Category Archives: quadrupole

DNP-Enhanced Ultrawideline Solid-State NMR Spectroscopy: Studies of Platinum in Metal-Organic Frameworks #DNPNMR

Kobayashi, T., et al., DNP-Enhanced Ultrawideline Solid-State NMR Spectroscopy: Studies of Platinum in Metal-Organic Frameworks. J Phys Chem Lett, 2016. 7(13): p. 2322-7.

Ultrawideline dynamic nuclear polarization (DNP)-enhanced (195)Pt solid-state NMR (SSNMR) spectroscopy and theoretical calculations are used to determine the coordination of atomic Pt species supported within the pores of metal-organic frameworks (MOFs). The (195)Pt SSNMR spectra, with breadths reaching 10000 ppm, were obtained by combining DNP with broadbanded cross-polarization and CPMG acquisition. Although the DNP enhancements in static samples are lower than those typically observed under magic-angle spinning conditions, the presented measurements would be very challenging using the conventional SSNMR methods. The DNP-enhanced ultrawideline NMR spectra served to separate signals from cis- and trans-coordinated atomic Pt(2+) species supported on the UiO-66-NH2 MOF. Additionally, the data revealed a dominance of kinetic effects in the formation of Pt(2+) complexes and the thermodynamic effects in their reduction to nanoparticles. A single cis-coordinated Pt(2+) complex was confirmed in MOF-253.

35Cl dynamic nuclear polarization solid-state NMR of active pharmaceutical ingredients #DNPNMR

Hirsh, D.A., et al., 35Cl dynamic nuclear polarization solid-state NMR of active pharmaceutical ingredients. Phys Chem Chem Phys, 2016. 18(37): p. 25893-25904.

In this work, we show how to obtain efficient dynamic nuclear polarization (DNP) enhanced 35Cl solid-state NMR (SSNMR) spectra at 9.4 T and demonstrate how they can be used to characterize the molecular-level structure of hydrochloride salts of active pharmaceutical ingredients (APIs) in both bulk and low wt% API dosage forms. 35Cl SSNMR central-transition powder patterns of chloride ions are typically tens to hundreds of kHz in breadth, and most cannot be excited uniformly with high-power rectangular pulses or acquired under conditions of magic-angle spinning (MAS). Herein, we demonstrate the combination of DNP and 1H-35Cl broadband adiabatic inversion cross polarization (BRAIN-CP) experiments for the acquisition of high quality wideline spectra of APIs under static sample conditions, and obtain signals up to 50 times greater than in spectra acquired without the use of DNP at 100 K. We report a new protocol, called spinning-on spinning-off (SOSO) acquisition, where MAS is applied during part of the polarization delay to increase the DNP enhancements and then the MAS rotation is stopped so that a wideline 35Cl NMR powder pattern free from the effects of spinning sidebands can be acquired under static conditions. This method provides an additional two-fold signal enhancement compared to DNP-enhanced SSNMR spectra acquired under purely static conditions. DNP-enhanced 35Cl experiments are used to characterize APIs in bulk and dosage forms with Cl contents as low as 0.45 wt%. These results are compared to DNP-enhanced 1H-13C CP/MAS spectra of APIs in dosage forms, which are often hindered by interfering signals arising from the binders, fillers and other excipient materials.

PRESTO polarization transfer to quadrupolar nuclei: implications for dynamic nuclear polarization

Perras, F.A., T. Kobayashi, and M. Pruski, PRESTO polarization transfer to quadrupolar nuclei: implications for dynamic nuclear polarization. Phys Chem Chem Phys, 2015. 17(35): p. 22616-22.

We show both experimentally and numerically on a series of model systems that in experiments involving transfer of magnetization from (1)H to the quadrupolar nuclei under magic-angle-spinning (MAS), the PRESTO technique consistently outperforms traditionally used cross polarization (CP), affording more quantitative intensities, improved lineshapes, better overall sensitivity, and straightforward optimization. This advantage derives from the fact that PRESTO circumvents the convoluted and uncooperative spin dynamics during the CP transfer under MAS, by replacing the spin-locking of quadrupolar nuclei with a single central transition selective 90 degrees pulse and using a symmetry-based recoupling sequence in the (1)H channel. This is of particular importance in the context of dynamic nuclear polarization (DNP) NMR of quadrupolar nuclei, where the efficient transfer of enhanced (1)H polarization is desired to obtain the highest sensitivity.

Dynamic nuclear polarization of (17)o: direct polarization

Michaelis, V.K., et al., Dynamic nuclear polarization of (17)o: direct polarization. J Phys Chem B, 2013. 117(48): p. 14894-906.

Dynamic nuclear polarization of (17)O was studied using four different polarizing agents: the biradical TOTAPOL and the monoradicals trityl and SA-BDPA, as well as a mixture of the latter two. Field profiles, DNP mechanisms, and enhancements were measured to better understand and optimize directly polarizing this low-gamma quadrupolar nucleus using both mono- and biradical polarizing agents. Enhancements were recorded at <88 K and were >100 using the trityl (OX063) radical and <10 with the other polarizing agents. The >10 000-fold savings in acquisition time enabled a series of biologically relevant small molecules to be studied with small sample sizes and the measurement of various quadrupolar parameters. The results are discussed with comparison to room temperature studies and GIPAW quantum chemical calculations. These experimental results illustrate the strength of high field DNP and the importance of radical selection for studying low-gamma nuclei.

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