Solid state nuclear magnetic resonance最新文献

Environmental science is an interdisciplinary field, which integrates chemical, physical, and biological sciences to study environmental problems and human impact on the environment. This article highlights the use of solid-state NMR spectroscopy (SSNMR) in studies of environmental processes and remediation with examples from both laboratory studies and samples collected in the field. The contemporary topics presented include soil chemistry, environmental remediation (e.g., heavy metals and radionuclides removal, carbon dioxide mineralization), and phosphorus recovery. SSNMR is a powerful technique, which provides atomic-level information about speciation in complex environmental samples as well as the interactions between pollutants and minerals/organic matter on different environmental interfaces. The challenges in the application of SSNMR in environmental science (e.g., measurement of paramagnetic nuclei and low-gamma nuclei) are also discussed, and perspectives are provided for the future research efforts.

The paper describes development of the detailed structure and circuit diagrams of the continuous wave NQR temperature sensor with increased conversion linearity. It is experimentally established that at amplitude modulation of 40% and change of input voltage in the range of 20–1000 ​mV, the circuit of a symmetric marginal oscillator with a linear active demodulator provides better linearity of transfer characteristic than the circuits of asymmetric marginal oscillators with JFET or diode detectors. As a thermometric substance of the proposed NQR sensor, copper oxide Cu₂O was used, which is characterized by a strong temperature dependence of the resonance frequency of ⁶³Cu NQR. In contrast to ³⁵Cl NQR in KClO₃, for cuprous oxide the temperature dependence of ⁶³Сu NQR frequency in the frequency range 26.621–25.658 ​MHz is linear in the temperature range 100–390 ​K. It is experimentally confirmed that the use of a low mass sample (less than 200 ​mg) as a thermometric substance of the proposed NQR sensor is quite sufficient for successfully observation of the resonance line at the SNR equal to 9.1 ​dB.

We present an algorithm suitable for automatically correcting rolling baseline coming from time-domain truncation induced by the dead time in pulse-acquire one-dimensional MAS NMR spectra. It relies on an iterative estimation of the baseline restricted in the time-domain by the dead time duration combined with a histogram filter allowing adaptive selection of the baseline points. This method does not make any assumption regarding the NMR resonances line shapes or widths and does not modify the acquired free induction decay points. This makes it suitable for accurate deconvolution and quantification of single-pulse MAS NMR spectra. The baseline correction accuracy is evaluated on synthetic solid-state spectra of ¹⁹F, ⁷¹Ga, and ²³Na by comparing the fitted baseline to the theoretical one. The versatility of the algorithm is also exemplified on three additional solid-state spectra of ²³Na and ⁷¹Ga. The algorithm is made available to the community through a user-friendly standalone Matlab® application.

We report the ¹H $T_1$ dispersion curve between 0 and 5 ​MHz for the synthetic opioid fentanyl citrate (C₂₈H₃₆N₂O₈). The structures in the curve can be used to estimate the ¹⁴N nuclear quadrupole resonance (NQR) frequencies of the material. Density functional theory predictions of the NQR parameters of several fentanyl citrate compounds are also reported. The predictions for the aniline nitrogen are consistent with structures in the observed $T_1$ data. To help interpret the fentanyl citrate results the $T_1$ dispersion curve for the explosive ammonium nitrate is also presented.

We present an approach towards the in situ solid state NMR monitoring of mechanochemical reactions in a ball mill. A miniaturized vibration ball mill is integrated into the measuring coil of a home-built solid state NMR probe, allowing for static solid state NMR measurements during the mechanochemical reaction within the vessel. The setup allows to quantitatively follow the product evolution of a prototypical mechanochemical reaction, the formation of zinc phenylphosphonate from zinc acetate and phenylphosphonic acid. MAS NMR investigations on the final reaction mixture confirmed a reaction yield of 89% in a typical example. Thus, NMR spectroscopy may in the future provide complementary information about reaction mechanisms of mechanochemical reactions and team up with other analytical methods which have been employed to follow reactions in situ, such as Raman spectroscopy or X-ray diffraction.

We propose a fast algorithm to energise a cryogen free magnet to a highly persistent state. A decay rate as low as 0.021 ​ppm/h can be achieved in less than an hour after reaching the target field. The decay rate drops further to 0.0004 ​ppm/h in the following 48 ​h. This procedure can be applied at different values of target field, which makes it feasible to use a single magnet for study of various NMR lines at different fields. The mechanism of establishing a highly stable magnetic field can be understood on the basis of the magnetic properties of the superconducting wire, which were studied using a vibrating sample magnetometer. The results confirm the high quality of the superconducting wire and joints.

Dynamic nuclear polarization (DNP) and indirect detection are two commonly applied approaches for enhancing the sensitivity of solid-state NMR spectroscopy. However, their use in tandem has not yet been investigated. With the advent of low-temperature fast magic angle spinning (MAS) probes with 1.3-mm diameter rotors capable of MAS at 40 ​kHz it becomes feasible to combine these two techniques. In this study, we performed DNP-enhanced 2D indirectly detected heteronuclear correlation (idHETCOR) experiments on ¹³C, ¹⁵N, ¹¹³Cd and ⁸⁹Y nuclei in functionalized mesoporous silica, CdS nanoparticles, and Y₂O₃ nanoparticles. The sensitivity of the 2D idHETCOR experiments was compared with those of DNP-enhanced directly-detected 1D cross polarization (CP) and 2D HETCOR experiments performed with a standard 3.2-mm rotor. Due to low CP polarization transfer efficiencies and large proton linewidth, the sensitivity gains achieved by indirect detection alone were lower than in conventional (non-DNP) experiments. Nevertheless, despite the smaller sample volume the 2D idHETCOR experiments showed better absolute sensitivities than 2D HETCOR experiments for nuclei with the lowest gyromagnetic ratios. For ⁸⁹Y, 2D idHETCOR provided 8.2 times better sensitivity than the 1 D⁸⁹Y-detected CP experiment performed with a 3.2-mm rotor.

Many interesting solid-state targets for biological research do not form crystalline structures; these materials include intrinsically disordered proteins, plant biopolymer composites, cell-wall polysaccharides, and soil organic matter. The absence of aligned repeating structural elements and atomic-level rigidity presents hurdles to achieving structural elucidation and obtaining functional insights. We describe strategies for adapting several solid-state NMR methods to determine the molecular structures and compositions of these amorphous biosolids.

The main spectroscopic problems in studying amorphous structures by NMR are over/under-sampling of the spin signals and spectral complexity. These problems arise in part because amorphous biosolids typically contain a mix of rigid and mobile domains, making it difficult to select a single experiment or set of acquisition conditions that fairly represents all nuclear spins in a carbon-based organic sample. These issues can be addressed by running hybrid experiments, such as using direct excitation alongside cross polarization-based methods, to develop a more holistic picture of the macromolecular system. In situations of spectral crowding or overlap, the structural elucidation strategy can be further assisted by coupling ¹³C spins to nuclei such as ¹⁵N, filtering out portions of the spectrum, highlighting individual moieties of interest, and adding a second or third spectral dimension to an NMR experiment in order to spread out the resonances and link them pairwise through space or through bonds. We discuss practical aspects and illustrations from the recent literature for 1D experiments that use cross or direct polarization and both homo- and heteronuclear 2D and 3D solid-state NMR experiments.

Experimental and theoretical investigations of indium-115 electric-field-gradient (EFG) tensors of indium(III) oxide, In₂O₃, have been presented. Field-stepwise-swept QCPMG solid-state ¹¹⁵In NMR experiments are carried out at T ​= ​120 ​K, observed at 52.695 ​MHz, and in the range of external magnetic fields between 4.0 and 6.5 ​T. The spectral simulations yield the quadrupolar coupling constant, C_Q value, of 183(2) MHz and the asymmetry parameter, η_Q, of 0.05(5), for In(1), and that of 126(2) MHz and η_Q of 0.86(5) for In(2). Quantum chemical calculations are carried out to provide ¹¹⁵In EFG tensor orientations with respect to the molecular structure. A relationship between operative frequencies and variable ranges of external magnetic fields is briefly discussed for field-swept solid-state ¹¹⁵In NMR.