization. Further characterization of phosphate proximities using SEDRA dipolar recoupling, cross-phase magnetization transfer using DARR and T₁/T₂ relaxation times demonstrate that the mineral phases formed in the presence of bone proteins are more complex than bimodal. They reveal disparities in the physical properties of the mineral layers, indicate the layers in which the proteins reside and highlight the effect that each protein imparts across the mineral layers.

Rotor-synchronous π pulses applied to protons (S) enhance homonuclear polarisation transfer between two spins (I) such as ¹³C or ¹⁵N as long as at least a single I–S heteronuclear dipolar-coupling interaction exists. The enhancement is maximum when the chemical-shift difference $\mathrm{\Delta \nu }$ between two spins equals an integer multiple, n, of the pulse-modulation frequency, which is half the rotor frequency ν_r. This condition, applied in the Pulse Induced Resonance with Angular dependent Total Enhancement (PIRATE) experiment, can be generalised for any spacing of the pulses k/ν_r such that $\Delta \nu =\frac{n{\nu }_r}{2k}$ . We show, using average Hamiltonian theory (AHT) and Floquet theory, that the resonance conditions promote a second-order recoupling consisting of a cross-term between the homonuclear and heteronuclear dipolar interactions in a three-spin system. The minimum requirement is a coupling between the two I spins and a coupling of one of the I spins to the S spin. The effective Hamiltonian at the resonance conditions contains three-spin operators of the form $2I_1^{\pm }{I}_2^{\mp }{S}_z$ with a non-zero effective dipolar coupling. Theoretical analysis shows that the effective strength of the resonance conditions decreases with increasing values of k and n. The theory is backed by numerical simulations, and experimental results on fully labelled ¹³C-glycine demonstrating the efficiency of the different resonance condition for $k=\mathrm{1,2}$ at various spinning frequencies.

TensorView for MATLAB is a GUI-based visualization tool for depicting second-rank Cartesian tensors as surfaces on three-dimensional molecular models. Both ellipsoid and ovaloid tensor display formats are supported, and the software allows for easy conversion of Euler angles from common rotation schemes (active, passive, ZXZ, and ZYZ conventions) with visual feedback. In addition, the software displays all four orientation-equivalent Euler angle solutions for the placement of a single tensor in the molecular frame and can report relative orientations of two tensors with all 16 orientation-equivalent Euler angle sets that relate them. The salient relations are derived and illustrated through several examples. TensorView for MATLAB expands and complements the earlier implementation of TensorView within the Mathematica programming environment and can be run without a MATLAB license. TensorView for MATLAB is available through github at https://github.com/LeoSvenningsson/TensorViewforMatlab, and can also be accessed directly via the NMRbox resource.

We show that multidimensional solid-state NMR ¹³C–¹³C correlation spectra of biomolecular assemblies and microcrystalline organic molecules can be acquired at natural isotopic abundance with only milligram quantities of sample. These experiments combine fast Magic Angle Spinning of the sample, low-power dipolar recoupling, and dynamic nuclear polarization performed with AsymPol biradicals, a recently introduced family of polarizing agents. Such experiments are essential for structural characterization as they provide short- and long-range distance information. This approach is demonstrated on diverse sample types, including polyglutamine fibrils implicated in Huntington's disease and microcrystalline ampicillin, a small antibiotic molecule.

Hydrogen bonding plays an important role in the structure and function of a wide range of materials. Solid-state ¹H nuclear magnetic resonance (NMR) spectroscopy provides a very sensitive tool to investigate the local structure of hydrogen atoms involved in hydrogen bonding. While there is extensive ¹H solid-state NMR data on O–H - - O hydrogen bonding in solid carboxylic acids, there has been no systematic ¹H solid-state NMR studies of hydroxyl groups in carbohydrates (and hydroxyl groups in general). With a view to studying the hydrogen bonding in more complex materials such as cellulose polymorphs, we carried out a detailed solid-state ¹H NMR investigation of the model compounds α-d-glucose and α-d-glucose monohydrate. Through a combination of fast magic-angle spinning (MAS), combined rotation and multiple pulse spectroscopy (CRAMPS), and two-dimensional (2D) correlation experiments carried out at ultrahigh magnetic fields, it was possible to assign all of the aliphatic (CH), hydroxyl (OH), and water (H₂O) ¹H chemical shifts in both forms of α-d-glucose. Plane-wave DFT calculations were employed to improve the hydrogen atom positions for α-d-glucose monohydrate and to calculate ¹H chemical shifts, providing additional support for the experimentally determined peak assignments. Finally, the relationship between the hydroxyl ¹H chemical shifts and their hydrogen bonding geometry was investigated and compared to the well-established relationship for carboxylic acid protons.