title: Density functional studies on isomerization of prostaglandin H2 to prostacyclin catalyzed by cytochrome P450.
abstract: 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(2) 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.
authors.affiliation: Faculty of Science, Ibaraki University, Bunkyo, Mito 310-8512, Japan.
authors.forename: Tetsuya K
authors.initials: TK
authors.lastname: Yanai
authors.forename: Seiji
authors.initials: S
authors.lastname: Mori
mesh_terms: D002384:Catalysis; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism*; D004579:Electron Transport; D011464:Epoprostenol / Q000096:biosynthesis*; D008665:Metalloporphyrins / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D044262:Prostaglandin H2 / Q000378:metabolism*
chemical_list: D008665:Metalloporphyrins; D044262:Prostaglandin H2; D003577:Cytochrome P-450 Enzyme System; D011464:Epoprostenol