Effects of (R)- and (S)-α-Hydroxylation of Acyl Chains in Sphingosine, Dihydrosphingosine, and Phytosphingosine Ceramides on Phase Behavior and Permeability of Skin Lipid Models.
Effects of (R)- and (S)-α-Hydroxylation of Acyl Chains in Sphingosine, Dihydrosphingosine, and Phytosphingosine Ceramides on Phase Behavior and Permeability of Skin Lipid Models.
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DOI：
10.3390/ijms22147468
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发表时间：
2021-07-12
影响因子：
5.6
通讯作者：
Vávrová K
中科院分区：
文献类型：
--
作者：
Kováčik A;Pullmannová P;Opálka L;Šilarová M;Maixner J;Vávrová K
具有α-羟基化酰基链的神经酰胺（Cers）约占所有可提取皮肤Cers的三分之一，并且是渗透性屏障稳态所需的。我们在此探讨了Cer羟基化对其在脂质模型中的行为的影响，所述脂质模型包括主要SC脂质、Cer/游离脂肪酸（C16-C24）/胆固醇和次要组分胆固醇硫酸酯。即，将具有连接至鞘氨醇（Cer AS）、二氢鞘氨醇（Cer AdS）和植物鞘氨醇（Cer AP）的（R）-α-羟基二十四烷酰基链的Cer与它们的非天然（S）-非对映异构体以及具有连接至鞘氨醇（Cer NS）、二氢鞘氨醇（Cer NdS）和植物鞘氨醇（Cer NP）的非羟基化二十四烷酰基链的Cer进行比较。通过比较几个生物物理参数（X射线衍射法测定的层状组织、链序、侧向堆积、相变和使用氘代脂质的红外光谱法测定的脂质混合）和这些模型的渗透性（水分损失和两个渗透性标志物），我们得出结论，Cer α-羟基化没有一般或共同的后果。相反，我们发现了多种效应，高度依赖于鞘氨醇基链、α-碳的构型和所用的渗透性标记。我们发现具有非天然Cer（S）-AS的模型膜比基于（R）-非对映体的模型膜具有更少的正交堆积的脂质链。此外，生理（R）-构型降低了Cer（R）-AdS对茶碱的膜渗透性，并增加了天然Cer（R）-AP模型系统中的脂质链顺序。因此，每个Cer亚类对皮肤脂质屏障的结构组织和功能做出独特的贡献。
Ceramides (Cers) with α-hydroxylated acyl chains comprise about a third of all extractable skin Cers and are required for permeability barrier homeostasis. We have probed here the effects of Cer hydroxylation on their behavior in lipid models comprising the major SC lipids, Cer/free fatty acids (C 16-C 24)/cholesterol, and a minor component, cholesteryl sulfate. Namely, Cers with (R)-α-hydroxy lignoceroyl chains attached to sphingosine (Cer AS), dihydrosphingosine (Cer AdS), and phytosphingosine (Cer AP) were compared to their unnatural (S)-diastereomers and to Cers with non-hydroxylated lignoceroyl chains attached to sphingosine (Cer NS), dihydrosphingosine (Cer NdS), and phytosphingosine (Cer NP). By comparing several biophysical parameters (lamellar organization by X-ray diffraction, chain order, lateral packing, phase transitions, and lipid mixing by infrared spectroscopy using deuterated lipids) and the permeabilities of these models (water loss and two permeability markers), we conclude that there is no general or common consequence of Cer α-hydroxylation. Instead, we found a rich mix of effects, highly dependent on the sphingoid base chain, configuration at the α-carbon, and permeability marker used. We found that the model membranes with unnatural Cer (S)-AS have fewer orthorhombically packed lipid chains than those based on the (R)-diastereomer. In addition, physiological (R)-configuration decreases the permeability of membranes, with Cer (R)-AdS to theophylline, and increases the lipid chain order in model systems with natural Cer (R)-AP. Thus, each Cer subclass makes a distinct contribution to the structural organization and function of the skin lipid barrier.
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影响因子：
6.5
作者：
BOUWSTRA, JA;GOORIS, GS;BRAS, W
通讯作者：
BRAS, W
影响因子：
3.4
作者：
Engelbrecht, Tanja N.;Schroeter, Annett;Neubert, Reinhard H. H.
通讯作者：
Neubert, Reinhard H. H.
影响因子：
3.9
作者：
Kovacik, Andrej;Pullmannova, Petra;Vavrova, Katerina
通讯作者：
Vavrova, Katerina
DOI：
10.1107/s0567740872006193
发表时间：
1972-01-01
期刊：
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL CRYSTALLOGRAPHY AND CRYSTAL CHEMISTRY
影响因子：
--
作者：
DAHLEN, B;PASCHER, I
通讯作者：
PASCHER, I
影响因子：
3.4
作者：
de Jager, MW;Gooris, GS;Bouwstra, JA
通讯作者：
Bouwstra, JA