Probing the Role of Ceramide Headgroup Polarity in Short-Chain Model Skin Barrier Lipid Mixtures by ²H Solid-State NMR Spectroscopy

Langmuir : the ACS Journal of Surfaces and Colloids
Sören StahlbergDaniel Huster

Abstract

The thermoptropic phase behaviors of two stratum corneum model 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-dependent (2)H 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 ...Continue Reading

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Citations

Feb 24, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Andrej KováčikKateřina Vávrová
Jan 23, 2017·Biochimica Et Biophysica Acta. Biomembranes·Barbora ŠkolováKateřina Vávrová
Jan 23, 2018·Experimental Dermatology·Apostolos PappasAnna Nicolaou
Mar 12, 2020·Physical Chemistry Chemical Physics : PCCP·Quoc Dat PhamDaniel Topgaard
Jan 1, 2018·Quarterly Reviews of Biophysics·Quoc Dat PhamDaniel Topgaard
Sep 15, 2017·Chemical Reviews·Trivikram R MoluguMichael F Brown
Aug 19, 2017·Langmuir : the ACS Journal of Surfaces and Colloids·Sören StahlbergDaniel Huster

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