Polymorphism of ceramide 6: a vibrational spectroscopic and X-ray powder diffraction investigation of the diastereomers of N-(alpha-hydroxyoctadecanoyl)-phytosphingosine.

A preparative chromatographic method was developed for the quantitative isolation of the diastereomers of synthetic N-(alpha-hydroxyoctadecanoyl)-phytosphingosine (DL-CER6). The L- and the D-compound were studied each by means X-ray powder diffraction, FT-Raman and FT-IR spectroscopy. The diastereomers exhibit different thermotropic polymorphism. Three lamellar crystalline and a lamellar liquid crystalline phase were found for L-CER6. The natural occurring D-CER6 forms an Lalpha phase with a larger repeating distance than the L-CER6. The two lamellar crystalline phases of the D-compound have a significant larger dimension than those of the L-compound. The addition of water lowers the phase transition temperatures but does not induce structural changes such as incorporation into the lamellar sheets.

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

The thermotropic properties of N-(alpha-hydroxyacyl)-sphingosine (CER[AS]) in dry and hydrated state were studied by means of X-ray powder diffraction and FT-Raman spectroscopy. The polymorphic states of the CER[AS]/water mixture (lamellar crystalline, lamellar hexagonal gel, liquid crystalline) depend on the thermal pre-treatment of the sample. Only by heating the CER[AS]/water mixture above the melting chain transition can the system be hydrated. At room temperature, both dry and hydrated states form lamellar structures, which differ in their repeat distance and packing of hydrocarbon chains. Above the melting chain transition, hydrated CER[AS] forms a liquid crystalline hexagonal phase, whereas anhydrous CER[AS] forms an isotropic liquid phase. The various phases of hydrated CER[AS] are distinguished on the basis of the corresponding Raman spectra.

Polymorphism of ceramide 3. Part 2: a vibrational spectroscopic and X-ray powder diffraction investigation of N-octadecanoyl phytosphingosine and the analogous specifically deuterated d(35) derivative.

In order to characterize the arrangements of the hydrocarbon chains of ceramide 3, the thermotropic phase behaviour of the ceramides N-octadecanoylphytosphingosine (CER3) and its chain deuterated derivative N-(d(35)-octadecanoyl)phytosphingosine (d(35)CER3) was studied by means of X-ray powder diffraction, FT-IR and Raman spectroscopy. CER3 and d(35)CER3 exhibit an identical thermotropic polymorphism involving three different crystalline phases. The selective deuteration of the fatty acid chain enables to distinguish the sphingoid part from the fatty acid part by means of FT-IR and Raman spectroscopy. It could be shown that both hydrocarbon chains are arranged in different subcells. Temperature dependent Raman measurements elucidate simultaneously the changes in the trans/gauche ratios and the packing of both the hydrocarbon chains of the fatty acid and of the sphingoid part. The phase behaviour of CER3 and d(35)CER3, both dry and hydrated, was investigated.

Polymorphism of ceramide 3. Part 1: an investigation focused on the head group of N-octadecanoylphytosphingosine.

The thermotropic phase behaviour of the ceramide N-octadecanoylphytosphingosine (CER3) was investigated using differential scanning calorimetry, X-ray powder diffraction and FT-IR spectroscopy. CER3 was shown to be a polymorphic substance depending on the crystallisation conditions. Three different solid states were found. The FT-IR results elucidate changes in the hydrogen bonding interactions of the ceramide head group. It was shown that the amide I and the amide II vibration bands are quite sensitive to the phase transitions of CER. There are clear shifts in the band positions of those bands passing the phase transitions. Furthermore, changes were observed in the NH- and OH- stretching region. The study shows that there are strong inter- and intramolecular hydrogen bonds between hydroxy groups in the ceramide head group. There are also strong hydrogen bonds to the amide oxygen as shown by the band positions of the amide vibrations. The H-bonding network and conformation of the head group of CER3 alters due to the phase transitions.

Phase behaviour of transkarbam 12.

Transkarbam 12 (T12), the carbamic acid salt of omega-aminocaproic acid dodecyl ester, is a recently synthesized substance, whose high permeation enhancing activity through the human skin was found for certain drugs. In this work, the thermotropic phase behaviour of T12 has been studied by means of various techniques, namely, DSC, FTIR and FT-Raman spectroscopy, X-ray powder diffraction, and DRS. The temperature development of the X-ray reflections as well as of the conformationally sensitive Raman bands and the IR bands have been observed. At room temperature, the hydrocarbon chains of T12 exhibit a highly ordered structure, arranged in an orthorhombic perpendicular subcell. On heating, two transitions occur at 54 and at 66 degrees C. The first transition is related to the disruption of the carbamate structure and changes in the polar head group. The other transition represents the melting of hydrocarbon chains and the subsequent release of carbon dioxide. The time required for the rebinding of carbon dioxide and the reformation of the carbamate structure is dependent upon numerous factors and it was not possible to precisely determine the length of this process.