Near‐infrared Fourier transform Raman spectroscopic analysis of proteins, water and lipids in intact normal stratum corneum and psoriasis scales

Abstract:  Previous biochemical studies demonstrated differences in the structure of lipids in normal skin and psoriatic lesions. Raman spectroscopy provides a unique possibility of studying the molecular structure of proteins, lipids and water in intact skin. Near‐infrared Fourier transform Raman spectroscopy was used to study changes in molecular structure and conformation of proteins and lipids of stratum corneum in healthy persons and patients with psoriasis. In vitro Raman spectra were obtained from intact psoriatic scales in 11 patients and from normal stratum corneum of forearm, elbow and heel in a group of age‐matched healthy persons. The spectra of stratum corneum differed between psoriasis and normal skin but not between investigated regions. No major changes of lipid band positions in Raman spectra were found, but the crystalline lipid structure was disrupted in psoriatic scales (assessed as the ratio of the symmetric methylene C–H stretching‐mode intensities, Slat). Major spectral differences were seen in the molecular structure of the proteins. In the spectra of psoriatic scales, the peak position of the amide I band, in comparison with the normal skin, was shifted to higher wavenumbers, suggesting unfolding of proteins. Moreover, alterations in the disulfide stretch bonds of proteins were found in psoriasis scales, resulting in a less energetically favourable gauche–gauche–trans conformation (band around 520 cm−1). Psoriatic scales and normal stratum corneum did not statistically differ in their water content. The findings further define the molecular abnormalities in the stratum corneum in psoriasis.

[1]  Brian C Wilson,et al.  New optical technologies for earlier endoscopic diagnosis of premalignant gastrointestinal lesions , 2002, Journal of gastroenterology and hepatology.

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

[3]  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.

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

[5]  P. Elias,et al.  Ultrastructural localization of calcium in psoriatic and normal human epidermis. , 1991, Archives of dermatology.

[6]  H. Tagami,et al.  Interrelationship between water-barrier and reservoir functions of pathologic stratum corneum. , 1985, Archives of dermatology.

[7]  M. Vaccaro,et al.  Changes in the distribution of actin-associated proteins in psoriatic keratinocytes. Immunohistochemical study using confocal laser scanning microscopy , 1997, Archives of Dermatological Research.

[8]  L. K. Hansen,et al.  Melanoma diagnosis by Raman spectroscopy and neural networks: structure alterations in proteins and lipids in intact cancer tissue. , 2004, The Journal of investigative dermatology.

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

[10]  M S Feld,et al.  Determination of human coronary artery composition by Raman spectroscopy. , 1997, Circulation.

[11]  H. Tagami,et al.  Water sorption-desorption test of the skin in vivo for functional assessment of the stratum corneum. , 1982, The Journal of investigative dermatology.

[12]  H. Wulf,et al.  Structure of water, proteins, and lipids in intact human skin, hair, and nail. , 1998, The Journal of investigative dermatology.

[13]  H. Bruining,et al.  In vitro and in vivo Raman spectroscopy of human skin. , 1998, Biospectroscopy.

[14]  R. Neubert,et al.  Noninvasive characterization of human stratum corneum of undiseased skin of patients with atopic dermatitis and psoriasis as studied by Fourier transform Raman spectroscopy. , 2001, Biopolymers.

[15]  T. Engels,et al.  Molecular dynamics simulations of stratum corneum lipid models: fatty acids and cholesterol. , 2001, Biochimica et biophysica acta.

[16]  H. Barr,et al.  Medical applications of Raman spectroscopy: from proof of principle to clinical implementation. , 2002, Biopolymers.

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

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

[19]  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.

[20]  H. Wulf,et al.  Water and protein structure in photoaged and chronically aged skin. , 1998, The Journal of investigative dermatology.

[21]  C. K. Cheng,et al.  The keratin polypeptides of psoriatic epidermis. , 1978, The Journal of investigative dermatology.

[22]  F. Watt,et al.  Immunoelectron microscopic analysis of cornified cell envelope formation in normal and psoriatic epidermis. , 1996, The journal of histochemistry and cytochemistry : official journal of the Histochemistry Society.

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