Density Functional Studies on Isomerization of Prostaglandin H-2 to Prostacyclin Catalyzed by Cytochrome P450

作者：Yanai Tetsuya K; Mori Seiji^*

来源：Chemistry - A European Journal, 2009, 15(17): 4464-4473.

DOI：10.1002/chem.200802550

• cytochromes
• density functional calculations
• electron transfer
• isomerization
• prostaglandins

Reaction mechanisms for the isomerization of prostaglandin H-2 to prostacyclin catalyzed by cytochrome P450 are investigated by the unrestricted Becke's three-parameter plus Lee-Yang-Parr density functional level of theory. The results show that the homolytic O-O bond cleavage of endoperoxide in prostaglandin H, is the rate-limiting step and that the isomerization proceeds through proton-coupled electron transfer. We located two reaction pathways through an Fe-IV-porphyrin intermediate and an Fe-III-porphyrin pi-cation radical intermediate.

• 出版日期2009