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  • 标题:Structural and stereoelectronic insights into oxygenase-catalyzed formation of ethylene from 2-oxoglutarate
  • 本地全文:下载
  • 作者:Zhihong Zhang ; Tristan J. Smart ; Hwanho Choi
  • 期刊名称:Proceedings of the National Academy of Sciences
  • 印刷版ISSN:0027-8424
  • 电子版ISSN:1091-6490
  • 出版年度:2017
  • 卷号:114
  • 期号:18
  • 页码:4667-4672
  • DOI:10.1073/pnas.1617760114
  • 语种:English
  • 出版社:The National Academy of Sciences of the United States of America
  • 摘要:Ethylene is important in industry and biological signaling. In plants, ethylene is produced by oxidation of 1-aminocyclopropane-1-carboxylic acid, as catalyzed by 1-aminocyclopropane-1-carboxylic acid oxidase. Bacteria catalyze ethylene production, but via the four-electron oxidation of 2-oxoglutarate to give ethylene in an arginine-dependent reaction. Crystallographic and biochemical studies on the Pseudomonas syringae ethylene-forming enzyme reveal a branched mechanism. In one branch, an apparently typical 2-oxoglutarate oxygenase reaction to give succinate, carbon dioxide, and sometimes pyrroline-5-carboxylate occurs. Alternatively, Grob-type oxidative fragmentation of a 2-oxoglutarate–derived intermediate occurs to give ethylene and carbon dioxide. Crystallographic and quantum chemical studies reveal that fragmentation to give ethylene is promoted by binding of l -arginine in a nonoxidized conformation and of 2-oxoglutarate in an unprecedented high-energy conformation that favors ethylene, relative to succinate formation.
  • 关键词:ethylene-forming enzyme ; 2-oxoglutarate-dependent oxygenases ; hydroxylase ; plant development ; oxidoreductase
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