The non‐homogenous distribution and aggregation of carotenoids in the stratum corneum correlates with the organization of intercellular lipids in vivo.

The human stratum corneum (SC) contains an abundant amount of carotenoid antioxidants, quenching free radicals and thereby protecting the skin. For the precise measurements of the depth‐dependent carotenoid concentration, confocal Raman microscopy is a suitable method. The quantitative concentration can be determined by the carotenoid‐related peak intensity of a Gaussian function approached at ≈1524 cm−1 using non‐linear regression. Results show that the carotenoid concentration is higher at the superficial layers of the SC then decreases to a minimum at 20% SC depth and increases again towards the bottom of the SC. In the present work, two carotenoid penetration pathways into the SC are postulated. The first pathway is from the stratum granulosum to the bottom of the SC, while in the second pathway, the carotenoids are delivered to the skin surface by sweat and/or sebum secretion and penetrate from outside. The carotenoids are aggregated at the superficial layers, which are shown by high correlation between the aggregation states of carotenoids and the lateral organization of lipids. At the 30%‐40% SC depths, the ordered and dense lipid molecules intensify the lipid‐carotenoid interactions and weaken the carotenoid‐carotenoid interaction and thus exhibit the disaggregation of carotenoids. At 90%‐100% SC depths, the carotenoid‐lipid interaction is weakened and the carotenoids have a tendency to be aggregated. Thus, the molecular structural correlation of carotenoid and SC lipid might be reserved in the intercellular space of the SC and also serves as the skeleton of the intercellular lipids. [ABSTRACT FROM AUTHOR]