Wavelength-dependent quantum yield for Z----E isomerization of bilirubin complexed with human serum albumin

The quantum yield, phi ZE, for configurational photoisomerization (4Z,15Z----4Z,15E) of bilirubin bound non-covalently to human serum albumin was determined (at 23 +/- 2 degrees C) by laser excitation and chromatographic analysis of products. Values obtained for photoexcitation at 465 nm were about one-half those previously reported. The quantum yield was dependent on excitation wavelength, decreasing from a value of 0.109 +/- 0.010 for excitation at 457.9 nm to a value of 0.054 +/- 0.005 for excitation at 514.5 nm. The wavelength dependence is consistent with rapid transfer of excitation energy between the two non-identical pyrromethenone chromophores of bilirubin in the singlet excited state. Since the quantum yields for photoisomerization and luminescence of bilirubin bound to serum albumin at room temperature are both low, internal conversion processes, rather than Z----E configurational isomerizations, are probably the major pathways for deactivation of photo-excited bilirubin.