Chain Length of Free Fatty Acids Influences the Phase Behavior of Stratum Corneum Model Membranes

Ramos, Adrian Paz; Lafleur, Michel

doi:10.1021/acs.langmuir.5b03271

Cited by 23 publications

(38 citation statements)

References 48 publications

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“…Upon heating above 60°C, the band position abruptly shifted toward high wavenumbers, reaching 2,095.6 cm 1 at 70°C. This value is characteristic of a disordered acyl chain (28,29) and the band shift was associated with the disordering of FFA24-d 47 chains, as previously observed for analogous mixtures (2,30). At low temperatures, the  s CH 2 band was found at around 2,850 cm 1 , a value indicative of high chain order (25,26).…”

Section: Resultssupporting

confidence: 75%

“…The FFA24 spectrum at 37°C, with a width at the base of 128 kHz, indicated a transition of the fatty acid toward a gel phase. Upon heating up to 60°C, the evolution of the spectrum showed an increase of chain rotational diffusion while remaining in an almost all-trans configuration (2,24). Heating above 60°C caused a transition toward a liquid-ordered phase (l o ).…”

Section: Resultsmentioning

confidence: 99%

“…At this point, the origin of skin impermeability is mainly associated with the presence of lipid crystalline phases. At physiological temperature, SC lipids are mainly in a crystalline state, forming solid orthorhombic structures, which is proposed to be highly impermeable (2)(3)(4).…”

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confidence: 99%

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Evidence of hydrocarbon nanodrops in highly ordered stratum corneum model membranes

Ramos

Gooris

Bouwstra

et al. 2018

Journal of Lipid Research

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The stratum corneum (SC), the top layer of skin, dictates the rate of both water loss through the skin and absorption of exogenous molecules into the body. The crystalline organization of the lipids in the SC is believed to be a key feature associated with the very limited permeability of the skin. In this work, we characterized the organization of SC lipid models that include, as in native SC, cholesterol, a series of FFAs (saturated with C16-C24 chains), as well as a ceramide bearing an oleate chain-linked to a very long saturated acyl chain [-melissoyl-oleoyloxy hexacosanoyl-D--sphingosine (Cer EOS)]. The latter is reported to be essential for the native SC lipid organization. Our H-NMR, infrared, and Raman spectroscopy data reveal that Cer EOS leads to the formation of highly disordered liquid domains in a solid/crystalline matrix. The lipid organization imposes steric constraint on Cer EOS oleate chains in such a way that these hydrocarbon nanodroplets remain in the liquid state down to -30°C. These findings modify the structural description of the SC substantially and propose a novel role of Cer EOS, as this lipid is a strong modulator of SC solid/liquid balance.

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 99%

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Evidence of hydrocarbon nanodrops in highly ordered stratum corneum model membranes

Ramos

Gooris

Bouwstra

et al. 2018

Journal of Lipid Research

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“…The FFAs found in the SC of healthy persons and AD patients showed variety in chain length distribution and saturation, which is in accordance with previous reports (Ananthapadmanabhan, Mukherjee, & Chandar, ; Mao‐Qiang, Elias, & Feingold, ; Paz Ramos & Lafleur, ). In the preliminary study, we applied the developed method to a smaller number of subjects to look for possible differences in FFA levels between AD patients and healthy controls.…”

Section: Resultssupporting

confidence: 92%

Quantification of free fatty acids in human stratum corneum using tandem mass spectrometry and surrogate analyte approach

Đapić

Kobetić

Brkljačić

et al. 2017

Biomedical Chromatography

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The free fatty acids (FFAs) are one of the major components of the lipids in the stratum corneum (SC), the uppermost layer of the skin. Relative composition of FFAs has been proposed as a biomarker of the skin barrier status in patients with atopic dermatitis (AD). Here, we developed an LC-ESI-MS/MS method for simultaneous quantification of a range of FFAs with long and very long chain length in the SC collected by adhesive tape (D-Squame). The method, based on derivatization with 2-bromo-1-methylpyridinium iodide and 3-carbinol-1-methylpyridinium iodide, allowed highly sensitive detection and quantification of FFAs using multiple reaction monitoring. For the quantification, we applied a surrogate analyte approach and internal standardization using isotope labeled derivatives of FFAs. Adhesive tapes showed the presence of several FFAs, which are also present in the SC, a problem encountered in previous studies. Therefore, the levels of FFAs in the SC were corrected using C12:0, which was present on the adhesive tape, but not detected in the SC. The method was applied to SC samples from patients with atopic dermatitis and healthy subjects. Quantification using multiple reaction monitoring allowed sufficient sensitivity to analyze FFAs of chain lengths C16-C28 in the SC collected on only one tape strip.

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“…Ramos et al obtained a structurally uniform LM from N-lignoceroyld-erythro-sphingosine and lignoceric acid. [20] Pullmannvá found that LM, with CER containing a C24 hydrocarbon chain, showed a stronger barrier profile than CER possessing a C16 hydrocarbon chain. [21] An LM structural change was observed when the CER was replaced by the hydroxyl-group-added CER.…”

Section: Introductionmentioning

confidence: 99%

In Situ Monitoring of Lipid Phase State Make Target Lipid Mixtures Similar to Intercellular Lipid in the Stratum Corneum

Fujii

Gato

Ozawa

et al. 2020

Euro J Lipid Sci & Tech

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In this study, lipid structural change is monitored using Raman spectroscopy during heat treatment, along with the impact of lipid states on the structural and physical properties during the preparation process of the dried and hydrated lipid mixture (LM) similar to intercellular lipid in stratum corneum. The microstructures and thermal behavior of these LMs change depending on the melting of lipid ingredients in the preparation process. It is recognized that variable temperature Raman spectroscopy (VT‐Raman) is a useful and attractive tool for the sensitive in situ monitoring of lipid state changes and lipid melting. The LMs can incorporate D2O into their structures regardless of preparation temperature due to increasing lattice distance by hydration. These results suggest that monitoring lipid structural changes during the heating step is important to precisely prepare target LMs. Practical Applications: This study reveals that VT‐Raman is a useful and attractive tool in in situ monitoring of lipid state change and lipid melting. The monitoring of the preparation process by VT‐Raman is necessary to precisely prepare the target LM similar to intercellular lipid of stratum corneum because the microstructures and thermal properties of these LMs change depending on the melting of lipid ingredients during the preparation process.

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Chain Length of Free Fatty Acids Influences the Phase Behavior of Stratum Corneum Model Membranes

Cited by 23 publications

References 48 publications

Evidence of hydrocarbon nanodrops in highly ordered stratum corneum model membranes

Evidence of hydrocarbon nanodrops in highly ordered stratum corneum model membranes

Quantification of free fatty acids in human stratum corneum using tandem mass spectrometry and surrogate analyte approach

In Situ Monitoring of Lipid Phase State Make Target Lipid Mixtures Similar to Intercellular Lipid in the Stratum Corneum

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