By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO4- radical has been investigated both in aqueous and water/acetonitrilemixed solutions. The results reveal tha...By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO4- radical has been investigated both in aqueous and water/acetonitrilemixed solutions. The results reveal that attack of the oxidizing SO4- radical on Phe leads directlyto the formation of Phe cation radical 3 with a strong absorption peak at 310 nm, then it proceeds in three competitive reactions via either hydroxylation, deprotonation or decarboxylation, which were found to be strongly dependent upon the ionization state of the substitutes -COOH and -NH2 and the nature of the solvents. Decarboxylation takes place only when the carboxyl group is deprotonated. At high pH deprotonation of Phe cation radical 3 is much easier to occur than that in neutral or acid solutions. Moreover, with addition of acetonitrile, deprotonation is more predominant than hydroxylation, whereas in aqueous solutions hydroxylation is much easier to occur.展开更多
文摘研究了两种炭黑(CB)对 PE的影响及PTC功能材料挤出后的特性,发现挤出后粒子和聚合物取向对材料电性能都有较大影响。经γ射线辐照后 HDPE/CB功能复合材料稳定性大为提高,初步探讨了辐射对PTC功能材料稳定性的影响。结合辐射交联等方法提高材料的稳定性。用扫描电镜(SEM)观测了一系列PE/CB的形态、CB的分布、链段的分子运动,并结合Fisher的 toy model对PE/CB机制做了较系统的解释。
基金S. J. Zhang thanks Professor K. Bobrowski for his instructive discussion concerning this work. This work was supported by the National Natural Science Foundation of China (Grant No. 39800036).
文摘By using time-resolved kinetic spectrophotometry and pulse radiolysis technique, the oxidation of Phe by SO4- radical has been investigated both in aqueous and water/acetonitrilemixed solutions. The results reveal that attack of the oxidizing SO4- radical on Phe leads directlyto the formation of Phe cation radical 3 with a strong absorption peak at 310 nm, then it proceeds in three competitive reactions via either hydroxylation, deprotonation or decarboxylation, which were found to be strongly dependent upon the ionization state of the substitutes -COOH and -NH2 and the nature of the solvents. Decarboxylation takes place only when the carboxyl group is deprotonated. At high pH deprotonation of Phe cation radical 3 is much easier to occur than that in neutral or acid solutions. Moreover, with addition of acetonitrile, deprotonation is more predominant than hydroxylation, whereas in aqueous solutions hydroxylation is much easier to occur.