杯[6]芳烃-双金属卟啉仿P450酶模型的研究 Ⅰ.对环己烯环氧化反应的催化活性

Study on P450 Enzymic Model Compound with Calix arene\|bismetalloporphyrins.Catalytic Performance on the Epoxidation of Cyclohexene

研究了杯［６］芳烃－双金属卟啉仿Ｐ４５０酶模型化合物对环己烯环氧化反应的催化性能．考察了温度、氧源浓度、催化剂浓度、底物浓度、卟啉环中位苯基上取代基、溶剂等因素对反应的影响．结果表明，杯［６］芳烃－双金属卟啉的催化性能优于相应的简单金属卟啉单体，且反应遵从Ｍｉｃｈａｅｌｉｓ－Ｍｅｎｔｅｎ规律．这是由于作为疏水结合部位的杯［６］芳烃大环的引入，导致多部位识别协同催化，从而极大地提高了金属卟啉的催化性能．

Catalytic performance of P450 enzymic model compound with calix arene\|bismetalloporphyrins was studied and the effects of the properties of oxidant, temperature, substrate concentration, catalyst concentration, substituent on the benzene ring of porphyrin, and solvent, etc, on the reaction rate were investigated. The results show that calixarene\|bismetalloporphyrin has a much higher catalytic activity than the correspoding monometalloporphyrin, and the reactions obey the Michaelis\|Menten kinetic law. The excellent catalytic property of calixarene\|bismetalloporphyrin was a result of the multiple recognition and cooperative catalysis (macrocyclic ring of calix arene as the hydrophobic binding site and two metallporphyrins as the catalytic sites).