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Kinetics of membrane raft formation: fatty acid domains in stratum corneum lipid models.
J Phys Chem B. 2006 Feb 09; 110(5):2378-86.JP

Abstract

The major barrier to permeability in skin resides in the outermost layer of the epidermis, the stratum corneum (SC). The major SC lipid components are ceramides, free fatty acids, and cholesterol. Ternary mixtures containing these constituents are widely used for physicochemical characterization of the barrier. Prior X-ray diffraction and IR spectroscopy studies have revealed the existence of ordered lipid chains packed in orthorhombic subcells. To monitor the kinetics of formation of regions rich in fatty acids, the current study utilizes a modification of the method (J. Phys. Chem. 1992, 96, 10008) developed to monitor component demixing in n-alkane mixtures. The approach is based on changes in the scissoring or rocking mode contours in the IR spectra of (orthorhombically packed) ordered chains. In the current study, equimolar mixtures of ceramides (either non-hydroxy fatty acid sphingosine ceramide or alpha-hydroxy fatty acid sphingosine ceramide) with chain perdeuterated fatty acids (either palmitic or stearic acid) and cholesterol reveal a time evolution of the scissoring contour of the deuterated fatty acid chains following quenching from relatively high temperatures where random mixing occurs. Segregation of domains enriched in the fatty acid component is observed. The kinetics of segregation are sensitive to the quenching temperature and to the chemical composition of the mixture. The kinetic regimes are conveniently catalogued with a power law of the form P=Ktalpha where P is a (measured) property related to domain composition. The time scales for demixing in these experiments are similar to times observed in several studies that have tracked the restoration of the in vivo permeability barrier following nonthermal challenges to SC integrity. Further evidence for the physiological importance of the current measurements is the detection of these phases in native SC. The current work constitutes the first direct, structure-based determination of the kinetics of barrier formation in relevant skin lipid barrier models.

Authors+Show Affiliations

International Specialty Products, 1361 Alps Road, Wayne, New Jersey 07470, USA. djmoore@ispcorp.comNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural

Language

eng

PubMed ID

16471828

Citation

Moore, David J., et al. "Kinetics of Membrane Raft Formation: Fatty Acid Domains in Stratum Corneum Lipid Models." The Journal of Physical Chemistry. B, vol. 110, no. 5, 2006, pp. 2378-86.
Moore DJ, Snyder RG, Rerek ME, et al. Kinetics of membrane raft formation: fatty acid domains in stratum corneum lipid models. J Phys Chem B. 2006;110(5):2378-86.
Moore, D. J., Snyder, R. G., Rerek, M. E., & Mendelsohn, R. (2006). Kinetics of membrane raft formation: fatty acid domains in stratum corneum lipid models. The Journal of Physical Chemistry. B, 110(5), 2378-86.
Moore DJ, et al. Kinetics of Membrane Raft Formation: Fatty Acid Domains in Stratum Corneum Lipid Models. J Phys Chem B. 2006 Feb 9;110(5):2378-86. PubMed PMID: 16471828.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Kinetics of membrane raft formation: fatty acid domains in stratum corneum lipid models. AU - Moore,David J, AU - Snyder,Robert G, AU - Rerek,Mark E, AU - Mendelsohn,Richard, PY - 2006/2/14/pubmed PY - 2006/9/29/medline PY - 2006/2/14/entrez SP - 2378 EP - 86 JF - The journal of physical chemistry. B JO - J Phys Chem B VL - 110 IS - 5 N2 - The major barrier to permeability in skin resides in the outermost layer of the epidermis, the stratum corneum (SC). The major SC lipid components are ceramides, free fatty acids, and cholesterol. Ternary mixtures containing these constituents are widely used for physicochemical characterization of the barrier. Prior X-ray diffraction and IR spectroscopy studies have revealed the existence of ordered lipid chains packed in orthorhombic subcells. To monitor the kinetics of formation of regions rich in fatty acids, the current study utilizes a modification of the method (J. Phys. Chem. 1992, 96, 10008) developed to monitor component demixing in n-alkane mixtures. The approach is based on changes in the scissoring or rocking mode contours in the IR spectra of (orthorhombically packed) ordered chains. In the current study, equimolar mixtures of ceramides (either non-hydroxy fatty acid sphingosine ceramide or alpha-hydroxy fatty acid sphingosine ceramide) with chain perdeuterated fatty acids (either palmitic or stearic acid) and cholesterol reveal a time evolution of the scissoring contour of the deuterated fatty acid chains following quenching from relatively high temperatures where random mixing occurs. Segregation of domains enriched in the fatty acid component is observed. The kinetics of segregation are sensitive to the quenching temperature and to the chemical composition of the mixture. The kinetic regimes are conveniently catalogued with a power law of the form P=Ktalpha where P is a (measured) property related to domain composition. The time scales for demixing in these experiments are similar to times observed in several studies that have tracked the restoration of the in vivo permeability barrier following nonthermal challenges to SC integrity. Further evidence for the physiological importance of the current measurements is the detection of these phases in native SC. The current work constitutes the first direct, structure-based determination of the kinetics of barrier formation in relevant skin lipid barrier models. SN - 1520-6106 UR - https://www.unboundmedicine.com/medline/citation/16471828/Kinetics_of_membrane_raft_formation:_fatty_acid_domains_in_stratum_corneum_lipid_models_ L2 - https://doi.org/10.1021/jp054875h DB - PRIME DP - Unbound Medicine ER -