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.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
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
