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质子化和氘代 1,2-二棕榈酰-sn-甘油-3-磷酸胆碱(DPPC)中的喇曼散射:构象和层序的指示剂。

Raman scattering in protonated and deuterated 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC): Indicators of conformational and lateral orders.

机构信息

Institute of Automation and Electrometry, Russian Academy of Sciences, Novosibirsk 630090, Russia.

Institute of Automation and Electrometry, Russian Academy of Sciences, Novosibirsk 630090, Russia.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2022 Feb 15;267(Pt 2):120583. doi: 10.1016/j.saa.2021.120583. Epub 2021 Nov 6.

Abstract

The use of deuterocarbons is an effective method in the Raman spectroscopy of multicomponent lipid materials and biological samples. Here, Raman spectra of hydrated multilamellar vesicles of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), its deuterated analog 1,2-dipalmitoyl-d62-sn-glycero-3-phosphocholine (DPPC), and DPPC-DPPC mixtures were studied in a wide temperature range to specify the Raman indicators of conformational and lateral orders. The temperature dependence of the 985 cm line in the deuterated phospholipid unequivocally indicates that this line corresponds to the CC stretching vibrations of deuterated hydrocarbon chains in the all-trans conformation. It was also concluded that the ratio of Raman intensities at the maximum of the peak of the symmetric CD stretching and at a maximum near 2168 cm reflects the conformational order of the hydrocarbon chain and can be used for an evaluation of the fraction of the all-trans sequences. The frequency of the symmetric CD stretching peak is sensitive to the phase state (gel or fluid) but has a low sensitivity to the partial conformational disordering within the gel phase. The Raman study of DPPC-DPPC mixtures reveals that the lateral order contributes to the ratio of intensities of the antisymmetric and symmetric CH stretching peaks as a prefactor enhancing the effect of conformational ordering.

摘要

氘代物的使用是多组分脂质材料和生物样品的拉曼光谱学中的一种有效方法。在这里,研究了水合的 1,2-二棕榈酰基-sn-甘油-3-磷酸胆碱(DPPC)的多层囊泡、其氘代类似物 1,2-二棕榈酰基-d62-sn-甘油-3-磷酸胆碱(DPPC-d62)和 DPPC-DPPC 混合物的在宽温度范围内的拉曼光谱,以指定构象和横向有序的拉曼指标。氘代磷脂中 985 cm 线的温度依赖性明确表明,该线对应于全反式构象中氘代烃链的 CC 伸缩振动。还得出结论,对称 CD 伸缩峰最大值处的拉曼强度比与在约 2168 cm 处的最大值附近的拉曼强度比反映了烃链的构象有序性,并且可用于评估全反式序列的分数。对称 CD 伸缩峰的频率对相态(凝胶或液体)敏感,但对凝胶相内的部分构象无序具有低灵敏度。DPPC-DPPC 混合物的拉曼研究表明,横向有序作为增强构象有序作用的前因子,有助于反式和对称 CH 伸缩峰强度比。

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