不同活性中心非血红素铁双加氧酶的生物模拟有机化学专业论文.docxVIP

不同滑陛中心非血红素铁双加氧酶的生物模拟Biomimetic 不同滑陛中心非血红素铁双加氧酶的生物模拟 Biomimetic studies for difierent active site of the non．heme iron dioxygenase Abstract Design and synthesis of structuraI and functional model complexes of the native enzyme to explore the structure—function relationship ofthe enzyme，the reaction mechanism of the enzyme as well as the activation mechanism of molecular oxygen have received considerable attention recently．In order to get insights into the different active site model ligands and electronic effects of the substituent group of the model ligands and substrates on the dioxygenation reactivi够for the active site of 4一hydroxyphenylpyruvate dioxygenase(HPPD) andfl-diketone dioxygenase(Dkel)model complexes，herein we report a series ofworks as follows： (1)Three new 2His一1 COO series model ligands L2NoaH(2·{[(Benzyl—pyridin一2一 ylmethyl)amino]methyl}-4／5一R-benzoic acid；R：4-OMe，4-Me，5-Br)have been designed， synthesized and characterized． (2)A series of the Fe“and Co¨ES(enzyme—substrate)model complexes with them and ligand L2NoNOzH and 3His．1C00 series model ligands L3NoRH(2．{[Bis(pyridine．2． ylmethyl)amino]methyl}一4／5一R—benzoic acid R：4-OMe，4-Me，5一Br，5-N02)，and a serial substrates PPK p-R—phenylpyuvic acid，R：OH，Me，H，Br，N02)(common substrate of HPPD and Dke 1)have also been synthesized and characterized． (3)The reactivity of the model complexes towards molecular oxygen have been investigated by monitoring the absorption changes of the model complexes with UV—vis，and the qualitative and quantitative reaction products analysis were also examined in detail by LC—MS and HPLC．The effects of different active sites，electronic effect of the ligands and substrates on the structure，properties and reactivity have also been investigated．On the basis of the spectroscopic，redox property，kinetic and products analysis results，we have been proposed the Dkel—type dioxygenation reaction mechanism of the model complexes． The results of the reactivity of the model complexes towards