title: Protein, lipid, and DNA radicals to measure skin UVA damage and modulation by melanin.
abstract: Afro-Caribbeans have a lower incidence of skin cancer than Caucasians, but the effectiveness of melanin as a photoprotective pigment is debated. We investigated the UVA and solar irradiation of ex vivo human skin and DMPO using electron spin resonance spectroscopy, to determine whether pigmented skin is protected by melanin against free radical damage. Initial ascorbate radicals in Caucasian skin were superseded by lipid and/or protein radical adducts with isotropic (a(H)=1.8 mT) and anisotropic spectra comparable to spectra in irradiated pig fat (a(H)=1.9 mT) and BSA. DNA carbon-centered radical adducts (a(H)=2.3 mT) and a broad singlet were detected in genomic DNA/melanin but were not distinguishable in irradiated Caucasian skin. Protein and lipid radicals (n=6 in Caucasian skin) were minimal in Afro-Caribbean skin (n=4) and intermediate skin pigmentations were variable (n=3). In irradiated Afro-Caribbean skin a shoulder to the melanin radical (also in UVA-irradiated pigmented melanoma cells and genomic DNA/melanin and intrinsic to pheomelanin) was detected. In this sample group, protein (but not lipid) radical adducts decreased directly with pigmentation. ESR/spin trapping methodology has potential for screening skin susceptibility to aging and cancer-related radical damage and for measuring protection afforded by melanin, sunscreens, and antiaging creams.
authors.affiliation: RAFT Institute of Plastic Surgery, Mount Vernon Hospital, Northwood, Middlesex HA6 2RN, UK. haywoodr@raft.ac.uk
authors.forename: Rachel
authors.initials: R
authors.lastname: Haywood
authors.forename: Fabrice
authors.initials: F
authors.lastname: Rogge
authors.forename: Martin
authors.initials: M
authors.lastname: Lee
mesh_terms: D004247:DNA / Q000528:radiation effects; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000032:analysis / Q000528:radiation effects*; D006801:Humans; D008055:Lipids / Q000528:radiation effects; D008543:Melanins / Q000378:metabolism*; D011506:Proteins / Q000528:radiation effects; D012867:Skin / Q000528:radiation effects*; D013472:Sunlight / Q000009:adverse effects; D014466:Ultraviolet Rays / Q000009:adverse effects*
chemical_list: D005609:Free Radicals; D008055:Lipids; D008543:Melanins; D011506:Proteins; D004247:DNA