scholarly journals A Coarse-Grained Model of Stratum Corneum Lipids: Free Fatty Acids and Ceramide NS

2016 ◽  
Vol 120 (37) ◽  
pp. 9944-9958 ◽  
Author(s):  
Timothy C. Moore ◽  
Christopher R. Iacovella ◽  
Remco Hartkamp ◽  
Annette L. Bunge ◽  
Clare MCabe
2018 ◽  
Vol 2018 ◽  
pp. 1-7 ◽  
Author(s):  
Philip W. Wertz

The primary purpose of the epidermis of terrestrial vertebrates is to produce the stratum corneum, which serves as the interface between the organism and the environment. As such, the stratum corneum provides a permeability barrier which both limits water loss through the skin and provides a relatively tough permeability barrier. This provides for a degree of resistance to mechanical trauma and prevents or limits penetration of potentially harmful substances from the environment. The stratum corneum consists of an array of keratinized cells embedded in a lipid matrix. It is this intercellular lipid that determines the permeability of the stratum corneum. The main lipids here are ceramides, cholesterol, and fatty acids. In addition, the skin surface of mammals, including humans, is coated by a lipid film produced by sebaceous glands in the dermis and secreted through the follicles. Human sebum consists mainly of squalene, wax monoesters, and triglycerides with small proportions of cholesterol and cholesterol esters. As sebum passes through the follicles, some of the triglycerides are hydrolyzed by bacteria to liberate free fatty acids. Likewise, near the skin surface, where water becomes available, some of the ceramides are acted upon by an epithelial ceramidase to liberate sphingosine, dihydrosphingosine, and 6-hydroxysphingosine. Some of the free fatty acids, specifically lauric acid and sapienic acid, have been shown to have antibacterial, antifungal, and antiviral activity. Also, the long-chain bases have broad spectrum antibacterial activity.


2020 ◽  
Vol 98 (9) ◽  
pp. 495-501
Author(s):  
Adrian Paz Ramos ◽  
Gert Gooris ◽  
Joke Bouwstra ◽  
Michael Molinari ◽  
Michel Lafleur

Stratum corneum (SC), the outermost layer of the epidermis, is the primary barrier to percutaneous absorption. The diffusion of substances through the skin occurs through the SC lipid fraction, which is essentially constituted of an equimolar mixture of ceramides, free fatty acids, and cholesterol. The lipid constituents of SC are mainly forming continuous multilamellar membranes in the solid/crystalline state. However, recent findings suggest the presence of a highly disordered (liquid) phase formed by the unsaturated C18 chain of ceramide EOS, surrounded by a highly ordered lipid environment. The aim of the present work was to study the lipid spatial distribution of model SC membranes composed of ceramide EOS, ceramide NS, a mixture of free fatty acids, and cholesterol, using Raman microspectroscopy and AFM-IR spectroscopy techniques. The enhanced spatial resolution at the tens of nanometers scale of the AFM-IR technique revealed that the lipid matrix is overall homogeneous, with the presence of small, slightly enriched, and depleted regions in a lipid component. No liquid domains of ceramide EOS were observed at this scale, a result that is consistent with the model proposing that the oleate nanodrops are concentrated in the central layer of the three-layer organization of the SC membranes forming the long periodicity phase. In addition, both Raman microspectroscopy and AFM-IR techniques confirmed the fluid nature of the unsaturated chain of ceramide EOS while the rest of the lipid matrix was found highly ordered.


2001 ◽  
Vol 117 (1) ◽  
pp. 44-51 ◽  
Author(s):  
Joachim W. Fluhr ◽  
Jack Kao ◽  
Sung K. Ahn ◽  
Kenneth R. Feingold ◽  
Peter M. Elias ◽  
...  

2010 ◽  
Vol 132 (13) ◽  
pp. 134505 ◽  
Author(s):  
K. R. Hadley ◽  
C. McCabe

1986 ◽  
Vol 87 (1) ◽  
pp. 68-71 ◽  
Author(s):  
Moniquc Nicollier ◽  
Théophile Massengo ◽  
Jean-Paul Rémy-Martin ◽  
René Laurent ◽  
Gérard-Louis Adessi

2021 ◽  
Author(s):  
Parashara Shamaprasad ◽  
Timothy C Moore ◽  
Donna Xia ◽  
Christopher R Iacovella ◽  
Annette L Bunge ◽  
...  

Molecular dynamics simulations of mixtures of the ceramide N-(tetracosanoyl)-sphingosine (NS), cholesterol, and a free fatty acid are performed to gain a molecular-level understanding of the structure of the lipids found in the stratum corneum layer of skin. A new coarse-grained model for cholesterol, developed using the multistate iterative Boltzmann inversion method, is compatible with previously developed coarse-grained forcefields for ceramide NS, free fatty acid, and water, and validated against atomistic simulations of these lipids using the CHARMM force field. Self-assembly simulations of multilayer structures using these coarse-grained force fields are performed, revealing that a large fraction of the ceramides adopt extended conformations, which cannot occur in the bilayer structures typically studied using simulation. Cholesterol fluidizes the membrane by promoting packing defects and it is observed that an increase in cholesterol content reduces the bilayer height, due to an increase in interdigitation of the C24 lipid tails, consistent with experimental observations. Through the use of a simple reverse-mapping procedure, a self-assembled coarse-grained multilayer system is used to construct an equivalent structure with atomistic resolution. Simulations of this atomistic structure are found to closely agree with experimentally derived neutron scattering length density profiles. Significant interlayer hydrogen bonding is observed in the inner layers of the atomistic multilayer structure that are not found in the outer layers in contact with water or in equivalent bilayer structures. These results identify several significant differences in the structure and hydrogen bonding of multilayer structures as compared to the more commonly studied bilayer systems, and, as such, highlight the importance of simulating multilayer structures for more accurate comparisons with experiment. These results also provide validation of the efficacy of the coarse-grained forcefields and the framework for multiscale simulation.


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