Chemiexcitation in the Peroxidative Metabolism of Diethylstilbestrol. Metabolic Products

Abstract

In the presence of the surfactant hexadecyltrimethyl ammonium bromide (CTAB) a cascade of electronically excited states accompanies the successive steps in the peroxidative metabolization of the strong estrogenic and tumourogenic diethylstilbestrol. Reversing the order by necessity, we report in this first paper results with the metabolites. Exposure of 4-hydroxypropiophenone, Z,Z-dienestrol or E,E-dienestrol to horseradish peroxidase and H2O2 promotes oxygen uptake and spectral alterations. Light emission is observed provided that the surfactant CTAB is present. With the three substrates, 4-hydroxybenzoic acid and a new metabolite, p-benzoquinone, have been identified. With both dienestrol isomers, 1-(4'-hydroxyphenyl)-propan-1-on-2-ol has been identified. In all cases the emission spectrum indicates the presence of several emitters. Possible chemiexcitation routes are pointed out. From the dramatic increase of the emission by enhancers, values as high as 1 x 10(-5) are inferred for the product of the quantum yields of chemiexcitation and energy transfer.