Two-dimensional NMR correlations of liquid crystals using switched angle spinning

We present the first application of switched angle spinning (SAS) to correlate the first-order dipolar spectrum of a liquid crystalline sample with the isotropic magic angle spinning (MAS) spectrum in a two-dimensional experiment. In this experiment we are able to select the degree of dipolar couplings introduced via mechanical manipulations of the liquid crystal director in a single oriented sample. The (19)F SAS-COSY correlation of iodotrifluoroethylene, an AMX spin system, dissolved in the nematic liquid crystal 4-octylphenyl-2-chloro-4-(4-heptylbenzoyloxy)-benzoate provides assignment of both the J and dipolar couplings in a single experiment. This work demonstrates the use of oriented samples and sample spinning to resolve homonuclear dipolar couplings using isotropic chemical shifts.     

1H–13C hetero-nuclear dipole–dipole couplings of methyl groups in stationary and magic angle spinning solid-state NMR experiments of peptides and proteins

¹³C NMR of isotopically labeled methyl groups has the potential to combine spectroscopic simplicity with ease of labeling for protein NMR studies. However, in most high resolution separated local field experiments, such as polarization inversion spin exchange at the magic angle (PISEMA), that are used to measure ¹H–¹³C hetero-nuclear dipolar couplings, the four-spin system of the methyl group presents complications. In this study, the properties of the ¹H–¹³C hetero-nuclear dipolar interactions of ¹³C-labeled methyl groups are revealed through solid-state NMR experiments on a range of samples, including single crystals, stationary powders, and magic angle spinning of powders, of ¹³C₃ labeled alanine alone and incorporated into a protein. The spectral simplifications resulting from proton detected local field (PDLF) experiments are shown to enhance resolution and simplify the interpretation of results on single crystals, magnetically aligned samples, and powders. The complementarity of stationary sample and magic angle spinning (MAS) measurements of dipolar couplings is demonstrated by applying polarization inversion spin exchange at the magic angle and magic angle spinning (PISEMAMAS) to unoriented samples.     

Variable angle NMR spectroscopy and its application to the measurement of residual chemical shift anisotropy

The successful measurement of anisotropic NMR parameters like residual dipolar couplings (RDCs), residual quadrupolar couplings (RQCs), or residual chemical shift anisotropy (RCSA) involves the partial alignment of solute molecules in an alignment medium. To avoid any influence of the change of environment from the isotropic to the anisotropic sample, the measurement of both datasets with a single sample is highly desirable. Here, we introduce the scaling of alignment for mechanically stretched polymer gels by varying the angle of the director of alignment relative to the static magnetic field, which we call variable angle NMR spectroscopy (VA-NMR). The technique is closely related to variable angle sample spinning NMR spectroscopy (VASS-NMR) of liquid crystalline samples, but due to the mechanical fixation of the director of alignment no sample spinning is necessary. Also, in contrast to VASS-NMR, VA-NMR works for the full range of sample inclinations between 0° and 90°. Isotropic spectra are obtained at the magic angle. As a demonstration of the approach we measure 13C-RCSA values for strychnine in a stretched PDMS/CDCl? gel and show their usefulness for assignment purposes. In this context special care has been taken with respect to the exact calibration of chemical shift data, for which three approaches have been derived and tested.     

Coherence transfer between spy nuclei and nitrogen-14 in solids

Coherence transfer from 'spy nuclei' such as (1)H or (13)C (S=1/2) was used to excite single- or double-quantum coherences of (14)N nuclei (I=1) while the S spins were aligned along the static field, in the manner of heteronuclear single-quantum correlation (HSQC) spectroscopy. For samples spinning at the magic angle, coherence transfer can be achieved through a combination of scalar couplings J(I,S) and second-order quadrupole-dipole cross-terms, also known as residual dipolar splittings (RDS). The second-order quadrupolar powder patterns in the two-dimensional spectra allow one to determine the quadrupolar parameters of (14)N in amino acids.     

Distribution effects on 1H double-quantum MAS NMR spectra

The effect of a distribution in the (1)H-(1)H dipolar coupling on (1)H double-quantum (DQ) magic angle spinning (MAS) nuclear magnetic resonance (NMR) spinning sideband patterns is considered. In disordered or amorphous materials a distribution in the magnitude of the (1)H-(1)H dipolar coupling is a realistic possibility. Simulations of the (1)H DQ MAS NMR spinning sideband spectra were performed with the two-spin approximation. These simulations reveal that a dipolar coupling distribution can greatly affect the DQ spectral shape and behavior of the DQ build-up. The spectral line shapes are quantified by measurement of the relative intensities of the DQ sidebands. These variations in the (1)H DQ NMR spectra are evaluated as a function of the width of the dipolar coupling distribution. As an example, the experimental DQ spinning sideband spectrum for a hydrated polyoxoniobate containing 15 H(2)O molecules per hexaniobate cluster, are better simulated with a distribution of dipolar couplings opposed to a single coupling constant.     

Optimizing STMAS

The 2D satellite transition magic angle spinning (STMAS) experiment generates efficiently high-resolution isotropic NMR spectra of half-integer quadrupolar nuclei. The experiment involves excitation and coherence transfer of satellite transitions into the central transition. It requires efficient refocusing of satellite transitions and sample spinning at a very accurate magic angle to cancel the first-order quadrupolar interaction effect. A review of all parameters relevant to optimizing the STMAS experiment is presented, including pulse sequence calibration, regulating spinning speed, magic angle adjustment, optimization of satellite transition excitation, and coherence transfer for both I = 3/2 and I > or =5/2 nuclei.     

Indirect detection of nitrogen-14 in solids via protons by nuclear magnetic resonance spectroscopy

This Communication describes the indirect detection of 14N nuclei (spin I=1) in solids by nuclear magnetic resonance (NMR) spectroscopy. The two-dimensional correlation method used here is closely related to the heteronuclear multiple quantum correlation (HMQC) experiment introduced in 1979 to study molecules in liquids, which has recently been used to study solids spinning at the magic angle. The difference is that the coherence transfer from neighboring 1H nuclei to 14N is achieved via a combination of J couplings and residual dipolar splittings (RDS). Projections of the two-dimensional correlation spectra onto the 14N dimension yield powder patterns which reflect the 14N quadrupolar interaction. In contrast to the indirect detection of 14N via 13C nuclei that was recently demonstrated [Gan, J. Am. Chem. Soc. 128 (2006) 6040; Cavadini et. al., J. Am. Chem. Soc., 128 (2006) 7706], this approach may benefit from enhanced sensitivity, and does not require isotopic enrichment in 13C, although the 1H line-widths may have to be reduced upon selective deuteration.     

Design and construction of a contactless mobile RF coil for double resonance variable angle spinning NMR

Variable angle spinning (VAS) experiments can be used to measure long-range dipolar couplings and provide structural information about molecules in oriented media. We present a probe design for this type of experiment using a contactless resonator. In this circuit, RF power is transmitted wirelessly via coaxial capacitive coupling where the coupling efficiency is improved by replacing the ordinary sample coil with a double frequency resonator. Our probe constructed out of this design principle has shown favorable properties at variable angle conditions. Moreover, a switched angle spinning correlation experiment is performed to demonstrate the probe's capability to resolve dipolar couplings in strongly aligned molecules.     

质子化学位移各向异性的测量

测量质子化学位移各向异性（CSA）有助于表征分子结构与其动力学,但由于¹H-¹H同核偶极耦合相互作用很强及质子各向异性化学位移较小,测量质子化学位移各向异性仍具有巨大挑战,特别是对含有多种质子的生物大分子,如蛋白质.本文简要综述了测量质子化学位移各向异性的方法,包括同核去耦慢速魔角旋转方法、超快魔角旋转方法、对称重耦（RN_n^v）方法、xCSA方法以及量子化学计算方法.我们重点介绍了在高速魔角旋转条件下蛋白质氨基质子化学位移各向异性的测量及它们与氢键长度、蛋白质二级结构之间的关系.     

MAS as a tool for suppressing dipolar field effects in high-resolution liquid NMR

We propose high-resolution magic angle spinning as a radical method for the suppression of dipolar field effects in liquid NMR. This technique works for any sample shape and any spatial distribution of nuclear magnetization. Furthermore, it removes any possibility of spectral clustering or instability due to the dipolar field.     

Experimental aspects of multidimensional solid-state NMR correlation spectroscopy.

The experimental parameters critical for the implementation of multidimensional solid-state NMR experiments that incorporate heteronuclear spin exchange at the magic angle are discussed. This family of experiments is exemplified by the three-dimensional experiment that correlates the (1)H chemical shift, (1)H-(15)N dipolar coupling, and (15)N chemical shift frequencies. The broadening effects of the homonuclear (1)H-(1)H dipolar couplings are suppressed using flip-flop (phase- and frequency-switched) Lee-Goldburg irradiations in both the (1)H chemical shift and the (1)H-(15)N dipolar coupling dimensions. The experiments are illustrated using the (1)H and (15)N chemical shift and dipolar couplings in a single crystal of (15)N-acetylleucine.     

Homonuclear correlation experiments for quadrupolar nuclei, spinning away from the magic angle

We present a set of homonuclear correlation experiments for half-integer quadrupolar spins in solids. In all these exchange-type experiments, the dipolar interaction is retained during the mixing time by spinning the sample at angles other than the “regular magic angle” (54.7°). The second-order quadrupolar interaction is averaged by different strategies for the different experiments. The multiple-quantum off magic angle spinning (MQOMAS) exchange experiment is essentially a regular MQMAS experiment where the quadrupolar interaction is averaged by combining magic angle spinning with a multiple- to single-quantum correlation scheme. The sample is spun at the magic angle at all times except during the mixing time which is added to establish homonuclear correlation. In the multiple-quantum P₄ magic angle spinning (MQP₄MAS) exchange experiment, the sample is spun at one of the angles at which the fourth-order Legendre polynomial vanishes (P₄ magic angle), the remaining second-order quadrupolar interaction now governed by a second-rank tensor is refocussed by the multiple to single-quantum correlation scheme. In the dynamic angle spinning (DAS) exchange experiment, the second-order quadrupolar interaction is averaged by correlating the evolution from two complementary angles. These experiments are demonstrated and compared, in view of their specific advantages and disadvantages, for ²³Na in the model compound Na₂SO₃.     

<Superscript>23</Superscript>Na and <Superscript>27</Superscript>Al NMR Study of Structure and Dynamics in Mordenite

Temperature dependencies of ²⁷Al and ²³Na nuclear magnetic resonance spectra and spin–lattice relaxations in mordenite have been studied in static and magic angle spinning regimes. Our data show that the spin–lattice relaxations of the ²³Na and ²⁷Al nuclei are mainly governed by interaction of nuclear quadrupole moments with electric field gradients of the crystal, modulated by translational motion of water molecules in the mordenite channels. At temperatures below 200 K, the dipolar interaction of nuclear spins with paramagnetic impurities becomes an important relaxation mechanism of the ²³Na and ²⁷Al nuclei.     

High-resolution NMR spectra in inhomogeneous fields utilizing the CRAZED sequence without coherence selection gradients

Coherence selection gradients have been considered as indispensable for high-resolution NMR spectroscopy in inhomogeneous fields utilizing the CRAZED-type sequences. However, our experimental results demonstrate that these gradients can be omitted if an appropriate phase cycling is applied. The measured linewidth of reconstructing 1D high-resolution spectral peaks does not depend on the dipolar correlation distance determined by the coherence selection gradients, but is only affected by diffusion and T(2) relaxation. This finding suggests the need to reconsider the mechanism for the iMQC-based high-resolution spectroscopy.     

Two-dimensional chemical shift/heteronuclear dipolar coupling spectra obtained with polarization inversion spin exchange at the magic angle and magic-angle sample spinning (PISEMAMAS)

High-resolution two-dimensional ¹⁵N chemical shift/¹H-¹⁵N dipolar coupling polarization inversion spin exchange at the magic angle (PISEMA) spectra of a polycrystalline sample of ¹⁵N-acetylvaline were obtained with and without magic-angle sample spinning. These spectra demonstrate the advantages of the PISEMA experiment over conventional approaches to separated local-field spectroscopy, especially the high resolution in the dipolar dimension where the spinning sidebands have uniformly narrow linewidths.     

1H-1H MAS correlation spectroscopy and distance measurements in a deuterated peptide

In this Communication, we demonstrate the use of deuteration together with back substitution of exchangeable protons as a means of attenuating the strong 1H-1H couplings that broaden 1H magic angle spinning (MAS) spectra of solids. The approach facilitates 15N-1H correlation experiments as well as experiments for the measurement of 1H-1H distances. The distance measurement relies on the excellent resolution in the 1H MAS spectrum and homonuclear double quantum recoupling techniques. The 1H-1H dipolar recoupling can be analyzed in an analytical fashion by fitting the data to a 2- or 3-spin system. The experiments are performed on a sample of the dipeptide N-Ac-Val-Leu-OH, which was synthesized from uniformly [2H, 15N] labeled materials and back-exchanged in H2O.     

NMR imaging of solids with magic angle spinning.

Different aspects of solid state NMR imaging are reviewed, with emphasis on imaging in combination with line narrowing, especially in combination with magic angle spinning. Experimental results obtained with the latter technique are discussed, along with the implications of magic angle spinning on slice selection.     

Effective dipolar couplings determined by dipolar dephasing of double-quantum coherences

It is shown how homonuclear distances and homonuclear dipolar lattice sums between spin-1/2 nuclei can be measured by a pulsed solid-state NMR experiment under magic-angle spinning conditions. The presented technique is based on double-quantum coherence filtering. Instead of measuring a build-up of double-quantum coherence the pulse sequence is designed to dephase double-quantum coherence. This is achieved by exciting double-quantum coherence either with the help of the through-space dipolar coupling or the through-bond dipolar coupling while the dephasing relies on the through-space dipolar coupling as selected by a gamma-encoded pulse sequence from the C/R symmetry class. Since dephasing curves can be normalized on zero dephasing, it is possible to analyze the initial dephasing regime and hence determine dipolar lattice sums (effective dipolar couplings) in multiple-spin systems. A formula for the effective dipolar coupling is derived theoretically and validated by numerical calculations and experiments on crystalline model compounds for (13)C and (31)P spin systems. The double-quantum dephasing experiment can be combined with constant-time data sampling to compensate for relaxation effects, consequently only two experimental data points are necessary for a single distance measurement. The phase cycling overhead for the constant-time experiment is minimal because a short cogwheel phase cycle exists. A 2D implementation is demonstrated on [(13)C(3)]alanine.     

Apparent diffusion behaviour of intermolecular double-quantum coherence modulated by a distant dipolar field in solution NMR

A modified correlated spectroscopy (COSY) revamped with asymmetric Z-gradient echo detection sequence was designed to investigate the influence of diffusion behaviour on intermolecular double-quantum coherence signal attenuation during the pre-acquisition period. Theoretical formulas were deduced and experimental measurements and simulations were performed. It is found that the diffusion behaviour of intermolecular double-quantum coherence in the pre-acquisition period may be different from that of conventional single-quantum coherence, depending on the relative orientation of diffusion weighting gradients to coherence selection gradients. When the orientation of the diffusion weighting gradients is parallel or anti-parallel to the orientation of the coherence selection gradients, the diffusion is modulated by the distant dipolar field. This study is helpful for understanding the signal properties in intermolecular double-quantum coherence magnetic resonance imaging.