Unleashing the Potential of17O NMR Spectroscopy Using Mechanochemistry (original) (raw)
17 O NMR spectroscopy has been the subject of vivid interest in recent years, because there is increasing evidence that it can provide unique insight into the structure and reactivity of many molecules and materials. However, due to the very poor natural abundance of oxygen-17, 17 O-labelling is generally a prerequisite. This is a real obstacle for most research groups, because of the high cost and/or strong experimental constraints of the most frequently used 17 O-labelling schemes. Here, we demonstrate for the first time that mechanosynthesis offers unique opportunities for enriching in 17 O a variety of organic and inorganic precursors of synthetic interest. The protocols are fast, user-friendly, and low-cost, which makes them highly attractive for a broad research community, and their suitability for 17 O solid state NMR applications is demonstrated.
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2004
17O solid state NMR of organic materials is developing rapidly. This article provides a snapshot of the current state of development of this field. The NMR techniques and enrichment protocols that are driving this progress are outlined. The 17O parameters derived from solid-state NMR experiments are summarized and the structural sensitivity of the approach to effects such as hydrogen bonding highlighted. The prospects and challenges for 17O solid-state NMR of biomolecules are discussed.
Journal of the American Chemical Society, 2012
We report a comprehensive variable-temperature solid-state 17 O NMR study of three 17 O-labeled crystalline sulfonic acids: 2-aminoethane-1-sulfonic acid (taurine, T), 3aminopropane-1-sulfonic acid (homotaurine, HT), and 4-aminobutane-1-sulfonic acid (ABSA). In the solid state, all three compounds exist as zwitterionic structures, NH 3 + −R−SO 3 − ,i n which the SO 3 − group is involved in various degrees of O•••H−N hydrogen bonding. High-quality 17 O NMR spectra have been obtained for all three compounds under both static and magic angle spinning (MAS) conditions at 21.1 T, allowing the complete set of 17 O NMR tensor parameters to be measured. Assignment of the observed 17 O NMR parameters to the correct oxygen sites in the crystal lattice was achieved with the aid of DFT calculations. By modeling the temperature dependence of 17 O NMR powder line shapes, we have not only confirmed that the SO 3 − groups in these compounds undergo a 3-fold rotational jump mechanism but also extracted the corresponding jump rates (10 2 −10 5 s −1) and the associated activation energies (E a) for this process (E a =4 8± 7, 42 ± 3, and 45 ± 1 kJ mol −1 for T, HT, and ABSA, respectively). This is the first time that SO 3 − rotational dynamics have been directly probed by solid-state 17 O NMR. Using the experimental activation energies for SO 3 − rotation, we were able to evaluate quantitatively the total hydrogen bond energy that each SO 3 − group is involved in within the crystal lattice. The activation energies also correlate with calculated rotational energy barriers. This work provides a clear illustration of the utility of solid-state 17 O NMR in quantifying dynamic processes occurring in organic solids. Similar studies applied to selectively 17 O-labeled biomolecules would appear to be very feasible.
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High-field 17 O NMR studies of the SiOAl bond in solids
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