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Techniques for enhancing the signals arising from low-γ, insensitive (I) nuclei are central to solid-state nuclear magnetic resonance. One of the leading and best-established methods to sensitize these unreceptive species is Hartmann–Hahn cross polarization (HH-CP), a polarization transfer mechanism often executed under MAS. Herein, we explore the possibility of utilizing the 1H dipolar order created via adiabatic demagnetization in the rotating frame (ADRF), to enhance the unreceptive spins under MAS. It is found that an efficient polarization transfer via ADRF-CPMAS is not only possible but can exceed, at least in some instances involving plastic crystals, the efficiency of an optimized HH-CPMAS transfer. The experiment requires low radiofrequency nutation fields on both the 1H- and the I-spin channels, and displays unusual matching conditions that are reminiscent of the zero- and double-quantum matching conditions arising under CPMAS, albeit centered at zero frequency and demanding the simultaneous involvement of several spins. The origin of these multi-spin transfer processes is analytically derived and numerically simulated in predictions that compare well with experimental 13C and 15N results collected on model compounds at different spinning speeds. These derivations start from descriptions that depart from traditional thermodynamic arguments, and treat instead the ADRF processes in static and spinning solids on the basis of coherent evolutions. The predictions of these analytical derivations are corroborated by numerical simulations. The effects of additional factors, including chemical shift anisotropies, J-couplings, and radiofrequency inhomogeneities, are also theoretically and experimentally explored. [ABSTRACT FROM AUTHOR]

Living systems rely on molecular building blocks with low structural symmetry. Therefore, constituent amino acids and nucleotides yield short-lived nuclear magnetic responses to electromagnetic radiation. Magnetic signals are at the basis of molecular imaging, structure determination and interaction studies. In solution state, as the molecular weight of analytes increases, coherences with long lifetimes are needed to yield advantageous through-space magnetisation transfers. Interactions between magnetic nuclei can only be detected provided the lifetimes of spin order are sufficient. In J-coupled pairs of nuclei, long-lived coherences (LLC's) connect states with different spin-permutation symmetry. Here in, we show sustained LLC's in protein Lysozyme, weighing 14.3 kDa, with lifetimes twice as long as those of classical magnetisation for the aliphatic protons of glycine residues. We found for the first time that, in a protein of significant molecular weight, LLC's yield substantial through-space magnetisation transfers: spin-order transfer stemming from LLC's overcame transfers from classical coherences by factors > 2. Furthermore, in agreement with theory, the permutation symmetry of LLC-based transfers allows mapping interacting atoms in the protein structure with respect to the molecular plane of glycine residues in a stereospecific manner. These findings can extend the scope of liquid-state high-resolution biomolecular spectroscopy. Solution NMR spectroscopy provides rich structural information on biomolecules, however, its resolution becomes limited when molecular size increases, due to short-lived nuclear magnetic responses to electromagnetic radiation. Here, the authors sustain long-lived coherences for the aliphatic protons of glycine residues within protein lysozyme, yielding substantial through-space magnetization transfers, and mapping interacting atoms in the protein structure. [ABSTRACT FROM AUTHOR]

A new scheme for the excitation of spins according to the joint values of their heteronuclear or homonuclear J couplings and of their chemical shifts, is proposed and demonstrated. The principles of the new pulses involved derive from those employed in NMR imaging for exciting arbitrary 2D spatial shapes, using so-called 'multidimensional' RF pulses. It is shown that if recast in a suitable spectroscopic framework, the distinction that π-pulses enable to establish between linear and bilinear interactions, support the selective excitation of coherences possessing arbitrary combinations of chemical shift and J-coupling values - a flexibility akin to that provided by a 2D J-resolved NMR spectrum. Details on the execution of the resulting 2D 'J-shift' RF pulses are given, and examples where excitation only addresses spins with particular chemical shift offsets fulfilling specific J-coupling displacements, are demonstrated. Additional instances where such pulses could be applied, as well as main limitations of this new approach, are briefly discussed. [ABSTRACT FROM AUTHOR]

Recent years have witnessed efforts geared at increasing the sensitivity of NMR experiments, by relying on the suitable tailoring and exploitation of relaxation phenomena. These efforts have included the use of paramagnetic agents, enhanced 1H-1H incoherent and coherent transfers processes in 2D liquid state spectroscopy, and homonuclear 13C-13C spin diffusion effects in labeled solids. The present study examines some of the opportunities that could open when exploiting spontaneous 1H-1H spin-diffusion processes, to enhance relaxation and to improve the sensitivity of dilute nuclei in solid state NMR measurements. It is shown that polarization transfer experiments executed under sufficiently fast magic-angle-spinning conditions, enable a selective polarization of the dilute low-γ spins by their immediate neighboring protons. Repolarization of the latter can then occur during the time involved in monitoring the signal emitted by the low-γ nuclei. The basic features involved in the resulting approach, and its potential to improve the effective sensitivity of solid state NMR measurements on dilute nuclei, are analyzed. Experimental tests witness the advantages that could reside from utilizing this kind of approach over conventional cross-polarization processes. These measurements also highlight a number of limitations that will have to be overcome for transforming selective polarization transfers of this kind into analytical methods of choice. [ABSTRACT FROM AUTHOR]

Line narrowing has been traditionally achieved in solid-state 1H NMR spectroscopy by applying pulse sequences that combine multiple-pulse operations with magic-angle spinning (MAS), to effectively average out the dipoledipole homonuclear Hamiltonian. The present study explores a new alternative that departs from the usual concept of directly acting on the strongly coupled spins with radiofrequency pulses; instead, we seek to achieve a net homonuclear dipolar decoupling in solids by exploring the reintroduction of MAS-averaged heteronuclear dipolar couplings between the 1H nuclei and directly bonded 13C or 15N nuclei. This recouplinganti-recoupling (RaR) scheme thus relies on the recoupling of the dipolar interaction with heteronuclear spins, which, under fast MAS, will exceed the strength and will not commute with the homonuclear 1H1H coupling one is intending to average out. Subsequent removal ('antiRecoupling') of these heteronuclear interactions can lead to narrowed 1H resonances, without ever pulsing on the aforementioned channel. The line-narrowing properties of RaR are illustrated with numerical simulations and with experiments on model organic solids. [ABSTRACT FROM AUTHOR]

Nitrogen is an element of utmost importance in chemistry, biology and materials science. Of its two NMR-active isotopes, 14N and 15N, solid-state NMR (SSNMR) experiments are rarely conducted upon the former, due to its low gyromagnetic ratio ( γ) and broad powder patterns arising from first-order quadrupolar interactions. In this work, we propose a methodology for the rapid acquisition of high quality 14N SSNMR spectra that is easy to implement, and can be used for a variety of nitrogen-containing systems. We demonstrate that it is possible to dramatically enhance 14N NMR signals in spectra of stationary, polycrystalline samples (i.e., amino acids and active pharmaceutical ingredients) by means of broadband cross polarization (CP) from abundant nuclei (e.g., 1H). The BRoadband Adiabatic INversion Cross- Polarization ( BRAIN-CP) pulse sequence is combined with other elements for efficient acquisition of ultra-wideline SSNMR spectra, including Wideband Uniform- Rate Smooth- Truncation ( WURST) pulses for broadband refocusing, Carr- Purcell Meiboom- Gill ( CPMG) echo trains for T2-driven S/N enhancement, and frequency-stepped acquisitions. The feasibility of utilizing the BRAIN-CP/WURST-CPMG sequence is tested for 14N, with special consideration given to (i) spin-locking integer spin nuclei and maintaining adiabatic polarization transfer, and (ii) the effects of broadband polarization transfer on the overlapping satellite transition patterns. The BRAIN-CP experiments are shown to provide increases in signal-to-noise ranging from four to ten times and reductions of experimental times from one to two orders of magnitude compared to analogous experiments where 14N nuclei are directly excited. Furthermore, patterns acquired with this method are generally more uniform than those acquired with direct excitation methods. We also discuss the proposed method and its potential for probing a variety of chemically distinct nitrogen environments. [ABSTRACT FROM AUTHOR]

A scheme enabling the complete sampling of multidimensional NMR domains within a single continuous acquisition is introduced and exemplified. Provided that an analyte's signal is sufficiently strong, the acquisition time of multidimensional NMR experiments can thus be shortened by orders of magnitude. This could enable the characterization of transient events such as proteins folding, 2D NMR experiments on samples being chromatographed, bring the duration of higher dimensional experiments (e.g., 4D NMR) into the lifetime of most proteins under physiological conditions, and facilitate the incorporation of spectroscopic 2D sequences into in vivo imaging investigations. The protocol is compatible with existing multidimensional pulse sequences and can be implemented by using conventional hardware; its performance is exemplified here with a variety of homonuclear 2D NMR acquisitions. [ABSTRACT FROM AUTHOR]

Recent interest has focused on solid-state NMR experiments which excite multiple-quantum (MQ) coherences in the presence of magic-angle spinning (MAS). Such experiments have been applied to both dipolar-coupled spin I 1/2 and half-integer quadrupolar systems. A feature common to both cases is the observation of interesting spinning sideband patterns in the indirect (MQ) dimension. In this paper, the origin of these patterns is reviewed in terms of two distinct mechanisms: first, rotor encoding of the dipolar or quadrupolar interaction caused by the change in the Hamiltonian active during the MQ reconversion period relative to the excitation period (reconversion rotor encoding, RRE); and, second, rotor modulation of the interaction during the evolution of the MQ coherences in the t1 dimension (evolution rotor modulation, ERM). Only the first mechanism is present for total spin coherences, while for lower-order MQ coherences both mechanisms contribute to the pattern. For dipolar and quadrupolar model systems, i.e., the three protons of a methyl group and quadrupolar nuclei with spin I 3/2 and I 5/2 and axially symmetric first-order quadrupolar interactions, analytical expressions are derived for all orders of MQ MAS signals. Simulations based on these analytical expressions and numerical density matrix simulations are compared with experimental spectra. Additional perturbing influences, such as the heteronuclear dipolar coupling between a quadrupolar and a spin I 1/2 nucleus, are taken into account. The effect of dipolar couplings on a quadrupolar MQ spectrum is found to be enhanced by the order of the observed MQ coherence. [ABSTRACT FROM AUTHOR]