Solid state nuclear magnetic resonance最新文献

The proton-phosphorus (H–P) cross-polarization (CP) is effective in Sn(HPO₄)₂·H₂O despite of the presence of paramagnetic ion impurities. Polarization constants T_H-P and ¹H T_1ρ times are measured in static Sn(HPO₄)₂·H₂O by the kinetic variable-temperature H–P CP experiments. The temperature dependence of the ¹H T_1ρ times is interpreted in terms of proton movements in the interlayer space occurring between the phosphate groups without participation of the water molecules. The process requires an activation energy of 8.7 ± 0.7 kcal/mol. The MAS effect on the ¹H T_1ρ times is shown and discussed.

High-resolution low-field nuclear magnetic resonance (NMR) spectroscopy has found wide application for characterization of liquid compounds because of the low maintenance cost of modern permanent magnets. Solid-state NMR so far is limited to low-resolution measurements of static powders, because of the limited space available in this type of magnet. Magic-angle sample spinning and low-magnetic fields are an attractive combination to achieve high spectral resolution especially for paramagnetic solids. Here we show that magic angle spinning modules can be miniaturized using 3D printing techniques so that high-resolution solid-state NMR in permanent magnets becomes possible. The suggested conical rotor design was developed using finite element calculations and provides sample spinning frequencies higher than 20 kHz. The setup was tested on various diamagnetic and paramagnetic compounds including paramagnetic battery materials. The only comparable experiments in low-cost magnets known so far, had been done in the early times of magic angle spinning using electromagnets at much lower sample spinning frequency. Our results demonstrate that high-resolution low-field magic-angle-spinning NMR does not require expensive superconducting magnets and that high-resolution solid-state NMR spectra of paramagnetic compounds are feasible. Generally, this could introduce low-field solid-state NMR for abundant nuclei standard as a routine analytical tool.

The study of a layered crystalline Sn(IV) phosphate by solid-state NMR has demonstrated that the ³¹P T₁ relaxation of phosphate groups, dependent on spinning rate is completely controlled by the limited spin diffusion to paramagnetic ions found by EPR. The spin-diffusion constant, D(SD), was estimated as 2.04 10⁻¹⁴ cm²s⁻¹. The conclusion was supported by the ³¹P T₁ time measurements in zirconium phosphate 1–1, also showing paramagnetic ions and in diamagnetic compound (NH₄)₂HPO₄.

Characterizing ion adsorption and diffusion in porous carbons is essential to understand the performance of such materials in a range of key technologies such as energy storage and capacitive deionisation. Nuclear Magnetic Resonance (NMR) spectroscopy is a powerful technique to get insights in these systems thanks to its ability to distinguish between bulk and adsorbed species and to its sensitivity to dynamic phenomena. Nevertheless, a clear interpretation of the experimental results is sometimes rendered difficult by the various factors affecting NMR spectra. A mesoscopic model to predict NMR spectra of ions diffusing in carbon particles is adapted to include dynamic exchange between the intra-particle space and the bulk electrolyte surrounding the particle. A systematic study of the particle size effect on the NMR spectra for different distributions of magnetic environments in the porous carbons is conducted. The model demonstrates the importance of considering a range of magnetic environments, instead of a single chemical shift value corresponding to adsorbed species, and of including a range of exchange rates (between in and out of the particle), instead of a single timescale, to predict realistic NMR spectra. Depending on the pore size distribution of the carbon particle and the ratio between bulk and adsorbed species, both the NMR linewidth and peak positions can be largely influenced by the particle size.

The mutual orientation of nuclear spin interaction tensors provides critical information on the conformation and arrangement of molecules in chemicals, materials, and biological systems at an atomic level. Proton is a ubiquitous and important element in a variety of substances, and its NMR is highly sensitive due to their virtually 100% natural abundance and large gyromagnetic ratio. Nevertheless, the measurement of mutual orientation between the ¹H CSA tensors has remained largely untouched in the past due to strong ¹H–¹H homonuclear interactions in a dense network of protons. In this study, we have developed a proton-detected 3D ¹H CSA/¹H CSA/¹H CS correlation method that utilizes three techniques to manage homonuclear interactions, namely fast magic-angle spinning, windowless C-symmetry-based CSA recoupling (windowless-ROCSA), and a band-selective ¹H–¹H polarization transfer. The asymmetric ¹H CSA/¹H CSA correlated powder patterns produced by the C-symmetry-based methods are highly sensitive to the sign and asymmetry parameter of the ¹H CSA, and the Euler angle β as compared to the symmetric pattern obtained by the existing γ-encoded R-symmetry-based CSA/CSA correlation methods and allows a larger spectral area for data fitting. These features are beneficial for determining the mutual orientation between the nuclear spin interaction tensors with improved accuracy.

A novel deuterium-excited and proton-detected quadruple-resonance three-dimensional (3D) ²H_αc_αNH MAS nuclear magnetic resonance (NMR) method is presented to obtain site-specific ²H_α deuterium quadrupolar couplings from protein backbone, as an extension to the 2D version of the experiment reported earlier. Proton-detection results in high sensitivity compared to the heteronuclei detection methods. Utilizing four independent radiofrequency (RF) channels (quadruple-resonance), we managed to excite the ²H_α, then transfer deuterium polarization to its attached C_α, followed by polarization transfers to the neighboring backbone nitrogen and then to the amide proton for detection. This experiment results in an easy to interpret HSQC-like 2D ¹H–¹⁵N fingerprint NMR spectrum, which contains site-specific deuterium quadrupolar patterns in the indirect third dimension. Provided that four-channel NMR probe technology is available, the setup of the ²H_αc_αNH experiment is relatively straightforward, by using low power deuterium excitation and polarization transfer schemes we have been developing. To our knowledge, this is the first demonstration of a quadruple-resonance MAS NMR experiment to link ²H_α quadrupolar couplings to proton-detection, extending our previous triple-resonance demonstrations. Distortion-free excitation and polarization transfer of ∼160–170 kHz ²H_α quadrupolar coupling were presented by using a deuterium RF strength of ∼20 kHz. From these ²H_α patterns, an average backbone order parameter of S = 0.92 was determined on a deuterated SH3 sample, with an average η = 0.22. These indicate that SH3 backbone represents sizable dynamics in the microsecond timescale where the ²H_α lineshape is sensitive. Moreover, site-specific ²H_α T₁ relaxation times were obtained for a proof of concept. This 3D ²H_αc_αNH NMR experiment has the potential to determine structure and dynamics of perdeuterated proteins by utilizing deuterium as a novel reporter.

We show that the temporal magnetic field distortion generated by the Cold Head operation can be removed and high quality Solid-State Magic Angle Spinning NMR results can be obtained with a cryogen-free magnet. The compact design of the cryogen-free magnets allows for the probe to be inserted either from the bottom (as in most NMR systems) or, more conveniently, from the top. The magnetic field settling time can be made as short as an hour after a field ramp. Therefore, a single cryogen-free magnet can be used at different fixed fields. The magnetic field can be changed every day without compromising the measurement resolution.