Institute of Organic Chemistry and Biochemistry, Academy of Sciences, Flemingovo náměstí 2, 16610, Prague, Czech Republic.
Department of Optics, Palacký University Olomouc, 17. listopadu 12, 77146, Olomouc, Czech Republic.
Chemphyschem. 2020 Jun 16;21(12):1272-1279. doi: 10.1002/cphc.202000261. Epub 2020 May 25.
Raman optical activity (ROA) is pursued as a promising method for structural analyses of sugars in aqueous solutions. In the present study, experimental Raman and ROA spectra of glucose and sorbose obtained in an extended range (50-4000 cm ) are interpreted using molecular dynamics and density functional theory, with the emphasis on CH stretching modes. A reasonable theoretical basis for spectral interpretation was obtained already at the harmonic level. Anharmonic corrections led to minor shifts of band positions (up to 25 cm ) below 2000 cm , while the CH stretching bands shifted more, by ∼180 cm , and better reproduced the experiment. However, the anharmonicities could be included on a relatively low approximation level only, and they did not always improve the harmonic band shapes. The dependence on the structure and conformation shows that the CH stretching ROA spectral pattern is a sensitive marker useful in saccharide structure studies.
拉曼旋光活性（ROA）被视为一种有前途的方法，可用于分析水溶液中的糖的结构。在本研究中，使用分子动力学和密度泛函理论对葡萄糖和山梨糖在扩展范围内（50-4000 cm）获得的实验拉曼和 ROA 光谱进行了解释，重点是 CH 伸缩模式。在谐波水平上已经获得了光谱解释的合理理论基础。在 2000 cm 以下，非谐校正导致带位置的微小位移（高达 25 cm），而 CH 伸缩带的位移更大，约为 180 cm，并且更好地再现了实验结果。然而，非谐性只能在相对较低的近似水平上包含，并且它们并不总是改善谐波带形状。对结构和构象的依赖性表明，CH 伸缩 ROA 光谱模式是一种在糖结构研究中有用的敏感标记。
