Covalently Bound Lipids of Human Stratum Corneum

Wertz, Philip W.; Madison, Kathi C.; Downing, Donald T.

doi:10.1111/1523-1747.ep13071317

Cited by 190 publications

(151 citation statements)

References 18 publications

Supporting

Mentioning

139

Contrasting

Unclassified

Order By: Relevance

“…For example, ceramides in human stratum corneum alone consist of at least eight subclasses [2][3][4][5][6], and even each ceramide class is a complex mixture of individual molecular species, which may consist of more than one isomer, as is revealed by the present method. Previous study by FAB in the structural characterization of ceramides using high-energy tandem mass spectrometry was limited in a small variety of ceramides and isomer differentiation among ceramide classes was not demonstrated [19].…”

Section: Discussionmentioning

confidence: 99%

“…One of these -hydroxyceramides is solvent-extractable and has an additional fatty acid esterified to the -hydroxyl group [1], while the other -hydroxyceramide is protein-bound [2]. Human stratum corneum ceramides are similar to those in pig [3], except for the existence of a second protein-bound ceramide having a -hydroxyacid and a 6-hydroxysphing-4-enine (V) [4]. The identification of the second protein-bound ceramide in human epidermis was recently reported [5,6].…”

mentioning

confidence: 99%

See 1 more Smart Citation

Structural studies on ceramides as lithiated adducts by low energy collisional-activated dissociation tandem mass spectrometry with electrospray ionization

Hsu

Turk

Stewart

et al. 2002

J. Am. Soc. Mass Spectrom.

Self Cite

103

View full text Add to dashboard Cite

We applied electrospray ionization (ESI) tandem quadrupole mass spectrometry to establish the fragmentation pathways of ceramides under low energy collisional-activated dissociation (CAD) by studying more than thirty compounds in nine subclasses. The product-ion spectra of the [M ϩ Li] ϩ ions of ceramides contain abundant fragment ions that identify the fatty acyl substituent and the long-chain base (LCB) of the molecules, and thus, the structure of ceramides can be easily determined. Fragment ions specific to each ceramide subclasses are also observed. These feature ions permit differentiation among different ceramide subclasses. The ion series arising from the classical C™C bond cleavages that were reported in the fast-atom bombardment (FAB)-high energy tandem mass spectrometry is not observable; however, the product-ion spectra contain multiple fragment ions informative for structural characterization and isomer identification. We also investigated the tandem mass spectra of the fragment ions generated by in-source CAD (pseudo-MS 3 ) and of the deuterium-labeling molecular species obtained by H/D exchange to support the ion structure assignments and the proposed fragmentation pathways that lead to the ion formation. (J Am Soc Mass Spectrom 2002, 13, 680 -695)

show abstract

Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

Structural studies on ceramides as lithiated adducts by low energy collisional-activated dissociation tandem mass spectrometry with electrospray ionization

Hsu

Turk

Stewart

et al. 2002

J. Am. Soc. Mass Spectrom.

Self Cite

103

View full text Add to dashboard Cite

show abstract

“…Contrary to the cell membrane lipids, the lipid hydrocarbon chains of both ceramides and fatty acids are predominantly saturated. The only SC lipids that contain non-saturated fatty acid residues (esterified to particularly long fatty acid chains of 30-32 carbon atoms) are the x-hydroxy (EO) ceramides; most of them exist covalently linked to proteins of the corneocyte envelope [25,40,41]. The conformation that the ceramides molecules adopt in vivo -splayed, hairpin, or V-shapeis still under debate [42,43].…”

Section: Composition and Local Environment Of The Sc Lipid Matrixmentioning

confidence: 99%

The physical chemistry of the stratum corneum lipids

Boncheva

2014

Intern J of Cosmetic Sci

View full text Add to dashboard Cite

SynopsisThe extracellular matrix of stratum corneum (SC) participates actively in the defensive performance of human skin. Understanding its physicochemical properties is essential for understanding the skin homoeostasis, for the development of efficient therapies for skin disorders and diseases and for ensuring the safety of products designed for topical application. This article summarizes the current knowledge of the composition, self-assembly and molecular organization of the SC lipids, reviews the evidence connecting these parameters and the barrier properties of human skin, and outlines the immediate issues in the field of SC lipid research. R ESUM E: La matrice extracellulaire du stratum corneum (SC) participe activement a la performance d efensive de la peau humaine. Comprendre ses propri et es physico-chimiques est essentielle pour comprendre l'hom eostasie de la peau, pour le d eveloppement de th erapies efficaces pour les troubles et les maladies de la peau, et pour assurer la s ecurit e des produits conc ßus pour une application topique. Cet article r esume les connaissances actuelles sur la composition, l'auto-assemblage, et l'organisation mol eculaire des lipides SC, examine les preuves reliant ces param etres et les propri et es de barri ere de la peau humaine, et d ecrit les probl emes imm ediats dans le domaine de la recherche sur les lipides SC. IntroductionThe field of skin research is replete with opportunities for those intent on working on scientifically interesting topics while making a noticeable, positive difference in people's lives [1]. The range of important problems that the field can help solving is broad. It comprises (i) reducing infant mortality, especially in the developing countries where defective skin barrier is the second major cause of preterm mortality [2][3][4][5][6]; (ii) improving the skin health of some 20-30% of the population in the developed countries which suffer from some sort of skin barrier dysfunction [7,8]; (iii) developing efficient strategies for the dermal and transdermal delivery of drugs and vaccines [9]; (iv) increasing the national and personal security by developing methods to retard or prevent the skin penetration of chemical warfare agents, toxic spills and pesticides [10, 11]; (v) enhancing the safety of topical products (e.g. fragrances, cosmetics, cleansing agents, sunscreens and insect repellents) [12]. Thus, the targets in skin research cover the full spectrum from counter-acting leaky skin and preventing its penetration by chemicals to pushing chemicals through it. One common major problem underlies these diverse topics: our insufficient understanding of the factors that determine skin permeability.Understanding the permeability of human skin to a large extent means understanding the extracellular lipid matrix of the stratum corneum (SC), the topmost skin layer which constitutes the main barrier to transdermal fluxes [13][14][15][16][17][18][19]. As the lipid matrix forms an uninterrupted pathway from the skin surface to the viable skin tissu...

show abstract

“…One minor but important component of the extruded lipids are the ω-hydroxyceramides, which become covalently attached to the outer surface of the protein envelope of the CE forming an ~5 nm thick lipid envelope coat surrounding each corneocyte (Swartzendruber et al, 1987;Wertz and Downing, 1987a;Wertz et al, 1989b). The ceramides are attached by way of ester bonds to glutamic acid and glutamine residues of several CE proteins, including involucrin, envoplakin and periplakin ( Wertz et al, 1989b;Marekov and Steinert, 1998). The protein-bound ω-hydroxyceramides are built from sphingosine coupled to highly saturated, uniquely long ( C 3 0 -3 6 ) chain fatty acids having a chain terminal ("ω" ) hydroxyl group (Wertz and Downing , 1991).…”

Section: The Mortarmentioning

confidence: 99%