{"title":"α-d-葡萄糖两种形态氢键的固体核磁共振结合量子化学计算研究","authors":"Darren H. Brouwer, Janelle G. Mikolajewski","doi":"10.1016/j.ssnmr.2022.101848","DOIUrl":null,"url":null,"abstract":"<div><p><span>Hydrogen bonding plays an important role in the structure and function of a wide range of materials. Solid-state </span><sup>1</sup><span>H 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 </span><sup>1</sup><span>H solid-state NMR data on O–H - - O hydrogen bonding in solid carboxylic acids, there has been no systematic </span><sup>1</sup><span>H solid-state NMR studies of hydroxyl<span><span> groups in carbohydrates (and hydroxyl groups in general). With a view to studying the hydrogen bonding in more complex materials such as </span>cellulose polymorphs, we carried out a detailed solid-state </span></span><sup>1</sup>H NMR investigation of the model compounds α-<span>d</span>-glucose and α-<span>d</span><span>-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 (H</span><sub>2</sub>O) <sup>1</sup>H chemical shifts in both forms of α-<span>d</span>-glucose. Plane-wave DFT calculations were employed to improve the hydrogen atom positions for α-<span>d</span>-glucose monohydrate and to calculate <sup>1</sup>H chemical shifts, providing additional support for the experimentally determined peak assignments. Finally, the relationship between the hydroxyl <sup>1</sup>H chemical shifts and their hydrogen bonding geometry was investigated and compared to the well-established relationship for carboxylic acid protons.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8000,"publicationDate":"2023-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"1","resultStr":"{\"title\":\"A combined solid-state NMR and quantum chemical calculation study of hydrogen bonding in two forms of α-d-glucose\",\"authors\":\"Darren H. Brouwer, Janelle G. Mikolajewski\",\"doi\":\"10.1016/j.ssnmr.2022.101848\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span>Hydrogen bonding plays an important role in the structure and function of a wide range of materials. Solid-state </span><sup>1</sup><span>H 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 </span><sup>1</sup><span>H solid-state NMR data on O–H - - O hydrogen bonding in solid carboxylic acids, there has been no systematic </span><sup>1</sup><span>H solid-state NMR studies of hydroxyl<span><span> groups in carbohydrates (and hydroxyl groups in general). With a view to studying the hydrogen bonding in more complex materials such as </span>cellulose polymorphs, we carried out a detailed solid-state </span></span><sup>1</sup>H NMR investigation of the model compounds α-<span>d</span>-glucose and α-<span>d</span><span>-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 (H</span><sub>2</sub>O) <sup>1</sup>H chemical shifts in both forms of α-<span>d</span>-glucose. Plane-wave DFT calculations were employed to improve the hydrogen atom positions for α-<span>d</span>-glucose monohydrate and to calculate <sup>1</sup>H chemical shifts, providing additional support for the experimentally determined peak assignments. Finally, the relationship between the hydroxyl <sup>1</sup>H chemical shifts and their hydrogen bonding geometry was investigated and compared to the well-established relationship for carboxylic acid protons.</p></div>\",\"PeriodicalId\":21937,\"journal\":{\"name\":\"Solid state nuclear magnetic resonance\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.8000,\"publicationDate\":\"2023-02-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"1\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Solid state nuclear magnetic resonance\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926204022000777\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Solid state nuclear magnetic resonance","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926204022000777","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
A combined solid-state NMR and quantum chemical calculation study of hydrogen bonding in two forms of α-d-glucose
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.
期刊介绍:
The journal Solid State Nuclear Magnetic Resonance publishes original manuscripts of high scientific quality dealing with all experimental and theoretical aspects of solid state NMR. This includes advances in instrumentation, development of new experimental techniques and methodology, new theoretical insights, new data processing and simulation methods, and original applications of established or novel methods to scientific problems.