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Fig 1.

Structures of stratum corneum and formation of the corneocyte lipid envelope (CLE).

(a) An image of the cornified barrier obtained by electron microscopy [5]. In stratum corneum, the corneocytes are bound together by the fusion of three substructures: (i) polymerized proteins forming the corneocyte envelope (CE), (ii) extracellular lamellar lipids between cells, and (iii) a monolayer of covalently bound ceramides and fatty acids, the corneocyte lipid envelope (CLE), covering the CE and forming a scaffold for the extracellular lamellar lipids. (b) Our working hypothesis [9] requires the LOX-catalyzed oxidation of the linoleate in esterified omega-hydroxyacyl-sphingosine (EOS), ceramide, facilitating hydrolysis of the ester bond, separating ceramide OS for coupling to the CE protein by transglutaminase, finally forming the CLE. Trihydroxy-linoleic acid (triol) cleaved from ceramide EOS is produced as the final metabolite. (i) 9-hydroperoxy-11,12-octadecadienoate, (ii) 9,10-epoxy-11E-13-hydroxyoctadecenoate (iii) 9,10,13-trihydroxy-11E-octadecenoate.

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Fig 2.

LC-MS analysis of triols. SIM chromatograms (m/z 329) of triols analyzed by reverse-phase LC-ESI-MS.

(a) Analysis of a mixture of authentic triols-1 to -8 (2 ng) as a standard, (b) triols of forehead skin in normal subjects and (c) atopic dermatitis patients, and (d) triols of forearm skin in normal subjects and (e) atopic dermatitis patients.

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Table 1.

Baseline characteristics and comparison of TEWL and the quantity of trihydroxy-linoleic acids between normal subjects and atopic dermatitis patients.

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Fig 3.

Correlation coefficients between trihydroxy-linoleic acid and TEWL.

(a) Forehead skin and (b) forearm skin of non-lesional area in atopic dermatitis.

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Fig 4.

The mRNA expression of enzymes involved in CLE formation upon IL-4 stimulation.

ALOX12B, ALOXE3 and ABHD9 mRNA levels of primary normal human epidermal keratinocytes were measured by real-time RT-PCR. The mean values of threshold cycle were 27.5 ± 0.5 (ALOX12B), 22.4 ± 0.1 (ALOXE3), 23.1 ± 0.4 (ABHD9), 15.4 ± 0.4 (β-actin), respectively. The amount of mRNA was normalized to that of β-actin using the ΔCt method, as described in the manufacturer’s protocol. Data are expressed as mean ± SD (n = 6). One-way ANOVA with repeated measures was used for the comparison. Because the initial P value was less than 0.05, Scheffe’s test was used to determine the significance between groups. *p < 0.05 versus control.

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