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      Imaging the Distribution of Sodium Dodecyl Sulfate in Skin by Confocal Raman and Infrared Microspectroscopy

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          ABSTRACT

          Purpose

          To image SDS distribution across different skin regions, to compare the permeability difference between porcine and human skin, and to evaluate the interaction between SDS and skin.

          Methods

          Full thickness porcine and human skin was treated with acyl chain perdeuterated SDS (SDS-d 25) at room temperature and at 34 °C for 3, 24 and 40 h. SDS distribution in skin was monitored by confocal Raman and IR microspectroscopic imaging. Permeation profiles of SDS-d 25 in skin were derived from the band intensities of the CD 2 stretching vibrations. The interaction between SDS and skin was monitored through the CH 2 and CD 2 stretching frequencies and the Amide I and II spectral region.

          Results

          SDS-d 25 penetrates both porcine and human skin in a time and temperature-dependent manner, with slightly higher permeability through the stratum corneum (SC) in porcine skin. When SDS permeates into the SC, its chains are more ordered compared to SDS micelles. The secondary structure of keratin in the SC is not affected by SDS-d 25.

          Conclusion

          The spatial distribution of SDS-d 25 in skin was obtained for the first time. Infrared microscopic imaging provides unique opportunities to measure concentration profiles of exogenous materials in skin and offers insights to interaction between permeants and skin.

          Electronic supplementary material

          The online version of this article (doi:10.1007/s11095-012-0748-y) contains supplementary material, which is available to authorized users.

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          Most cited references38

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          Structural investigations of human stratum corneum by small-angle X-ray scattering.

          The structure of human stratum corneum was investigated with small-angle X-ray scattering (SAXS). At room temperature the scattering curve was characterized by a strong intensity at low scattering vector (Q less than 0.8 nm-1) and two complicated diffraction peaks originating from a lamellar structure of the lipids. The lamellar lipid structure in the stratum corneum transformed to a disordered structure between 65 degrees C and 75 degrees C, the same temperature region at which a thermal lipid transition occurred. After cooling down to room temperature a recrystallization of at least a part of the lipids took place, after which only one unit cell with a repeat distance of 13.4 nm could be detected. Comparison of the scattering curve of the stratum corneum after crystallization with the scattering curve of the stratum corneum before recrystallization leads to the conclusion that in the original curve the lipids are arranged in two unit cells with repeat distances of 6.4 nm and 13.4 nm. From model calculations it appears that the latter unit cell consists of more than one bilayer. The scattering curves of stratum corneum hydrated to various levels were measured. A change in the water content of stratum corneum between 6% w/w and 60% w/w (fully hydrated) did not result in swelling of the bilayers, but the scattering curve obtained with stratum corneum hydrated to 60% w/w differed from those at lower hydration levels: the scattering curve at 60% w/w showed only the diffraction peaks corresponding to a unit cell with a repeat distance of 6.4 nm. This observation implies that the ordering of a part of the lipids is reduced at very high water contents, which may explain the strong penetration-enhancing effects of water in the stratum corneum.
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            Molecular organization of the lipid matrix in intact Stratum corneum using ATR-FTIR spectroscopy.

            ATR-FTIR spectroscopy is useful in investigating the lateral organization of Stratum corneum (SC) lipids in full-thickness skin. Based on studies of the thermotropic phase transitions in n-tricosane and in excised human skin, the temperature dependence of the CH2 scissoring bandwidth emerged as a measure of the extent of orthorhombic and hexagonal phases. This dependence provides a simpler measure of the lateral order in lipid assemblies than the common spectroscopic approaches based on difference spectra, curve fitting of the CH2 scissoring region, and the position of the CH2 stretching vibrations. It has the advantages of ease of determination, relatively low variability, and high discriminative power for the type of lateral intermolecular chain packing. A comparison of the lateral organization of the lipids at the SC surface of mammalian skin using the scissoring bandwidth revealed considerable differences between human abdominal skin (containing mostly orthorhombic phases), porcine ear skin (containing mostly hexagonal phases), and reconstructed human epidermis (containing mostly disordered phases). This parameter also correctly described the different effects of propylene glycol (minimally disturbing) and oleic acid (formation of a highly disordered phase) on the SC lipids in excised human skin. The procedure described here is applicable to in vivo studies in the areas of dermatology, transdermal drug delivery, and skin biophysics.
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              New acylceramide in native and reconstructed epidermis.

              Culturing of normal human keratinocytes at the air-liquid interface results in the formation of fully differentiated epidermis under in vitro conditions. Although the reconstructed epidermis shows a close resemblance to native tissue, there are still some differences in the stratum corneum lipid profile and intercellular lipid organization. As ceramides belong to one of the major stratum corneum lipid classes, the aim of this study was to characterize this fraction in more detail. For this purpose, individual ceramide fractions were isolated by column chromatography and characterized by a combination of nuclear magnetic resonance spectroscopy, high-performance thin-layer chromatography, and gas chromatography. The results of this study show that in both the native and reconstructed human epidermis the extractable ceramide fraction contains, in addition to the well known acylceramides (EOS, EOH), a new acylceramide in which the omega-O-acylhydroxyacid is amide-linked to phytosphingosine (EOP). The same three sphingoid base moieties (S, P, H) are also found in ceramides with amide-linked nonhydroxy and alpha-hydroxyacids. Whereas the same types of ceramides were present in both tissues, some differences in their fatty acid profiles have been found. In reconstructed epidermis the content of linoleic acid in all three acylceramides fraction was significantly lower; the ceramide(NS) fraction was enriched in short fatty acids and the ceramide(AS) fraction was enriched in long chain alpha-hydroxyacids. These differences together with a lower content of free fatty acids may explain the differences between native and reconstructed tissue in stratum corneum lipid organization observed earlier by X-ray diffraction.
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                Author and article information

                Contributors
                +1-9088741859 , +1-9089043984 , gmao@its.jnj.com
                Journal
                Pharm Res
                Pharm. Res
                Pharmaceutical Research
                Springer US (Boston )
                0724-8741
                1573-904X
                4 April 2012
                4 April 2012
                August 2012
                : 29
                : 8
                : 2189-2201
                Affiliations
                [1 ]Johnson & Johnson Consumer Companies, Inc., 199 Grandview Rd., Skillman, New Jersey 08558-9418 USA
                [2 ]Department of Chemistry, Rutgers University, Newark, New Jersey USA
                Article
                748
                10.1007/s11095-012-0748-y
                3399083
                22477073
                54dd3e19-581f-48d4-8b3f-776634e1f3a9
                © The Author(s) 2012
                History
                : 30 November 2011
                : 22 March 2012
                Categories
                Research Paper
                Custom metadata
                © Springer Science+Business Media, LLC 2012

                Pharmacology & Pharmaceutical medicine
                skin,infrared (ir) imaging,permeation/penetration,surfactant,confocal raman microscopy

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