Hydrogen bonding plays an important role in the structure and function of a wide range of materials. Solid-state ¹H nuclear magnetic resonance (NMR) spectroscopy provides a very sensitive tool to investigate the local structure of hydrogen atoms involved in hydrogen bonding. While there is extensive ¹H solid-state NMR data on O–H - - O hydrogen bonding in solid carboxylic acids, there has been no systematic ¹H solid-state NMR studies of hydroxyl groups in carbohydrates (and hydroxyl groups in general). With a view to studying the hydrogen bonding in more complex materials such as cellulose polymorphs, we carried out a detailed solid-state ¹H NMR investigation of the model compounds α-d-glucose and α-d-glucose monohydrate. Through a combination of fast magic-angle spinning (MAS), combined rotation and multiple pulse spectroscopy (CRAMPS), and two-dimensional (2D) correlation experiments carried out at ultrahigh magnetic fields, it was possible to assign all of the aliphatic (CH), hydroxyl (OH), and water (H₂O) ¹H chemical shifts in both forms of α-d-glucose. Plane-wave DFT calculations were employed to improve the hydrogen atom positions for α-d-glucose monohydrate and to calculate ¹H chemical shifts, providing additional support for the experimentally determined peak assignments. Finally, the relationship between the hydroxyl ¹H chemical shifts and their hydrogen bonding geometry was investigated and compared to the well-established relationship for carboxylic acid protons.

氢键在多种材料的结构和功能中起着重要作用。固态¹ H 核磁共振 (NMR) 光谱提供了一种非常灵敏的工具来研究参与氢键合的氢原子的局部结构。虽然有大量关于固体羧酸中 O–H - - O 氢键的¹ H 固态 NMR 数据，但还没有对碳水化合物中的羟基（和一般的羟基）进行系统的¹ H 固态 NMR 研究。为了研究更复杂的材料（例如纤维素多晶型物）中的氢键，我们对模型化合物 α- d -葡萄糖和 α-进行了详细的固态¹ H NMR 研究d -葡萄糖一水合物。通过结合快速魔角旋转 (MAS)、组合旋转和多脉冲光谱学 (CRAMPS) 以及在超高磁场下进行的二维 (2D) 相关实验，可以分配所有脂肪族 (CH )、羟基 (OH) 和水 (H ₂ O) ¹ H 在两种形式的 α- d-葡萄糖中发生化学位移。平面波 DFT 计算用于改善 α- d-葡萄糖一水合物的氢原子位置并计算¹ H 化学位移，为实验确定的峰分配提供额外支持。^{最后，羟基1}之间的关系研究了 H 化学位移及其氢键几何结构，并将其与羧酸质子的既定关系进行了比较。