Recent developments in solid-state nuclear magnetic resonance of quadrupolar nuclei and applications to biological systems

Abstract

Recent advances in nuclear magnetic resonance (NMR) methodology and improvements in high-field NMR instrumentation have generated a new wave of research interests in the application of solid-state NMR to the study of quadrupolar nuclei. These developments now permit increasingly complex biological systems to be probed by quadrupolar NMR. In this review I describe a few recent developments in NMR studies of quadrupolar nuclei and demonstrate the potential of solid-state quadrupolar NMR in the study of biological systems. In particular, I discuss the application of solid-state NMR of (17)O, 67Zn, 59Co, 23Na, and 39K nuclei with a prognosis for future work.

Ultra‐wideline 27Al NMR Investigation of Three‐ and Five‐Coordinate Aluminum Environments

“…[6] Solid-state 27 Al NMR spectroscopy has been applied to investigate countless aluminum-containing materials, including microporous and mesoporous solids, such as zeolites, aluminosilicates, and molecular sieves; natural and man-made minerals and gemstones; aluminum coordination compounds and organoaluminum complexes; as well as assorted aluminum-containing biological systems. [4,5,[7][8][9][10] An interesting aspect of solid-state 27 Al NMR spectroscopy is the relatively facile differentiation of aluminum species with variation in coordination number, ligand identity, and molecular symmetry. Four-and six-coordinate aluminum species are very common, and readily distinguished by 27 Al NMR spectroscopy.…”

Solid-State 25Mg NMR Spectroscopic and Computational Studies of Organic Compounds. Square-Pyramidal Magnesium(II) Ions in Aqua(magnesium) Phthalocyanine and Chlorophyll a

“…1,2 A particularly important trend is that solid-state NMR has emerged as a viable technique to study metal binding sites involving low-γ quadrupolar nuclei with half-integer spins such as 39 K (spin-3/2), 67 Zn (spin-5/2), and 25 Mg (spin-5/2) in organic and biological compounds. [3][4][5][6][7][8][9][10][11][12][13][14][15][16] These metal ions are biologically important, but technically difficult to study by NMR spectroscopy.…”

Theoretical Study of the 67Zn Electric-Field-Gradient Tensors in Zinc(II) Coordination Complexes

“…[3][4][5] Recently, solid-state 67 Zn NMR spectroscopy has emerged as a viable method for detecting Zn(II) ions even in large molecular systems. [6][7][8][9][10][11][12][13][14] During these 67 Zn NMR studies, it has become increasingly apparent that a better understanding of the 67 Zn NMR properties is needed. One fundamental question is how the 67 Zn NMR tensors, both the chemical shift tensor and the electric-field-gradient (EFG) tensor, are related to the chemical environment and molecular structure.…”

“…The fact that a reasonable amount of reliable 67 Zn EFG data has been accumulated in the past several years from experimental solidstate NMR studies makes the theoretical examination of 67 Zn EFG tensors timely and possible. In this paper, we report a systematic quantum-mechanical investigation for the 67 Zn EFG tensors in six Zn(II) coordination complexes: zinc acetate dihydrate (1), bis(acetato)bis(imidazole)zinc (2), tetrakis(imidazole)zinc perchlorate (3), tetrakis(thiourea)zinc nitrate (4), zinc formate dihydrate (5), and bis(acetato)bis(urea)zinc (6). These Zn(II) coordination complexes were chosen because both reliable X-ray crystallographic and solid-state 67 Zn NMR data are available in the literature.…”