物理化学学报 >> 1999, Vol. 15 >> Issue (03): 253-258.doi: 10.3866/PKU.WHXB19990311

研究论文 上一篇    下一篇

细胞色素P-450铁卟啉模拟酶的快速混合停流吸收谱

夏春谷, 李臻, 尉迟力, 李树本   

  1. 中国科学院兰州化学物理研究所 羟基合成与选择氧化国家重点实验室,兰州 730000
  • 收稿日期:1998-06-08 修回日期:1998-10-05 发布日期:1999-03-15
  • 通讯作者: 夏春谷

Rapid-Mixing Stopped-Flow Studies of lron Porphrin Enzyme-Mimic Systems

Xia Chun-Gu, Li Zhen, Wei Chi-Li, Li Shu-Ben   

  1. State Key Laboratory for Oxo Synthesis Selective Oxidation,Lnzhou Institute of Chemical Physics,Chinese Academy of Science,Lanzhou 730000
  • Received:1998-06-08 Revised:1998-10-05 Published:1999-03-15
  • Contact: Xia Chun-Gu

摘要:

采用快速混合停流技术 ,在实际反应条件下 ,考察了不同铁卟啉配合物FeⅢ(Por.)Cl(Por.=TPP、TMOPP和TFPP)与单氧给体过氧苯甲酸m-CPBA构建的模拟酶体系中催化活性物种的生成及催化烯烃环氧化过程 .在氧给体m CPBA作用下 ,FeⅢ(TPP)Cl和FeⅢ(TMOPP)Cl均生成了四价铁氧卟啉配合物 ,具有较高的催化环氧化活性 ,但存在严重的氧化分解 ;而FeⅢ(TFPP)Cl则生成了一种较稳定的中间体 ,以致催化活性较低 ,但当溶液中含有一定量的甲醇时 ,催化活性将出现大幅度的提高 .

关键词: 铁卟啉, 过氧苯甲酸, 二苯基丁二烯, 环氧化, 停流

Abstract:

The reactions of different iron porphrin complexes Fe Ⅲ(TPP)Cl [tetraphenylporphinatoiron(III) chloride],Fe Ⅲ(TMOPP)Cl [tetrakis(4-methoxy-phenyl)porphinatoiron(III) chloride] and Fe Ⅲ(TFPP)Cl [tetrakis(pentafluoro-phenyl)porphinatoiron(III) chloride] with single oxygen atom donor m chloroperoxybenzoic acid ( m CPBA) under ambient conditions has been investigated by rapid mixing stopped flow spectrophotometry. It is shown that the same oxoiron(IV) porphyrin complexes intermediates are produced, and the Fe Ⅲ(TFPP)Cl model system that incorporated electronic and steric protection of the oxidation vulnerable meso position is more stable. Preliminary substituent effect data reveal the following trends for Fe Ⅲ(Pro.)Cl decomposition: Fe Ⅲ(TMOPP)Cl > Fe Ⅲ(TPP)Cl > Fe Ⅲ(TFPP)Cl. Epoxidization reactivity of 1,4 diphenylbutadiene by Fe Ⅲ(TPP)Cl or Fe Ⅲ(TMOPP)Cl with m CPBA is enhanced, although the catalytic reactivity of Fe Ⅲ(TFPP)Cl m CPBA model system in CH 2Cl 2 is lower, but is faster in the presence of methanol.

Key words: Irom porphrin complexes, m-chloroperoxybenzoic acid, Diphenylbutadiene, Epoxidization, Stopped-flow