Diagnosis of malignant melanoma and basal cell carcinoma by in vivo NIR-FT Raman spectroscopy is independent of skin pigmentation

There is a general need for methods to obtain fast in vivo diagnosis of skin tumours. Raman spectroscopy measures molecular structure and may thus have potential as a tool for skin tumour diagnosis. The purpose of this study was to investigate how skin pigmentation influenced the Raman spectra and skin tumour diagnostics in vivo. We obtained Raman spectra in vivo from the normal skin of 55 healthy persons with different skin pigmentation (Fitzpatrick skin type I-VI) and in vivo from 25 basal cell carcinomas, 41 pigmented nevi and 15 malignant melanomas. Increased skin pigmentation resulted in a higher spectral background caused by fluorescence, which could be removed by background correction. After background correction, we found only a negligible effect of pigmentation on the major spectral bands, and the comparison of the intensity of these bands allowed us to differentiate between normal skin and the different skin lesions independent of skin type. The diagnosis of skin lesions is possible due to significant (p < 0.05) differences found in the water band around 3250 cm(-1), the protein specific band around 1250 cm(-1) (amide-III) and the amide-III ratio that describes the protein/lipid ratio by comparing bands around 1250 cm(-1) with bands around 1300 cm(-1). We have shown that NIR-FT Raman spectroscopy is useable for malignant melanoma and basal cell carcinoma diagnostics in vivo and that pigmentation of the skin or lesion does not influence the diagnosis, but larger data sets are required to establish accurate diagnostic power.

[1]  S. Centeno,et al.  Surface enhanced Raman scattering (SERS) and FTIR characterization of the sepia melanin pigment used in works of art , 2008 .

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

[3]  D I McLean,et al.  Rapid near-infrared Raman spectroscopy system for real-time in vivo skin measurements. , 2001, Optics letters.

[4]  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.

[5]  H. Bruining,et al.  In vivo confocal Raman microspectroscopy of the skin: noninvasive determination of molecular concentration profiles. , 2001, The Journal of investigative dermatology.

[6]  Haishan Zeng,et al.  Raman spectroscopy of in vivo cutaneous melanin. , 2004, Journal of biomedical optics.

[7]  F. Khachik,et al.  Non-invasive raman spectroscopic detection of carotenoids in human skin. , 2000, The Journal of investigative dermatology.

[8]  D. McLean,et al.  Real-time Raman Spectroscopy for in Vivo Skin Cancer Diagnosis Raman Spectroscopy of Skin Cancer , 2022 .

[9]  Pier Francesco Biagi,et al.  Raman and optical spectroscopy of eumelanin films , 2005 .

[10]  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.

[11]  Haishan Zeng,et al.  Cutaneous melanin exhibiting fluorescence emission under near-infrared light excitation. , 2006, Journal of biomedical optics.

[12]  Monika Gniadecka,et al.  Alterations in collagen structure in hypermobility and Ehlers-Danlos syndromes detected by Raman spectroscopy in vivo , 2000, European Conference on Biomedical Optics.

[13]  J. Simon,et al.  Characterization of the Fe(III)-binding Site in Sepia Eumelanin by Resonance Raman Confocal Microspectroscopy¶ , 2004 .

[14]  H. Wulf,et al.  Water and Protein Structure in Photoaged and Chronically Aged Skin , 1998 .

[15]  T. B. Bakker Schut,et al.  Discriminating basal cell carcinoma from its surrounding tissue by Raman spectroscopy. , 2002, The Journal of investigative dermatology.

[16]  Haishan Zeng,et al.  Monte Carlo simulation of near infrared autofluorescence measurements of in vivo skin. , 2011, Journal of photochemistry and photobiology. B, Biology.

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

[18]  H. Wulf,et al.  Autofluorescence of human skin is age-related after correction for skin pigmentation and redness. , 2001, The Journal of investigative dermatology.

[19]  T. Hirschfeld,et al.  FT-Raman Spectroscopy: Development and Justification , 1986 .

[20]  H. Wulf,et al.  Pheomelanin and eumelanin in human skin determined by high‐performance liquid chromatography and its relation to in vivo reflectance measurements , 2006, Photodermatology, photoimmunology & photomedicine.

[21]  H. Ohguro,et al.  Raman Microscopy of Freeze‐dried Mouse Eyeball‐slice in Conjunction with the “in vivo Cryotechnique” , 2007, Microscopy research and technique.

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

[23]  Anita Mahadevan-Jansen,et al.  In vivo nonmelanoma skin cancer diagnosis using Raman microspectroscopy , 2008, Lasers in surgery and medicine.

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

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

[26]  Christoph Krafft,et al.  Methodology for fiber-optic Raman mapping and FTIR imaging of metastases in mouse brains , 2007, Analytical and bioanalytical chemistry.

[27]  Airton Abrahão Martin,et al.  FT-Raman spectroscopy for the differentiation between cutaneous melanoma and pigmented nevus. , 2010, Acta cirurgica brasileira.

[28]  J. Sawatzki,et al.  In vivo evidence for compromised phenylalanine metabolism in vitiligo. , 1998, Biochemical and biophysical research communications.

[29]  M. Pacheco,et al.  Differentiating normal and basal cell carcinoma human skin tissues in vitro using dispersive Raman spectroscopy: a comparison between principal components analysis and simplified biochemical models. , 2010, Photomedicine and laser surgery.

[30]  Monika Gniadecka,et al.  Natural variations and reproducibility ofin vivo near-infrared Fourier transform Raman spectroscopy of normal human skin , 2002 .