Laboratory of Bioorganic Chemistry, Department of Pharmaceutical Technochemistry, Josai University, 1–1 Keyaki-dai, Sakado, Saitama 350–0295, Japan.
Biol Pharm Bull. 2013;36(3):407-11. doi: 10.1248/bpb.b12-00818.
Substrate activities of various linear polyamines to human spermine oxidase (hSMO) were investigated. The activities were evaluated by monitoring the amount of H2O2 released from sample polyamines by hSMO. H2O2 was measured by a HPLC method that analyzed fluorescent dimers derived from the oxidation of homovanillic acid in the presence of horseradish peroxidase. Six triamines were tested and were found not to be hSMO substrates. Of sixteen tetramines tested, spermine (Spm) was the most active substrate, followed by homospermine and N-butylated Spm. Pentamines showed a characteristic pattern of substrate activity. Of thirteen pentamines tested, 3343 showed higher substrate activity than Spm, and 4343 showed similar activity to Spm. The activities of the other pentamines were as follows: 3443, 4443, 4344, 3344, 4334, 4444, and 3334 (in decreasing order). Product amines released from these pentamines by hSMO were then analyzed by HPLC. Triamine was the only observed product, and the amount of triamine was nearly equivalent to that of released H2O2. A marked difference in the pH dependency curves between tetramines and pentamines suggested that hSMO favored reactions with a non-protonated secondary nitrogen at the cleavage site. The Km and Vmax values for Spm and 3343 at pH 7.0 and 9.0 were consistent with the higher substrate activity of 3343 compared to Spm, as well as with the concept of a non-protonated secondary nitrogen at the cleavage site being preferred, and 3343 was well degraded at a physiological pH by hSMO.
研究了各种线性多胺对人精脒氧化酶(hSMO)的底物活性。通过监测 hSMO 从样品多胺中释放的 H2O2 量来评估活性。通过 HPLC 方法测量 H2O2,该方法分析了辣根过氧化物酶存在下从高香草酸氧化衍生的荧光二聚体。测试了六种三胺,发现它们不是 hSMO 的底物。在测试的十六个四胺中,精脒(Spm)是最活跃的底物,其次是同精脒和 N-丁基化 Spm。戊胺显示出特征性的底物活性模式。在测试的 13 种戊胺中,3343 的底物活性高于 Spm,而 4343 的活性与 Spm 相似。其他戊胺的活性如下:3443、4443、4344、3344、4343、4444 和 3334(依次递减)。然后通过 HPLC 分析 hSMO 从这些戊胺中释放的产物胺。三胺是唯一观察到的产物,释放的 H2O2 的量几乎与三胺的量相当。四胺和戊胺的 pH 依赖性曲线之间存在明显差异,表明 hSMO 有利于在裂解部位具有非质子化的仲氮的反应。在 pH 7.0 和 9.0 时,Spm 和 3343 的 Km 和 Vmax 值与 3343 相对于 Spm 的较高底物活性一致,也与裂解部位的非质子化仲氮被优先选择的概念一致,并且 3343 在生理 pH 下被 hSMO 很好地降解。