The intriguing molecular dynamics of Cer[EOS] in rigid skin barrier lipid layers requires improvement of the model

Fandrei, Ferdinand; Havrišák, Tomáš; Opálka, Lukáš; Engberg, Oskar; Smith, Albert A.; Pullmannová, Petra; Kučerka, Norbert; Ondrejčeková, Veronika; Demé, Bruno; Nováková, Lucie; Steinhart, Miloš; Vávrová, Kateřina; Huster, Daniel

doi:10.1016/j.jlr.2023.100356

Cited by 9 publications

(17 citation statements)

References 79 publications

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“…The same decrease in the degree of order can also be observed at the double bond. The fatty acid chain, which was the linoleate tail of the CER-EOS, was highly disordered, which corresponded to the models of the skin barrier lipids by Fandrei . The snapshot of the fatty acid chain of CER-EOS in the slab is shown in Figure g–i.…”

Section: Resultsmentioning

confidence: 99%

“…The fatty acid chain, which was the linoleate tail of the CER-EOS, was highly disordered, which corresponded to the models of the skin barrier lipids by Fandrei. 62 The snapshot of the fatty acid chain of CER-EOS in the slab is shown in Figure 2g−i. The simulation results showed a lower order parameter of the CER-EOS linoleate tail in LPP-1 than in LPP-2 and LPP-3, and partial linoleate tail of the CER-EOS leaf the slab and entered the bilayer, which explained the lower order parameter near the ester group in LPP-2.…”

Section: Resultsmentioning

confidence: 99%

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Models of the Three-Component Bilayer of Stratum Corneum: A Molecular Simulation Study

Jiang,

Liu,

Yuan

et al. 2024

J. Phys. Chem. B

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The construction of the stratum corneum (SC) is crucial to the problems of transdermal drug delivery. SC consists of the keratinocyte layers and the lipid matrix surrounding it. Among them, the lipid matrix is the barrier for many exogenous molecules, mainly composed of ceramides (CERs), free fatty acids (FFA), and cholesterol (CHOL). In this work, we developed single-component (CERs, CER-NS, and CER-EOS) and six three-component models, and each model was simulated by using the GROMOS-54A7 force field. Short-period phase (SPP) and long-period phase (LPP) systems were established separately, and area per lipid (APL), thickness, order of carbon chain (S CD ), and density distribution were analyzed. The transition of CER-NS and CER-EOS in LPP was observed. The results of hydrogen bonds in the lipid systems indicated that a strong hydrogenbond network was formed between the skin−lipid bilayers. Umbrella sampling method simulations were performed to calculate the free energy change of ethanol moving into the skin−lipid bilayer. The results revealed that ethanol molecules pulled some water molecules into the membrane when they passed through SPP-1. Our findings provided some insights and models of the stratum corneum that could be used for the subsequent mechanism of macromolecule permeation through membranes in drugs, cosmetics, and so on.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Models of the Three-Component Bilayer of Stratum Corneum: A Molecular Simulation Study

Jiang,

Liu,

Yuan

et al. 2024

J. Phys. Chem. B

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“…A similar increase in LPP repeat distance was previously reported for SC lipid samples enriched in 𝜔-O-acylceramides, where the LPP repeat distance increased by 2.2 nm (from 12.2 nm with 10-30% 𝜔-O-acylceramides of the ceramide fraction to 14.4 nm with 90% 𝜔-O-acylceramides). [34] A possible mechanism for this increase in repeat distance is the partial stretching of the distal parts of the N-acyl chain in 𝜔-O-acylceramides (which are largely isotropic at 30% 𝜔-Oacylceramides [22] ) at their higher concentration or a more pronounced reorganization of these lamellae. A plausible hypothesis is that CLE may attract some free lipids (other than 𝜔-Oacylceramides) that can fill the voids between the sparsely covalently bound lipids to form a mature CLE, following a principle similar to the formation of tethered lipid membranes.…”

Section: Cles Fluidize and Rearrange Neighboring Free Lipidsmentioning

confidence: 99%

“…[42][43][44] The adhesion of extracellular lipids to the corneocyte surface will logically be higher when the protein is hydrophobized by covalent CLE lipids than in the absence of CLE. The covalently bound ultralong lipids in CLE may also help to organize domains with different properties (which are likely to be layered rather than laterally segregated in these multilamellar systems [22] ) due to the different properties of the ultralong acyl and sphingoid chains, i.e., they may act similarly to surfactants (or lineactants in 2D systems). [45,46]…”

Section: Cles Fluidize and Rearrange Neighboring Free Lipidsmentioning

confidence: 99%

“…[19] Furthermore, linoleate chain ester-bound in ultralong 𝜔-O-acylceramide species (≈2-3 mol% of skin lipids) is isotropic. [20][21][22] However, although isolated human SC lipids in vitro are able to assemble into a proper lamellar structure, LPP, they require additional fluidization to reduce nanoscopic packing defects and permeability. [23] We hypothesized that the corneocyte lipid envelope, CLE (Figure 1c), a lipid monolayer coating the corneocyte surface, [1,24] may template and locally fluidize the extracellular lipids.…”

Section: Introductionmentioning

confidence: 99%

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Lipid Monolayer on Cell Surface Protein Templates Functional Extracellular Lipid Assembly

Dwivedi,

Mazumder,

Pullmannová

et al. 2024

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When the ancestors of men moved from aquatic habitats to the drylands, their evolutionary strategy to restrict water loss is to seal the skin surface with lipids. It is unknown how these rigid ceramide‐dominated lipids with densely packed chains squeeze through narrow extracellular spaces and how they assemble into their complex multilamellar architecture. Here it is shown that the human corneocyte lipid envelope, a monolayer of ultralong covalently bound lipids on the cell surface protein, templates the functional barrier assembly by partly fluidizing and rearranging the free extracellular lipids in its vicinity during the sculpting of a functional skin lipid barrier. The lipid envelope also maintains the fluidity of the extracellular lipids during mechanical stress. This local lipid fluidization does not compromise the permeability barrier. The results provide new testable hypotheses about epidermal homeostasis and the pathophysiology underlying diseases with impaired lipid binding to corneocytes, such as congenital ichthyosis. In a broader sense, this lipoprotein‐mediated fluidization of rigid (sphingo)lipid patches may also be relevant to lipid rafts and cellular signaling events and inspire new functional materials.

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The molecular arrangement of ceramides in the unit cell of the long periodicity phase of stratum corneum models shows a high adaptability to different ceramide head group structures

Nădăban,

Gooris,

Beddoes

et al. 2024

Biochimica et Biophysica Acta (BBA) - Biomembranes

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The intriguing molecular dynamics of Cer[EOS] in rigid skin barrier lipid layers requires improvement of the model

Cited by 9 publications

References 79 publications

Models of the Three-Component Bilayer of Stratum Corneum: A Molecular Simulation Study

Models of the Three-Component Bilayer of Stratum Corneum: A Molecular Simulation Study

Lipid Monolayer on Cell Surface Protein Templates Functional Extracellular Lipid Assembly

The molecular arrangement of ceramides in the unit cell of the long periodicity phase of stratum corneum models shows a high adaptability to different ceramide head group structures

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