scholarly journals Kinetic study of photochemical and thermal conversion of bilirubin IX α and its photoproducts

1983 ◽  
Vol 209 (3) ◽  
pp. 695-700 ◽  
Author(s):  
K Isobe ◽  
S Itoh ◽  
S Onishi ◽  
T Yamakawa ◽  
T Ogino ◽  
...  

A kinetic study of the photochemical and thermal conversion of photoisomers, especialy peaks 0 and 3 [(EE)-bilirubin IX alpha and (EZ)- and (ZE)-bilirubin IX alpha], under anaerobic conditions, was performed by using reversed-phase high-pressure liquid chromatography. Peaks 0 and 3 are spontaneously, photochemically and thermally converted. Short-term photoirradiation of bilirubin gives a mixture containing not only the geometric isomers (EE)-, (EZ)- and (ZE)-bilirubin IX alpha, but also peak 2, (EZ)-cyclobilirubin IX alpha. On prolonged irradiation, cyclization and 15Z leads to 15E isomerization lead to gradual accumulation of two pairs of photoproducts: (EZ)-cyclobilirubin IX alpha A and B and (EE)-cyclobilirubin IX alpha A and B.

1981 ◽  
Vol 193 (3) ◽  
pp. 1029-1031 ◽  
Author(s):  
K Isobe ◽  
S Onishi

Kinetic study of the photochemical interconversion of three geometric photoisomers of bilirubin, namely peaks 1, 2 and 3, under anaerobic conditions was performed by using high-pressure liquid chromatography. Rapid and definite interconversion among these three peaks and the parent pigment occurred on radiation by blue light.


1984 ◽  
Vol 220 (2) ◽  
pp. 377-383 ◽  
Author(s):  
T Yokoyama ◽  
T Ogino ◽  
S Onishi ◽  
K Isobe ◽  
S Itoh ◽  
...  

In photochemical experiments on bilirubin III alpha (no endo-vinyl group), IX alpha (one endo-vinyl group) and XIII alpha (two endo-vinyl groups) and in the photochemical, thermal and catalytical reversion of their photoproducts under anaerobic conditions, much more instability and complexity of photoproducts of bilirubin XIII alpha were observed than for those of bilirubin IX alpha or III alpha. On the basis of present and previous results of photochemical experiments in vitro and the fact that large amounts of (EZ)-cyclobilirubin IX alpha appear in the bile during phototherapy of neonatal hyperbilirubinaemia [Onishi, Kawade, Itoh, Isobe & Sugiyama (1980) Biochem. J. 190, 527-532], it is concluded that the endo-vinyl group plays a crucial role in the photochemical reaction of bilirubin IX alpha. On reversed-phase high-pressure liquid chromatography of photoisomers, it was found that the retention times of geometric isomers and E-cyclized structural isomers were shortened compared with those of Z-isomer and E-isomer, respectively, as precursor substances.


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