The Importance of Free Fatty Chain Length on the Lipid Organization in the Long Periodicity Phase

The skin’s barrier ability is an essential function for terrestrial survival, which is controlled by intercellular lipids within the stratum corneum (SC) layer. In this barrier, free fatty acids (FFAs) are an important lipid class. As seen in inflammatory skin diseases, when the lipid chain length is reduced, a reduction in the barrier’s performance is observed. In this study, we have investigated the contributing effects of various FFA chain lengths on the lamellar phase, lateral packing. The repeat distance of the lamellar phase increased with FFA chain length (C20–C28), while shorter FFAs (C16 to C18) had the opposite behaviour. While the lateral packing was affected, the orthorhombic to hexagonal to fluid phase transitions were not affected by the FFA chain length. Porcine SC lipid composition mimicking model was then used to investigate the proportional effect of shorter FFA C16, up to 50% content of the total FFA mixture. At this level, no difference in the overall lamellar phases and lateral packing was observed, while a significant increase in the water permeability was detected. Our results demonstrate a FFA C16 threshold that must be exceeded before the structure and barrier function of the long periodicity phase (LPP) is affected. These results are important to understand the lipid behaviour in this unique LPP structure as well as for the understanding, treatment, and development of inflammatory skin conditions.     

In Situ Ultraviolet Raman Study on the Phase Transition of Hafnia up to 2085 K

We have recently demonstrated that the Raman scattering through ultraviolet (UV) excitation is eminently well suited for in situ investigation of materials at high temperatures up to 1773 K. Here we report successful Raman measurements of HfO₂ up to 2085 K, using only a 100 mW power of UV laser line. The monoclinic-to-tetragonal transformation finished around 2080 K on heating, while the monoclinic phase appeared at 2018 K on cooling.     

Supercritical Fluids in Catalysis: Opportunities of In Situ Spectroscopic Studies and Monitoring Phase Behavior

A number of homogeneous and heterogeneous catalytic reactions have been successfully performed in supercritical fluids (SCFs). An overview on recent developments in the areas of alkylation, isomerization, hydrogenation, partial oxidation, amination, and CO₂-fixation using heterogeneous catalysts and supercritical fluids is given. Additionally, strategies towards a more fundamental understanding of catalytic reactions in supercritical fluids are outlined. One aspect is the identification of phase behavior in such multicomponent systems. Their complexity and the input of in situ monitoring is discussed. It is proposed that binary fluid mixtures are an ideal guide for simplifying and understanding the phase behavior in reaction mixtures. In order to strengthen the future use of this knowledge, e.g., for optimization of reactions in SCFs, an overview on the different topologies of binary mixtures is given. Another aspect is in situ characterization of the catalytic reaction and their intermediates, the intermolecular interactions in the fluid, the heterogeneous catalyst phase, and the solid/fluid interphase. The opportunities of various available spectroscopic tools, applicable in situ, are also reviewed by referring to examples from homogeneous catalysis or low-pressure studies.     

Application of Single Molecule Fluorescence Microscopy to Characterize the Penetration of a Large Amphiphilic Molecule in the Stratum Corneum of Human Skin

We report here on the application of laser-based single molecule total internal reflection fluorescence microscopy (TIRFM) to study the penetration of molecules through the skin. Penetration of topically applied drug molecules is often observed to be limited by the size of the respective drug. However, the molecular mechanisms which govern the penetration of molecules through the outermost layer of the skin are still largely unknown. As a model compound we have chosen a larger amphiphilic molecule (fluorescent dye ATTO-Oxa12) with a molecular weight >700 Da that was applied to excised human skin. ATTO-Oxa12 penetrated through the stratum corneum (SC) into the viable epidermis as revealed by TIRFM of cryosections. Single particle tracking of ATTO-Oxa12 within SC sheets obtained by tape stripping allowed us to gain information on the localization as well as the lateral diffusion dynamics of these molecules. ATTO-Oxa12 appeared to be highly confined in the SC lipid region between (intercellular space) or close to the envelope of the corneocytes. Three main distinct confinement sizes of 52 ± 6, 118 ± 4, and 205 ± 5 nm were determined. We conclude that for this amphiphilic model compound several pathways through the skin exist.