Sensitivity of the C–H Stretching Band in Raman Spectra to Phospholipid Order

IF 2.4 3区 化学 Q2 SPECTROSCOPY
Yulia V. Zaytseva, Konstantin A. Okotrub, Nikolai V. Surovtsev
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Abstract

Phospholipid bilayers, which are a major component of cellular membranes and some drug delivery vehicles, can be in different states of order depending on the conformations of the hydrocarbon tails and their mutual arrangement. The important task of experimental characterization of phospholipid order is often addressed using Raman spectra of the C–H stretching bands. Such characterization uses some empirical relationships for apparent maxima in the spectra, although the origin of the sensitivity of the C–H band to phospholipid order and its model description remain unclear. Surely, a correct description of the sensitivity of the C–H band to phospholipid order is critical for its proper application. Here, we provide a description of the ordering sensitivity of the C–H stretching band using a polarized Raman experiment with hydrated aligned multibilayers of a saturated phospholipid. By this way, Raman contributions from symmetric and antisymmetric vibrations of CH2 were obtained in a model-free manner. Experiments in a wide temperature range and the use of isotopic isolation helped us to consider separately the effects of conformational and lateral order of chains. The conformational sensitivity of the spectrum of antisymmetric vibrations was confirmed by DFT modeling. The outcomes of the study allowed us to provide recommendations for the use of the Raman spectrum of the C–H stretching band to characterize the conformational and lateral order of phospholipid-containing materials.

Abstract Image

拉曼光谱中的 C-H 伸展带对磷脂阶次的敏感性
磷脂双分子层是细胞膜和某些药物输送载体的主要成分,根据碳氢化合物尾部的构象及其相互排列,磷脂双分子层可以处于不同的有序状态。磷脂秩的实验表征这一重要任务通常使用 C-H 伸展带的拉曼光谱来完成。尽管 C-H 带对磷脂秩的敏感性的来源及其模型描述仍不清楚,但这种表征使用了光谱中明显最大值的一些经验关系。当然,正确描述 C-H 带对磷脂阶次的敏感性对其正确应用至关重要。在此,我们利用饱和磷脂水合排列多层的偏振拉曼实验,对 C-H 伸展带的有序敏感性进行了描述。通过这种方法,以无模型的方式获得了来自 CH2 对称和非对称振动的拉曼贡献。宽温度范围内的实验和同位素隔离的使用帮助我们分别考虑了链的构象和横向顺序的影响。DFT 建模证实了反对称振动谱的构象敏感性。研究结果使我们能够为使用 C-H 伸展带的拉曼光谱来表征含磷脂材料的构象和横向顺序提供建议。
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来源期刊
CiteScore
5.40
自引率
8.00%
发文量
185
审稿时长
3.0 months
期刊介绍: The Journal of Raman Spectroscopy is an international journal dedicated to the publication of original research at the cutting edge of all areas of science and technology related to Raman spectroscopy. The journal seeks to be the central forum for documenting the evolution of the broadly-defined field of Raman spectroscopy that includes an increasing number of rapidly developing techniques and an ever-widening array of interdisciplinary applications. Such topics include time-resolved, coherent and non-linear Raman spectroscopies, nanostructure-based surface-enhanced and tip-enhanced Raman spectroscopies of molecules, resonance Raman to investigate the structure-function relationships and dynamics of biological molecules, linear and nonlinear Raman imaging and microscopy, biomedical applications of Raman, theoretical formalism and advances in quantum computational methodology of all forms of Raman scattering, Raman spectroscopy in archaeology and art, advances in remote Raman sensing and industrial applications, and Raman optical activity of all classes of chiral molecules.
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