氮杂冠醚化双Schiff碱配合物催化羧酸酯水解的研究  

Study on aza crown ether substituted bis-Schiff base complexes catalyze carboxylic acid esters hydrolysis

作　　者：程杰[1] 李建章[1] 何锡阳[1] 曾俊[1] 肖正华[1] 胡伟[1] 

机构地区：[1]四川理工学院化学与制药工程学院,绿色化学四川省高校重点实验室,四川自贡643000

出　　处：《化学研究与应用》2012年第4期574-579,共6页Chemical Research and Application

基　　金：绿色催化四川省高校重点实验室(LZJ01)资助项目;自贡市科技局重点项目(10X01)资助项目;四川理工学院人才引进科研基金(2009ZR1)资助项目;国家自然科学基金(20072025)资助项目

摘　　要：将4种氮杂冠醚取代的双Schiff碱钴(II)、锰(III)配合物作为仿水解酶模型催化羧酸酯(PNPP)水解。考察了Schiff碱配合物中氮杂冠醚取代的位置、氮杂冠醚的数目对其仿水解酶性能的影响;探讨了Schiff配合物催化PNPP水解的动力学和机理;提出了配合物催化PNPP水解的动力学模型。结果表明,在25℃条件下随着缓冲溶液pH值的增大,配合物催化PNPP水解速率提高;四种氮杂冠醚取代的双Schiff碱配合物在催化PNPP水解反应中表现出良好的催化活性;氮杂冠醚3-取代的Schiff碱配合物CoL2的催化活性高于5-取代的Schiff碱配合物CoL1,含有2个氮杂冠醚的配合物CoL3的催化活性高于含有1个氮杂冠醚的配合物CoL2。Four aza crown ether substituted bis-Schiff base transition-mental complexes have been used as mimic hydrolytic enzyme model catalyzing carboxylic acid esters（PNPP） hydrolysis.The effects of substitutent position of aza-crown and amount of aza-crown of Schiff base complexes were studied.The kinetics on PNPP hydrolysis catalyzed by these complexes was investigated.The kinetic mathematical model of PNPP cleavage catalyzed by these complexes was proposed.The results showed that the rate for the catalytic PNPP hydrolysis was increased following the increase of pH of the buffer solution;four complexes exhibited high activity in the catalytic PNPP hydrolysis;The catalytic activity of unsymmetrical Schiff base complexes of 3-substitute benzo-10-aza-crown groups（CoL 2） is larger than that of 5-substitute benzo-10-aza-crown groups（CoL 1）,and the catalytic activity of Schiff base complexes with two benzo-10-aza-crown ether pendants（CoL 3） is larger than that of Schiff base complexes with one benzo-10-aza-crown ether pendants（CoL 2）.

关 键 词：氮杂冠醚 双SCHIFF碱 过渡金属配合物 PNPP水解 动力学研究 

分 类 号：O643.12[理学—物理化学]