高等学校化学学报

高等学校化学学报 ›› 2006, Vol. 27 ›› Issue (5): 920.doi:

• 研究论文 • 上一篇    下一篇

桥联双β-环糊精对N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸的手性识别及机理研究

郝雅琼1, 王立旭1, 马立军1, 吴玉清1, 刘俊秋1, 罗贵民2, 杨光弟1   

  1. 1. 吉林大学超分子结构和材料教育部重点实验室, 2. 分子酶学与工程教育部重点实验室, 长春 130012
  • 收稿日期:1900-01-01 修回日期:1900-01-01 出版日期:2006-05-10 发布日期:2006-05-10
  • 通讯作者: 吴玉清

Chiral Discrimination of N-[4(1-pyrene)butyroyl]-D/L-phenylalanine in Binding with Tellurium/Selenium Bridged-bis-β-cyclodextrins

HAO Ya-Qiong1, WANG Li-Xu1, MA Li-Jun1, WU Yu-Qing1*, LIU Jun-Qiu1, LUO Gui-Min2, YANG Guang-Di1   

  1. 1. Key Laboratory for Supramolecular Structure and Materials of Ministry of Education, 2. Key Laboratory of Molecular
    Enzymology and Engineering of Ministry of Education, Jilin University, Changchun 130012, China
  • Received:1900-01-01 Revised:1900-01-01 Online:2006-05-10 Published:2006-05-10
  • Contact: WU Yu-Qing

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摘要：

利用紫外-可见吸收和荧光发射光谱, 结合非线性最小二乘法拟合曲线以及分子力学(MM2)模拟系统地研究了手性分子N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸(PDP和PLP, 总称PPs)与β-环糊精(β-CD)、 2-位硒桥联双β-CD(2-SeCD)和2-位碲桥联双β-CD(2-TeCD)的包结能力大小及这3个环糊精对PPs手性识别能力的差异和识别机理. 研究结果表明, PPs不能与单疏水空腔的β-CD形成很好的包结复合物, 与具有较长桥联链的2-TeCD结合能力最强. 2-TeCD与PDP和PLP的结合常数分别为2.33×104和6.07×103 L/mol, 对PPs的手性识别比达到KD/KL=3.84, 高于2-SeCD(KD/KL=2.61). 用MM2模拟得出了PPs与这两个双环糊精形成复合物的三维结构: PPs的绝大部分位于双环糊精两个空腔之间, 但是在这两个复合物中, 苯环与芘环所成的二面角不同. 此外, PPs与这两个双环糊精作用时均存在明显的氢键相互作用, 且2-TeCD强于2-SeCD.

关键词: N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸; 硒、 碲桥联双β-环糊精; 非线性最小二乘法拟合; 分子模拟

Abstract:

The binding ability and chiral discrimination of β-cyclodextrin(β-CD), 2,2′-diseleno-bridged β-cyclodextrins(2-SeCD)and 2,2′-ditelluro-bridged β-cyclodextrins(2-TeCD)with PPs were investigated in aqueous solution by using UV-Vis and fluorescence spectroscopy as well as MM2 calculation. The stability constants of complexes were obtained by using least-square curve fitting. From the results of UV-Vis and fluorescence spectroscopy, it was shown that β-CD could not form inclusion complexation with PPs while 2-SeCD and 2-TeCD could. The binding ability between 2-TeCD and PDP was higher(Ks=2.33×104 L/mol) than that of 2-SeCD/PDP(Ks=3.03×103 L/mol). Meanwhile, the high chiral discrimination of PPs was also performed in binding with 2-TeCD(KD/KL=3.84)and 2-SeCD(KD/KL=2.61). Furthermore, the MM2 calculation illustrates that PPs were located between the two cavities of 2-SeCD or 2-TeCD, however, the dihedral angle between phenyl ring and pyrene ring was different from each other when they were included in two bis-cyclodextrins. Meanwhile, MM2 also demonstrates that the intermolecular hydrogen bonding interaction in 2-TeCD/PPs complex was relative stronger than that in 2-SeCD/PPs.

Key words: N-[4(1-pyrene)butyroyl]-D/L-phenylalanine; 2,2′-Diseleno bridged bis-β-cyclodextrin; 2,2′-Ditelluro bridged bis-β-cyclodextrin; Least-square curve fitting; MM2 simulation

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