化学学报 ›› 2009, Vol. 67 ›› Issue (11): 1223-1230. 上一篇    下一篇

研究论文

新型水溶性手性Salen配合物的合成及性质研究

刘 阁 曹小辉 郭莉芹 闫伟伟 王建辉
矫 志 阮文娟* 朱志昂

  

  1. (南开大学化学系 天津 300071)

  • 收稿日期:2008-06-27 修回日期:2008-11-28 出版日期:2009-06-14 发布日期:2009-06-14
  • 通讯作者: 阮文娟

Study on Synthesis and Properties of Novel Water Soluble Chiral Salen Complexes

Liu, Ge Cao, Xiaohui Guo, Liqin Yan, Weiwei Wang, Jianhui
Jiao, Zhi Ruan, Wenjuan* Zhu, Zhiang
  

  1. (College of Chemistry, Nankai University, Tianjin 300071)
  • Received:2008-06-27 Revised:2008-11-28 Online:2009-06-14 Published:2009-06-14
  • Contact: Ruan, Wenjuan

合成并表征了新型水溶性手性Salen 配体(R,R)-N,N’-二{4-[2-(三甲胺基)乙氧基]水杨醛}-1,2-环己二胺二高氯酸盐(L)及金属配合物ML [M=Zn(II), Cu(II), Ni(II), Co(II), Fe(III), Mn(III)]. 讨论了手性配体L及配合物ZnL的电子光谱和圆二色光谱性质, 用UV-Vis光谱滴定和CD光谱滴定法研究了ZnL对手性氨基酸对映异构体的分子识别. 测定了主体ZnL与客体氨基酸轴向配位反应的配位数(n)、缔合常数(K)及热力学函数 测得缔合常数的大小顺序为KPhe>KVal>KThr. 研究发现反应是放热、熵减小的过程. 用凝胶电泳的方法初步研究了此类手性金属配合物在H2O2存在下对DNA的裂解作用.

关键词: 水溶性手性Salen配合物, 合成和性质, 手性氨基酸, 分子识别, DNA裂解

Chiral salen ligand with quaternary ammonium groups, (R,R)-1,2-bis{4-[2-(trimethylammonium)- ethoxy]-2-hydroxy-salicylideneamino}cyclohexane perchlorate (L) and ML complexes [M=Zn(II), Cu(II), Ni(II), Co(II), Fe(III), Mn(III)] were synthesized and characterized. The electronic spectra and circular dichroism spectra were discussed. By UV-Vis and CD spectrophotometry, the molecular recognition of the host ZnL toward amino acid was studied. The coordination number (n), equilibrium constants (K) and thermodynamic parameters between the complex ZnL and a series of chiral amino acid ligands were measured. The results show that the equilibrium constants decrease in the order of KPhe>KVal>KThr. The reaction is an exothermic process with entropy decrease. The cleavage reaction of DNA with the chiral salen metal complexes in the presence of H2O2 was studied by means of gelatin electrophoresis.

Key words: chiral salen complex of water solubility, synthesis and property, chiral amino acid, molecular recognition, DNA cleavage