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Article

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

1
Skin Barrier Research Group, Faculty of Pharmacy in Hradec Králové, Charles University, Akademika Heyrovského 1203, 500 05 Hradec Králové, Czech Republic
2
Faculty of Chemical Technology, University of Chemistry and Technology in Prague, Technická 5, 166 28 Prague, Czech Republic
*
Author to whom correspondence should be addressed.
Academic Editor: Philip W. Wertz
Int. J. Mol. Sci. 2021, 22(14), 7468; https://0-doi-org.brum.beds.ac.uk/10.3390/ijms22147468
Received: 28 May 2021 / Revised: 8 July 2021 / Accepted: 9 July 2021 / Published: 12 July 2021
(This article belongs to the Special Issue Barrier Function of Skin and Oral Mucosa)
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. View Full-Text
Keywords: skin barrier; stratum corneum; lipids; ceramides; hydroxylation; biophysics; permeability skin barrier; stratum corneum; lipids; ceramides; hydroxylation; biophysics; permeability
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MDPI and ACS Style

Kováčik, A.; Pullmannová, P.; Opálka, L.; Šilarová, M.; Maixner, J.; Vávrová, K. 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. Int. J. Mol. Sci. 2021, 22, 7468. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms22147468

AMA Style

Kováčik A, Pullmannová P, Opálka L, Šilarová M, Maixner J, Vávrová K. 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. International Journal of Molecular Sciences. 2021; 22(14):7468. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms22147468

Chicago/Turabian Style

Kováčik, Andrej, Petra Pullmannová, Lukáš Opálka, Michaela Šilarová, Jaroslav Maixner, and Kateřina Vávrová. 2021. "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" International Journal of Molecular Sciences 22, no. 14: 7468. https://0-doi-org.brum.beds.ac.uk/10.3390/ijms22147468

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