In Vestigation Of Metal Complex And Metallomicelle Mimicking Hydrolytic Metalloenzyme And Peroxidase

Metal complex and metallomicelle as model compounds for artificial enzyme have been widely and extensively studied. In this dissertation, a series of homo- and hetero-dinuclear oxamido-bridged complexes have been synthesized, and the catalytic hydrolyses of carboxylic acid esters and phosphate by these complexes have been systematically investigated, and the catalytic mechanisms have also been dissected. At the same time, the feasibility of using the metallomicelle, a good hydrolytic metalloenzyme model, as the mimicking model for peroxidase was explored.In order to explore the catalytic function of metal ions on hydrolysis of carboxylate. the hydrolysis of p-nitrophenyl acetate (PNPA) catalyzed by the metallomicelle made of Cu(II), diamine and cationic surfactant CTAB has been quantitatively investigated. On the basis of the results, the catalytic property of micelle has also been concluded.The hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by the homo- and hetero-dinuclear oxamido-bridged complexes has been kinetically studied, and the results indicated that Zn(II) complex exhibited higher reactivity than Cu(II) complex did. The effects of metal cations of dinuclear complexes on hydrolysis of PNPP has been detailedly discussed.The hydrolytic kinetics of PNPP promoted by metallomicelles formed from two homo-dinuclear oxamido-bridged complexes and different surfactants, respectively, have been investigated, and it showed that metallomicelle made of cationic surfactant and complexes was the good catalytic system for PNPP hydrolysis, and this case has been discussed by electrostatic interaction of micelle.The hydrolysis of NPP catalyzed by metallomicelles formed by heterodinuclear complexes with different ligands and nonionic surfactant Brij35 has been quantitatively investigated, and the results indicated that the complexes with similar ligand in structure showed different catalytic function on NPP hydrolysis, and the difference has been explained by the different activation degrees of coordinating water molecules induced by different polarities of ligands.The metallomicelles made of three Cu(II)Ni(II) heterodinuclear oxamido-bridged complexes and diffent surfactants, respectively, catalyzing the BNPP hydrolysis have been studied comparatively. It has been found that these metallomicelles all showed relatively high reactivity, and the different catalytic functions of metallomicelles have been ascribed to the different polarities of ligands and micelles.The metallomicelles made of Co(II) complexes containing imidazole groups and different surfactants has been employed to catalyze the oxidation of phenol by H2O2, and the satisfactory results have been obtained. These results have given us some useful information for not only the study field of micellar catalysis but also further investigation of metallomicelle mimicking peroxidase.