水溶性手性Salen Mn(III)的光谱性质及其对氨基酸客体的分子识别研究  

Study on Spectral Characterization of Water Soluble Chiral Salen Mn(III) Complexes and the Recognition of Amino Acids

作　　者：朱必学[1] 阮文娟[1] 高峰[1] 胡国航[1] 朱志昂[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《化学学报》2004年第1期58-65,共8页Acta Chimica Sinica

基　　金：国家自然科学基金 (Nos.2 0 1 71 0 2 4 ;2 0 2 71 0 30 );天津市自然科学基金 (No.0 2 360 4 0 1 1 );教育部留学回国人员科研基金资助项目

摘　　要：合成并表征了手性配体SalenH2 及其锰配合物 .详细讨论了配体及配合物的红外光谱、电子吸收光谱和圆二色光谱性质 .研究结果表明 ,SalenMn(III)配合物在水溶液中为Δ构型 ,进一步证明了配合物中双偶氮螯环结构的确具有很高的刚性 .用紫外 -可见光谱滴定方法测定了锰配合物与氨基酸分子识别过程的缔合常数 ,实验结果表明 :主体SalenMn(III)对每一对氨基酸对映异构体的识别能力均表现为对D 型的识别能力比对L 型大 ,对具有相同对映构型的不同氨基酸客体的识别能力按Phe ,Val和Thr顺序依次递减 .圆二色光谱 (CD)考察结果与热力学研究结果一致 .此外 ,采用分子力学方法考察了主客体体系的最低能量构象 ,并对该构象进行了量子化学计算 ,从理论上对实验事实作了进一步解释 .The chiral salen H 2 and chiral salen Mn(III) complex were synthesized and characterized. The infrared spectra, electronic absorption spectra and circular dichroism spectra properties were discussed. The results show that the conformation of five-coordinate salen Mn(III) complex is Δ in water solution. The associative constants (K) of the molecular recognition reactions were determined by means of UV-vis spectral titration technique. And the order of K are K D>K L and K(Phe)>K(Val)>K(Thr). Circular dichroism (CD) spectra were studied and the results are consistent with that from the thermodynamics of association reaction of the host-guest system.In addition,the conformations with minimal energy of salen Mn(III) and each host-guest molecular system were sought by simulated annealing method. Quantum chemical calculations were performed based on these conformations to explain the experimental data.

关 键 词：席夫碱 锰 手性配合物 Salen Mn 光谱性质 氨基酸 分子识别 分子力学 客体 水溶性 圆二色光谱 

分 类 号：O657.3[理学—分析化学]