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

机译:冷凝相肽的结构:振动圆形二色性和拉曼光学活性技术的见解

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摘要

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.
机译:肽和蛋白质是天然的手性分子系统,使其与基于手性的光谱方法的结构和构象感测是明显和长期使用的诊断应用。扩展到测量振动过渡的振动转变的振动转变,以振动圆形二色(VCD)和拉曼光学活性(ROA)的形式,扩大了可能提供结构洞察力的兴奋的数量和类型,并且可以提供交替,在某些情况下提供交替。 ,更独特的构象探针。由于肽中的主要重复结构元素是局部成酰胺基团,因此VCD通过酰胺偶联感测聚合物结构,其直接依赖于二级结构。通过与光谱特征的经验相关性的验证来确定这些结构组分的类型和相对贡献已经是VCD对肽和蛋白质的主要应用,尽管现在通过广泛的理论建模加强了这一点。监测环境扰动引起的结构和构象变化提供了另一个重要应用。最近,VCD已被用于检测聚集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,具有比肽更多的蛋白质的应用,并且对局部配置和侧链具有更高的敏感性。该综述涵盖了使用VCD进行的肽研究的范围,并延伸它们以与实施例蛋白和ROA应用进行比较。

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