Thermally induced molecular disorder in human stratum corneum lipids compared with a model phospholipid system; FT-Raman spectroscopy

Abstract

The molecular basis of lipid packing in human stratum corneum and a model phospholipid system has been studied as a function of temperature using Fourier Transform (FT) Raman spectroscopy. Thermally induced molecular rearrangements of the model lipid system, dipalmitoylphosphatidyl choline (DPPC), and stratum corneum were investigated using FT Raman spectroscopy coupled to a heating chamber. Spectra were recorded for a range of sample temperatures and the results for the two systems were compared, producing previously unreported information of the thermal behaviour for the different systems. Discrete thermal events were recorded for both systems by plotting band separation of the lipid υ(CH2) symmetric and asymmetric stretching modes against temperature. The main thermal events observed for DPPC included a `pre-melting' between 37 and 39°C, the main transition observed between 41 and 42°C, a `post-transition' between 42 and 43°C and three minor transitions at 58–60, 65–70 and 75–80°C. No evidence was found for the pre-transition of DPPC, previously observed at 34–35°C. The main transitions for human stratum corneum were observed at 35–45, 55, 72 and 83°C, measured from lipid CH2 stretching and bending vibrations. The keratin thermal transition at about 100°C exerted little effect on the lipid bands and no characterisable structural changes were reflected in the keratotic bands.