A New Tool for NMR Crystallography: Complete 13C/15N Assignment of Organic Molecules at Natural Isotopic Abundance Using DNP-Enhanced Solid-State NMR

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• 作者：Katharina M盲rker ; Morgane Pingret ; Jean-Marie Mouesca ; Didier Gasparutto ; Sabine Hediger ; Ga毛l De Pa毛pe
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：November 4, 2015
• 年：2015
• 卷：137
• 期：43
• 页码：13796-13799
• 全文大小：319K
• ISSN：1520-5126

文摘

NMR crystallography of organic molecules at natural isotopic abundance (NA) strongly relies on the comparison of assigned experimental and computed NMR chemical shifts. However, a broad applicability of this approach is often hampered by the still limited ¹H resolution and/or difficulties in assigning ¹³C and ¹⁵N resonances without the use of structure-based chemical shift calculations. As shown here, such difficulties can be overcome by ¹³C鈥?sup>13C and for the first time ¹⁵N鈥?sup>13C correlation experiments, recorded with the help of dynamic nuclear polarization. We present the complete de novo ¹³C and ¹⁵N resonance assignment at NA of a self-assembled 2鈥?deoxyguanosine derivative presenting two different molecules in the asymmetric crystallographic unit cell. This de novo assignment method is exclusively based on aforementioned correlation spectra and is an important addition to the NMR crystallography approach, rendering firstly ¹H assignment straightforward, and being secondly a prerequisite for distance measurements with solid-state NMR.