反式七元瓜环与N,N'-二苄基-4,4'-联吡啶氯化物的络合行为研究

doi:10.7503/cjcu20160458

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (2): 212.doi: 10.7503/cjcu20160458

反式七元瓜环与N,N'-二苄基-4,4'-联吡啶氯化物的络合行为研究

高中政¹, 杨立国², 白东¹, 陈丽霞¹, 陶朱¹, 肖昕¹()

1. 贵州大学贵州省大环化学及超分子化学重点实验室, 贵阳 550025
2. 安阳工学院化学与环境工程学院, 安阳 455000

收稿日期:2016-06-27 出版日期:2017-02-10 发布日期:2016-12-28
作者简介:联系人简介: 肖昕, 男, 博士, 教授, 主要从事超分子化学研究. E-mail: gyhxxiaoxin@163.com
基金资助:
国家自然科学基金(批准号: 21561007)、河南省高等学校重点科研项目计划(批准号: 16A150001)、贵州大学研究生创新基金(批准号: 研理工2016008)和贵州省高层次创新型人才培养计划(批准号: 2016-5657)资助

Interaction of Inverted Cucurbit[7]uril with N,N'-dibenzyl -4,4'-pyridine Chloride^†

GAO Zhongzheng¹, YANG Liguo², BAI Dong¹, CHEN Lixia¹, TAO Zhu¹, XIAO Xin^1,^*()

1.Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province,Guizhou University, Guiyang 550025, China
2.College of Chemistry and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, China

Received:2016-06-27 Online:2017-02-10 Published:2016-12-28
Contact: XIAO Xin E-mail:gyhxxiaoxin@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(No.21561007), the Universitiy Key Scientific Research Program Foundation of Henan Province, China(No.16A150001), the Graduate Student Innovative Funding of Guizhou University, China(No.2016008) and the Innovation Program for High-level Talents of Guizhou Province, China(No.2016-5657)

摘要/Abstract

摘要：

利用核磁共振技术、紫外-可见吸收光谱、荧光发射光谱、等温量热滴定及基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)等方法研究了N,N'-二苄基-4,4'-联吡啶氯化物(G1, 客体分子)与反式七元瓜环(iQ[7], 主体分子)的相互作用及形成的主客体包结配合物的结构特征. 结果表明, 客体分子两端的苄基部分分别进入iQ[7]的空腔, 而4,4'-联吡啶则一部分被iQ[7]的空腔所包结, 另一部分处于iQ[7]的端口, 形成包结比为2:1的哑铃型主客体超分子组装体.

关键词: 反式七元瓜环, N,N'-二苄基-4,4'-联吡啶氯化物, 超分子自组装

Abstract:

An inclusion complex formed on self-assembly of the inverted cucurbit[7]uril(iQ[7]) host with N,N'-dibenzyl-4,4'-pyridine chloride(G1) guest was investigated by ¹H NMR technique, electronic absorption and fluorescence spectroscopies, isothermal titration calorimetry(ITC) experiments and MALDI-TOF mass spectrometry. The experimental results showed that iQ[7] can encapsulate the benzyl moiety of the guest in its hydrophobic cavity to form dumbbell-type host-guest supramolecular assembly, and the inclusion ratio is 2:1. While a part of 4,4'-bipyridine is located inside the cavity of the iQ[7] host, the other part remains outside of the portal of the iQ[7] host.

Key words: Inverted cucurbit[7]uril, N,N'-dibenzyl-4,4'-pyridine chloride, Supramolecular self-assembly

中图分类号:

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高中政, 杨立国, 白东, 陈丽霞, 陶朱, 肖昕. 反式七元瓜环与N,N'-二苄基-4,4'-联吡啶氯化物的络合行为研究. 高等学校化学学报, 2017, 38(2): 212.

GAO Zhongzheng, YANG Liguo, BAI Dong, CHEN Lixia, TAO Zhu, XIAO Xin. Interaction of Inverted Cucurbit[7]uril with N,N'-dibenzyl -4,4'-pyridine Chloride^†. Chem. J. Chinese Universities, 2017, 38(2): 212.

图/表 6

Fig.1 Structures of the inverted cucurbit[7]uril (iQ[7])(A) and the guest G1(B)

Fig.2 1H NMR spectra(500 MHz, D2O) showing the interaction between G1 and iQ[7] at 20 ℃a. iQ[7]; b. n(iQ[7]):n(G1)=0.4; c. n(iQ[7]):n(G1)=0.9; d. n(iQ[7]):n(G1)=1.2; e. n(iQ[7]):n(G1)=2.0; f. G1.

Fig.3 COSY spectrum of G1 and iQ[7] with n(iQ[7])/n(G1)=1.2 in D2O at 20 ℃

Fig.4 Corrected heat rate(A) and normalized fit(B) for the complexation of iQ[7] and G1 in aqueous solution at 25 ℃

Fig.5 Absorption spectra(A) and fluorescence spectra(B) for G1(2.0×10-5 mol/L) with increasing the amount of iQ[7]Inset in (A) shows the absorbance vs. n(iQ[7])/n(G1) plot; inset in (B) shows the fluorescence vs. n(iQ[7])/n(G1) plot. n(iQ[7])/n(G1) from a to p: 0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 2.0, 2.2, 2.4, 2.6, 2.8, 3.0.

Fig.6 Mode of binding interaction between G1 and iQ[7]

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反式七元瓜环与N,N'-二苄基-4,4'-联吡啶氯化物的络合行为研究

Interaction of Inverted Cucurbit[7]uril with N,N'-dibenzyl -4,4'-pyridine Chloride^†

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反式七元瓜环与N,N'-二苄基-4,4'-联吡啶氯化物的络合行为研究

Interaction of Inverted Cucurbit[7]uril with N,N'-dibenzyl -4,4'-pyridine Chloride†

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Interaction of Inverted Cucurbit[7]uril with N,N'-dibenzyl -4,4'-pyridine Chloride^†