Salen Zn对氨基酸甲酯体系的手性分子识别研究  

Studies on Chiral Molecular Recognition of Salen Zn with Amino Acid Esters

作　　者：阮文娟[1] 张玉玲[1] 赵小菁[1] 江冬青[1] 朱志昂[1] 

机构地区：[1]南开大学化学系,天津300071

出　　处：《高等学校化学学报》2003年第9期1657-1661,共5页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20171024;20271030);天津市自然科学基金(批准号:023604011);教育部留学回国人员科研基金

摘　　要：用光谱滴定法测定了手性Salen Zn与D-和L-氨基酸甲酸客体在CHCl_3中的分子识别反应的缔合常数,其大小顺序为 K(LeuOMe)>K(ValOMe)>K(AlaOMe);K(ThrOMe)>K(SerOMe)>K(TyrOMe);且X(D型)>K(L型)。根据van‘t Hoff方程确定了反应体系的热力学函数△rG^Q_m,△rH^Q_m和△rS^Q_m,并对体系的熵-焓补偿关系和对映体选择性进行了讨论.用分子力学和量子化学方法,对体系的识别行为进行了计算研究,从理论上对实验现象及识别过程的规律性给予了合理解释。Using UV-Vis spectrophotometer technique, the association constants of chiral molecular recognition reaction were measured between Salen Zn and series D- and L-amino acid esters in CHCl3. The association constants decrease in the orders of K(LeuOMe) >K(ValOMe)>K(AlaOMe); K(ThrOMe)>K (SerOMe)>K(TyrOMe) and K(D)>K(L). The thermodynamic parameters ΔrGm , ΔrHm , and ΔrSim were determined by Van't Hoff equation. The phenomenon of enthalpy-entropy compensation and enan-tiomer selection were discussed. In addition, the theory studies by means of molecular mechanics and quantum chemistry computation were performed, which gave the reasonable explanation for the experimental results and the behavior of molecular recognition.

关 键 词：Salen-Zn 氨基酸甲酯体系 手性分子识别 熵-焓补偿 分子力学 量子化学计算 

分 类 号：O625.636[理学—有机化学] O641.121[理学—化学]