N Chemical Shift Tensor Magnitude and Orientation in the Molecular Frame of Uracil Determined via MAS NMR

The potential of heteronuclear MAS NMR spectroscopy for the characterization of ¹⁵N chemical shift (CS) tensors in multiply labeled systems has been illustrated, in one of the first studies of this type, by a measurement of the chemical shift tensor magnitude and orientation in the molecular frame for the two ¹⁵N sites of uracil. Employing polycrystalline samples of ¹⁵N₂ and 2-¹³C,¹⁵N₂-labeled uracil, we have measured, via ¹⁵N–¹³C REDOR and ¹⁵N–¹H dipolar-shift experiments, the polar and azimuthal angles (θ, ψ) of orientation of the ¹⁵N–¹³C and ¹⁵N–¹H dipolar vectors in the ¹⁵N CS tensor frame. The (θ_NC, ψ_NC) angles are determined to be (92 ± 10°, 100 ± 5°) and (132 ± 3°, 88 ± 10°) for the N1 and N3 sites, respectively. Similarly, (θ_NH, ψ_NH) are found to be (15 ± 5°, −80 ± 10°) and (15 ± 5°, 90 ± 10°) for the N1 and N3 sites, respectively. These results obtained based only on MAS NMR measurements have been compared with the data reported in the literature.     

Revealing the configuration and crystal packing of organic compounds by solid-state NMR spectroscopy: methoxycarbonylurea, a case study

The molecular configuration and intermolecular arrangement of polycrystalline methoxycarbonylurea (MCU) has been studied by a combination of chemical editing, rotational echo double resonance (REDOR) spectroscopy and ab initio calculations. From the multispin IS(n) REDOR experiments several dipolar couplings were determined and converted into distance constraints. Intra- and intermolecular dipolar couplings were distinguished by isotope dilution. The configuration of the MCU molecule can be determined from three torsion angles Psi1, Psi2, and Psi3. Ab initio calculations showed that these angles are either 0 degrees or 180 degrees (Z or E). From the REDOR experiments, the E configuration was found for Psi1 and Psi2 and the Z configuration for Psi3. Thus the configuration of MCU in the solid state was determined to be EEZ. Distance constraints for the intermolecular arrangement of MCU were obtained by performing REDOR experiments on 13C15N2 MCU with different degrees of isotope dilution and on a cocrystallized 1:1 mixture of 13C(urea) MCU and 15N(amide) MCU. By combining these distance constraints with molecular modeling, three different possible packing motifs for MCU molecules were found. The molecules in these motifs are arranged as linear chains with methoxy groups at the borders of the chains. All the intermolecular hydrogen bond donors and acceptors in the interior of the chain are saturated.     

A frequency-selective REDOR experiment for an SI2 spin system

A frequency-selective REDOR experiment is described for SI₂ spin systems. The experiment causes the net dipolar dephasing of the S spin to evolve only under the influence of one of the I spins. The experiment is based on a single pair of appropriately phased 90° I-spin pulses, and the I spin causing the S-spin dipolar dephasing is determined by the relative phases between the two 90° pulses. The experiment is demonstrated on a sample of ¹⁵N₂-l-asparagine.     

Structure determination of aligned systems by solid-state NMR magic angle spinning methods

Single crystal rotational echo double resonance (REDOR) experiments can be used to determine the three-dimensional orientation of heteronuclear bond vectors in an amino acid, as well as the crystal's orientation relative to the rotor fixed frame (RFF). We also demonstrate that for samples uniaxially aligned along the rotor axis, the polar tilt angle of a bond vector relative to the RFF can be measured by use of an analytical expression that describes the REDOR curve for that system. These bond orientations were verified by X-ray indexing of the single crystal sample, and were shown to be as accurate as +/- 1 degrees .     

Recoupling of residual dipolar couplings in single-domain polymer-stabilized liquid crystals undergoing magic-angle spinning

Measurement of dipolar couplings, chemical shift anisotropies, and quadrupole couplings in oriented media such as liquid crystals are of great importance for extraction of structural parameters in biological macromolecules. Here, we introduce a new technique, SAD-REDOR, that consists of recoupling heteronuclear dipolar couplings in molecules dissolved in a single-domain liquid crystal or other oriented medium through the combined use of magic-angle spinning and rotor-synchronized radiofrequency pulses. This application of the REDOR pulse sequence to oriented media offers several advantages such as selectivity over the type of coupling recovered and tunable scaling of the interaction. The effectiveness of the technique is demonstrated both theoretically and experimentally, using the recently developed polyacrylamide-stabilized Pf1 phage medium and 15N-labeled benzamide as the aligned molecule.     

Recollections of REDOR

Rotational-echo, double-resonance NMR (REDOR) is an experiment designed to measure heteronuclear dipolar couplings in solids and is most often used to obtain structural details in solids. A brief history of its inception and development is presented.     

Rotary resonance echo double resonance for measuring heteronuclear dipolar coupling under MAS

A rotary resonance echo double resonance (R-REDOR) experiment is described for measuring heteronuclear dipolar coupling under magic-angle spinning. Rotary resonance reintroduces both dipolar coupling and chemical shift anisotropy with an rf field matching the spinning frequency. The resonance effect from chemical shift anisotropy can be refocused with a rotary resonance echo. The R-REDOR experiment thus measures the dephasing of the rotary resonance echo from the heteronuclear dipolar coupling to determine the dipolar coupling constant. The rotary resonance experiment is suitable for measuring dipolar coupling with quadrupolar nuclei because it applies the recoupling rf only to the observed spin-1/2. The rotary resonance scheme has the advantages of a long T2' and susceptible to spinning frequency fluctuation.