Probing the Role of Ceramide Headgroup Polarity in Short-Chain Model Skin Barrier Lipid Mixtures by ²H Solid-State NMR Spectroscopy.
Probing the Role of Ceramide Headgroup Polarity in Short-Chain Model Skin Barrier Lipid Mixtures by ²H Solid-State NMR Spectroscopy.
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通过 2H 固态核磁共振波谱探讨神经酰胺头基极性在短链模型皮肤屏障脂质混合物中的作用
DOI：
10.1021/acs.langmuir.5b04173
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
D. Huster
中科院分区：
文献类型：
--
作者：
S. Stahlberg;S. Lange;B. Dobner;D. Huster
本文比较了Cer[NS 18]或Cer[NP 18]与硬脂酸和胆固醇等摩尔组成的两层皮层模型脂质混合物的热致相行为。混合物的每种组分都被特定地氘代，使得温度依赖性2H NMR光谱允许解开这些脂质混合物的复杂相多晶型。虽然Cer[NS]基于鞘氨醇主链，但Cer[NP]具有植物鞘氨醇，其将额外的羟基引入神经酰胺的头基并消除双键。从NMR光谱，可以确定所有脂质对各个相的单独贡献。两种脂质混合物的比较揭示了含有Cer[NP]的混合物具有形成更多流体相的趋势。它的结论是，额外的羟基的植物鞘氨醇含有神经酰胺Cer[NP 18]的混合物与链匹配的硬脂酸和胆固醇创建一个包装缺陷，不稳定的正交相态的典型SC混合物。与含有Cer[NS 18]的脂质混合物相比，这种空间冲突有利于凝胶相并促进含有Cer[NP]的脂质混合物在较低温度下形成流体相。
The thermoptropic phase behaviors of twostratum corneummodel lipid mixtures composed of equimolar contributions of either Cer[NS18] or Cer[NP18] with stearic acid and cholesterol were compared. Each component of the mixture was specifically deuterated such that the temperature-dependent2H NMR spectra allowed disentanglement of the complicated phase polymorphism of these lipid mixtures. While Cer[NS] is based on the sphingosine backbone, Cer[NP] features a phytosphingosine, which introduces an additional hydroxyl group into the headgroup of the ceramide and abolishes the double bond. From the NMR spectra, the individual contributions of all lipids to the respective phases could be determined. The comparison of the two lipid mixtures reveals that Cer[NP] containing mixtures have a tendency to form more fluid phases. It is concluded that the additional hydroxyl group of the phytosphingosine-containing ceramide Cer[NP18] in mixture with chain-matched stearic acid and cholesterol creates a packing defect that destabilizes the orthorhombic phase state of canonical SC mixtures. This steric clash favors the gel phase and promotes formation of fluid phases of Cer[NP] containing lipid mixtures at lower temperature compared to those containing Cer[NS18].
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