Solid state nuclear magnetic resonance最新文献

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.

This study uses ³⁵Cl and ²H solid-state NMR (SSNMR) spectroscopy and dispersion-corrected plane-wave density functional theory (DFT) calculations to characterize the molecular-level structures and dynamics of hydrates of active pharmaceutical ingredients (APIs). We use ³⁵Cl SSNMR to measure the EFG tensors of the chloride ions to characterize hydrated forms of hydrochloride salts of APIs, along with two corresponding anhydrous forms. DFT calculations are used to refine the crystal structures of the APIs and determine relationships between the ³⁵Cl EFG tensors and the spatial arrangements of proximate hydrogen bonds, which are particularly influenced by interactions with water molecules. We find that the relationship between ³⁵Cl EFG tensors and local hydrogen bonding geometries is complex, but meaningful structure/property relationships can be garnered through use of DFT calculations. Specifically, for every case in which such a comparison could be made, we find that the hydrate has a smaller magnitude of C_Q than the corresponding anhydrous form, indicating a chloride ion environment with a ground-state electron density of higher spherical symmetry in the former. Finally, variable-temperature ³⁵Cl and ²H SSNMR experiments on a deuterium-exchanged sample of the API cimetidine hydrochloride monohydrate are used to monitor temperature-dependent influences on the spectra that may arise from motional influences on the ³⁵Cl and ²H EFG tensors. From the ²H SSNMR spectra, we determine that the motions of water molecules are characterized by jump-like motions about their C₂ rotational axes that occur on timescales that are unlikely to influence the ³⁵Cl central-transition (+1/2 ↔︎ −1/2) powder patterns (this is confirmed by ³⁵Cl SSNMR). Together, these methods show great promise for the future study of APIs in their bulk and dosage forms, especially variable hydrates in which crystallographic water content varies with external conditions such as humidity.

We present a theoretical and numerical description of the spin dynamics associated with TRAPDOR-HMQC (T-HMQC) experiment for a ¹H (I) – ³⁵Cl (S) spin system under fast magic angle spinning (MAS). Towards this an exact effective Hamiltonian describing the system is numerically evaluated with matrix logarithm approach. The different magnitudes of the heteronuclear and pure S terms in the effective Hamiltonian allow us to suggest a truncation approximation, which is shown to be in excellent agreement with the exact time evolution. Limitations of this approximation, especially at the rotary resonance condition, are discussed. The truncated effective Hamiltonian is further employed to monitor the buildup of various coherences during TRAPDOR irradiation. We observe and explain a functional resemblance between the magnitude of different terms in the truncated effective Hamiltonian and the amplitudes of various coherences during TRAPDOR irradiation, as function of crystallite orientation. Subsequently, the dependence of the sign (phase) of the T-HMQC signal on the coherence type generated is investigated numerically and analytically. We examine the continuous creation and evolution of various coherences at arbitrary times, i.e., at and between avoided level crossings. Behavior between consecutive crossings is described analytically and reveals ‘quadrature’ evolution of pairs of coherences and coherence interconversions. The adiabatic, sudden, and intermediate regimes for T-HMQC experiments are discussed within the approach established by A. J. Vega. Equations as well as numerical simulations suggest the existence of a driving coherence which builds up between consecutive crossings and then gets distributed at crossings among other coherences. In the intermediate regime, redistribution of the driving coherence to other coherences is almost uniform such that coherences involving S-spin double-quantum terms may be efficiently produced.