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.