Structure of water, proteins, and lipids in intact human skin, hair, and nail.

Raman spectroscopy is a nondestructive analytical method for determining the structure and conformation of molecular compounds. It does not require sample preparation or pretreatment. Recently, near-infrared Fourier transform Raman spectroscopy has emerged as being specially suited for investigations of biologic material. In this study, we obtained near-infrared Fourier transform Raman spectra of intact human skin, hair, nail, and stratum corneum. We disclosed major spectral differences in conformational behavior of lipids and proteins between normal skin, hair, and nail. The amide I and III band location indicated that the majority of proteins in all samples have the same secondary alpha-helix structure. Positions of (S-S) stretching bands of proteins revealed a higher stability of the disulfide bonds in the hair and the nail. Analysis of vibrations of protein -CH groups showed that in the hair and the nail the proteins are apparently highly folded, interacting with the surroundings only to a small degree. The position of lipid specific peaks in spectra of hair, nail, and stratum corneum suggested a highly ordered, lamellar crystalline lipid structure. A greater lipid fluidity was found in whole skin. Assessment of the structure of water clusters revealed that mainly bound water is present in the human skin, stratum corneum, and nail. In conclusion, structural changes of water, proteins, and lipids in intact skin and skin appendages may be analyzed by Raman spectroscopy. This technique may be used in the future in a noninvasive analysis of structural changes in molecular compounds in the skin, hair, and nail associated with different dermatologic diseases.

[1]  Christopher J. Frank,et al.  Raman spectroscopy of normal and diseased human breast tissues. , 1995, Analytical chemistry.

[2]  D. Torchia,et al.  Solid-state NMR studies of the dynamics and structure of mouse keratin intermediate filaments. , 1988, Biochemistry.

[3]  G. Walrafen,et al.  Linearity between Structural Correlation Length and Correlated-Proton Raman Intensity from Amorphous Ice and Supercooled Water up to Dense Supercritical Steam , 1995 .

[4]  S. White,et al.  Structure of lamellar lipid domains and corneocyte envelopes of murine stratum corneum. An X-ray diffraction study. , 1988, Biochemistry.

[5]  G. Walrafen,et al.  Raman intensities and interactions in aqueous lysozyme solutions , 1978 .

[6]  K. Aoki,et al.  Raman studies of bovine serum albumin-ionic detergent complexes and conformational change of albumin molecule induced by detergent binding , 1982 .

[7]  R. Clark,et al.  Spectroscopy of biological systems , 1986 .

[8]  M. Hollingsworth,et al.  An X-Ray Diffraction Study , 1992 .

[9]  D. Downing,et al.  Lipids are covalently attached to rigid corneocyte protein envelopes existing predominantly as beta-sheets: a solid-state nuclear magnetic resonance study. , 1995, The Journal of investigative dermatology.

[10]  O. Nielsen.  The structure of liquid water. A low frequency (10–400 cm−1) Raman study , 1979 .

[11]  H. H. Thodberg,et al.  Optimal minimal neural interpretation of spectra , 1992 .

[12]  J. Lévêque,et al.  Oriented structure in human stratum corneum revealed by X-ray diffraction. , 1991, The Journal of investigative dermatology.

[13]  P. Gemperline,et al.  Spectroscopic calibration and quantitation using artificial neural networks , 1990 .

[14]  L. J. Lis,et al.  Laser Raman spectroscopy of lipid-protein systems. Differences in the effect of intrinsic and extrinsic proteins on the phosphatidylcholine Raman spectrum. , 1976, Biochimica et biophysica acta.

[15]  R. Rand,et al.  Detection of changes in the environment of hydrocarbon chains by Raman spectroscopy and its application to lipid-protein systems. , 1973, Biochimica et biophysica acta.

[16]  S. P. Verma,et al.  Changes of Raman scattering in the CU-stretching region during thermally induced unfolding of ribonuclease. , 1977, Biochemical and biophysical research communications.

[17]  G. Thomas,et al.  Raman spectroscopy of proteins and their assemblies. , 1995, Sub-cellular biochemistry.

[18]  B P Gaber,et al.  On the quantitative interpretation of biomembrane structure by Raman spectroscopy. , 1977, Biochimica et biophysica acta.

[19]  S. P. Verma,et al.  Raman spectra of some saturated, unsaturated and deuterated C18 fatty acids in the HCH-deformation and CH-stretching regions. , 1977, Biochimica et biophysica acta.

[20]  O. Nielsen,et al.  Assessment of correction procedures for reduction of Raman spectra , 1988 .

[21]  Vibrational Spectra and Molecular Conformations of Dialkyl Disulfides , 1973 .

[22]  Howell G. M. Edwards,et al.  Fourier transform Raman and infrared vibrational study of human skin: Assignment of spectral bands , 1992 .

[23]  Yukihiro Ozaki,et al.  Near‐infrared Fourier transform Raman spectroscopic study of human brain tissues and tumours , 1994 .

[24]  M. Gniadecka,et al.  Potential for high‐frequency ultrasonography, nuclear magnetic resonance, and Raman spectroscopy for skin studies , 1997, Skin research and technology : official journal of International Society for Bioengineering and the Skin (ISBS) [and] International Society for Digital Imaging of Skin (ISDIS) [and] International Society for Skin Imaging.

[25]  Anthony T. Tu,et al.  Raman spectroscopy in biology: Principles and applications , 1982 .

[26]  S. Petersen,et al.  Studies of hydrogen-bonded 5'-guanosine monophosphate self-associates using low-frequency Raman scattering , 1982 .

[27]  M. Kawai,et al.  Stratum corneum lipids serve as a bound-water modulator. , 1990, The Journal of investigative dermatology.

[28]  G. Imokawa,et al.  Molecular analysis of elastic properties of the stratum corneum by solid-state 13C-nuclear magnetic resonance spectroscopy. , 1995, The Journal of investigative dermatology.

[29]  J J Bulgin,et al.  The use of differential thermal analysis to study the bound water in stratum corneum membranes. , 1967, Biochimica et biophysica acta.

[30]  A. Tu,et al.  Laser Raman spectroscopy of snake venom neurotoxins: conformation. , 2009, International journal of peptide and protein research.

[31]  T. Miyazawa,et al.  S–S AND C–S STRETCHING VIBRATIONS AND MOLECULAR CONFORMATIONS OF DIALKYL DISULFIDES AND CYSTINE , 1972 .

[32]  H. Edwards,et al.  Raman spectra of human keratotic biopolymers: Skin, callus, hair and nail , 1994 .

[33]  Peptide backbone conformation and microenvironment of protein side chains , 1986 .

[34]  Felix Franks,et al.  Water:A Comprehensive Treatise , 1972 .

[35]  Howard I. Maibach,et al.  Bioengineering of the skin : water and the stratum corneum , 2004 .

[36]  M. Fontana,et al.  Raman spectroscopy of protein–water interactions in aqueous solutions , 1976 .

[37]  H. Wulf,et al.  Diagnosis of Basal Cell Carcinoma by Raman Spectroscopy , 1997 .

[38]  H. Edwards,et al.  Fourier-transform Raman spectroscopy of mammalian and avian keratotic biopolymers. , 1997, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[39]  O. Nielsen,et al.  Raman spectroscopic studies of some biochemically relevant molecules , 1995 .

[40]  G. Imokawa,et al.  A possible function of structural lipids in the water-holding properties of the stratum corneum. , 1985, The Journal of investigative dermatology.

[41]  H. Wulf,et al.  Distinctive Molecular Abnormalities in Benign and Malignant Skin Lesions: Studies by Raman Spectroscopy , 1997, Photochemistry and photobiology.

[42]  Yasushi Maeda,et al.  The structure of water in polymer systems as revealed by Raman spectroscopy , 1995 .

[43]  P. Wertz,et al.  The role of the corneocyte lipid envelopes in cohesion of the stratum corneum. , 1989, Journal of Investigative Dermatology.

[44]  I. H. Blank,et al.  Factors which influence the water content of the stratum corneum. , 1952, The Journal of investigative dermatology.

[45]  Roger Hayward,et al.  The Hydrogen Bond , 1960 .

[46]  L. J. Lis,et al.  Raman spectroscopic detection and examination of the interaction of amino acids, polypeptides and proteins with the phophatidylcholine lamellar structure. , 1976, Biochimica et biophysica acta.

[47]  G. Walrafen,et al.  Raman and Infrared Spectral Investigations of Water Structure , 1972 .

[48]  W. Damert,et al.  Raman intensities of carbon-carbon stretching modes in a model membrane , 1980 .

[49]  R. Neubert,et al.  Structure of stratum corneum lipids characterized by FT-Raman spectroscopy and DSC. I. ceramides , 1996 .

[50]  O. Nielsen,et al.  Hydrogen bonding in liquid formamide. A low frequency Raman study , 1982 .

[51]  K. Walkley.  Bound Water in Stratum Corneum Measured by Differential Scanning Calorimetry , 1972 .

[52]  J. L. Lippert,et al.  Laser Raman investigation of the effect of cholesterol on conformational changes in dipalmitoyl lecithin multilayers. , 1971, Proceedings of the National Academy of Sciences of the United States of America.

[53]  Brian W. Barry,et al.  Potential applications of FT-Raman spectroscopy for dermatological diagnostics , 1995 .

[54]  J. Koenig,et al.  Raman spectroscopic study of mechanically deformed poly‐L‐alanine , 1974 .

[55]  C. Fajolles,et al.  Low-frequency Raman spectra of fluorobenzene in the liquid state , 1989 .

[56]  R. Alfano,et al.  Raman, fluorescence, and time-resolved light scattering as optical diagnostic techniques to separate diseased and normal biomedical media. , 1992, Journal of photochemistry and photobiology. B, Biology.

[57]  S. Krishnamurthy,et al.  Low‐frequency Raman spectrum of supercooled water , 1983 .

[58]  O. Nielsen.  Chapter 2. Low-frequency spetroscopic studies of interactions in liquids , 1993 .

[59]  J. Koenig,et al.  Raman scattering of collagen, gelatin, and elastin , 1975, Biopolymers.