試験管内胆汁色素生成過程に関する研究

第2編 Hemin誘導体からVerdohemochrome生成過程に対する反応液の影響について

抄録

The formation process of verdohemochrome from pyridine hemin by O₂ in the presence of ascorbic acid on the use of pyridine chloroform as the reaction solution was spectrochemically observed, in comparison with that on the use of pyridine water. And the results were as follows.
1. The formation process of verdohemochrome from pyridine hemin by O₂ in the presence of ascorbic acid on the use of pyridine chloroform as the reaction solution spectrophoto metrically showed the same process with that on the use of pyridine water and verdohemochrome was finally produced. The reaction construction was same to that on the use of pyridine water and the compound with the absorption maximum at 630mμ., as a intermediate product, was found in this reaction.
2. On the use of pyridine chloroform with the pyridine concentration below 10% as the reaction solution, the stadium thought to have only pure compound with the absorption maximum at 630mμ. was observed. And both of the formation process of the compound with the absorption maximum at 630mμ. from pyridine hemin and of verdohemochrome from the compound with the absorption maximum at 630mμ. were clearly observed in the same reaction. The above results were caused by that the compound with the absorption maximum at 630mμ. from pyridine hemin was formed with momentary speed on the use of pyridine chloroform in the low concentration.
3. The property of verdohemochrome obtained from pyridine hemin in pyridine chloroform agreed with that of verdohemochrome obtained from pyridine hemin in pyridine water and biliverdin was obtained from it by HCl.
4. The formation velocity of the compound with the absorption maximum at 630mμ. from pyridine hemin was very rapid on the use of pyridine in the low concentration (2.5-5%), when the concentration of ascorbic acid was kept constant. And it decreased with increasing pyridine concentration; at higher concentration of pyridine it decreased remarkably. This had relation to pyridine itself, and not to water or chloroform in the reaction solution. On the other hand, it's velocity was proportional to the concentration of ascorbic acid, when pyridine concentration was kept constant.
5. The necessary concentration of ascorbic acid for the formation of verdohemochrome from pyridine heroin in pyridine chloroform was not related to the pyridine concentration, and it was 6.3 Mol. to 1 Mol. of hemin and it was equivalent to 1/3 on the use of 20 % pyridine water.
6. The yield of verdohemohcrome was not related to the pyridine concentration up to a concentration of 20%, and it was the best with smallest amount of ascorbic acid discribed the above, but it became less regularly with increasing ascorbic acid concentration over the above. It became much less in 60% pyridine chloroform.
7. The velocity of th reaction was easily influenced by the pyridine concentration and the yield of verdohemochrome was easily influenced by the concentration of ascorbic acid.
8. The necessary concentration of ascorbic acid for the formation of verdohemochrome had relation with the presence and it's quantity of water in the reaction solution, and the less water decreased, the less was the ascorbic acid and it had no direct relation with pyridine. On the other hand, the catalytic action of pyridine hemin, the compound with the absorption maximum at 630mμ. and verdohemochrome had relation to the former and it was remarkably influenced, and it was reinforced with the decrease of water. The secondary reaction of the above reaction had same relation with the above.
9. The secondary reaction on the use of pyridine chloroform was due to the abnormal decomposition of the compound with the absorption maximum at 630mμ. and verdohemochrome as same as that on the use of pyridine water.
10. In this reaction, the existence of water was not necessary.