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NMR parameters such as indirect nuclear spin–spin coupling (J), nuclear magnetic shielding (σ), direct dipolar coupling (D), and electric field gradient (V) are properly described by second-rank tensors. Each may be decomposed into isotropic, symmetric, and antisymmetric components; the number of these three components which may be nonzero is a distinguishing attribute of each interaction tensor. The rank-1 antisymmetric portion of J (Janti) holds the distinction of remaining the only nonzero part of these fundamental NMR interaction tensors which has never been observed experimentally. Accordingly, effects from Janti are usually ignored, but it is important to consider when this is valid. An experimental strategy for observing Janti in powdered samples of tightly coupled homonuclear spin pairs, based on ideas originally presented by Andrew and Farnell (Mol. Phys. 1968, 15, 157), is described. The theory of Andrew and Farnell is extended to powder samples, and methods for analyzing NMR spectra from powdered samples are presented. It is found that, in certain rare cases, Janti has the potential to affect the NMR line shapes from AB spin systems, but that even in these systems, the most intense features of the spectra are not affected and may be analyzed independently of Janti. Furthermore, Janti will only have an observable effect on the NMR spectra when its magnitude is comparable with that of Jiso and with the difference in chemical shifts (in Hz) between the two sites. Finally, the first experimental attempts to measure Janti are reported, and experimental proof that no elements of Janti(119Sn,119Sn) in hexa(p-tolyl)ditin are larger than 2900 Hz is given. The benefits of modern double-quantum filtering NMR pulse sequences in isolating effects from Janti are also illustrated. [ABSTRACT FROM AUTHOR]

The `out-and-back' 3D HCP experiment, using gradient- and sensitivity-enhanced detection, provides a convenient method for assignment of the 31P NMR spectra and accurate measurement of the 31P chemical shifts of ribonucleic acids. The 13C resolution in such spectra can be doubled, at the cost of a 50% reduction in sensitivity, by combining 13C evolution during the 13C-\31P\ de- and rephasing periods. The multiple connectivities observable for a given 31P, including correlations to the intranucleotide C5′H2 and C4′H groups, and the C2′H, C3′H and C4′H groups of the preceding nucleotide, permit independent measurements of the 31P shift. The 13C spectrum of these groups is typically crowded for an RNA molecule in isotropic solution and overlap becomes more problematic in media used to achieve partial alignment. However, many of these correlations are resolvable in the combined-evolution HCP spectrum. The difference in 31P chemical shift between isotropic solution and a medium containing liquid crystalline Pf1 provides information on the orientation of phosphate groups. The intensities measured in the 3D HCP spectrum, obtained for an isotropic sample, yield values for the 3JC2′P and 3JC4′P couplings, thereby providing important restraints for the backbone torsion angles ε and β. The experiments are illustrated for a uniformly 13C-enriched, 24-residue stem-loop RNA sequence, and results for the helical stem region show close agreement between observed Δδ(31P) values and those predicted for a model A-form RNA helix when using a uniform 31P CSA tensor. This confirms that Δδ(31P) values can be used directly as restraints in refining nucleic acid structures. [ABSTRACT FROM AUTHOR]