Spectral editing in solid-state MAS NMR of quadrupolar nuclei using selective satellite inversion

A sensitivity enhancement method based on selective adiabatic inversion of a satellite transition has been employed in a (pi/2)CT-(pi)ST1-(pi/2)CT spectral editing sequence to both enhance and resolve multisite NMR spectra of quadrupolar nuclei. In addition to a total enhancement of 2.5 times for spin 3/2 nuclei, enhancements up to 2.0 times is reported for the edited sites in a mixture of rubidium salts.     

Observation of hydroxyl groups by 17O solid-state multiple quantum MAS NMR in sol-gel-produced silica

17O NMR parameters (CQ, eta, delta(iso) and T1) are reported for both Si-O-Si and Si-OH fragments within a silica gel. The Si-OH units have a wide spread of parameters but are typically characterised by a very short T1 (approximately 0.1 ms) and CQ < 200 kHz. These observations have extremely important implications for the quantification of such units in these gels and related glassy materials by 17O NMR. In light of these observations, the 17O NMR experiments have been optimised and a distinct resonance from the OH group is observed in 1D static and magic angle spinning (MAS) NMR measurements as well in the multiple quantum (MQ) experiment.     

Methylene spectral editing in solid-state 13C NMR by three-spin coherence selection

A robust new solid-state nuclear magnetic resonance (NMR) method for selecting CH2 signals in magic-angle spinning (MAS) 13C NMR spectra is presented. Heteronuclear dipolar evolution for a duration of 0.043 ms, under MREV-8 homonuclear proton decoupling, converts 13C magnetization of CH2 groups into two- and three-spin coherences. The CH2 selection in the SIJ (C H H) spin system is based on the three-spin coherence S(x)I(z)J(z), which is distinguished from 13C magnetization (S(x)) by a 1H 0 degrees/90 degrees pulse consisting of two 45 degrees pulses. The two-spin coherences of the type S(y)I(z) are removed by a 13C 90 degrees x-pulse. The three-spin coherence is reconverted into magnetization during the remainder of the rotation period, still under MREV-8 decoupling. The required elimination of 13C chemical-shift precession is achieved by a prefocusing 180 degrees pulse bracketed by two rotation periods. The selection of the desired three-spin coherence has an efficiency of 13% theoretically and of 8% experimentally relative to the standard CP/MAS spectrum. However, long-range couplings also produce some three-spin coherences of methine (CH) carbons. Therefore, the length of the 13C pulse flipping the two-spin coherences is increased by 12% to slightly invert the CH signals arising from two-spin coherences and thus cancel the signal from long-range three-spin coherences. The signal intensity in this cleaner spectrum is 6% relative to the regular CP/TOSS spectrum. The only residual signal is from methyl groups, which are suppressed at least sixfold relative to the CH2 peaks. The experiment is demonstrated on cholesteryl acetate and applied to two humic acids.     

Spectral editing of 13C NMR spectra via two-dimensional pulse techniques

Two-dimensional pulse techniques for subspectral editing in ¹³C NMR spectroscopy are described. The experiments are compared with existing one-dimensional editing methods with respect to sensitivity, information content, and practical performance. In combination with a computer program for fully automatic extraction of one-dimensional edited subspectra and radiofrequency field strength information, the two-dimensional presented experiments are useful as setup experiments in ¹³C NMR.     

Proton-detected scalar coupling based assignment strategies in MAS solid-state NMR spectroscopy applied to perdeuterated proteins

Assignment of proteins in MAS (magic angle spinning) solid-state NMR relies so far on correlations among heteronuclei. This strategy is based on well dispersed resonances in the ¹⁵N dimension. In many complex cases like membrane proteins or amyloid fibrils, an additional frequency dimension is desirable in order to spread the amide resonances. We show here that proton detected HNCO, HNCA, and HNCACB type experiments can successfully be implemented in the solid-state. Coherences are sufficiently long lived to allow pulse schemes of a duration greater than 70 ms before incrementation of the first indirect dimension. The achieved resolution is comparable to the resolution obtained in solution-state NMR experiments. We demonstrate the experiments using a triply labeled sample of the SH3 domain of chicken α-spectrin, which was re-crystallized in H₂O/D₂O using a ratio of 1/9. We employ paramagnetic relaxation enhancement (PRE) using EDTA chelated Cu^II to enable rapid data acquisition.     

Spectral editing in (13)C MAS NMR under moderately fast spinning conditions

Novel procedures for the spectral assignment of peaks in high-resolution solid-state (13)C NMR are discussed and demonstrated. These methods are based on the observation that at moderate and already widely available rates of magic-angle spinning (10--14 kHz MAS), CH and CH(2) moieties behave to a large extent as if they were effectively isolated from the surrounding proton reservoir. Dipolar-based analogs of editing techniques that are commonly used in liquid-state NMR such as APT and INEPT can then be derived, while avoiding the need for periods of homonuclear (1)H--(1)H multipulse decoupling. The resulting experiments end up being very simple, essentially tuning-free, and capable of establishing unambiguous distinctions among CH, CH(2), and --C--/-CH(3) carbon sites. The principles underlying such sequences were explored using both numerical calculations and experimental measurements, and once validated their editing applications were illustrated on a number of compounds.     

Aromatic spectral editing techniques for magic-angle-spinning solid-state NMR spectroscopy of uniformly 13C-labeled proteins

The four aromatic amino acids in proteins, namely histidine, phenylalanine, tyrosine, and tryptophan, have strongly overlapping ¹³C chemical shift ranges between 100 and 160 ppm, and have so far been largely neglected in solid-state NMR determination of protein structures. Yet aromatic residues play important roles in biology through π–π and cation–π interactions. To better resolve and assign aromatic residues' ¹³C signals in magic-angle-spinning (MAS) solid-state NMR spectra, we introduce two spectral editing techniques. The first method uses gated ¹H decoupling in a proton-driven spin-diffusion (PDSD) experiment to remove all protonated ¹³C signals and retain only non-protonated carbon signals in the aromatic region of the ¹³C spectra. The second technique uses chemical shift filters and ¹H–¹³C dipolar dephasing to selectively detect the Cα, Cβ and CO cross peaks of aromatic residues while suppressing the signals of all aliphatic residues. We demonstrate these two techniques on amino acids, a model peptide, and the microcrystalline protein GB1, and show that they significantly simplify the 2D NMR spectra and both reveal and permit the ready assignment of the aromatic residues' signals.     

Atomic refinement using orientational restraints from solid-state NMR

We describe a procedure for using orientational restraints from solid-state NMR in the atomic refinement of molecular structures. Minimization of an energy function can be performed through either (or both) least-squares minimization or molecular dynamics employing simulated annealing. The energy, or penalty, function consists of terms penalizing deviation from "ideal" parameters such as covalent bond lengths and terms penalizing deviation from orientational data. Thus, the refinement strives to produce a good fit to orientational data while maintaining good stereochemistry. The software is in the form of a module for the popular refinement package CNS and is several orders of magnitude faster than previous software for refinement with orientational data. The short computer time required for refinement removes one of the difficulties in protein structure determination with solid-state NMR.     

Scalable solid-state quantum processor using subradiant two-atom states

We propose a realization of a scalable, high-performance quantum processor whose qubits are represented by the ground and subradiant states of effective dimers formed by pairs of two-level systems coupled by resonant dipole-dipole interaction. The dimers are implanted in low-temperature solid host material at controllable nanoscale separations. The two-qubit entanglement either relies on the coherent excitation exchange between the dimers or is mediated by external laser fields.     

Calculation of solid-state NMR lineshapes using contour analysis

Two new methods for calculating lineshapes in solid-state NMR spectra are described. The first method, which we refer to as semi-analytical, allows the rapid calculation of quadrupolar central-transition lineshapes in both static and magic-angle spinning cases. The second method, which is fully numerical, allows the calculation of lineshapes resulting from any combination of interactions, including quadrupolar, dipolar and chemical shift anisotropy, and is not restricted to cases in which the principal axis systems for the different interactions are aligned. Both methods are derived from consideration of the contour lines on a plot of the resonance frequency against the Euler angles, allowing the intensity of the lineshape to be calculated at each frequency. Consequently, highly accurate lineshapes can be calculated more rapidly than previously possible, since only orientations contributing to each specific frequency are considered. For our semi-analytical method, the intensity of each point in the lineshape can be directly calculated in tens of milliseconds on a standard PC. In contrast, established methods can take several hours to calculate the same lineshape.     

Resolution enhancement in MAS solid-state NMR by application of 13C homonuclear scalar decoupling during acquisition

Spectral resolution imposes a major problem on the evaluation of MAS solid-state NMR experiments as larger biomolecular systems are concerned. We show in this communication that decoupling of the (13)C-(13)C homonuclear scalar couplings during stroboscopic detection can be successfully applied to increase the spectral resolution up to a factor of 2-2.5 and sensitivity up to a factor of 1.2. We expect that this approach will be useful for the study of large biomolecular systems like membrane proteins and amyloidogenic peptides and proteins where spectral overlap is critical. The experiments are demonstrated on a uniformly (13)C,(15)N-labelled sample of Nac-Val-Leu-OH and applied to a uniformly (13)C,(15)N-enriched sample of a hexameric amyloidogenic peptide.     

13C and 15N spectral editing inside histidine imidazole ring through solid-state NMR spectroscopy

Histidine usually exists in three different forms (including biprotonated species, neutral τ and π tautomers) at physiological pH in biological systems. The different protonation and tautomerization states of histidine can be characteristically determined by ¹³C and ¹⁵N chemical shifts of imidazole ring. In this work, solid-state NMR techniques were developed for spectral editing of ¹³C and ¹⁵N sites in histidine imidazole ring, which provides a benchmark to distinguish the existing forms of histidine. The selections of ¹³C_γ, ¹³C_δ2, ¹⁵N_δ1, and ¹⁵N_ε2 sites were successfully achieved based on one-bond homo- and hetero-nuclear dipole interactions. Moreover, it was demonstrated that ¹H, ¹³C, and ¹⁵ chemical shifts were roughly linearly correlated with the corresponding atomic charge in histidine imidazole ring by theoretical calculations. Accordingly, the ¹H, ¹³C and ¹⁵N chemical shifts variation in different protonation and tautomerization states could be ascribed to the atomic charge change due to proton transfer in biological process.     

Sample restriction using magnetic field gradients in high-resolution solid-state NMR

Many solid-state NMR experiments are sensitive to inhomogeneity in the radiofrequency field. We propose a method to restrict the sample volume, in magic angle spinning experiments, using a static magnetic field gradient and a selective pulse. The position of the gradient is calculated for our experimental configuration and we have simulated the effects of selective pulses to determine the excited volume. The resulting sequences are applied to a sample of sodium acetate using frequency-switched Lee–Goldburg proton–proton homonuclear dipolar decoupling. A gain of a factor of 2 on the carbon resolution is experimentally observed.     

Line shapes of multiple quantum NMR coherences in one-dimensional quantum spin chains in solids

General formulae for intensities of multiple quantum (MQ) NMR coherences in systems of nuclear spins coupled by the dipole-dipole interactions are derived. The second moments of the MQ coherences of zero- and second orders are calculated for infinite linear chains in the approximation of the nearest neighbor interactions. Supercomputer simulations of intensities of MQ coherences of linear chains are performed at different times of preparation and evolution periods of MQ NMR experiments. The second moments obtained from the developed theory are compared with the results of the supercomputer analysis of MQ NMR dynamics. The linewidth information in MQ NMR experiments is discussed.     

Efficient heteronuclear dipolar decoupling in solid-state NMR using frequency-swept SPINAL sequences

Aiming to improve heteronuclear spin decoupling efficiency in NMR spectroscopy of solids and liquid crystals, we have modified the original Small Phase Incremental ALteration (SPINAL) sequence by incorporating a frequency sweep into it. For the resulting sequence, termed SW_f-SPINAL, the decoupling performance of a large number of sweep variants was explored by both numerical simulations and NMR experiments. It is found that introducing a frequency sweep generally increases both the ‘on-resonance’ decoupling performance and the robustness towards parameter offsets compared to the original SPINAL sequence. This validates the concept of extending the range of efficient decoupling by introducing frequency sweeps, which was recently suggested in the context of the frequency-swept SW_f-TPPM method. The sequence found to be best performing among the SW_f-SPINAL variants consists of fully swept 16 pulse pairs and is designated (32)-SPINAL-32. Its good decoupling performance for rigid spin systems is confirmed by numerical simulations and also experimentally, by evaluating the CH₂ resonance of a powder sample of l-tyrosine under MAS. For moderate MAS frequencies, the new sequence matches the decoupling achieved with SW_f-TPPM, and outperforms all other tested sequences, including TPPM and SPINAL-64. (32)-SPINAL-32 also shows excellent decoupling characteristics for liquid crystalline systems, as exemplified by experiments on the 5CB liquid crystal.     

Sample restriction using radiofrequency field selective pulses in high-resolution solid-state NMR

In this article a method is suggested for restricting a sample (spatial localization) by preparing the magnetization with a phase-modulated radiofrequency pulse which inverts magnetization only over a very narrow range of radiofrequency field strengths. This is the most efficient method, in terms of sensitivity, of restricting the sample to improve rf homogeneity. The method is demonstrated by using it to improve the resolution obtained in a homonuclear dipolar decoupling experiment.     

Spin-state selection in solid-state NMR

Spin-state selection in solid-state NMR is demonstrated, using similar pulse sequences as used in liquid-state NMR. The different transitions of all three carbon resonances in fully 13C-labeled L-alanine are separated in different spectra. By selecting spin-states, the contribution of the J-coupling to the linewidth is removed, leading to a considerable enhancement in resolution. The spin-state-selective technique is demonstrated for magic-angle spinning frequencies from 6 to 35kHz. Other experimental conditions affecting the sensitivity of the experiments are discussed. Sensitivity losses due to the introduction of the spin-state-selective filter are shown to be acceptable. Finally, spin-state selection was used to experimentally confirm the differential broadening expected for the two transitions of the CH3 resonance.     

全固态激光中的光谱合成技术

对多种全固态激光中的光谱合成技术进行了探讨和研究,包括光纤激光、Yb:YAG板条激光和半导体激光。对于光纤激光,探讨了基于单个多层介质膜（MLD）光栅、一对MLD光栅、多个体布拉格光栅三种衍射光学元件的光谱合成技术中色散造成的光束质量退化问题,指出子束光谱线型的二阶矩全宽决定了光束质量的退化量,但所允许的光谱宽度又依赖于具体的技术选择途径。进而比较了三种光谱合成方案的优缺点。对于固体激光,实验演示了基于Yb:YAG晶体的板条激光实现光谱合成的原理可行性。通过设计一个基于MLD光栅的振荡器内的光谱合成装置,实现了7束子激光最高241 W的光谱合成输出,合成后光束质量β因子约4.1,表明大功率Yb:YAG板条激光具有通过光谱合束技术实现功率进一步提升的潜力。对于半导体激光,提出并设计了大模场外腔半导体激光+快轴光谱合成的技术。实验演示了9个1 mm宽LD芯片沿快轴方向的光谱合成,用β因子评价合成后的光束质量,在慢轴方向β≈6.3,在快轴方向β≈1.6,表明快轴光谱合成造成的光束质量退化是完全可控的。