单手性臂α-猪去氧胆酸类分子钳的设计与微波合成  

Design and Microwave Synthesis of Chiral Single-armed Molecular Tweezers Derived from α-Hyodeoxycholic Acid

作　　者：王健[1,3] 袁小亚[2] 王金月[3] 陈淑华[1] 

机构地区：[1]四川大学化学学院,成都610064 [2]重庆交通大学理学院,重庆 [3]四川宜宾学院化学化工系,宜宾

出　　处：《应用化学》2009年第5期501-506,共6页Chinese Journal of Applied Chemistry

基　　金：国家自然科学基金(20072026,20272038)资助项目

摘　　要：以α-猪去氧胆酸为隔离基,在3位桥联不同的D,L-氨基酸甲酯作手性臂,采用微波辐射法,合成了具有不同手性中心和裂穴的新型分子钳受体,其结构均经1H NMR、IR及元素分析测试技术得以确证。采用紫外光谱滴定法考察了这些受体对D,L-氨基酸甲酯的识别性能。结果表明,这类分子钳受体对所考察的客体D/L-氨基酸甲酯具有良好的识别配合性能,主客体间形成1∶1型超分子配合物。根据Hildebrand-Benesi方程,以1/ΔA对1/[G]0作图,均得出良好的线性关系,由直线的斜率和截距计算出配合物的稳定常数(Ka),进而计算出相应的自由能变化(-ΔG0)。初步研究结果表明,这类分子钳受体由于在结构上的微环境改变,导致其对映选择性识别性能的差异。A novel type of molecular tweezers with different chiral center and cleft has been designed and synthesized with α-hyodeoxycholic acid as spacer and D/L-amino acid methyl ester as chiral arm attached at 3-position under microwave irradiation. Their structures were elucidated by ^1H NMR, FTIR spectra and elemental analysis. Their molecular recognition properties for D/L-amino acid methyl esters were investigated by UV-Vis spectral titration, which showed that all these molecular clefts possessed a good recognition ability for D/L-amino acid methyl esters. The supramolecular complexes formed between the tweezers and various substrates consisted of a 1：1 type of host to guest of molecules. Based on the Hildebrand-Benesi equation,plotting 1/△A vs 1/[ G]0 gave a straight line. From the line slopes and intercepts, the stability constants（Ka） of the complexes were calculated and thereafter the correspondent Gibbs free energies （ -△G^0 ） were also obtained. Preliminary results indicate that due to the structural micro-environmental changes, the synthesized chiral single-armed molecular tweezers exhibit different enantio-selectivity for D/L-amino acid methyl esters.

关 键 词：α-猪去氧胆酸 分子钳 合成 识别性能 

分 类 号：O641.3[理学—物理化学]