Structure of Condensed Phase Peptides: Insights from Vibrational Circular Dichroism and Raman Optical Activity Techniques.,Chemical Reviews

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Structure of Condensed Phase Peptides: Insights from Vibrational Circular Dichroism and Raman Optical Activity Techniques.
Chemical Reviews ( IF 51.4 ) Pub Date : 2020-02-26 , DOI: 10.1021/acs.chemrev.9b00636
Timothy A Keiderling ₁

Affiliation

Peptides and proteins are naturally chiral molecular systems so that sensing their structure and conformation with chirality-based spectral methods is an obvious and long-used diagnostic application. Extending chiroptical techniques to measurement of vibrational transitions, in the form of vibrational circular dichroism (VCD) and Raman optical activity (ROA), expands the number and types of excitations available that might provide structural insight and can provide an alternate and, in some cases, a more distinctive conformational probe. Since the dominant repeating structural element in peptides is the locally achiral amide group, VCD senses the polymeric structure through amide coupling, which is directly dependent on secondary structure. Determination of the type and relative contribution of these structural components through empirical correlation with spectral character has been the main application of VCD for peptides and proteins, although this is now reinforced by extensive theoretical modeling. Monitoring structural and conformational change induced by environmental perturbations provides another important application. More recently, VCD has been used to detect morphological variations in fibril states of aggregated peptides and proteins. ROA has parallel secondary structural sensitivities, with more applications for proteins than peptides, and has more sensitivity to local configuration and side chains. This review covers the range of peptide studies done with VCD and extends them to compare with example protein and ROA applications.

中文翻译：

凝聚相肽的结构：振动圆二色性和拉曼光学活性技术的见解。

肽和蛋白质是天然的手性分子系统，因此使用基于手性的光谱方法检测其结构和构象是一项显而易见且长期使用的诊断应用。将整脊技术扩展为振动圆二色性（VCD）和拉曼光学活性（ROA）形式的振动跃迁，扩展了可用的激发的数量和类型，这些激发和激发可以提供结构上的见解，并且可以提供替代方法，在某些情况下，一种更具特色的构象探针。由于肽中的主要重复结构元素是局部非手性酰胺基，VCD通过酰胺偶联感测聚合物结构，酰胺偶联直接取决于二级结构。通过与光谱特性的经验相关性确定这些结构成分的类型和相对贡献一直是VCD在肽和蛋白质上的主要应用，尽管现在已通过广泛的理论建模得到了加强。监测环境扰动引起的结构和构象变化提供了另一个重要的应用。最近，VCD已用于检测聚集的肽和蛋白质的原纤维状态的形态变化。ROA具有平行的二级结构敏感性，与肽相比，蛋白质的应用更多，并且对局部结构和侧链的敏感性更高。这篇综述涵盖了用VCD进行的肽研究的范围，并将其扩展为与示例蛋白质和ROA应用进行比较。

更新日期：2020-02-27

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