Selectively Enhanced 1H–1H Correlations in Proton-Detected Solid-State NMR under Ultrafast MAS Conditions
Selectively Enhanced 1H–1H Correlations in Proton-Detected Solid-State NMR under Ultrafast MAS Conditions
复制标题
超快 MAS 条件下质子检测固态 NMR 中选择性增强的 1H–1H 相关性
DOI：
10.1021/acs.jpclett.0c02412
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发表时间：
2020
影响因子：
5.7
通讯作者：
Jun Yang
中科院分区：
文献类型：
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作者：
Zhengfeng Zhang;Andres Oss;Mai-Liis Org;Ago Samoson;Mingyue Li;Huan Tan;Yongchao Su;Jun Yang
质子探测固体核磁共振技术已成为一种强有力的分析技术，通过1H-1H相关性进行结构解析，这主要是通过宽带方法建立的。我们提出了一类新的频率选择性同素偶联方法，在超快魔角旋转（MAS）下选择性地增强感兴趣的1H-1H相关性。这些方法被称为选择性相位优化再偶联（SPR），在150 kHz MAS下，与广泛使用的射频驱动再偶联（RFDR）相比，这些方法可以提供1003倍的灵敏度增强，以在质子化三肽N-甲酰基-Met-Leu-Phe（fMLF）中捕获1HN-1HN接触，并成功地用于探测药物分子中的长距离1H-1H接触，盐酸吡格列酮（PIO-HCl）。SPR不仅在频率选择性再耦合方面非常高效，而且易于实现，赋予它在超快MAS条件下探测1H-1H接触以用于有机固体如蛋白质和药物的结构解析的巨大潜力。
Proton-detected solid-state NMR has emerged as a powerful analytical technique in structural elucidation via1H–1H correlations, which are mostly established by broadband methods. We propose a new class of frequency-selective homonuclear recoupling methods to selectively enhance1H–1H correlations of interest under ultrafast magic-angle spinning (MAS). These methods, dubbed as selective phase-optimized recoupling (SPR), can provide a sensitivity enhancement by a factor of ∼3 over the widely used radio-frequency-driven recoupling (RFDR) to observe1HN–1HNcontacts in a protonated tripeptideN-formyl-Met-Leu-Phe (fMLF) under 150 kHz MAS and are successfully utilized to probe a long-range1H–1H contact in a pharmaceutical molecule, the hydrochloride form of pioglitazone (PIO-HCl). SPR is not only highly efficient in frequency-selective recoupling but also easy to implement, imparting to it great potential to probe1H–1H contacts for the structural elucidation of organic solids such as proteins and pharmaceuticals under ultrafast MAS conditions.