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The so-called t 1 noise, which arises due to random instabilities in the spectrometer hardware, remains the primary source of noise that limits the sensitivity of most 2D NMR experiments, particularly in the expanding group of solid-state NMR methods that utilize dipolar-recoupling. In this communication we revisit the relationship between the signal intensity and the t 1 noise produced. It is shown that since the latter scales linearly with the signal strength, the use of a conventional relaxation delay of 1.3T 1 may prove far from optimal. In cases where the fluctuations occur on a shorter timescale than the recycle delay, a considerably faster repetition rate should be used to maximize the time sensitivity in a 2D experiment than what is used to maximize the sensitivity in 1D. This is demonstrated with the acquisition of 1 H{ 13 C} Dipolar-mediated Heteronuclear Multiple-Quantum Correlation (D-HMQC) type spectra in which the sensitivity could be nearly doubled by choosing a very short relaxation delay corresponding to 0.2T 1 ., (Published by Elsevier Inc.)

Heavy spin-1/2 nuclides are known to possess very large chemical shift anisotropies that can challenge even the most advanced magic-angle-spinning (MAS) techniques. Wide manifolds of overlapping spinning sidebands and insufficient excitation bandwidths often obfuscate meaningful spectral information and force the use of static, low-resolution solid-state (SS)NMR methods for the characterization of materials. To address these issues, we have merged fast-magic-angle-turning (MAT) and dipolar heteronuclear multiple-quantum coherence (D-HMQC) experiments to obtain D-HMQC-MAT pulse sequences which enable the rapid acquisition of 2D SSNMR spectra that correlate isotropic 1 H chemical shifts to the indirectly detected isotropic "infinite-MAS" spectra of heavy spin-1/2 nuclides. For these nuclides, the combination of fast MAS and 1 H detection provides a high sensitivity, which rivals the DNP-enhanced ultra-wideline SSNMR. The new pulse sequences were used to determine the Pt coordination environments in a complex mixture of decomposition products of transplatin and in a metal-organic framework with Pt ions coordinated to the linker ligands., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Simulations performed on model, static, samples have shown that the microwave power is non-uniformly distributed in the magic angle spinning (MAS) rotor when using conventional dynamic nuclear polarization (DNP) instrumentation. Here, we applied the stray-field magic angle spinning imaging (STRAFI-MAS) experiment to generate a spatial map of the DNP enhancements in a full rotor, which is spun at a low rate in a commercial DNP-MAS NMR system. Notably, we observed that the enhancement factors produced in the center of the rotor can be twice as large as those produced at the top of the rotor. Surprisingly, we observed that the largest enhancement factors are observed along the axis of the rotor as opposed to against its walls, which are most directly irradiated by the microwave beam. We lastly observed that the distribution of enhancement factors can be moderately improved by degassing the sample and increasing the microwave power. The inclusion of dielectric particles greatly amplifies the enhancement factors throughout the rotor. The STRAFI-MAS approach can provide useful guidance for optimizing the access of microwave power to the sample, and thereby lead to further increases in sensitivity of DNP-MAS NMR., (Published by Elsevier Inc.)

A simple method is shown for optimization of (1)H homonuclear dipolar decoupling at MAS rates exceeding 10 kHz. By monitoring the intensity of a spin-echo under the decoupling conditions, it is possible to optimize the amplitude of the RF magnetic field, the cycle time of the decoupling sequence and the resonance offset within minutes. As a result, the decoupling efficiency can be quickly and reliably fine-tuned without using a reference sample. The utility of this method has been confirmed by studying the resolution patterns for the supercycled PMLG scheme, which were found to be in excellent agreement with earlier theoretical predictions and verified in high-resolution 2D (1)H-(1)H experiments., (Copyright (c) 2009 Elsevier Inc. All rights reserved.)

Two-dimensional through-bond (1)H{(13)C} solid-state NMR experiments utilizing fast magic angle spinning (MAS) and homonuclear multipulse (1)H decoupling are presented. Remarkable efficiency of polarization transfer can be achieved at MAS rates exceeding 40 kHz, which is instrumental in these measurements. Schemes utilizing direct and indirect detection of heteronuclei are compared in terms of resolution and sensitivity. A simple procedure for optimization of (1)H homonuclear decoupling sequences under these conditions is proposed. The capabilities of these techniques were confirmed on two naturally abundant solids, tripeptide N-formyl-L-methionyl-L-leucyl-L-phenylalanine (f-MLF-OH) and brown coal.

Indirectly detected, through-bond NMR correlation spectra between (13)C and (1)H nuclei are reported for the first time in solid state. The capabilities of the new method are demonstrated using naturally abundant organic-inorganic mesoporous hybrid materials. The time performance is significantly better, almost by a factor of 10, than in the corresponding (13)C detected experiment. The proposed scheme represents a new analytical tool for studying other solid-state systems and the basis for the development of more advanced 2D and 3D correlation methods.

A remarkable enhancement of sensitivity can be often achieved in 29Si solid-state NMR by applying the well-known Carr-Purcell-Meiboom-Gill (CPMG) train of rotor-synchronized pi pulses during the detection of silicon magnetization. Here, several one- and two-dimensional (1D and 2D) techniques are used to demonstrate the capabilities of this approach. Examples include 1D 29Si{X} CPMAS spectra and 2D 29Si{X} HETCOR spectra of mesoporous silicas, zeolites and minerals, where X=1H or 27Al. Data processing methods, experimental strategies and sensitivity limits are discussed and illustrated by experiments. The mechanisms of transverse dephasing of 29Si nuclei in solids are analyzed. Fast magic angle spinning, at rates between 25 and 40 kHz, is instrumental in achieving the highest sensitivity gain in some of these experiments. In the case of 29Si-29Si double-quantum techniques, CPMG detection can be exploited to measure homonuclear J-couplings.

Hetero-nuclear coherence transfers in HMQC and refocused-INEPT experiments involving half-integer quadrupolar nuclei in solids are analyzed. 1D and 2D schemes are considered under MAS for the general case of multi-spin systems SI(n) (n4), where S is an observed nucleus. These results are also discussed in the context of high-resolution schemes featuring MQMAS or STMAS. The theoretical predictions are verified experimentally in a series of 1D and 2D experiments performed at 9.4 and 18.8T.

A systematic experimental and numerical evaluation of several basic approaches to multiple-quantum magic angle spinning (MQMAS) NMR is presented for spin-32 nuclei. The approaches use identical MQ excitation, via a single RF pulse of high power, and three types of methods for conversion to observable coherence: (a) nutation by strong continuous wave pulse; (b) rotation-induced adiabatic coherence transfer (RIACT), and (c) fast amplitude modulation (FAM-1). The optimization strategies and maximum achievable MQMAS efficiencies of (87)Rb in RbNO(3) and LiRbSO(4) are investigated using several coherence transfer schemes under a wide range of experimental parameters. These parameters include the strength of the RF magnetic field nu(RF), the sample rotation speed nu(R), the length of the conversion period, and the modulation frequency in FAM-1. The data provide new insights into the spin dynamics involved in these techniques and the experimental guidelines for achieving the best sensitivity. The RF requirements for maximum efficiency of conversion depend on the method to be used. In general, FAM-1 performs better than the nutation and RIACT methods in terms of efficiency and off-resonance behavior, especially when nu(RF) is small compared to the quadrupole frequency nu(Q). The experiments performed using nutation, RIACT, and FAM-1 methods yield similar resolution in the isotropic dimension, regardless of nu(RF)., (Copyright 2000 Academic Press.)

It is known that the patterns of spinning sidebands observed in the multiple-quantum dimension of MQMAS spectra are often significantly wider than expected from the anisotropies of relevant interactions. It has been recently shown by others that these sidebands are generated due to the rotor-driven reorientations that the quadrupole tensors of the crystallites undergo during the evolution period between the multiple- and single-quantum conversion processes. We present an experimental and theoretical study of the effects of the spinning speed nuR and RF field strength nuRF on the development of these sideband patterns. The theoretical analysis relies upon numerical simulations and includes propagation of the density matrix during the entire MQMAS experiment. The possibility of additional rotational encoding during the RF pulses is discussed. Both the theoretical and experimental results show the benefits of using the highest available nuR and nuRF. Copyright 1998 Academic Press.