Dynamic Nuclear Polarization NMR Spectroscopy of Microcrystalline Solids

This is a very interesting article, since it demonstrates how DNP can be tremendously helpful for the characterization of small molecules (e.g. quality control of pharmaceutical formulas). Here, DNP-enhanced 13C-13C correlation spectra are presented that are recorded using unlabeled material and the glass-forming solvents were carefully chosen so the analyte remains unaltered.

Rossini, A.J., et al., Dynamic Nuclear Polarization NMR Spectroscopy of Microcrystalline Solids. J. Am. Chem. Soc., 2012.


Dynamic nuclear polarization (DNP) solid-state NMR has been applied to powdered microcrystalline solids to obtain sensitivity enhancements on the order of 100. Glucose, sulfathiazole, and paracetamol were impregnated with bis-nitroxide biradical (bis-cyclohexyl-TEMPO-bisketal, bCTbK) solutions of organic solvents. The organic solvents were carefully chosen to be nonsolvents for the compounds, so that DNP-enhanced solid-state NMR spectra of the unaltered solids could be acquired. A theoretical model is presented that illustrates that for externally doped organic solids characterized by long spin?lattice relaxation times (T1(1H) > 200 s), 1H?1H spin diffusion can relay enhanced polarization over micrometer length scales yielding substantial DNP enhancements (ε). ε on the order of 60 are obtained for microcrystalline glucose and sulfathiazole at 9.4 T and with temperatures of ca. 105 K. The large gain in sensitivity enables the rapid acquisition of 13C-13C correlation spectra at natural isotopic abundance. It is anticipated that this will be a general method for enhancing the sensitivity of solid-state NMR experiments of organic solids.

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