Itoh S, Onishi S
Biochem J. 1985 Feb 15;226(1):251-8. doi: 10.1042/bj2260251.
The present study was performed to elucidate why the photochemical reaction of (ZZ)-bilirubin bound to human serum albumin is singularly selective, and only one of the two (EZ)- and (ZE)-bilirubins, the (ZE)-isomer, is produced. In a kinetic study of the photochemical reaction in vitro, the sum of the relative rate constants of photochemical transformation of (EZ)-bilirubin into both (EZ)-cyclobilirubin and (ZZ)-bilirubin, with a significant preference for the former, was proved to be considerably larger than that of the transformation of (ZZ)-bilirubin into (EZ)-bilirubin. Therefore only one of the geometrical isomers, namely (ZE)-bilirubin, is apparently formed. It was concluded that (EZ)-bilirubin photochemically undergoes (EZ)-cyclization, i.e. structural photoisomerization, while bound to its high-affinity site on human serum albumin, and is an intermediate in the transformation of (ZZ)-bilirubin into (EZ)-cyclobilirubin.
进行本研究是为了阐明与人类血清白蛋白结合的(ZZ)-胆红素的光化学反应为何具有独特的选择性,并且在两种(EZ)-和(ZE)-胆红素中,仅产生(ZE)-异构体这一种。在体外光化学反应的动力学研究中,已证明(EZ)-胆红素光化学转化为(EZ)-环胆红素和(ZZ)-胆红素(前者明显占优)的相对速率常数之和,远大于(ZZ)-胆红素转化为(EZ)-胆红素的速率常数之和。因此,显然仅形成一种几何异构体,即(ZE)-胆红素。得出的结论是,(EZ)-胆红素在与人血清白蛋白上的高亲和力位点结合时,会发生光化学(EZ)-环化,即结构光异构化,并且是(ZZ)-胆红素转化为(EZ)-环胆红素过程中的中间体。