Polymorphism of ceramide 3. Part 2: a vibrational spectroscopic and X-ray powder diffraction investigation of N-octadecanoyl phytosphingosine and the analogous specifically deuterated d35 derivative

FTIR spectroscopic studies of lipid dynamics in phytosphingosine ceramide models of the stratum corneum lipid matrix

“…This is not unexpected for the phytosphingosine ceramide chains since hexagonal chain packing was previously reported in X-ray diffraction studies on the non-hydrated equimolar ternary Cer NP system and for hydrated and non-hydrated pure phytosphingosine ceramides (Rerek et al, 2001;Ohta and Hatta, 2002;Raudenkolb et al, 2003aRaudenkolb et al, , 2003b. Segregated domains of d 35 -stearic acid would be expected to show orthorhombic packing, however this is not observed initially nor after repeated heating and cooling cycles.…”

“…We have recently described major differences in intermolecular H-bonding, water penetration, and chain behavior between hydrated phytosphingosine and sphingosine ceramides (Rerek et al, 2001). Experimental evidence from a range of techniques (DSC, X-ray, Raman) indicates that phytosphingosine ceramide samples, in various mixtures and degrees of hydration, behave distinctly from the corresponding sphingosine ceramide systems (Ohta and Hatta, 2002;Raudenkolb et al, 2003aRaudenkolb et al, , 2003b. Particularly interesting is that phytosphingosine ceramides, in contrast to sphingosine ceramide systems, appear to form mixtures with stearic acid (Ohta and Hatta, 2002).…”

Progress in the analysis of Stratum corneum ceramides

“…For synthetic ceramides of phytosphingosine type, the polymorphism and the hydrogen-bonding network of the headgroups have been elucidated [106][107][108][109][110][111]. The hydration properties of phytosphingosine and sphingosine ceramides were also characterized [108][109][110]112]. The combination of differential scanning calorimetry (DSC) with vibrational spectroscopic measurements offers the possibility to describe the thermotropic behavior of binary mixtures of ceramide with other constituents of the stratum corneum lipid matrix (e.g.…”

“…Such crystal data are reported for tetracosanoylphytosphingosine [123]. Based on X-ray powder diffraction studies, the lamellar repeat distance of the lipid bilayer as a function of temperature and information on the subcell arrangement of the chains were obtained for various ceramides [108][109][110]112]. It has been demonstrated that the combination of X-ray powder diffraction with vibration spectroscopic methods is a powerful tool for elucidating molecular properties of ceramides.…”

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

“…Applying DSC, X-ray powder diffraction, FTIR and Raman spectroscopy in conjunction, Raudenkolb et al [47,48] elucidated in detail the polymorphism of CER NP in terms of changes in the hydrogen bonding network of the head group, in the trans/gauche ratio and packing of both hydrocarbon chains of the fatty acid and sphingoid part. Depending on the crystallization conditions, anhydrous CER NP shows three lamellar crystalline phases, ␣ , ␤ , and ␦ .…”