Oxidative breakdown and conversion of urocanic acid isomers by hydroxyl radical generating systems

cis-Urocanic acid (cis-UCA), formed from tr ans-urocanic acid (trans-UCA) b y photoisomerization, has been shown to mimic suppressive effects of UV on the immune system. It is our hypothesis that UCA oxidation products in the skin play a role in the process of immunosuppression. Recently, both UCA is omers were found to be good hydroxyl radical scavengers and in this context we investigated the formation of products resulting from the interaction o f hydroxyl radicals with UCA. Hydroxyl radicals were generated by (1) UV/H2 O2 (photooxidation), (2) ferrous ions/H2O2 (Fenton oxidation) and (3) cupri c ions/ascorbic acid. Oxidation products were identified by spectrometric m ethods and assessed by reversed-phase HPLC analysis. The photooxidation of UCA was induced by W-B and UV-C, but not by UV-A radiation. Photooxidation and Fenton oxidation of trans-UCA. as well as of cis-UCA yielded comparable chromatographic patterns of UCA oxidation products. Several of the formed products were identified. The formation of three identified imidazoles was shown in UV-B exposed corneal layer samples, derived from human skin. (C) 2 001 Elsevier Science B.V. All rights reserved.