12R‐lipoxygenase activity is reduced in photodamaged facial stratum corneum. A novel activity assay indicates a key function in corneocyte maturation

Background During the late stage of keratinocyte differentiation, corneocytes gain a strong protein–lipid structure: the corneocyte envelopes (CE), composed of the inner corneocyte protein envelope (CPE) and the outer corneocyte lipid envelope (CLE). The hydrophobicity of CEs depends on the covalent attachment of linoleoyl‐acyl‐ceramides by transglutaminases (TG). These ceramides are processed by a range of other enzymes, including 12R‐lipoxygenase (12R‐LOX), before the covalent attachment of the free ω‐hydroxyceramides to the CPE surface to form the CLE. The mechanical strength of CE is obtained with the formation of isodipeptide bonds by TG. The increase in hydrophobicity and rigidity leads to CE maturation which supports the integrity and mechanical resistance of the stratum corneum (SC).