Zhu Fujiang, Isaacs Neil W, Hecht Lutz, Tranter George E, Barron Laurence D
WestCHEM, Department of Chemistry, University of Glasgow, Glasgow G12 8QQ, Scotland, UK.
Chirality. 2006 Feb;18(2):103-15. doi: 10.1002/chir.20225.
On account of its sensitivity to chirality, Raman optical activity (ROA), which may be measured as a small difference in the intensity of vibrational Raman scattering from chiral molecules in right- and left-circularly polarized incident light, or as the intensity of a small circularly polarized component in the scattered light, is a powerful probe of the structure of biomolecules. Protein ROA spectra provide information on secondary and tertiary structures of polypeptide backbones, backbone hydration and side-chain conformations, and on structural elements present in unfolded states. Carbohydrate ROA spectra provide information on the central features of carbohydrate stereochemistry, especially that of the glycosidic link. Glycoprotein ROA spectra provide information on both the polypeptide and carbohydrate components. This article describes the ROA technique and presents and discusses the ROA spectra of a selection of proteins, carbohydrates, and a glycoprotein. The many structure-sensitive bands in protein ROA spectra are favorable for applying pattern recognition techniques, illustrated here using nonlinear mapping, to determine structural relationships between different proteins.
由于对手性的敏感性,拉曼光学活性(ROA)是生物分子结构的有力探测手段。它可以通过测量手性分子在右旋和左旋圆偏振入射光中振动拉曼散射强度的微小差异来测定,也可以通过测量散射光中一个小的圆偏振分量的强度来测定。蛋白质的ROA光谱提供了多肽主链的二级和三级结构、主链水化和侧链构象以及未折叠状态下存在的结构元件的信息。碳水化合物的ROA光谱提供了碳水化合物立体化学核心特征的信息,尤其是糖苷键的信息。糖蛋白的ROA光谱提供了多肽和碳水化合物成分的信息。本文描述了ROA技术,并展示和讨论了一系列蛋白质、碳水化合物和一种糖蛋白的ROA光谱。蛋白质ROA光谱中许多对结构敏感的谱带有利于应用模式识别技术(本文使用非线性映射进行说明)来确定不同蛋白质之间的结构关系。