Characterisation of a new ceramide EOS species: synthesis and investigation of the thermotropic phase behaviour and influence on the bilayer architecture of stratum corneum lipid model membranes
Characterisation of a new ceramide EOS species: synthesis and investigation of the thermotropic phase behaviour and influence on the bilayer architecture of stratum corneum lipid model membranes
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DOI：
10.1039/c1sm05134b
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发表时间：
2011-09
期刊：
影响因子：
3.4
通讯作者：
T. Engelbrecht;T. Hauß;Kevin Süβ;Alexander Vogel;Matthew Roark;S. Feller;R. Neubert;B. Dobner
中科院分区：
文献类型：
--
作者：
T. Engelbrecht;T. Hauß;Kevin Süβ;Alexander Vogel;Matthew Roark;S. Feller;R. Neubert;B. Dobner
已知角质层的脂质，特别是神经酰胺，对皮肤屏障性质起关键作用。因此，独特的ω-酰基神经酰胺EOS被认为是形成保护性包膜的先决条件。我们报道了一种新的神经酰胺EOS衍生物的化学合成，该衍生物构成饱和和支链的ω-酰基链而不是天然存在的ω-酯化亚油酸部分，因此显示出对氧化影响的改善的稳定性。此外，用差示扫描量热法（DSC）和傅里叶变换拉曼光谱研究了新的神经酰胺的热致相行为。结果表明相行为类似于已知的天然存在的神经酰胺EOS。链包装行为以及相变温度被发现是可比的两种神经酰胺物种。此外，本研究解决的问题，通过中子衍射的特点导向四层角质层脂质模型膜的基础上，新的神经酰胺EOS衍生物。结果表明，形成了一个稳定的双层结构与膜参数相媲美的四元模型系统含有天然存在的神经酰胺EOS物种。额外的分子动力学模拟证实了从中子衍射和拟议的脂双层排列中获得的发现。
The lipids of the stratum corneum, particularly the ceramides, are known to play a crucial role for the skin barrier properties. Thereby, the unique ω-acyl ceramide EOS is regarded to be a precondition for the formation of a protective envelope. We report on the chemical synthesis of a new ceramide EOS derivative constituting a saturated and branched ω-acyl chain instead of the naturally occurring ω-esterified linoleic acid moiety, therefore showing an improved stability against oxidative influences. In addition, the thermotropic phase behaviour of the new ceramide was studied using differential scanning calorimetry (DSC) and Fourier transform Raman spectroscopy. The results indicate a phase behaviour similar to the one known for the naturally occurring ceramide EOS. Chain packing behaviour as well as phase transition temperatures are found to be comparable for both ceramide species. Furthermore, the present study addresses the issue of characterising oriented quaternary stratum corneum lipid model membranes based on the new ceramide EOS derivative by means of neutron diffraction. The results indicate the formation of a stable bilayer architecture with membrane parameters comparable to the quaternary model systems containing naturally the occurring ceramide EOS species. Additional molecular dynamics simulations corroborated the findings received from neutron diffraction and the proposed lipid bilayer arrangement.