Depth dependence of stratum corneum lipid ordering: a slow-tumbling simulation for electron paramagnetic resonance

We investigated the structural ordering of stratum corneum (SC) lipid by means of electron paramagnetic resonance (EPR) slow-tumbling simulation in conjunction with spin probe studies. The SC of human mid-volar forearm was stripped consecutively from three to six times. The EPR probe method detected a characteristic peak of sebaceous matter in the first SC stripping. The order parameter values obtained by the slow-tumbling simulation (S(0)) showed significant differences between each layer compared with those indicated by the conventional order parameter (S) using hyperfine couplings. Although the conventional S values were in the range of 0.56 (outermost layer) to 0.61 (bottom layer), the S(0) values by the simulation changed from 0.22 to 0.96. The present results suggest that the structural ordering of the outermost SC layer is less tight, whereas the structure of inner layers becomes more rigid. Therefore, we concluded that the EPR probe method recognizes sebaceous matters, whereas EPR in conjunction with the simulation allows quantitative evaluation of SC lipid ordering in relation to skin depth.