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角鲨烯在正构烷烃和角鲨烷中的扩散。

Diffusion of squalene in n-alkanes and squalane.

机构信息

Department of Chemistry, St. Louis University , 3501 Laclede Ave., St. Louis, Missouri 63103.

出版信息

J Phys Chem B. 2014 Feb 27;118(8):2157-63. doi: 10.1021/jp411471r. Epub 2014 Feb 14.

Abstract

Squalene, an intermediate in the biosynthesis of cholesterol, has a 24-carbon backbone with six methyl groups and six isolated double bonds. Capillary flow techniques have been used to determine its translational diffusion constant, D, at room temperature in squalane, n-C16, and three n-C8-squalane mixtures. The D values have a weaker dependence on viscosity, η, than predicted by the Stokes-Einstein relation, D = kBT/(6πηr). A fit to the modified relation, D/T = ASE/η(p), gives p = 0.820 ± 0.028; p = 1 for the Stokes-Einstein limit. The translational motion of squalene appears to be much like that of n-alkane solutes with comparable chain lengths; their D values show similar deviations from the Stokes-Einstein model. The n-alkane with the same carbon chain length as squalene, n-C24, has a near-equal p value of 0.844 ± 0.018 in n-alkane solvents. The values of the hydrodynamic radius, r, for n-C24, squalene, and other n-alkane solutes decrease as the viscosity increases and have a common dependence on the van der Waals volumes of the solute and solvent. The possibility of studying squalene in lipid droplets and membranes is discussed.

摘要

角鲨烯是胆固醇生物合成的中间产物,具有 24 个碳原子的主链,带有六个甲基和六个孤立的双键。已经使用毛细管流动技术在 squalane、n-C16 和三种 n-C8-squalane 混合物中测定了室温下角鲨烯的平移扩散常数 D。D 值对粘度 η 的依赖性比 Stokes-Einstein 关系 D = kBT/(6πηr)预测的要弱。对修正关系 D/T = ASE/η(p)的拟合给出了 p = 0.820 ± 0.028;对于 Stokes-Einstein 极限,p = 1。角鲨烯的平移运动类似于具有可比链长的 n-烷烃溶质;它们的 D 值表现出与 Stokes-Einstein 模型的相似偏差。与角鲨烯具有相同碳链长度的 n-烷烃 n-C24 在 n-烷烃溶剂中具有接近相等的 p 值 0.844 ± 0.018。n-C24、角鲨烯和其他 n-烷烃溶质的水力学半径 r 值随粘度的增加而减小,并且与溶质和溶剂的范德华体积有共同的依赖性。讨论了在脂质滴和膜中研究角鲨烯的可能性。

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