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Raman study of temperature-induced hydrocarbon chain disorder in saturated phosphatidylcholines.
Chemistry and Physics of Lipids ( IF 3.4 ) Pub Date : 2020-05-23 , DOI: 10.1016/j.chemphyslip.2020.104926
Yu V Zaytseva 1 , S V Adichtchev 1 , N V Surovtsev 1
Affiliation  

Raman spectra of hydrated bilayers of 1,2-dilauroyl-sn-glycero-3-phosphocholine (12:0 PC), 1,2-dimyristoyl-sn-glycero-3-phosphocholine (14:0 PC), and 1,2-distearoyl-sn-glycero-3-phosphocholine (18:0 PC) were studied in a wide temperature range to characterize the temperature-dependent hydrocarbon chain disorder of the saturated phosphatidylcholines. Temperature dependencies of the Raman line intensities were analyzed for the antisymmetric CH2 stretching and CC stretching vibrations, which are sensitive to the lipid order. It was found that chain disordering processes occur significantly below the gel-fluid transition. The chain conformational order characterized by the CC stretching line intensity can be well described by a model involving the excitation of the ordered conformational state to the kinked and highly disordered, fluid-like state. A relation between the excitation energy to the disordered state and the enthalpy of the gel-fluid transition is discussed, including also data for other phosphatidylcholines studied before. Temperature behavior of the antisymmetric CH2 stretching line indicates that non-conformational degrees of freedom are released above ∼ 200 K. Experimental findings concerning the hydrocarbon chain length dependence of the Raman polarizability of antisymmetric CH2 stretching vibrations and a low-temperature solid-solid phase transition, identified in 12:0 PC at heating, are also discussed in the work.



中文翻译:

拉曼研究温度诱导的饱和磷脂酰胆碱中的烃链紊乱。

1,2-二月桂酰-sn-甘油-3-磷酸胆碱(12:0 PC),1,2-二肉豆蔻酰基-sn-甘油-3-磷酸胆碱(14:0 PC)和1,2的水合双层的拉曼光谱-二硬脂酰-sn-甘油-3-磷酸胆碱(18:0 PC)在较宽的温度范围内进行了研究,以表征饱和磷脂酰胆碱的温度依赖性烃链紊乱。分析了对脂质顺序敏感的反对称CH 2拉伸和CC拉伸振动对拉曼谱线强度的温度依赖性。已经发现,链紊乱过程明显发生在凝胶-流体转变以下。CC表征的链构象顺序拉伸线强度可以通过一个模型来很好地描述,该模型涉及将有序构象态激发为扭结和高度无序的类流体态。讨论了激发能到无序态与凝胶-流体转变焓之间的关系,还包括之前研究的其他磷脂酰胆碱的数据。反对称CH 2拉伸线的温度行为表明,非构象自由度在〜200 K以上释放。关于反对称CH 2拉伸振动的拉曼极化率和低温固-体的烃链长度依赖性的实验结果在工作中还讨论了在12:0 PC加热时识别的相变。

更新日期:2020-05-23
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