Synthesis and Catalytic Properties of Cu~(2+) Complexes with 4-Amino-antipyrine Schiff bases in Dye Degradation

摘要

Four 4-aminoantipyrine Schiffbases HL~a, HL~b, HL~c, HL~d and L~e were synthesized and characterized from 4-aminoantipyrine and corresponding aromatic aldehydes. The reaction of the Schiffbaes with CuCl_2 were studied. And five mononuclear Cu~(2+) complexes, CuL~aOH, CuL~b OH- H_2O, CuL~c OH, CuL~dOH and CuL~e(OH)_2- H_2O were obtained and characterized by IR spectra,UV-Vis spectra and elemental analysis. The catalytic degradation of acid blue 9 was investigated by UV-Vis spectra, using the five synthetic Schiff base copper complexes as oxidase model compound. It was found that the five complexes all have catalytic effect. The catalytic activity of the three complexes, CuL~a OH, CuL~bOH- H_2O and CuL~c-OH are better. It was found that the catalytic properties of the three complexes were similar with the enzymatic properties. Then the K_m of CuL~a-OH,CuL~b-OH-H_2O and CuL~c-OH was deterrmined with K_m =1.15×10(-2) ,4.79×l0~(-2) and 6.89×l0~(-2) mmol / L, respectively. It is showed that the CuL~aOH, CuL~b-OH H_2O and CuL~c-OH could be used as oxidase model compounds to catalyze the acid blue 9 degradation. The products of the acid blue 9 degradation was analyzed by HPLC method. It was found the degradation product was maleic acid. The degradation mechanism of the acid blue 9 was deduced. And the catalytic cycle for enzyme model compounds was deduced. Three novel biomimetic catalysts with acid blue 9 degradation properties were obtained, which provides theoretical and experimental supports for a new dye removal technology.