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Spectroscopic characterization of mechanisms of oxidation of Phe by SO_4~- radical: A pulse radiolysis study
引用本文:储高升,张淑娟,姚思德,韩镇辉,都志文,张志成. Spectroscopic characterization of mechanisms of oxidation of Phe by SO_4~- radical: A pulse radiolysis study[J]. 中国科学B辑(英文版), 2002, 45(4)
作者姓名:储高升  张淑娟  姚思德  韩镇辉  都志文  张志成
作者单位:CHU Gaosheng ZHANG Shujuan,YAO SideHAN Zhenhui DU Zhiwen & ZHANG ZhichengDepartment of Applied Chemistry,University of Science and Technology of China,Hefei 230026,China;Laboratory of Radiation Chemistry,Shanghai Institute of N
基金项目: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).
摘    要: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.


Spectroscopic characterization of mechanisms of oxidation of Phe by SO.-4 radical: A pulse radiolysis study
CHU Gaosheng ZHANG Shujuan,YAO SideHAN Zhenhui DU Zhiwen , ZHANG Zhicheng. Spectroscopic characterization of mechanisms of oxidation of Phe by SO.-4 radical: A pulse radiolysis study[J]. Science in China(Chemistry), 2002, 45(4)
Authors:CHU Gaosheng ZHANG Shujuan  YAO SideHAN Zhenhui DU Zhiwen & ZHANG Zhicheng
Affiliation:1. Department of Applied Chemistry, University of Science and Technology of China, Hefei 230026, China
2. Laboratory of Radiation Chemistry, Shanghai Institute of Nuclear Research, Chinese Academy of Sciences, Shanghai 201800, China
Abstract: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.
Keywords:Phe   pulse radiolysis   SO4- radical   oxidation   mechanism.
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