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- Name help_outline N-[ω-(9R)-hydroperoxy-(10E,12Z)-octadecadienoyloxy]acyl-β-D-glucosyl-(1↔1)-octadecasphing-4E-enine Identifier CHEBI:134624 Charge 0 Formula C43H77NO12R SMILEShelp_outline C(=C/CCCCCCCCCCCCC)\[C@@H](O)[C@@H](NC(*OC(CCCCCCC[C@H](/C=C/C=C\CCCCC)OO)=O)=O)CO[C@H]1[C@@H]([C@H]([C@@H]([C@H](O1)CO)O)O)O 2D coordinates Mol file for the small molecule Search links Involved in 2 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
- Name help_outline N-[ω-(9R,10R)-epoxy-(13R)-hydroxy-(11E)-octadecadienoyloxy]acyl-β-D-glucosyl-(1↔1)-octadecasphing-4E-enine Identifier CHEBI:134626 Charge 0 Formula C43H77NO12R SMILEShelp_outline C(=C/CCCCCCCCCCCCC)\[C@@H](O)[C@@H](NC(*OC(CCCCCCC[C@@H]1[C@@H](/C=C/[C@@H](CCCCC)O)O1)=O)=O)CO[C@H]2[C@@H]([C@H]([C@@H]([C@H](O2)CO)O)O)O 2D coordinates Mol file for the small molecule Search links Involved in 1 reaction(s) Find molecules that contain or resemble this structure Find proteins in UniProtKB for this molecule
Cross-references
| RHEA:40503 | RHEA:40504 | RHEA:40505 | RHEA:40506 | |
|---|---|---|---|---|
| Reaction direction help_outline | undefined | left-to-right | right-to-left | bidirectional |
| UniProtKB help_outline |
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Publications
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Lipoxygenases mediate the effect of essential fatty acid in skin barrier formation: a proposed role in releasing omega-hydroxyceramide for construction of the corneocyte lipid envelope.
Zheng Y., Yin H., Boeglin W.E., Elias P.M., Crumrine D., Beier D.R., Brash A.R.
A barrier to water loss is vital to maintaining life on dry land. Formation of the mammalian skin barrier requires both the essential fatty acid linoleate and the two lipoxygenases 12R-lipoxygenase (12R-LOX) and epidermal lipoxygenase-3 (eLOX3), although their roles are poorly understood. Linoleat ... >> More
A barrier to water loss is vital to maintaining life on dry land. Formation of the mammalian skin barrier requires both the essential fatty acid linoleate and the two lipoxygenases 12R-lipoxygenase (12R-LOX) and epidermal lipoxygenase-3 (eLOX3), although their roles are poorly understood. Linoleate occurs in O-linoleoyl-ω-hydroxyceramide, which, after hydrolysis of the linoleate moiety, is covalently attached to protein via the free ω-hydroxyl of the ceramide, forming the corneocyte lipid envelope, a scaffold between lipid and protein that helps seal the barrier. Here we show using HPLC-UV, LC-MS, GC-MS, and (1)H NMR that O-linoleoyl-ω-hydroxyceramide is oxygenated in a regio- and stereospecific fashion by the consecutive actions of 12R-LOX and eLOX3 and that these products occur naturally in pig and mouse epidermis. 12R-LOX forms 9R-hydroperoxy-linoleoyl-ω-hydroxyceramide, further converted by eLOX3 to specific epoxyalcohol (9R,10R-trans-epoxy-11E-13R-hydroxy) and 9-keto-10E,12Z esters of the ceramide; an epoxy-ketone derivative (9R,10R-trans-epoxy-11E-13-keto) is the most prominent oxidized ceramide in mouse skin. These products are absent in 12R-LOX-deficient mice, which crucially display a near total absence of protein-bound ω-hydroxyceramides and of the corneocyte lipid envelope and die shortly after birth from transepidermal water loss. We conclude that oxygenation of O-linoleoyl-ω-hydroxyceramide is required to facilitate the ester hydrolysis and allow bonding of the ω-hydroxyceramide to protein, providing a coherent explanation for the roles of multiple components in epidermal barrier function. Our study uncovers a hitherto unknown biochemical pathway in which the enzymic oxygenation of ceramides is involved in building a crucial structure of the epidermal barrier. << Less
J. Biol. Chem. 286:24046-24056(2011) [PubMed] [EuropePMC]
This publication is cited by 6 other entries.