Spectroscopic characterization of mechanisms of oxidation of Phe by SO_4~- radical: A pulse radiolys

来源 :Science in China(Series B,Chemistry) | 被引量 : 0次 | 上传用户:sophia971
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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. 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 / acetonitrile mixed solutions. The results reveal the attack of the oxidizing SO4-radical on Phe leads directly to 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 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 , while in aqueous solutions hydroxylation is much easier to occur.
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