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Arrangement of ceramide [EOS] in a stratum corneum lipid model matrix: new aspects revealed by neutron diffraction studies

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Abstract

The lipid matrix in stratum corneum (SC) plays a key role in the barrier function of the mammalian skin. The major lipids are ceramides (CER), cholesterol (CHOL) and free fatty acids (FFA). Especially the unique-structured ω-acylceramide CER[EOS] is regarded to be essential for skin barrier properties by inducing the formation of a long-periodicity phase of 130 Å (LPP). In the present study, the arrangement of CER[EOS], either mixed with CER[AP] and CHOL or with CER[AP], CHOL and palmitic acid (PA), inside a SC lipid model membrane has been studied for the first time by neutron diffraction. For a mixed CER[EOS]/CER[AP]/CHOL membrane in a partly dehydrated state, the internal membrane nanostructure, i.e. the neutron scattering length density profile in the direction normal to the surface, was obtained by Fourier synthesis from the experimental diffraction patterns. The membrane repeat distance is equal to that of the formerly used SC lipid model system composed of CER[AP]/CHOL/PA/ChS. By comparing both the neutron scattering length density profiles, a possible arrangement of synthetic long-chain CER[EOS] molecules inside a SC lipid model matrix is suggested. The analysis of the internal membrane nanostructure implies that one CER[EOS] molecule penetrates from one membrane layer into an adjacent layer. A 130 Å periodicity phase could not be observed under experimental conditions, either in CER/CHOL mixtures or in CER/CHOL/FFA mixture. CER[EOS] can be arranged inside a phase with a repeat unit of 45.2 Å which is predominately formed by short-chain CER[AP] with distinct polarity.

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Abbreviations

CER[AP] :

N-(α-hydroxyoctadecanoyl)-phytosphingosine

CER[EOS] :

30-Linoyloxy-triacontanoic acid-[(2S,3R)-1,3-dihydroxyocta-dec-4-en-zyl]-amide

PA :

Palmitic acid

CHOL :

Cholesterol

ChS :

Cholesterol sulphate

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Acknowledgments

The authors are grateful to Professor Dr A. B. Balagurov for the calculations done for cholesterol crystal. Financial assistance of Hahn–Meitner Institute (Berlin, Germany) is gratefully acknowledged. D. Kessner would like to thank the Graduiertenförderung des Landes Sachsen–Anhalt for funding. The authors would like to thank Evonik Goldschmidt GmbH (Essen, Germany) for the gift of CER[EOS] and CER[AP].

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Authors and Affiliations

  1. Institute of Pharmacy, Martin Luther University Halle/Wittenberg, Wolfgang-Langenbeck-Straße 4, 06120, Halle Saale, Germany

    Doreen Kessner & Reinhard H. H. Neubert

  2. Frank Laboratory of Neutron Physics, Joint Institute for Nuclear Research, Dubna, Moscow Reg, Russia

    Mikhail Kiselev

  3. Institute of Applied Dermatopharmacy, Martin Luther University, Halle Saale, Germany

    Siegfried Wartewig

  4. Hahn–Meitner Institute, Berlin, Germany

    Silvia Dante & Thomas Hauß

  5. Physical Biochemistry, Department of Chemistry, Darmstadt University of Technology, Darmstadt, Germany

    Thomas Hauß

  6. Evonik Goldschmidt GmbH, Essen, Germany

    Peter Lersch

Authors
  1. Doreen Kessner
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  2. Mikhail Kiselev
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  3. Silvia Dante
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  4. Thomas Hauß
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  7. Reinhard H. H. Neubert
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Correspondence to Reinhard H. H. Neubert.

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Kessner, D., Kiselev, M., Dante, S. et al. Arrangement of ceramide [EOS] in a stratum corneum lipid model matrix: new aspects revealed by neutron diffraction studies. Eur Biophys J 37, 989–999 (2008). https://doi.org/10.1007/s00249-008-0328-6

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  • DOI: https://doi.org/10.1007/s00249-008-0328-6

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