On the autoxidation of bilirubin.
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Biomedical subjects
Publications and source records attributed to D A Lightner.
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Chromic acid degradation of a d-urobilin, obtained after incubation of bilirubin in fecal bacterial cultures, gave methylvinylmaleimide and methylethylmaleimide. The d-urobilin, molecular weight 588, C(33)H(40)-N(4)O(6), clearly showed the presence of both vinyl and ethyl resonances in the nuclear magnetic resonance spectrum. These results point unambiguously to a urobilin structure with one vinyl and one ethyl beta-substituent.
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Irradiation of an oxygenated methanolic solution of bilirubin IXalpha in the absence of known singlet oxygen sensitizers gave methylvinylmaleimide among other products.
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Measurements of the temperature dependence of the circular dichroism spectra of l-stercobilin and d-urobilin show that the conformations of these optically-active urobilinoids change with temperature between 163 and 297 degrees K. These conformational changes depend critically on the hydrogen bonding characteristics of the solvent. Thus, in methanol-glycerol (9:1), the chiral sense of the helical conformation of the dipyrrylmethene chromophore is reversed on lowering the temperature, whereas in chloroform, reversal does not occur.
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