Broad developments in experimental NMR techniques have opened new and exciting opportunities for application of solid state nuclear magnetic resonance (SS NMR) in studies of gas hydrates and inclusion compounds in general. Perhaps the most important advance of the last 10 years was the extension into very high magnetic fields beyond 20 T. This progress is especially significant in studies concerned with low-γ, low natural abundance, and quadrupolar nuclei. This work reports our recent exploration of clathrate hydrates and other inclusion compounds (β-quinol, tert-Bu-Calix[4], and dodecasil-3C) with SS NMR of nuclei that were not so long ago completely out of reach for NMR, namely 131Xe, 83Kr, and 33S. Although 129Xe is a widely used NMR probe, applications of the low-γ isotope 131Xe were very scarce. Being a quadrupolar spin 3/2 nucleus, 131Xe provides an additional probe for sampling the electric field gradients in inclusion compounds. Another nucleus that has been seriously under-explored is 83Kr, with its very low γ being the main obstacle, and along with quadrupolar coupling we report the first detection of the chemical shift anisotropy in krypton. The relative values of the Sternheimer antishielding factors for 131Xe and 83Kr, obtained by comparison of the spectra of the two in identical cage environments, are also discussed. Though 33S NMR of solids is notoriously difficult due to its low γ, low natural abundance, and relatively large quadrupolar moment, working at the field of 21.1 T it was possible to acquire, in a reasonable time, natural abundance 33S SS NMR spectra of various H2S and SO2 gas hydrates and inclusion compounds. In most cases the spectra are dominated by the quadrupolar interactions, providing information on the symmetry of the cages encapsulating the guest molecules, and also show the effects of very rapid reorientation of the encaged H2S and SO2. The impact of the introduction of new NMR nuclei on hydrate research is discussed.
Insight into Lipid Surface Recognition and Reversible Conformational Adaptations of an Exchangeable Apolipoprotein by Multidimensional Heteronuclear NMR Techniques