物理化学学报 >> 2016, Vol. 32 >> Issue (3): 624-630.doi: 10.3866/PKU.WHXB201512291

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超分子作用对2-(2-氨基苯基)苯并噻唑分子内质子转移的影响

向俊峰,易平贵*(),任志勇,于贤勇,陈建,刘武,李桃梅   

  • 收稿日期:2015-08-28 发布日期:2016-03-04
  • 通讯作者: 易平贵 E-mail:yipinggui@sohu.com
  • 基金资助:
    国家自然科学基金(21172066, 20971041);湖南省高校科技创新团队项目(湘教通[2012]318)

Effect of Supra-Molecular Interaction on the Intramolecular Proton Transfer of 2-(2-Aminophenyl)benzothiazole

Jun-Feng XIANG,Ping-Gui YI*(),Zhi-Yong REN,Xian-Yong YU,Jian CHEN,Wu LIU,Tao-Mei LI   

  • Received:2015-08-28 Published:2016-03-04
  • Contact: Ping-Gui YI E-mail:yipinggui@sohu.com
  • Supported by:
    the National Natural Science Foundation of China(21172066, 20971041);Hunan University of Technology Team Projects , China(湘教通[2012]318)

摘要:

采用稳态荧光、瞬态荧光及量子化学计算等手段对2-(2-氨基苯基)苯并噻唑(APBT)在不同溶剂中的质子转移进行了研究。结果表明,溶剂的极性及质子化对APBT的质子转移有较大的影响,通过对超分子作用的考察,发现七元瓜环(CB[7])的加入对APBT质子转移起到了一定的抑制作用, APBT与CB[7]能形成化学计量比为1:1的主客体包合物,同时测定了包合物的结合常数等热力学参数。此外,核磁共振氢谱和包合物的理论计算表明APBT分子进入了CB[7]的疏水空腔。

关键词: 质子转移, 七元瓜环, 极化连续介质模型, 热力学, 主客体化学

Abstract:

The excited-state intramolecular proton transfer of 2-(2-aminophenyl)benzothiazole (APBT) in different environments was detected by steady-state and transient fluorescence spectral measurements and quantum chemical calculations. The results showed that the polarity and protonation of the solution strongly affect the proton transfer of APBT. When APBT and cucurbit[7]uril (CB[7]) were mixed with each other, we found that the proton transfer process of APBT was restrained by the formation of a complex with a stoichiometric ratio of 1 : 1. The association constant and thermodynamic parameters of this complex were calculated. 1H NMR spectroscopy and quantum chemical calculation data indicated that a 1 : 1 APBT@CB[7] complex of the amine or imine tautomer of APBT formed.

Key words: Proton transfer, Cucurbit[7]uril, Polarizable continuum model, Thermodynamics, Host-guest chemistry

MSC2000: 

  • O641