Effects of singlet oxygen on the extracellular matrix protein collagen: oxidation of the collagen crosslink histidinohydroxylysinonorleucine and histidine.
The reaction of singlet oxygen, a putative agent of skin photodamage, with the dermal collagen crosslink histidinohydroxylysinonorleucine (HHL) and its precursor histidine is reported. Reaction studies were performed with both purified HHL and bovine dermal tissue. We demonstrate that singlet oxygen can selectively oxidize HHL and histidine amino acid residues in dermal tissue and that intermediate oxidation products of histidine lead to new crosslink products. A novel mechanism for crosslink formation was proposed to involve nucleophilic addition to a transient imidazolone intermediate formed from singlet oxygen oxidation of the histidine imidazole moiety. The implication for such adduct formation and histidine oxidation in collagen proteins is the expression of aberrant collagen crosslinks, perturbation of the dermal collagen function, and hence an altered dermal state.
Au
V
V
Skin Biophysics and Delivery, Unilever Research US, Edgewater, New Jersey 07020, USA. van.au@unilever.com
Madison
S A
SA
D000818:Animals; D002417:Cattle; D003094:Collagen / Q000378:metabolism*; D004151:Dipeptides / Q000378:metabolism*; D016326:Extracellular Matrix Proteins / Q000378:metabolism; D006639:Histidine / Q000031:analogs & derivatives* / Q000378:metabolism*; D006909:Hydroxyproline / Q000378:metabolism; D066298:In Vitro Techniques; D008239:Lysine / Q000378:metabolism; D008297:Male; D010084:Oxidation-Reduction; D010100:Oxygen / Q000378:metabolism*; D010103:Oxygen Isotopes; D010777:Photochemistry; D012395:Rose Bengal / Q000378:metabolism; D012867:Skin / Q000378:metabolism; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet
D004151:Dipeptides; D016326:Extracellular Matrix Proteins; D010103:Oxygen Isotopes; C075793:histidinohydroxylysinonorleucine; D012395:Rose Bengal; D006639:Histidine; D003094:Collagen; D008239:Lysine; D006909:Hydroxyproline; D010100:Oxygen