Hydration properties of N-(α-hydroxyacyl)-sphingosine: X-ray powder diffraction and FT–Raman spectroscopic studies

Raudenkolb, Steve; Wartewig, S.; Brezesinski, Gerald; Funari, Sérgio S.; Neubert, Reinhard H.H.

doi:10.1016/j.chemphyslip.2005.03.005

Cited by 14 publications

(8 citation statements)

References 24 publications

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“…from a phase with lower curvature to a phase with a higher curvature, has been observed for other lipid systems [72]. However, there are no evidences in the literature of non-lamellar structures in the SC at ambient temperatures, although there are indications of a reversed hexagonal phase in ceramide mixtures at high temperatures [73,74]. The exothermic heat effect could also be related to an increase in the local curvature at the boundaries between the domains of different lamellar structures.…”

Section: Solid and Fluid Sc Lipidsmentioning

confidence: 88%

Stratum corneum hydration: Phase transformations and mobility in stratum corneum, extracted lipids and isolated corneocytes

Silva

Topgaard

Kocherbitov

et al. 2007

Biochimica et Biophysica Acta (BBA) - Biomembranes

106

102

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The outermost layer of skin, stratum corneum (SC), functions as the major barrier to diffusion. SC has the architecture of dead keratin filled cells embedded in a lipid matrix. This work presents a detailed study of the hydration process in extracted SC lipids, isolated corneocytes and intact SC. Using isothermal sorption microcalorimetry and relaxation and wideline (1)H NMR, we study these systems at varying degrees of hydration/relative humidities (RH) at 25 degrees C. The basic findings are (i) there is a substantial swelling both of SC lipids, the corneocytes and the intact SC at high RH. At low RHs corneocytes take up more water than SC lipids do, while at high RHs swelling of SC lipids is more pronounced than that of corneocytes. (ii) Lipids in a fluid state are present in both extracted SC lipids and in the intact SC. (iii) The fraction of fluid lipids is lower at 1.4% water content than at 15% but remains virtually constant as the water content is further increased. (iv) Three exothermic phase transitions are detected in the SC lipids at RH=91-94%, and we speculate that the lipid re-organization is responsible for the hydration-induced variations in SC permeability. (v) The hydration causes swelling in the corneocytes, while it does not affect the mobility of solid components (keratin filaments).

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Section: Solid and Fluid Sc Lipidsmentioning

confidence: 88%

Stratum corneum hydration: Phase transformations and mobility in stratum corneum, extracted lipids and isolated corneocytes

Silva

Topgaard

Kocherbitov

et al. 2007

Biochimica et Biophysica Acta (BBA) - Biomembranes

106

102

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“…The alkyl chains are not highly ordered due to the extremely mismatch in the length of the acyl-chain residue. The latter causes a distinct fluidity of the chains preventing the formation of order as being known for many other shorter chain ceramides (Raudenkolb et al, 2003a(Raudenkolb et al, , 2005b.…”

Section: Raman Spectroscopymentioning

confidence: 98%

“…Utilization of Raman spectroscopy for elucidating phase transitions, the population of trans and gauche conformers, and the state of order as well as the packing properties of hydrocarbon chains of lipids is well established (Kirchoff and Levin, 1987;Mendelsohn and Moore, 1998;Raudenkolb et al, 2005b).…”

Section: Raman Spectroscopymentioning

confidence: 99%

Impact of the long chain ω-acylceramides on the stratum corneum lipid nanostructure. Part 1: Thermotropic phase behaviour of CER[EOS] and CER[EOP] studied using X-ray powder diffraction and FT-Raman spectroscopy

Kessner

Brezesinski

Funari³

et al. 2010

Chemistry and Physics of Lipids

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The stratum corneum (SC), the outermost layer of the mammalian skin, is the main skin barrier. Ceramides (CERs) as the major constituent of the SC lipid matrix are of particular interest. At the moment, 11 classes of CERs are identified, but the effect of each single ceramide species is still not known. Therefore in this article, the thermotropic behaviour of the long chain omega-acylceramides CER[EOS] and CER[EOP] was studied using X-ray powder diffraction and FT-Raman spectroscopy. It was found that the omega-acylceramides CER[EOS] and CER[EOP] do not show a pronounced polymorphism which is observed for shorter chain ceramides as a significant feature. The phase behaviour of both ceramides is strongly influenced by the extremely long acyl-chain residue. The latter has a much stronger influence compared with the structure of the polar head group, which is discussed as extremely important for the appearance of a rich polymorphism. Despite the strong influence of the long chain, the additional OH-group of the phyto-sphingosine type CER[EOP] influences the lamellar repeat distance and the chain packing. The less polar sphingosine type CER[EOS] is stronger influenced by the long acyl-chain residue. Hydration is necessary for the formation of an extended hydrogen-bonding network between the polar head groups leading to the appearance of a long-periodicity phase (LPP). In contrast, the more polar CER[EOP] forms the LPP with densely packed alkyl chains already in the dry state.

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“…In particular, the longitudinal acoustic mode undoubtedly demonstrates the existence of all-trans (planar zig-zag) conformation of chains. The X-ray diffraction pattern for CER AS at room temperature indicates a lamellar crystalline phase L C with a periodicity of 5.4 nm and a monoclinic subcell M II in which the chains pack all with their chain planes parallel and the zig-zag structure of adjacent chains runs in phase [38] . The transition from the crystalline state to the melt with a midpoint at 89 ° C is reversible.…”

Section: Cer As Anhydrousmentioning

confidence: 99%

“…The properties of hydrous CER AS have been investigated by means of FTIR spectroscopy [40,41] , X-ray powder diffraction and Raman spectroscopy [38] . The polymorphic states of the CER AS/water mixture depend on the thermal pre-treatment of the sample.…”

Section: Cer As Hydrousmentioning

confidence: 99%

Properties of Ceramides and Their Impact on the Stratum Corneum Structure: A Review

Wartewig

Neubert

2007

Skin Pharmacol Physiol

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The lipid matrix of the stratum corneum (SC) is the major diffusion-rate-limiting pathway by which most drugs intracellularly pass the SC. The major lipid classes extracted from the SC are ceramides, cholesterol and free fatty acids. Ceramides that comprise nine subclasses play a crucial role in maintaining the barrier function of the skin. A profound knowledge of the physical properties of ceramides is essential for a deeper understanding of the impact of each ceramide species on the barrier function. The review summarizes the thermotropic and/or lyotropic behaviour of sphingosine-type ceramides (CER AS, CER NS) and phytosphingosine-type ceramides (CER AP, CER NP) revealed by differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy and Fourier transform Raman spectroscopy in past decades. Polymorphism is a characteristic feature of ceramides. At physiological temperatures, all crystalline phases of ceramides exhibit lamellar structures with highly ordered hydrocarbon chains. The differential behaviour of the head groups of ceramides may be an important determinant for the skin barrier function.

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Hydration properties of N-(α-hydroxyacyl)-sphingosine: X-ray powder diffraction and FT–Raman spectroscopic studies

Cited by 14 publications

References 24 publications

Stratum corneum hydration: Phase transformations and mobility in stratum corneum, extracted lipids and isolated corneocytes

Stratum corneum hydration: Phase transformations and mobility in stratum corneum, extracted lipids and isolated corneocytes

Impact of the long chain ω-acylceramides on the stratum corneum lipid nanostructure. Part 1: Thermotropic phase behaviour of CER[EOS] and CER[EOP] studied using X-ray powder diffraction and FT-Raman spectroscopy

Properties of Ceramides and Their Impact on the Stratum Corneum Structure: A Review

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